21
Research Article Construction of Zinc Oxide into Different Morphological Structures to Be Utilized as Antimicrobial Agent against Multidrug Resistant Bacteria M. F. Elkady, 1,2 H. Shokry Hassan, 3 Elsayed E. Hafez, 4 and Ahmed Fouad 1 1 Fabrication Technology Department, Advanced Technology and New Materials Research Institute (ATNMRI), City of Scientific Research and Technological Applications, Alexandria 21934, Egypt 2 Chemical and Petrochemical Engineering Department, Egypt-Japan University of Science and Technology, New Borg El-Arab City, Alexandria 21934, Egypt 3 Electronic Materials Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City of Scientific Research and Technological Applications, Alexandria 21934, Egypt 4 Plant Protection and Biomolecular Diagnosis Department, Arid Lands Cultivation Research Institute, City of Scientific Research and Technological Applications, New Borg El-Arab City, Alexandria 21934, Egypt Correspondence should be addressed to H. Shokry Hassan; [email protected] Received 13 May 2015; Accepted 20 August 2015 Academic Editor: Claudio Pettinari Copyright © 2015 M. F. Elkady et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Nano-ZnO has been successfully implemented in particles, rods, and tubes nanostructures via sol-gel and hydrothermal techniques. e variation of the different preparation parameters such as reaction temperature, time, and stabilizer agents was optimized to attain different morphological structures. e influence of the microwave annealing process on ZnO crystallinity, surface area, and morphological structure was monitored using XRD, BET, and SEM techniques, respectively. e antimicrobial activity of zinc oxide produced in nanotubes structure was examined against four different multidrug resistant bacteria: Gram-positive (Staphylococcus aureus and Bacillus subtilis) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) strains. e activity of produced nano-ZnO was determined by disc diffusion technique and the results revealed that ZnO nanotubes recorded high activity against the studied strains due to their high surface area equivalent to 17.8m 2 /g. e minimum inhibitory concentration (MIC) of ZnO nanotubes showed that the low concentrations of ZnO nanotubes could be a substitution for the commercial antibiotics when approached in suitable formula. Although the annealing process of ZnO improves the degree of material crystallinity, however, it declines its surface area and consequently its antimicrobial activity. 1. Introduction Nanotechnology offers unique approaches to control a wide variety of biological and medical processes that occur at nanometer length and it is believed to have a successful impact on biology and medicine [1]. In this world of emerging nanotechnology, one of the primary concerns is the potential environment impact of nanoparticles (NPs) [2]. An efficient way to estimate nan- otoxicity is to monitor the response of bacteria exposed to these particles. Resistance of bacteria to bactericides and antibiotics has increased in recent years due to the development of resistant strains. Some antimicrobial agents are extremely irritant and toxic and there is much interest in finding ways to formulate new types of safe and cost-effective biocidal materials [3, 4]. Previous studies have shown that antimicrobial formulations in the form of nanoparticles could be used as effective bactericidal materials [5, 6]. Recently, it has been demonstrated that highly reactive metal oxide nanoparticles exhibit excellent biocidal action against Gram- positive and Gram-negative bacteria [7]. us, the prepara- tion, characterization, surface modification, and functional- ization of nanosized inorganic particles open the possibility Hindawi Publishing Corporation Bioinorganic Chemistry and Applications Volume 2015, Article ID 536854, 20 pages http://dx.doi.org/10.1155/2015/536854

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Research ArticleConstruction of Zinc Oxide into DifferentMorphological Structures to Be Utilized as AntimicrobialAgent against Multidrug Resistant Bacteria

M F Elkady12 H Shokry Hassan3 Elsayed E Hafez4 and Ahmed Fouad1

1Fabrication Technology Department Advanced Technology and New Materials Research Institute (ATNMRI)City of Scientific Research and Technological Applications Alexandria 21934 Egypt2Chemical and Petrochemical Engineering Department Egypt-Japan University of Science and TechnologyNew Borg El-Arab City Alexandria 21934 Egypt3Electronic Materials Research Department Advanced Technology and New Materials Research Institute (ATNMRI)City of Scientific Research and Technological Applications Alexandria 21934 Egypt4Plant Protection and Biomolecular Diagnosis Department Arid Lands Cultivation Research InstituteCity of Scientific Research and Technological Applications New Borg El-Arab City Alexandria 21934 Egypt

Correspondence should be addressed to H Shokry Hassan hassanshokrygmailcom

Received 13 May 2015 Accepted 20 August 2015

Academic Editor Claudio Pettinari

Copyright copy 2015 M F Elkady et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Nano-ZnOhas been successfully implemented in particles rods and tubes nanostructures via sol-gel and hydrothermal techniquesThe variation of the different preparation parameters such as reaction temperature time and stabilizer agents was optimized toattain different morphological structuresThe influence of the microwave annealing process on ZnO crystallinity surface area andmorphological structure wasmonitored using XRD BET and SEM techniques respectivelyThe antimicrobial activity of zinc oxideproduced in nanotubes structure was examined against four different multidrug resistant bacteria Gram-positive (Staphylococcusaureus and Bacillus subtilis) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) strains The activity of producednano-ZnO was determined by disc diffusion technique and the results revealed that ZnO nanotubes recorded high activity againstthe studied strains due to their high surface area equivalent to 178m2g The minimum inhibitory concentration (MIC) of ZnOnanotubes showed that the low concentrations of ZnO nanotubes could be a substitution for the commercial antibiotics whenapproached in suitable formula Although the annealing process of ZnO improves the degree of material crystallinity however itdeclines its surface area and consequently its antimicrobial activity

1 Introduction

Nanotechnology offers unique approaches to control a widevariety of biological and medical processes that occur atnanometer length and it is believed to have a successfulimpact on biology and medicine [1]

In this world of emerging nanotechnology one of theprimary concerns is the potential environment impact ofnanoparticles (NPs) [2] An efficient way to estimate nan-otoxicity is to monitor the response of bacteria exposedto these particles Resistance of bacteria to bactericidesand antibiotics has increased in recent years due to the

development of resistant strains Some antimicrobial agentsare extremely irritant and toxic and there is much interest infinding ways to formulate new types of safe and cost-effectivebiocidal materials [3 4] Previous studies have shown thatantimicrobial formulations in the formof nanoparticles couldbe used as effective bactericidal materials [5 6] Recentlyit has been demonstrated that highly reactive metal oxidenanoparticles exhibit excellent biocidal action against Gram-positive and Gram-negative bacteria [7] Thus the prepara-tion characterization surface modification and functional-ization of nanosized inorganic particles open the possibility

Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2015 Article ID 536854 20 pageshttpdxdoiorg1011552015536854

2 Bioinorganic Chemistry and Applications

of formulation of a new generation of bactericidal materials[8]

Application of nano-zinc oxide in food systems may beeffective at inhibiting certain food-borne pathogens It wasreported that nano-zinc oxide possesses strong antimicrobialactivity against Listeriamonocytogenes Salmonella enteritidisand Escherichia coli O1571198677 [9] Moreover nano-zinc oxidehas a good potential to be coated on a plastic film to makeantimicrobial packaging against bacteria such as Escherichiacoli and Staphylococcus aureus [10]

By controlling the structure precisely at nanoscale dimen-sions one can control and modify its surface layer forenhanced aqueous solubility biocompatibility or bioconju-gation nanoparticles exhibit attractive properties like highstability and the ability to modify their surface characteristicseasily [11]

Sol-gel and hydrothermal methods have been consideredto be the most attractive nanomaterials fabrication toolsin the recent years and they have an edge over all otherprocessing methods due to their reliable control of theshape and size of the nano-zinc oxide without requiring theexpensive and complex equipment

The hydrothermal technique occupies a unique placeowing to its advantages over conventional technologies Thehydrothermal processing of advanced materials has lots ofadvantages and can be used to give high product purityand homogeneity crystal symmetry metastable compoundswith unique properties narrow particle size distributionsa lower sintering temperature a wide range of chemicalcompositions single-step processes dense sintered powderssubmicron particles to nanoparticles with a narrow sizedistribution using simple equipment lower energy require-ments fast reaction times and the lowest residence timeas well as for the growth of crystals with polymorphicmodifications for the growth of crystals with low to ultralowsolubility and as a host of other applications [12]

The sol-gel process can shortly be defined as the conver-sion of a precursor solution into an inorganic solid via inor-ganic polymerization reactions induced by water In generalthe precursor or starting compound is either an inorganic(no carbon) metal salt (chloride nitrate sulphate acetateetc) or a metal organic compound such as an alkoxide Metalalkoxides are the most widely used precursors because theyreact readily with water and are known for many metalsSome alkoxides which are widely used in industry arecommercially available at low cost (Zn Si Ti Al and Zr)whereas other ones are hardly available or only available atvery high costs (Mn Fe CoNi Cu YNb andTa) In generalthe preparation of nano-zinc oxide from zinc acetate usingsol-gel processing is one of the most successful techniqueswhich produced nanostructures of the best crystalline quality[13ndash15]

The objective of this investigation is to synthesize nano-zinc oxide with different morphological structures usinghydrothermal and sol-gel techniques to investigate theantimicrobial activity of the most proper synthesized nano-zinc oxide that attains the highest surface area against Gram-positive and Gram-negative bacteria The influence of theannealing process using Microwave Assisted Technology

(MAT) on the antimicrobial efficiency of the most properprepared nano-zinc oxide will be assigned

2 Materials and Methods

21 Synthesis of Nano-Zinc Oxide via Sol-Gel and Hydrother-mal Techniques Zinc oxide nanopowder with differentmorphological structures was synthesized via sol-gel andhydrothermal techniques The variation of the preparationconditionswas optimized in order to attain ZnOnanopowderwith high surface area 14mM aqueous solution of zincacetate dihydrate was mixed with 025mM of different stud-ied surfactants and the solution pH was adjusted at 9 using50mM of sodium hydroxide The resulting reactant solutionmixture was heated at various temperatures on agitated hotplate for the sol-gel technique Regarding the hydrothermalpreparation technique the solution reaction mixture wasaged in an autoclave at 50Kpsi for different reaction timeintervals The resulting ZnO white powders were washedseveral times with distilled water and absolute ethanol toremove any residual salts and centrifuged at 6000 rpm for 30minutes to separate the nano-zinc oxide Finally the resultantpowders were dried at 60∘C under air atmosphere overnightThe different parameters experiments were carried out todetermine the optimum conditions for zinc oxide formationThe different preparation parameters such as the reactiontemperatures (60 70 80 and 90∘C) reaction time (3 6 12 24and 48 hours) and surfactant types (PVA PVP CTAB PEGand TEA) were optimized to attain zinc oxide with differentmorphological nanostructures

22 Annealing of Prepared ZnO Nanopowders Annealingprocess is known to affect the extent of material crystalliza-tion [16] The most proper morphological nanostructuredzinc oxide (nanotube) will be annealed at three different tem-peratures 500 700 and 900∘C for one hour usingMicrowaveAssisted Technology (MAT)The annealed samples were thenallowed to cool down naturally back to room temperatureprior to characterizationThe influence of annealing temper-ature on zinc oxide crystallinity and morphological structurewas examined The antimicrobial efficiency of the preparedZnO in nanotube morphology after and before annealingprocess was compared using one type of Gram-positive andanother of Gram-negative bacteria isolate

23 Characterization of ZnO Nanopowders The physicalproperties of the synthesized nano-zinc oxide with differentmorphological structures were investigated using differenttechniques The morphological structure and the chemi-cal compositions of the prepared ZnO nanopowder andannealed samples were examined

231 X-Ray Diffraction Analysis (XRD) X-ray powder dif-fractometry was carried out using (Shimadzu 7000) diffrac-tometer with Cu K120572 radiation beam (120582 = 0154060 nm) todetermine the crystalline structure of the different preparedZnOnanopowdersThefinely powdered samples of the nano-zinc oxide were packed into a flat aluminum sample holder

Bioinorganic Chemistry and Applications 3

where the X-ray source was a rotating anode operating at30 kV and 30mA with a copper target Data were collectedbetween 10∘ and 80∘ in 2120579

232 Scanning Electron Microscopy (SEM) The scanningelectron microscope is based on scanning a finely focusedelectron beam across the surface of a specimenThe reflectedsignals are collected and their intensities are displayed ona cathode-ray-tube screen by brightness modulation Theease of sample imaging using scanning electron microscope(JEOL JSM 6360LA Japan) over large distances is quiteappealing The SEM is also extensively employed for thegeneration of dimensional and spatial relationship details ofstructure elementsThe surface of the prepared and annealedZnO nanopowders was scanned to investigate the homo-geneity of the nanopowder and to measure the dimensionalstructures of the different prepared powdersrsquo architecturalmorphology

233 Surface Area (BET) In order to monitor the effectof annealing process on the zinc oxide surface area andsubsequently on its antimicrobial activity the average porediameter and specific surface area BET (Brunauer-Emmett-Teller) of the most proper prepared ZnO in nanotube mor-phological structure before and after annealing process weremeasured on a Quantachrome NOVA 1000 (Boynton BeachFL USA) in nitrogen atmosphere

24 Bacterial Isolates The purified bacterial isolates Gram-positive bacteria (Staphylococcus aureus ATCC 29213 andBacillus subtilis ATCC 23857) and Gram-negative bacteria(Escherichia coli ATCC 25922 and Pseudomonas aeruginosaATCC 27853) were kindly provided by Professor ElsayedElsayed Hafez (Plant Protection and Biomolecular DiagnosisDepartment Arid Lands Cultivation Research Institute Cityof Scientific Research and Technological Applications (SRTACity)) All the bacterial isolates were grown and maintainedon nutrient broth

25 Antimicrobial Procedure Antimicrobial bioassay wascarried out using zinc oxide prepared in nanotubes structurebefore and after annealing against different bacterial isolatesGram-positive bacteria (Staphylococcus aureus and Bacillussubtilis) and Gram-negative bacteria (Escherichia coli andPseudomonas aeruginosa) using agar diffusion techniquein sterilized Petri dishes on the media suitable for testedorganisms [17] Clean Petri dishes containing the mediasuitable for the growth of the tested pathogens were preparedand inoculated with the tested organisms Using sterilizedcork borer wells were made in the media Some wells wereinoculated with 100120583L of 10 and 30mg for each nano-zincoxide suspension sample All Petri dishes were incubatedat conditions as illustrated before [18] Then plates wereincubated at 37∘C for 24 h The measured inhibition zoneswere considered as bactericidal activity of the examinedZnO concentration The minimum inhibitory concentration(MIC) of zinc oxide was demonstrated for each strain isolatein separate manner

3 Results and Discussion

31 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Sol-Gel Technique Inorder to attain different morphological nanostructures fromthe synthesized zinc oxide using two different techniquesthe variation impact of preparation parameters for zincoxide production will be examined Sol-gel technique wasutilized for nano-zinc oxide production in the presence ofdifferent surfactant agentsThe crystalline andmorphologicalstructures of the different produced materials were screenedusing XRD and SEM respectively

311 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Pres-ence of Surfactant In an aqueous solution metal cationsM+119885 are solvated by water giving rise to aqua ionstypically [M(OH2)119899]

+119885 The MndashOH2 bond is polarizedwhich facilitates deprotonation of the coordinated water Indilute solutions a range of monomeric species exist suchas ([M(OH2)119899minus119901(OH)119901]

+(119911minus119901)) and other hydroxyl species[M(OH)119899] ultimately oxygen ions are formed In order toform the polynuclear species which subsequently developinto metal oxide particles reactions involving condensationreactions must occur Two important processes have beenrecognized olation is the formation of an ldquoolrdquo bridge byreaction of a hydroxo- and aquo species as follows [19]

MndashOH +MndashOH2 997888rarr MndashOHndashM +H2O (1)

Oxolation leads to an ldquooxordquo bridge by the dehydration ofhydroxospecies

M2ndash (OH)2 997888rarr MndashOndashM +H2O (2)

Zinc hydroxide is amphoteric and complexation by OHminuscan lead to soluble species such as ldquo[Zn(OH)3]

minusrdquo andldquo[Zn(OH)4]

minus2rdquo and hence ldquozinc hydroxiderdquo is more solublein basic solution [20]

(A) Effect of Surfactant Type on Both the Crystalline andMorphological Structures of Prepared ZnO The surfactantshould be characterized by its alkaline nature Based onthis concept polyvinylpyrrolidone (PVP) polyvinyl alco-hol (PVA) cetyltrimethylammonium bromide (CTAB) tri-ethanolamine (TEA) and polyethylene glycol (PEG) wereselected as surfactant agents where they contain base radicalin their structures as investigated in Figure 1 This figuredemonstrated that these surfactants may act as a weak basedue to their single lone pair of electrons attached on eithernitrogen or oxygen atoms inside their structures and used ascomplexing agents with the metals leading to dissolution ofzinc hydroxide into zinc oxide [21 22]

(i) Crystalline Structure (XRD)TheX-ray diffraction patternsof the nanocrystalline phases of the prepared zinc oxidenanopowder using different surfactant agents were compared

4 Bioinorganic Chemistry and Applications

NO

nCH2 CH

(a)OH

n

(b)

N+

Brminus

(c)

OH

OH

N

HO∙∙

(d)

H

H

n

OO

(e)

Figure 1 Chemical structure of (a) PVP (b) PVA (c) CTAB (d) TEA and (e) PEG

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 2 XRD patterns for ZnO nanopowders via sol-gel techniquewith different surfactant agents (A) PVP (B) PVA (C) CTAB (D)TEA and (E) PEG

with the zinc oxide wurtzite phase (JCPDS card number01-089-1397) It was indicated from Figure 2 that all theprepared ZnO samples using the different surfactant agentsshowedwurtzite crystal structurewith high intensity Figure 2illustrates both the 2120579 values for reference wurtzite phase(JCPDS card number 01-089-1397 119886 = 03253 nm 119888 =05213 nm and 119906 = 16025) and the measured 2120579 values forthe different synthesized ZnO nanopowders in the presenceof different surfactants The sharp peaks indicate that theproducts are well crystallized and oriented [23] All thediffraction peaks can be well indexed to the hexagonal phaseof ZnO reported in JCPDS card number 01-089-1397 and noother characteristic peaks are observed [24 25]

(ii) Morphological Structure (SEM) Figure 3 investigated themorphological structures of the different preparedZnO in thepresence of different surfactants The formation of different

nanorods and nanoparticles that possess well-defined hexag-onal faces was indicated for the different studied surfactantsIn case of using PVP and PVA as surfactants a large quantityof straight rods and a small amount of irregular ones areformed It was observed that the aspect ratio (the averagelength-to-diameter ratio) of formed nanorods decreasedfrom 9 to 4 with the surfactant change from PVP to PVAThesuggested mechanism for nanorods ZnO formation in thepresence of either PVP or PVA may be considered due to thedecomposition of Zn(OH)2 within 60 minutesrsquo heating thatformed ZnO nucleationThe remaining reaction timemay beconsidered as the time of nuclei growth in other directionsthat resulted from dissolution and reprecipitation of theexisting ZnO particles that formed the nanorods structuresOn the other hand it was evident from Figure 3 thatZnO formed in nanoparticles structure with lower diametersranged from 30 to 50 nm in the presence of CTAB TEAand PEG as surfactants Accordingly all the reaction timefor ZnO formation in case of utilizing CTAB TEA and PEGas surfactants may be spent for decomposition of Zn(OH)2to form ZnO nucleation that was promoted into crystallinestructures of nanoparticles at the same nucleation directionSo it is concluded that the surfactant type affects the size andmorphology of ZnO formed according to the nucleation andgrowth mechanisms [26] It is indispensable to understandthe growth mechanism in order to control and designtailored structures In the ZnO and surfactant system thechemical adsorption is basically assigned to the coordinationbetween the surfactant and Zn2+ ions or ZnO Generallysurfactants were used as capping agent because there is astrong interaction between the surfaces of nanocrystals andsurfactant based on the strong coordination ability of O andN atoms in the surfactant It is believed that the selectiveadsorption of surfactants on various crystallographic planesof the nanocrystals played a vital role in controlling themorphology of the products [27] Based on the degree ofadsorption the electrostatic force of attraction and inter-action between the surfactant molecules and Zn2+ ionicgroup a particular morphology with specific orientation issynthesized [28] where the surfactant in aqueous solution

Bioinorganic Chemistry and Applications 5

0047120583m0066120583m

0060120583m

0055120583m

0059120583m

(a)

0081120583m

0068120583m

0057120583m

0073120583m0080120583m

0068120583m

(b)

0046120583m

0029120583m

0053120583m0050120583m

(c)

0037120583m

0036120583m

0049120583m0039120583m

0052120583m0032120583m

(d)

0037120583m

0036120583m

0049120583m

0052120583m

0039120583m

0032120583m

(e)

Figure 3 SEMmicrographs of ZnO prepared using sol-gel technique with different surfactant agents (a) PVP (b) PVA (c) CTAB (d) TEAand (e) PEG

formed a microreactor through various interactions Whenreactants were added the precursors of ZnO nucleated inthis reactor [29] Subsequently the reactor could significantlyprevent the growth of some special crystalline faces andalso preferentially promoted other crystalline facesrsquo growth(Figure 4)

Furthermore by coordinating the water from the dehy-dration reaction of the ZnO precursor surfactant may accel-erate ZnO nucleation and promote ZnO crystallization [29]So it is possible to realize that the nucleation and growthof ZnO can be also controlled by the coordination betweensurfactant and water [30] Concerning the PVP and PVAbehaviors for ZnO formation it was observed that the density

of ZnO rods increases Accordingly it may be predicted thatthe surfactant accelerates the nucleation of ZnO [31] SoPVP and PVA produced nanorods structure where CTABPEG and TEA produced nanoparticles Accordingly PVPwas selected as the optimum surfactant that produces ZnOin nanorods structures

(B) Effect of Reaction Temperature on Both the Crystallineand Morphological Structures of Prepared ZnO The tem-perature influenced morphology evolution and its effect onphysicochemical properties of synthesized nano-zinc oxideSo simple study on the relationship between the reactiontemperature and the morphological structures of synthesized

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

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Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Page 2: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

2 Bioinorganic Chemistry and Applications

of formulation of a new generation of bactericidal materials[8]

Application of nano-zinc oxide in food systems may beeffective at inhibiting certain food-borne pathogens It wasreported that nano-zinc oxide possesses strong antimicrobialactivity against Listeriamonocytogenes Salmonella enteritidisand Escherichia coli O1571198677 [9] Moreover nano-zinc oxidehas a good potential to be coated on a plastic film to makeantimicrobial packaging against bacteria such as Escherichiacoli and Staphylococcus aureus [10]

By controlling the structure precisely at nanoscale dimen-sions one can control and modify its surface layer forenhanced aqueous solubility biocompatibility or bioconju-gation nanoparticles exhibit attractive properties like highstability and the ability to modify their surface characteristicseasily [11]

Sol-gel and hydrothermal methods have been consideredto be the most attractive nanomaterials fabrication toolsin the recent years and they have an edge over all otherprocessing methods due to their reliable control of theshape and size of the nano-zinc oxide without requiring theexpensive and complex equipment

The hydrothermal technique occupies a unique placeowing to its advantages over conventional technologies Thehydrothermal processing of advanced materials has lots ofadvantages and can be used to give high product purityand homogeneity crystal symmetry metastable compoundswith unique properties narrow particle size distributionsa lower sintering temperature a wide range of chemicalcompositions single-step processes dense sintered powderssubmicron particles to nanoparticles with a narrow sizedistribution using simple equipment lower energy require-ments fast reaction times and the lowest residence timeas well as for the growth of crystals with polymorphicmodifications for the growth of crystals with low to ultralowsolubility and as a host of other applications [12]

The sol-gel process can shortly be defined as the conver-sion of a precursor solution into an inorganic solid via inor-ganic polymerization reactions induced by water In generalthe precursor or starting compound is either an inorganic(no carbon) metal salt (chloride nitrate sulphate acetateetc) or a metal organic compound such as an alkoxide Metalalkoxides are the most widely used precursors because theyreact readily with water and are known for many metalsSome alkoxides which are widely used in industry arecommercially available at low cost (Zn Si Ti Al and Zr)whereas other ones are hardly available or only available atvery high costs (Mn Fe CoNi Cu YNb andTa) In generalthe preparation of nano-zinc oxide from zinc acetate usingsol-gel processing is one of the most successful techniqueswhich produced nanostructures of the best crystalline quality[13ndash15]

The objective of this investigation is to synthesize nano-zinc oxide with different morphological structures usinghydrothermal and sol-gel techniques to investigate theantimicrobial activity of the most proper synthesized nano-zinc oxide that attains the highest surface area against Gram-positive and Gram-negative bacteria The influence of theannealing process using Microwave Assisted Technology

(MAT) on the antimicrobial efficiency of the most properprepared nano-zinc oxide will be assigned

2 Materials and Methods

21 Synthesis of Nano-Zinc Oxide via Sol-Gel and Hydrother-mal Techniques Zinc oxide nanopowder with differentmorphological structures was synthesized via sol-gel andhydrothermal techniques The variation of the preparationconditionswas optimized in order to attain ZnOnanopowderwith high surface area 14mM aqueous solution of zincacetate dihydrate was mixed with 025mM of different stud-ied surfactants and the solution pH was adjusted at 9 using50mM of sodium hydroxide The resulting reactant solutionmixture was heated at various temperatures on agitated hotplate for the sol-gel technique Regarding the hydrothermalpreparation technique the solution reaction mixture wasaged in an autoclave at 50Kpsi for different reaction timeintervals The resulting ZnO white powders were washedseveral times with distilled water and absolute ethanol toremove any residual salts and centrifuged at 6000 rpm for 30minutes to separate the nano-zinc oxide Finally the resultantpowders were dried at 60∘C under air atmosphere overnightThe different parameters experiments were carried out todetermine the optimum conditions for zinc oxide formationThe different preparation parameters such as the reactiontemperatures (60 70 80 and 90∘C) reaction time (3 6 12 24and 48 hours) and surfactant types (PVA PVP CTAB PEGand TEA) were optimized to attain zinc oxide with differentmorphological nanostructures

22 Annealing of Prepared ZnO Nanopowders Annealingprocess is known to affect the extent of material crystalliza-tion [16] The most proper morphological nanostructuredzinc oxide (nanotube) will be annealed at three different tem-peratures 500 700 and 900∘C for one hour usingMicrowaveAssisted Technology (MAT)The annealed samples were thenallowed to cool down naturally back to room temperatureprior to characterizationThe influence of annealing temper-ature on zinc oxide crystallinity and morphological structurewas examined The antimicrobial efficiency of the preparedZnO in nanotube morphology after and before annealingprocess was compared using one type of Gram-positive andanother of Gram-negative bacteria isolate

23 Characterization of ZnO Nanopowders The physicalproperties of the synthesized nano-zinc oxide with differentmorphological structures were investigated using differenttechniques The morphological structure and the chemi-cal compositions of the prepared ZnO nanopowder andannealed samples were examined

231 X-Ray Diffraction Analysis (XRD) X-ray powder dif-fractometry was carried out using (Shimadzu 7000) diffrac-tometer with Cu K120572 radiation beam (120582 = 0154060 nm) todetermine the crystalline structure of the different preparedZnOnanopowdersThefinely powdered samples of the nano-zinc oxide were packed into a flat aluminum sample holder

Bioinorganic Chemistry and Applications 3

where the X-ray source was a rotating anode operating at30 kV and 30mA with a copper target Data were collectedbetween 10∘ and 80∘ in 2120579

232 Scanning Electron Microscopy (SEM) The scanningelectron microscope is based on scanning a finely focusedelectron beam across the surface of a specimenThe reflectedsignals are collected and their intensities are displayed ona cathode-ray-tube screen by brightness modulation Theease of sample imaging using scanning electron microscope(JEOL JSM 6360LA Japan) over large distances is quiteappealing The SEM is also extensively employed for thegeneration of dimensional and spatial relationship details ofstructure elementsThe surface of the prepared and annealedZnO nanopowders was scanned to investigate the homo-geneity of the nanopowder and to measure the dimensionalstructures of the different prepared powdersrsquo architecturalmorphology

233 Surface Area (BET) In order to monitor the effectof annealing process on the zinc oxide surface area andsubsequently on its antimicrobial activity the average porediameter and specific surface area BET (Brunauer-Emmett-Teller) of the most proper prepared ZnO in nanotube mor-phological structure before and after annealing process weremeasured on a Quantachrome NOVA 1000 (Boynton BeachFL USA) in nitrogen atmosphere

24 Bacterial Isolates The purified bacterial isolates Gram-positive bacteria (Staphylococcus aureus ATCC 29213 andBacillus subtilis ATCC 23857) and Gram-negative bacteria(Escherichia coli ATCC 25922 and Pseudomonas aeruginosaATCC 27853) were kindly provided by Professor ElsayedElsayed Hafez (Plant Protection and Biomolecular DiagnosisDepartment Arid Lands Cultivation Research Institute Cityof Scientific Research and Technological Applications (SRTACity)) All the bacterial isolates were grown and maintainedon nutrient broth

25 Antimicrobial Procedure Antimicrobial bioassay wascarried out using zinc oxide prepared in nanotubes structurebefore and after annealing against different bacterial isolatesGram-positive bacteria (Staphylococcus aureus and Bacillussubtilis) and Gram-negative bacteria (Escherichia coli andPseudomonas aeruginosa) using agar diffusion techniquein sterilized Petri dishes on the media suitable for testedorganisms [17] Clean Petri dishes containing the mediasuitable for the growth of the tested pathogens were preparedand inoculated with the tested organisms Using sterilizedcork borer wells were made in the media Some wells wereinoculated with 100120583L of 10 and 30mg for each nano-zincoxide suspension sample All Petri dishes were incubatedat conditions as illustrated before [18] Then plates wereincubated at 37∘C for 24 h The measured inhibition zoneswere considered as bactericidal activity of the examinedZnO concentration The minimum inhibitory concentration(MIC) of zinc oxide was demonstrated for each strain isolatein separate manner

3 Results and Discussion

31 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Sol-Gel Technique Inorder to attain different morphological nanostructures fromthe synthesized zinc oxide using two different techniquesthe variation impact of preparation parameters for zincoxide production will be examined Sol-gel technique wasutilized for nano-zinc oxide production in the presence ofdifferent surfactant agentsThe crystalline andmorphologicalstructures of the different produced materials were screenedusing XRD and SEM respectively

311 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Pres-ence of Surfactant In an aqueous solution metal cationsM+119885 are solvated by water giving rise to aqua ionstypically [M(OH2)119899]

+119885 The MndashOH2 bond is polarizedwhich facilitates deprotonation of the coordinated water Indilute solutions a range of monomeric species exist suchas ([M(OH2)119899minus119901(OH)119901]

+(119911minus119901)) and other hydroxyl species[M(OH)119899] ultimately oxygen ions are formed In order toform the polynuclear species which subsequently developinto metal oxide particles reactions involving condensationreactions must occur Two important processes have beenrecognized olation is the formation of an ldquoolrdquo bridge byreaction of a hydroxo- and aquo species as follows [19]

MndashOH +MndashOH2 997888rarr MndashOHndashM +H2O (1)

Oxolation leads to an ldquooxordquo bridge by the dehydration ofhydroxospecies

M2ndash (OH)2 997888rarr MndashOndashM +H2O (2)

Zinc hydroxide is amphoteric and complexation by OHminuscan lead to soluble species such as ldquo[Zn(OH)3]

minusrdquo andldquo[Zn(OH)4]

minus2rdquo and hence ldquozinc hydroxiderdquo is more solublein basic solution [20]

(A) Effect of Surfactant Type on Both the Crystalline andMorphological Structures of Prepared ZnO The surfactantshould be characterized by its alkaline nature Based onthis concept polyvinylpyrrolidone (PVP) polyvinyl alco-hol (PVA) cetyltrimethylammonium bromide (CTAB) tri-ethanolamine (TEA) and polyethylene glycol (PEG) wereselected as surfactant agents where they contain base radicalin their structures as investigated in Figure 1 This figuredemonstrated that these surfactants may act as a weak basedue to their single lone pair of electrons attached on eithernitrogen or oxygen atoms inside their structures and used ascomplexing agents with the metals leading to dissolution ofzinc hydroxide into zinc oxide [21 22]

(i) Crystalline Structure (XRD)TheX-ray diffraction patternsof the nanocrystalline phases of the prepared zinc oxidenanopowder using different surfactant agents were compared

4 Bioinorganic Chemistry and Applications

NO

nCH2 CH

(a)OH

n

(b)

N+

Brminus

(c)

OH

OH

N

HO∙∙

(d)

H

H

n

OO

(e)

Figure 1 Chemical structure of (a) PVP (b) PVA (c) CTAB (d) TEA and (e) PEG

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 2 XRD patterns for ZnO nanopowders via sol-gel techniquewith different surfactant agents (A) PVP (B) PVA (C) CTAB (D)TEA and (E) PEG

with the zinc oxide wurtzite phase (JCPDS card number01-089-1397) It was indicated from Figure 2 that all theprepared ZnO samples using the different surfactant agentsshowedwurtzite crystal structurewith high intensity Figure 2illustrates both the 2120579 values for reference wurtzite phase(JCPDS card number 01-089-1397 119886 = 03253 nm 119888 =05213 nm and 119906 = 16025) and the measured 2120579 values forthe different synthesized ZnO nanopowders in the presenceof different surfactants The sharp peaks indicate that theproducts are well crystallized and oriented [23] All thediffraction peaks can be well indexed to the hexagonal phaseof ZnO reported in JCPDS card number 01-089-1397 and noother characteristic peaks are observed [24 25]

(ii) Morphological Structure (SEM) Figure 3 investigated themorphological structures of the different preparedZnO in thepresence of different surfactants The formation of different

nanorods and nanoparticles that possess well-defined hexag-onal faces was indicated for the different studied surfactantsIn case of using PVP and PVA as surfactants a large quantityof straight rods and a small amount of irregular ones areformed It was observed that the aspect ratio (the averagelength-to-diameter ratio) of formed nanorods decreasedfrom 9 to 4 with the surfactant change from PVP to PVAThesuggested mechanism for nanorods ZnO formation in thepresence of either PVP or PVA may be considered due to thedecomposition of Zn(OH)2 within 60 minutesrsquo heating thatformed ZnO nucleationThe remaining reaction timemay beconsidered as the time of nuclei growth in other directionsthat resulted from dissolution and reprecipitation of theexisting ZnO particles that formed the nanorods structuresOn the other hand it was evident from Figure 3 thatZnO formed in nanoparticles structure with lower diametersranged from 30 to 50 nm in the presence of CTAB TEAand PEG as surfactants Accordingly all the reaction timefor ZnO formation in case of utilizing CTAB TEA and PEGas surfactants may be spent for decomposition of Zn(OH)2to form ZnO nucleation that was promoted into crystallinestructures of nanoparticles at the same nucleation directionSo it is concluded that the surfactant type affects the size andmorphology of ZnO formed according to the nucleation andgrowth mechanisms [26] It is indispensable to understandthe growth mechanism in order to control and designtailored structures In the ZnO and surfactant system thechemical adsorption is basically assigned to the coordinationbetween the surfactant and Zn2+ ions or ZnO Generallysurfactants were used as capping agent because there is astrong interaction between the surfaces of nanocrystals andsurfactant based on the strong coordination ability of O andN atoms in the surfactant It is believed that the selectiveadsorption of surfactants on various crystallographic planesof the nanocrystals played a vital role in controlling themorphology of the products [27] Based on the degree ofadsorption the electrostatic force of attraction and inter-action between the surfactant molecules and Zn2+ ionicgroup a particular morphology with specific orientation issynthesized [28] where the surfactant in aqueous solution

Bioinorganic Chemistry and Applications 5

0047120583m0066120583m

0060120583m

0055120583m

0059120583m

(a)

0081120583m

0068120583m

0057120583m

0073120583m0080120583m

0068120583m

(b)

0046120583m

0029120583m

0053120583m0050120583m

(c)

0037120583m

0036120583m

0049120583m0039120583m

0052120583m0032120583m

(d)

0037120583m

0036120583m

0049120583m

0052120583m

0039120583m

0032120583m

(e)

Figure 3 SEMmicrographs of ZnO prepared using sol-gel technique with different surfactant agents (a) PVP (b) PVA (c) CTAB (d) TEAand (e) PEG

formed a microreactor through various interactions Whenreactants were added the precursors of ZnO nucleated inthis reactor [29] Subsequently the reactor could significantlyprevent the growth of some special crystalline faces andalso preferentially promoted other crystalline facesrsquo growth(Figure 4)

Furthermore by coordinating the water from the dehy-dration reaction of the ZnO precursor surfactant may accel-erate ZnO nucleation and promote ZnO crystallization [29]So it is possible to realize that the nucleation and growthof ZnO can be also controlled by the coordination betweensurfactant and water [30] Concerning the PVP and PVAbehaviors for ZnO formation it was observed that the density

of ZnO rods increases Accordingly it may be predicted thatthe surfactant accelerates the nucleation of ZnO [31] SoPVP and PVA produced nanorods structure where CTABPEG and TEA produced nanoparticles Accordingly PVPwas selected as the optimum surfactant that produces ZnOin nanorods structures

(B) Effect of Reaction Temperature on Both the Crystallineand Morphological Structures of Prepared ZnO The tem-perature influenced morphology evolution and its effect onphysicochemical properties of synthesized nano-zinc oxideSo simple study on the relationship between the reactiontemperature and the morphological structures of synthesized

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

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Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

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Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 3: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 3

where the X-ray source was a rotating anode operating at30 kV and 30mA with a copper target Data were collectedbetween 10∘ and 80∘ in 2120579

232 Scanning Electron Microscopy (SEM) The scanningelectron microscope is based on scanning a finely focusedelectron beam across the surface of a specimenThe reflectedsignals are collected and their intensities are displayed ona cathode-ray-tube screen by brightness modulation Theease of sample imaging using scanning electron microscope(JEOL JSM 6360LA Japan) over large distances is quiteappealing The SEM is also extensively employed for thegeneration of dimensional and spatial relationship details ofstructure elementsThe surface of the prepared and annealedZnO nanopowders was scanned to investigate the homo-geneity of the nanopowder and to measure the dimensionalstructures of the different prepared powdersrsquo architecturalmorphology

233 Surface Area (BET) In order to monitor the effectof annealing process on the zinc oxide surface area andsubsequently on its antimicrobial activity the average porediameter and specific surface area BET (Brunauer-Emmett-Teller) of the most proper prepared ZnO in nanotube mor-phological structure before and after annealing process weremeasured on a Quantachrome NOVA 1000 (Boynton BeachFL USA) in nitrogen atmosphere

24 Bacterial Isolates The purified bacterial isolates Gram-positive bacteria (Staphylococcus aureus ATCC 29213 andBacillus subtilis ATCC 23857) and Gram-negative bacteria(Escherichia coli ATCC 25922 and Pseudomonas aeruginosaATCC 27853) were kindly provided by Professor ElsayedElsayed Hafez (Plant Protection and Biomolecular DiagnosisDepartment Arid Lands Cultivation Research Institute Cityof Scientific Research and Technological Applications (SRTACity)) All the bacterial isolates were grown and maintainedon nutrient broth

25 Antimicrobial Procedure Antimicrobial bioassay wascarried out using zinc oxide prepared in nanotubes structurebefore and after annealing against different bacterial isolatesGram-positive bacteria (Staphylococcus aureus and Bacillussubtilis) and Gram-negative bacteria (Escherichia coli andPseudomonas aeruginosa) using agar diffusion techniquein sterilized Petri dishes on the media suitable for testedorganisms [17] Clean Petri dishes containing the mediasuitable for the growth of the tested pathogens were preparedand inoculated with the tested organisms Using sterilizedcork borer wells were made in the media Some wells wereinoculated with 100120583L of 10 and 30mg for each nano-zincoxide suspension sample All Petri dishes were incubatedat conditions as illustrated before [18] Then plates wereincubated at 37∘C for 24 h The measured inhibition zoneswere considered as bactericidal activity of the examinedZnO concentration The minimum inhibitory concentration(MIC) of zinc oxide was demonstrated for each strain isolatein separate manner

3 Results and Discussion

31 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Sol-Gel Technique Inorder to attain different morphological nanostructures fromthe synthesized zinc oxide using two different techniquesthe variation impact of preparation parameters for zincoxide production will be examined Sol-gel technique wasutilized for nano-zinc oxide production in the presence ofdifferent surfactant agentsThe crystalline andmorphologicalstructures of the different produced materials were screenedusing XRD and SEM respectively

311 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Pres-ence of Surfactant In an aqueous solution metal cationsM+119885 are solvated by water giving rise to aqua ionstypically [M(OH2)119899]

+119885 The MndashOH2 bond is polarizedwhich facilitates deprotonation of the coordinated water Indilute solutions a range of monomeric species exist suchas ([M(OH2)119899minus119901(OH)119901]

+(119911minus119901)) and other hydroxyl species[M(OH)119899] ultimately oxygen ions are formed In order toform the polynuclear species which subsequently developinto metal oxide particles reactions involving condensationreactions must occur Two important processes have beenrecognized olation is the formation of an ldquoolrdquo bridge byreaction of a hydroxo- and aquo species as follows [19]

MndashOH +MndashOH2 997888rarr MndashOHndashM +H2O (1)

Oxolation leads to an ldquooxordquo bridge by the dehydration ofhydroxospecies

M2ndash (OH)2 997888rarr MndashOndashM +H2O (2)

Zinc hydroxide is amphoteric and complexation by OHminuscan lead to soluble species such as ldquo[Zn(OH)3]

minusrdquo andldquo[Zn(OH)4]

minus2rdquo and hence ldquozinc hydroxiderdquo is more solublein basic solution [20]

(A) Effect of Surfactant Type on Both the Crystalline andMorphological Structures of Prepared ZnO The surfactantshould be characterized by its alkaline nature Based onthis concept polyvinylpyrrolidone (PVP) polyvinyl alco-hol (PVA) cetyltrimethylammonium bromide (CTAB) tri-ethanolamine (TEA) and polyethylene glycol (PEG) wereselected as surfactant agents where they contain base radicalin their structures as investigated in Figure 1 This figuredemonstrated that these surfactants may act as a weak basedue to their single lone pair of electrons attached on eithernitrogen or oxygen atoms inside their structures and used ascomplexing agents with the metals leading to dissolution ofzinc hydroxide into zinc oxide [21 22]

(i) Crystalline Structure (XRD)TheX-ray diffraction patternsof the nanocrystalline phases of the prepared zinc oxidenanopowder using different surfactant agents were compared

4 Bioinorganic Chemistry and Applications

NO

nCH2 CH

(a)OH

n

(b)

N+

Brminus

(c)

OH

OH

N

HO∙∙

(d)

H

H

n

OO

(e)

Figure 1 Chemical structure of (a) PVP (b) PVA (c) CTAB (d) TEA and (e) PEG

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 2 XRD patterns for ZnO nanopowders via sol-gel techniquewith different surfactant agents (A) PVP (B) PVA (C) CTAB (D)TEA and (E) PEG

with the zinc oxide wurtzite phase (JCPDS card number01-089-1397) It was indicated from Figure 2 that all theprepared ZnO samples using the different surfactant agentsshowedwurtzite crystal structurewith high intensity Figure 2illustrates both the 2120579 values for reference wurtzite phase(JCPDS card number 01-089-1397 119886 = 03253 nm 119888 =05213 nm and 119906 = 16025) and the measured 2120579 values forthe different synthesized ZnO nanopowders in the presenceof different surfactants The sharp peaks indicate that theproducts are well crystallized and oriented [23] All thediffraction peaks can be well indexed to the hexagonal phaseof ZnO reported in JCPDS card number 01-089-1397 and noother characteristic peaks are observed [24 25]

(ii) Morphological Structure (SEM) Figure 3 investigated themorphological structures of the different preparedZnO in thepresence of different surfactants The formation of different

nanorods and nanoparticles that possess well-defined hexag-onal faces was indicated for the different studied surfactantsIn case of using PVP and PVA as surfactants a large quantityof straight rods and a small amount of irregular ones areformed It was observed that the aspect ratio (the averagelength-to-diameter ratio) of formed nanorods decreasedfrom 9 to 4 with the surfactant change from PVP to PVAThesuggested mechanism for nanorods ZnO formation in thepresence of either PVP or PVA may be considered due to thedecomposition of Zn(OH)2 within 60 minutesrsquo heating thatformed ZnO nucleationThe remaining reaction timemay beconsidered as the time of nuclei growth in other directionsthat resulted from dissolution and reprecipitation of theexisting ZnO particles that formed the nanorods structuresOn the other hand it was evident from Figure 3 thatZnO formed in nanoparticles structure with lower diametersranged from 30 to 50 nm in the presence of CTAB TEAand PEG as surfactants Accordingly all the reaction timefor ZnO formation in case of utilizing CTAB TEA and PEGas surfactants may be spent for decomposition of Zn(OH)2to form ZnO nucleation that was promoted into crystallinestructures of nanoparticles at the same nucleation directionSo it is concluded that the surfactant type affects the size andmorphology of ZnO formed according to the nucleation andgrowth mechanisms [26] It is indispensable to understandthe growth mechanism in order to control and designtailored structures In the ZnO and surfactant system thechemical adsorption is basically assigned to the coordinationbetween the surfactant and Zn2+ ions or ZnO Generallysurfactants were used as capping agent because there is astrong interaction between the surfaces of nanocrystals andsurfactant based on the strong coordination ability of O andN atoms in the surfactant It is believed that the selectiveadsorption of surfactants on various crystallographic planesof the nanocrystals played a vital role in controlling themorphology of the products [27] Based on the degree ofadsorption the electrostatic force of attraction and inter-action between the surfactant molecules and Zn2+ ionicgroup a particular morphology with specific orientation issynthesized [28] where the surfactant in aqueous solution

Bioinorganic Chemistry and Applications 5

0047120583m0066120583m

0060120583m

0055120583m

0059120583m

(a)

0081120583m

0068120583m

0057120583m

0073120583m0080120583m

0068120583m

(b)

0046120583m

0029120583m

0053120583m0050120583m

(c)

0037120583m

0036120583m

0049120583m0039120583m

0052120583m0032120583m

(d)

0037120583m

0036120583m

0049120583m

0052120583m

0039120583m

0032120583m

(e)

Figure 3 SEMmicrographs of ZnO prepared using sol-gel technique with different surfactant agents (a) PVP (b) PVA (c) CTAB (d) TEAand (e) PEG

formed a microreactor through various interactions Whenreactants were added the precursors of ZnO nucleated inthis reactor [29] Subsequently the reactor could significantlyprevent the growth of some special crystalline faces andalso preferentially promoted other crystalline facesrsquo growth(Figure 4)

Furthermore by coordinating the water from the dehy-dration reaction of the ZnO precursor surfactant may accel-erate ZnO nucleation and promote ZnO crystallization [29]So it is possible to realize that the nucleation and growthof ZnO can be also controlled by the coordination betweensurfactant and water [30] Concerning the PVP and PVAbehaviors for ZnO formation it was observed that the density

of ZnO rods increases Accordingly it may be predicted thatthe surfactant accelerates the nucleation of ZnO [31] SoPVP and PVA produced nanorods structure where CTABPEG and TEA produced nanoparticles Accordingly PVPwas selected as the optimum surfactant that produces ZnOin nanorods structures

(B) Effect of Reaction Temperature on Both the Crystallineand Morphological Structures of Prepared ZnO The tem-perature influenced morphology evolution and its effect onphysicochemical properties of synthesized nano-zinc oxideSo simple study on the relationship between the reactiontemperature and the morphological structures of synthesized

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 4: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

4 Bioinorganic Chemistry and Applications

NO

nCH2 CH

(a)OH

n

(b)

N+

Brminus

(c)

OH

OH

N

HO∙∙

(d)

H

H

n

OO

(e)

Figure 1 Chemical structure of (a) PVP (b) PVA (c) CTAB (d) TEA and (e) PEG

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 2 XRD patterns for ZnO nanopowders via sol-gel techniquewith different surfactant agents (A) PVP (B) PVA (C) CTAB (D)TEA and (E) PEG

with the zinc oxide wurtzite phase (JCPDS card number01-089-1397) It was indicated from Figure 2 that all theprepared ZnO samples using the different surfactant agentsshowedwurtzite crystal structurewith high intensity Figure 2illustrates both the 2120579 values for reference wurtzite phase(JCPDS card number 01-089-1397 119886 = 03253 nm 119888 =05213 nm and 119906 = 16025) and the measured 2120579 values forthe different synthesized ZnO nanopowders in the presenceof different surfactants The sharp peaks indicate that theproducts are well crystallized and oriented [23] All thediffraction peaks can be well indexed to the hexagonal phaseof ZnO reported in JCPDS card number 01-089-1397 and noother characteristic peaks are observed [24 25]

(ii) Morphological Structure (SEM) Figure 3 investigated themorphological structures of the different preparedZnO in thepresence of different surfactants The formation of different

nanorods and nanoparticles that possess well-defined hexag-onal faces was indicated for the different studied surfactantsIn case of using PVP and PVA as surfactants a large quantityof straight rods and a small amount of irregular ones areformed It was observed that the aspect ratio (the averagelength-to-diameter ratio) of formed nanorods decreasedfrom 9 to 4 with the surfactant change from PVP to PVAThesuggested mechanism for nanorods ZnO formation in thepresence of either PVP or PVA may be considered due to thedecomposition of Zn(OH)2 within 60 minutesrsquo heating thatformed ZnO nucleationThe remaining reaction timemay beconsidered as the time of nuclei growth in other directionsthat resulted from dissolution and reprecipitation of theexisting ZnO particles that formed the nanorods structuresOn the other hand it was evident from Figure 3 thatZnO formed in nanoparticles structure with lower diametersranged from 30 to 50 nm in the presence of CTAB TEAand PEG as surfactants Accordingly all the reaction timefor ZnO formation in case of utilizing CTAB TEA and PEGas surfactants may be spent for decomposition of Zn(OH)2to form ZnO nucleation that was promoted into crystallinestructures of nanoparticles at the same nucleation directionSo it is concluded that the surfactant type affects the size andmorphology of ZnO formed according to the nucleation andgrowth mechanisms [26] It is indispensable to understandthe growth mechanism in order to control and designtailored structures In the ZnO and surfactant system thechemical adsorption is basically assigned to the coordinationbetween the surfactant and Zn2+ ions or ZnO Generallysurfactants were used as capping agent because there is astrong interaction between the surfaces of nanocrystals andsurfactant based on the strong coordination ability of O andN atoms in the surfactant It is believed that the selectiveadsorption of surfactants on various crystallographic planesof the nanocrystals played a vital role in controlling themorphology of the products [27] Based on the degree ofadsorption the electrostatic force of attraction and inter-action between the surfactant molecules and Zn2+ ionicgroup a particular morphology with specific orientation issynthesized [28] where the surfactant in aqueous solution

Bioinorganic Chemistry and Applications 5

0047120583m0066120583m

0060120583m

0055120583m

0059120583m

(a)

0081120583m

0068120583m

0057120583m

0073120583m0080120583m

0068120583m

(b)

0046120583m

0029120583m

0053120583m0050120583m

(c)

0037120583m

0036120583m

0049120583m0039120583m

0052120583m0032120583m

(d)

0037120583m

0036120583m

0049120583m

0052120583m

0039120583m

0032120583m

(e)

Figure 3 SEMmicrographs of ZnO prepared using sol-gel technique with different surfactant agents (a) PVP (b) PVA (c) CTAB (d) TEAand (e) PEG

formed a microreactor through various interactions Whenreactants were added the precursors of ZnO nucleated inthis reactor [29] Subsequently the reactor could significantlyprevent the growth of some special crystalline faces andalso preferentially promoted other crystalline facesrsquo growth(Figure 4)

Furthermore by coordinating the water from the dehy-dration reaction of the ZnO precursor surfactant may accel-erate ZnO nucleation and promote ZnO crystallization [29]So it is possible to realize that the nucleation and growthof ZnO can be also controlled by the coordination betweensurfactant and water [30] Concerning the PVP and PVAbehaviors for ZnO formation it was observed that the density

of ZnO rods increases Accordingly it may be predicted thatthe surfactant accelerates the nucleation of ZnO [31] SoPVP and PVA produced nanorods structure where CTABPEG and TEA produced nanoparticles Accordingly PVPwas selected as the optimum surfactant that produces ZnOin nanorods structures

(B) Effect of Reaction Temperature on Both the Crystallineand Morphological Structures of Prepared ZnO The tem-perature influenced morphology evolution and its effect onphysicochemical properties of synthesized nano-zinc oxideSo simple study on the relationship between the reactiontemperature and the morphological structures of synthesized

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

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Page 5: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 5

0047120583m0066120583m

0060120583m

0055120583m

0059120583m

(a)

0081120583m

0068120583m

0057120583m

0073120583m0080120583m

0068120583m

(b)

0046120583m

0029120583m

0053120583m0050120583m

(c)

0037120583m

0036120583m

0049120583m0039120583m

0052120583m0032120583m

(d)

0037120583m

0036120583m

0049120583m

0052120583m

0039120583m

0032120583m

(e)

Figure 3 SEMmicrographs of ZnO prepared using sol-gel technique with different surfactant agents (a) PVP (b) PVA (c) CTAB (d) TEAand (e) PEG

formed a microreactor through various interactions Whenreactants were added the precursors of ZnO nucleated inthis reactor [29] Subsequently the reactor could significantlyprevent the growth of some special crystalline faces andalso preferentially promoted other crystalline facesrsquo growth(Figure 4)

Furthermore by coordinating the water from the dehy-dration reaction of the ZnO precursor surfactant may accel-erate ZnO nucleation and promote ZnO crystallization [29]So it is possible to realize that the nucleation and growthof ZnO can be also controlled by the coordination betweensurfactant and water [30] Concerning the PVP and PVAbehaviors for ZnO formation it was observed that the density

of ZnO rods increases Accordingly it may be predicted thatthe surfactant accelerates the nucleation of ZnO [31] SoPVP and PVA produced nanorods structure where CTABPEG and TEA produced nanoparticles Accordingly PVPwas selected as the optimum surfactant that produces ZnOin nanorods structures

(B) Effect of Reaction Temperature on Both the Crystallineand Morphological Structures of Prepared ZnO The tem-perature influenced morphology evolution and its effect onphysicochemical properties of synthesized nano-zinc oxideSo simple study on the relationship between the reactiontemperature and the morphological structures of synthesized

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 6: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

6 Bioinorganic Chemistry and Applications

Individual

Initial ZnO nuclei

Nucleation andgrowth of ZnO

nuclei

hexagonal plates

SurfactantZnO

Surfactant chain

Large ZnO

interaction

Figure 4 Schematic representation of ZnO nanorods formationmechanism

10 20 30 40 50 60 70 800

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C80∘C

90∘C

Figure 5 XRD patterns for ZnO nanopowders via sol-gel techniqueat different reaction temperatures (A) 60∘C (B) 70∘C (C) 80∘C and(D) 90∘C

nano-zinc oxidewill be examinedThenucleation and growthmechanisms for different ZnO architectural structure will bediscussed according to their characterizations

(i) Crystalline Structure (XRD)The standard XRD patterns ofthe different produced ZnO are used for relative comparisonof crystal structures for the ZnO nanopowders preparedat different reaction temperatures Figure 5 showed thatthe as-synthesized ZnO nanopowders produced diffractionpatterns and they are well indexed as crystalline hexagonalphase wurtzite structure which can be indexed with thezinc oxide wurtzite phase (JCPDS card number 01-089-1397)No peak attributable to possible impurities is observed Thesharp diffraction peaks signify that the as-prepared ZnOnanostructures have high crystallinity [32]

(ii) Morphological Structure (SEM)Themost proper selectedsurfactant (PVP) at different reaction temperatures (60 7080 and 90∘C) was tested for production of different zincoxide configurations Figure 6 indicated that ZnO formedat either 60 or 80∘C has nanoparticles configuration with

average diameters ranging between 25 and 57 nm Howeverthose produced at 70∘C have nanorods morphologies withaverage aspect ratio of 4 Also nanoplates of ZnO havebeen produced at 90∘C This behavior may be attributedto the fact that the growth kinetic process of ZnO is slowat low temperatures so the growth of nanospecies takesplace at higher temperature to obtain differentmorphologicalstructures However rise in reaction temperature results inincrease in reaction rate so ZnO grains rapidly grow whichleads to formation of nanorods with random orientations at70∘C Also at higher temperature breaking rate of complexedmetal ions releases more metal ions for rapid nucleationand growth process The morphology evolution of ZnO asinfluence of temperature is due to nanorods getting squeezedtogether to form nanoparticles [33] So the most preferredtemperature for production of uniform zinc oxide nanorodsis 70∘C So the reaction temperature has determinative effectson nano-zinc oxide formation [34]

It is generally believed that crystal formation of ZnO insolutions can be divided into two stages crystal nucleationand growthThe effective reason for the reaction temperatureaffecting the morphology of ZnO could be attributed todifferent reaction pathways solubility of the precursor andrate of the reaction which influenced the crystal nucleationand growth [35] This explains the case of ZnO production at70∘C where at this case the growth rate dominates over therate of nucleation which tends to form ZnO with nanorodstructures (Figure 6(b)) However the ZnO deformationmechanism was inverted for 60 80 and 90∘C where thenucleation rate is relatively higher than the rate of growthat lower and higher temperatures [36] This creates greatamounts of ZnOnuclei and limits the crystal growth rate andthen large-scale hexagonal ZnO particles were produced Athigher temperature 90∘C nanoplates have been obtained Sothe most proper reaction temperature is that which producesuniform size distribution of ZnO nanorods with high aspectratio of 70∘C

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnO The time of thereaction solution is a key factor to the growth of nano-zincoxide crystals Therefore time of the reaction mixture at thepredetermined optimum conditions of zinc acetate precursorin the presence of PVP surfactant adjusting the reactiontemperature at 70∘C was varied in the range of 3 6 12 24and 48 hours The structural and morphological propertiesare changed and identified with the help of XRD and SEMtechniques

(i) Crystalline Structure (XRD) Figure 7 showed XRD pat-terns for ZnO nanopowder that was prepared at differentreaction time intervals (3 6 12 24 and 48 hours) All thediffraction peaks can be indexed as the hexagonal wurtzitestructure with high crystallinity No impurity peaks havebeen detected from the XRD spectrum where the entirecrystalline precursors have decomposed and grew into ZnOsingle crystals [37] Moreover it is clear that the increase inthe reaction time improves the degree of crystallinity of theformed ZnO [38]

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

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Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

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Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 7: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 7

0055120583m

0039120583m

0041120583m0045120583m

0038120583m

0052120583m

(a)

0047120583m

0055120583m

0060120583m

0059120583m

0066120583m

(b)

0025120583m

0043120583m

0057120583m

0041120583m

(c) (d)

Figure 6 SEMmicrographs of ZnO prepared using sol-gel technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘C and (d)90∘C

10 20 30 40 50 60 70 800

(E)

(D)

(C)

(B)

(A)

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 7 XRD patterns for ZnO nanopowders via sol-gel techniquewith different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 h and(E) 48 h

(ii) Morphological Structure (SEM) SEM images of the ZnOprepared at various reaction times were investigated inFigure 8 It is clear that the ZnO nanostructures depended onthe growth time where different morphological structures ofnanoparticles and nanorods can be realized For short growthperiods of 3 hours (Figure 8(a)) aggregate nanorods struc-tures are indicated As the reaction period increased above6 h the nanorods disappeared and nanoparticles architecturemorphology of ZnO can be achieved However for highergrowth time 6 12 24 and 48 h nanoparticles structures havepredominated The suggested mechanism for ZnO may beconsidered as the ZnO nanorods structures are formed fromthe decomposition of Zn(OH)2 within 60 minutesrsquo heatingafter which the following time growth of the particles mustresult from dissolution and reprecipitation of the existingZnO particles [39] This is a slow process as significantchanges in the particle dimensions are only seen after 6hoursrsquo ageing As the reaction time increased above 6 hoursthe formed nanorods structure of ZnO was converted tonanoparticles and nanoplatesThatmay be due to the increasein the stirring period of the formed ZnO nanoparticles after

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

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Page 8: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

8 Bioinorganic Chemistry and Applications

0055120583m

0047120583m0066120583m

0060120583m

0059120583m

(a)

0057120583m

0079120583m

0070120583m

0063120583m

(b)

0053120583m

0045120583m

0058120583m

0069120583m

(c)

0082120583m

0040120583m

0038120583m

0062120583m

(d)

0036120583m0032120583m

0046120583m

0031120583m

0052120583m0038120583m

(e)

Figure 8 SEM micrographs of ZnO prepared using sol-gel technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 h and (e)48 h

6 h and destruction of the initial oriented growth chain ofZnO leading to particle formation from ZnO with hexagonalnanoparticle and nanoplates shapes Consequently the SEMresults indicated that the optimum reaction time for ZnOnanorod formation with high degree of crystallinity and highaspect ratio was selected to be 3 hours

32 Synthesis and Characterization of Nano-Zinc Oxide withDifferent Morphological Structures via Hydrothermal Tech-nique Hydrothermal technique has been used in nano-zincoxide synthesis at constant pressure

321 Synthesis of Nano-Zinc Oxide inthe Presence of Surfactant

(1) Mechanism of Nano-Zinc Oxide Formation in the Presenceof Surfactant In order to predict the formation mechanisminvolved in the hydrothermal process of ZnO synthesis in thepresence of surfactant agent the following chemical reactionsmay have been suggested

Zn (CH3COO) sdot 2H2O + [Zn (OH)119899]2minus119899

997888rarr [Zn2O (OH)2119899minus2]4minus2119899+H2O

(3)

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Page 9: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 9

10 20 30 40 50 60 70 800

(00

4)

(20

2)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(E)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

PVP

PVA

CTAB

TEA

PEG

2120579 (deg)

Figure 9 XRD patterns for ZnO nanopowders via hydrothermaltechnique with different surfactant agents (A) PVP (B) PVA (C)CTAB (D) TEA and (E) PEG

Zn2+ + 2OHminus 997888rarr Zn (OH)2 (4)

Zn (OH)2 larrrarr ZnO +H2O (5)

At the beginning of this process reaction (3) where 119899 =2 or 4 was suspected to happen in solution a Zn(OH)2precipitate is formed [40] So the crystal structure of ZnOwas constructed by reduction of Zn(OH)2 to formZnO usingsurfactant So surfactant not only accelerates the reaction ofthe growth units but also leads to their oriented growth andthe surface tension of solution is reduced which decreases theenergy needed to form a new phase [41]

(A) Effect of Surfactant Type on Both the Crystallineand Morphological Structures of Prepared ZnO The differ-ent polyvinylpyrrolidone (PVP) polyvinyl alcohol (PVA)cetyltrimethylammonium bromide (CTAB) triethanolamine(TEA) and polyethylene glycol (PEG) weakly basic materialswere tested as surfactant agents for ZnO production

(i) Crystalline Structure (XRD) Figure 9 elucidates that theprepared ZnO samples using the different surfactant agentsshowed wurtzite crystal structure (hexagonal phase) withhigh intensity The sharp peaks indicated that the productsare well crystallized and oriented [22] All the diffractionpeaks can be well indexed to the hexagonal phase of ZnOreported in JCPDS card number 01-089-1397 and no othercharacteristic peaks are observed [23]

(ii)Morphological Structure (SEM)Thedifferent attained zincoxide morphological structures according to the surfactantvariation are investigated in Figure 10 These images showedthat ZnO morphologies were strongly dependent on thesurfactant type in the hydrothermal process Figure 10(a)showed the formation of nanorods in the presence of PVPas surfactant Also hexagonal hollow tubes are formed using

PVA surfactant However it is believed that the mechanismof ZnO nanotubes from nanowire-rod-like ZnO powderscan be explained with the Kirkendall effect [42 43] In theKirkendall effect diffusion of atoms causes oversaturation oflattice voids It is considered that this oversaturation causescondensation of more voids close to the interface Thereforethese Kirkendall voids change properties of the interface andforce it to formmultiwalled nanotubes [28] Furthermore thepresence of other studied surfactants (CTAB TEA and PEG)tends to form nanorods ZnO

(B) Effect of Reaction Temperature on Both the CrystallineandMorphological Structures of Prepared ZnO Regarding thegreat influence of the reaction temperature on the morpho-logical structure of synthesized ZnO using sol-gel techniquethe variation of this parameter will be monitored for thehydrothermal technique

(i) Crystalline Structure (XRD) It was proved that the for-mation of ZnO powder depends on the reaction temperature[33] In order to determine the drawback of the formed ZnOin its crystallinity XRDpatterns of the ZnOnanopowder pre-pared under different temperatures (60 70 80 and 90∘C) areshown in Figure 11 [32] All the diffraction peaks can be wellindexed to the hexagonal phase of ZnO reported in JCPDScard number 01-089-1397 and no obvious characteristic peaksare observed for other impurities

(ii) Morphological Structure (SEM) Figure 12 illustrated thesurface morphology of nano-zinc oxide produced at differentreaction temperatures It is observed that ZnO formed at 6070 and 80∘C has nanorods configuration with aspect ratio 6(Figures 12(a) 12(b) and 12(c)) however that produced at90∘C has nanoplates morphology Nevertheless with lowergrowth temperature below 90∘C the formed ZnO producednanorods This may be owing to the decrease in the growthrate Where at low temperatures the growth kinetic tends tobe slow two-dimensional (2D) growth of nanospecies takesplace which leads to formation of rod morphology Howeverthe rise in temperature increases the reaction rate so ZnOgrains rapidly grow which leads to formation of hexagonalparticles and belts with random orientations [33]

It is generally believed that the effective reason for thereaction temperature affecting the morphology of ZnO couldbe attributed to different reaction pathways solubility of theprecursor and rate of the reaction which influenced thecrystal nucleation and growth [44] It is concluded from theprevious results of ZnOmorphology that lower temperaturesproduced nanorods structure where higher temperaturesproduced nanobelts So reaction temperature of 70∘C wasselected as the optimum temperature

(C) Effect of Reaction Time on Both the Crystalline andMorphological Structures of Prepared ZnOThe reaction timeof the reaction mixture at the predetermined optimumconditions in the presence of PVP surfactant using sodiumhydroxide solution at 70∘C and constant pressure was variedin the range of 3 6 12 24 and 48 hours The structural andmorphological properties are changed and identified

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Journal of

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Quantum Chemistry

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CatalystsJournal of

Page 10: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

10 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

(e)

Figure 10 SEM micrographs of ZnO prepared using hydrothermal technique with different surfactant agents (a) PVP (b) PVA (c) CTAB(d) TEA and (e) PEG

(i) X-Ray Diffraction Analyses The XRD patterns of five dif-ferent times of reaction were obtained as shown in Figure 13All the diffraction peaks could be indexed to hexagonalwurtzite ZnO (JCPDS card number 01-089-1397) with highcrystallization No characteristic peaks were observed forother impurities such as Zn or Zn(OH)2 [45] The increasein the reaction time improves the degree of crystallinity ofthe formed ZnO These results are compatible with outcomeof McBride and others [41] who have studied the effect ofreaction time on zinc oxide crystalline structure using theaqueous chemical growth technique

(ii) Morphological Structure (SEM) Figure 14 illustratedthat ZnO nanostructures depended on the growth time forthe hydrothermal technique where different morphologicalstructures of nanorods nanoplates and nanoparticles canbe seen For short growth periods of 3 hours (Figure 14(a))aggregate nanorods structures are indicated As the reac-tion period increased at 6 h the nanorods disappeared andnanoplates architecturemorphology of ZnO can be achievedHowever for higher growth time above 6 h nanoparticlesstructures have predominated

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

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Carbohydrate Chemistry

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

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Quantum Chemistry

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CatalystsJournal of

Page 11: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 11

10 20 30 40 50 60 70 80

0(A)

(B)

(C)

(D)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

60∘C

70∘C

80∘C

90∘C

Figure 11 XRD patterns for ZnO nanopowders via hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

0046120583m

0056120583m

0035120583m

0037120583m

0048120583m

0041120583m

0045120583m

(a)

0038120583m0050120583m

0039120583m

0039120583m 0032120583m

0037120583m

(b)

(c) (d)

Figure 12 SEMmicrographs of ZnO prepared using hydrothermal technique at different reaction temperatures (a) 60∘C (b) 70∘C (c) 80∘Cand (d) 90∘C

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 12: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

12 Bioinorganic Chemistry and Applications

10 20 30 40 50 60 70 800

(A)

(B)

(C)

(D)

(E)(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

Inte

nsi

ty (

au

)

2120579 (deg)

48h

24h

12h

6h

3h

Figure 13 XRD patterns for ZnO nanopowders via hydrothermal technique with different reaction times (A) 3 h (B) 6 h (C) 12 h (D) 24 hand (E) 48 h

33 Influence of Annealing Process on Zinc Oxide PhysicalProperties As all known and expected the prepared zincoxide nanotube produced from the hydrothermal techniquein the presence of PVA as stabilizing agent will attain thehighest surface area value compared with the other preparedarchitecture morphology of ZnO Accordingly this samplewas assigned as the most proper prepared zinc oxide sampleto test the influence of the annealing process on the materialcrystallinity morphology and surface area

(i) Crystalline Structure (XRD) Figure 15 investigated theinfluence of the annealing temperature on zinc oxide degreeof crystallinity It was explored from the comparable XRDpatterns that the as-prepared nanotube ZnO attains the low-est crystallinity degree compared with the different annealedsamples Moreover it was elucidated that as the annealingtemperature increased the diffraction characteristics peaks ofZnO became narrower and exhibit a higher intensity whichfurther suggests that the nanotubes become more crystallinewhich may change the material morphology [46]

(ii) Morphological Structure (SEM) In order to elucidatethe effect of annealing temperature on the zinc oxidemorphological structure the structure of the most properprepared sample in nanotube morphology was comparedwith the different structures after annealing the sample atthree various temperatures It was indicated from Figure 16that the annealing temperature has significant impact onthe ZnO morphological structure as expected from XRDresults However the annealing of nanotube sample at 500∘Cimproves the orientation degree of ZnOnanotubes comparedwith the as-prepared sample However as the annealing tem-perature improved up to 700∘C the morphological structureof ZnOwas converted completely into cup-like structurewithaverage diameter of 05 micrometers This conversion at themorphological structure may be regarded as the microwaveannealing process of ZnO that enhances the grain-growth

Table 1 Effect of annealing temperature on ZnO surface area andpore size

ZnO sample Surface aream2g

Average poresize nm

As-prepared nanotube(hydrothermal technique) 178 2786

500∘C annealing 167 2554700∘C annealing 72 1146900∘C annealing 24 53

rate and increases the densification behavior of the materialsthat yield the microcups structures [47] At the higheststudied annealing temperature of 900∘C the nanotube mor-phology of ZnO tends to aggregate to form aggregated tubesthat may be attributed to the high annealing temperaturethat may break down the nanotubes boundaries to yieldaggregated microtube morphological structure [48]

(iii) Surface Area (BET) With respect to the high impactof the microwave assisted annealing process on zinc oxidecrystallinity and morphological structures the influence ofthe annealing process on thematerial surface area and its poresizewas tabulated inTable 1 It was investigated from this tablethat the annealing process decreases the zinc oxide surfacearea and its pore size This may be attributed to sinteringimpact of the annealing temperature on the material thatdissolving thematerials boundaries and form large aggregatesfrom nanoscale into microscale dimensions that by its roledramatically decrease the material surface area and its poresize Moreover it was evident from Table 1 that the as-prepared nanotube ZnO has high surface area and pore sizeslightly affected after microwave annealing at 500∘C Thedepression at the material surface area was noticed afterannealing at 700∘C where at this temperature the materialsurface area decreased from 178 to 72m2g These results

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 13: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 13

0038120583m

0039120583m

0039120583m 0032120583m

0037120583m

0050120583m

(a) (b)

0039120583m

0056120583m 0055120583m 0031120583m

0050120583m

0039120583m

(c)

0046120583m

0046120583m

0032120583m

0032120583m

0032120583m

0032120583m0027120583m0027120583m

0046120583m

0050120583m

(d)

(e)

Figure 14 SEMmicrographs of ZnO prepared using hydrothermal technique with different reaction times (a) 3 h (b) 6 h (c) 12 h (d) 24 hand (e) 48 h

10 20 30 40 50 60 70 800

(20

2)

(00

4)

(20

1)

(11

2)

(20

0)

(10

3)

(11

0)

(10

2)

(10

1)

(00

2)

(10

0)

(D)

(C)

(B)

(A)

Inte

nsi

ty (

au

)

As prepared

2120579 (deg)

900∘C

700∘C

500∘C

Figure 15 XRD patterns of nanotube ZnO after and before annealing at different temperatures (A) as prepared (B) 500∘C annealing (C)700∘C annealing and (D) 900∘C annealing

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 14: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

14 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 16 SEM micrographs of ZnO nanotubes after and before annealing at different temperatures (a) as prepared (b) 500∘C annealing(c) 700∘C annealing and (d) 900∘C annealing

give prediction that the annealed ZnO samples will haveless antimicrobial activity compared with the as-preparednanotube ZnO sample

34 Antimicrobial Activity of Nanotubes Zinc Oxide Regard-ing the high surface area of the as-prepared zinc oxidenanotube produced from the hydrothermal technique inthe presence of PVA as stabilizing agent which was equiv-alent to 178m2g its bactericidal activity was tested invitro against four standard bacterial isolates Gram-positive(Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa)strainsTable 2 and Figure 17 indicate that Escherichia coliwashighly affected by nano-zinc oxide where the growth inhibi-tion reached 32 and 29mm using 30 and 15mgmL of nano-zinc oxide respectively The presence of an inhibition zoneclearly indicated the antibacterial activity of zinc oxide nan-otubes However by increasing the concentration of nano-ZnO in discs the inhibition zone has also been increased[49] The minimum inhibitory concentration (MIC) fromthe synthesized nano-ZnO was 00585mgmLThis recordedMIC value is very small compared with that published in

another research of 34mgmL for antibacterial properties ofZnO nanoparticles tested on Escherichia coli [49]

The antibacterial efficiency of ZnO nanotubes was alsoinvestigated against Pseudomonas aeruginosa The resultsreveal a high activity of the obtained nano-zinc oxide and theminimum inhibitory concentration (MIC) was 0234mgmLas illustrated in Table 2 From Figure 18 it was observedthat Pseudomonas aeruginosa was highly affected by nano-zinc oxide where the growth inhibition ranged between 37and 32mm with zinc oxide suspension concentration of 30and 15mgmL respectively These results indicated that zincoxide nanotubes had antibacterial effects on Pseudomonasaeruginosa which is partly in accordance with the previousreports [44] on the antibacterial properties of nano-ZnO

Antimicrobial activity of ZnO nanotubes against Staphy-lococcus aureus is illustrated in Figure 19 and its inhibitionzones (mm) were tabulated in Table 2 indicating that zincoxide nanotubes have moderate activity (24 and 22mm)against Staphylococcus aureus when concentrations 30 and15mgmL were used [44 45]

Figure 20 investigated the activity of nanotube zinc oxideagainst Bacillus subtilis using the disc diffusion method Theimprovement at the inhibition zones from 21mm to 23mm

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 15: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 15

(a)

(c) (d)

(e)

(b)

Figure 17 The antimicrobial activity of zinc oxide nanotubes against Escherichia coli using disc diffusion method ((a) (b) (c) (d) and (e))Different concentrations of the synthesized ZnO

was observed as nanotube zinc oxide concentration increasedfrom 15mgmL to 30mgmLThe synergetic effect of the zincoxide nanotubes was observed by the increase in diameter ofinhibition zones (mm) which has been recorded in Table 2These results agreed well with the growth inhibition demon-strated against zinc oxide nanoparticles [49]

Accordingly it was established from these results thatthe Bacillus subtilis strain represents stronger zinc oxideantiresistance bacterial isolates

Based on all MICs obtained by the different synthesizedZnO our synthesized ZnO nanotubes have high MIC which

makes them candidate to be used as antibacterial in differentapplications On the other hand from the results obtained indisc agar diffusion method it can be suggested that in com-parison with Gram-negative bacteria the growth of Gram-positive bacteria is inhibited at higher concentrations of ZnOnanotubes According to the results it can be concluded thatzinc oxide nanotubes are effective antibacterial agents bothon Gram-positive and Gram-negative bacteria

35 Influence of Annealing Process on Zinc Oxide Antimi-crobial Activity In order to elucidate the influence of the

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 16: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

16 Bioinorganic Chemistry and Applications

Table 2 The antimicrobial activity as measurable inhibition zones against different bacterial strains using various concentrations of ZnOnanotubes suspensions

ZnO concentration (mgmL) Zinc oxide inhibition zones (mm)Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Bacillus subtilis

30 32 37 24 2315 29 32 22 2175 27 28 21 19375 26 27 20 181875 23 26 19 170938 22 24 18 150468 21 21 16 00234 19 18 14 00117 17 0 0 000585 13 0 0 0002925 0 0 0 0

(a) (b)

(d)(c)

Figure 18The antimicrobial activity of zinc oxide nanotubes against Pseudomonas aeruginosa using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

microwave annealing process of nanotube zinc oxide onantimicrobial activity the annealed ZnO samples were exam-ined against the Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas aeruginosa) isolates at the optimumpredetermined ZnO concentrations of 15 and 30mgmL Itwas explored from Figures 21 and 22 that the annealingprocess of ZnO has negative impact on its antimicrobial

activity for both Gram-positive and Gram-negative bacteriaFigure 21 indicated that the inhibition zones of ZnO againstBacillus subtilis decreased from sim22mm for the as-preparedZnO nanotubes to sim14mm for the annealed sample at500∘C and these inhibition zones tend to be less than 5mmfor the annealed samples at 900∘C With respect to theGram-negative strain (Pseudomonas aeruginosa) Figure 22

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 17: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 17

(d)(c)

(a) (b)

Figure 19 The antimicrobial activity of zinc oxide nanotubes against Staphylococcus aureus using disc diffusion method ((a) (b) (c) and(d)) Different concentrations of the synthesized ZnO

(a) (b)

(c)

Figure 20The antimicrobial activity of zinc oxide nanotubes against Bacillus subtilis using disc diffusionmethod ((a) (b) and (c)) Differentconcentrations of the synthesized ZnO

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 18: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

18 Bioinorganic Chemistry and Applications

(a) (b)

(c) (d)

Figure 21 The influence of annealing process of zinc oxide on its antimicrobial activity against Bacillus subtilis using disc diffusion method(a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

(a) (b)

(c) (d)

Figure 22The influence of annealing process of zinc oxide on its antimicrobial activity against Pseudomonas aeruginosa using disc diffusionmethod (a) As-prepared nanotube ZnO (b) annealed ZnO at 500∘C (c) annealed ZnO at 700∘C and (d) annealed ZnO at 900∘C

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 19: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Bioinorganic Chemistry and Applications 19

evidenced that the inhibitions zones decline from sim35mmfor the as-prepared nanotubes to sim21mm for the annealedsample at 500∘C and these inhibition zones tend to declineless than 10mm for the annealed samples at 900∘C Thedepression at the inhibition zones of ZnO annealed samplescompared with the as-prepared nanotube ZnO sample maybe attributed to the decline at the material surface area afterannealing which was proved previously as the action of theannealing temperature

4 Conclusion

Nano-zinc oxide with different morphological structures wassuccessfully synthesized using two different techniques Thesamples were examined using X-ray diffraction (XRD) andscanning electron microscopy (SEM) to be sure that theyare in nanoscale with different morphological structures(particles rods and tubes) The surfactant has a significantrole in both the rate of nucleation and growth mechanismswhich are responsible for the structure of nano-ZnO formedThe improvement in the reaction temperature enhances boththe reaction rate and the degree of ZnO crystallinity TheZnOmorphological structure was strongly dependent on thereaction time The synthesized zinc oxide nanotubes havea strong antimicrobial activity against some Gram-positiveand Gram-negative bacteria This antimicrobial activity wasdecreased with increasing annealing temperature of ZnOfrom 500 to 900∘C Accordingly the synthesized ZnO nan-otubes can be utilized as nanocontrol materials against themedicinal bacteria Gram-positive bacteria seemed to bemore resistant to zinc oxide nanotubes comparedwithGram-negative bacteria It was found that the antibacterial activityof zinc oxide nanotubes increased with increasing powderconcentration

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was supported by the Egyptian Science andTechnology Development Fund (STDF) (Grant no 10763)

References

[1] C Zandonella ldquoCell nanotechnology the tiny toolkitrdquo Naturevol 423 pp 10ndash12 2003

[2] M Veerapandian and K Yun ldquoFunctionalization of bio-molecules on nanoparticles specialized for antibacterial appli-cationsrdquo Applied Microbiology and Biotechnology vol 90 no 5pp 1655ndash1667 2011

[3] H Shokry Hassan M F Elkady A H El-Shazly and H SBamufleh ldquoFormulation of synthesized zinc oxide nanopowderinto hybrid beads for dye separationrdquo Journal of Nanomaterialsvol 2014 Article ID 967492 14 pages 2014

[4] M F Elkady H Shokry Hassan and E M El-Sayed ldquoBasicviolet decolourization using alginate immobilized nanozirco-nium tungestovanadate matrix as cation exchangerrdquo Journal ofChemistry In press

[5] C GuH Zhang andM Lang ldquoPreparation ofmono-dispersedsilver nanoparticles assisted by chitosan-g-poly(120576-caprolactone)micelles and their antimicrobial applicationrdquo Applied SurfaceScience vol 301 pp 273ndash279 2014

[6] R Sivaraj P K S M Rahman P Rajiv S Narendhran andR Venckatesh ldquoBiosynthesis and characterization of Acalyphaindica mediated copper oxide nanoparticles and evaluation ofits antimicrobial and anticancer activityrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 129 pp25ndash258 2014

[7] R Dobrucka ldquoApplication of nanotechnology in food packag-ingrdquo Journal of Microbiology Biotechnology and Food Sciencesvol 3 no 5 pp 353ndash359 2014

[8] I Sondi and B Salopek-Sondi ldquoSilver nanoparticles as antimi-crobial agent a case study on E coli as a model for Gram-negative bacteriardquo Journal of Colloid and Interface Science vol275 no 1 pp 177ndash182 2004

[9] T Jin D Sun J Y Su H Zhang and H-J Sue ldquoAntimicrobialefficacy of zinc oxide quantum dots against Listeria monocy-togenes Salmonella Enteritidis and Escherichia coli O157H7rdquoJournal of Food Science vol 74 no 1 pp M46ndashM52 2009

[10] X Li Y Xing Y Jiang Y Ding and W Li ldquoAntimicrobialactivities of ZnO powder-coated PVC film to inactivate foodpathogensrdquo International Journal of Food Science and Technol-ogy vol 44 no 11 pp 2161ndash2168 2009

[11] H Otsuka Y Nagasaki and K Kataoka ldquoPEGylated nanopar-ticles for biological and pharmaceutical applicationsrdquoAdvancedDrug Delivery Reviews vol 55 no 3 pp 403ndash419 2003

[12] K Byrappa andT Adschiri ldquoHydrothermal technology for nan-otechnologyrdquo Progress in Crystal Growth and Characterizationof Materials vol 53 no 2 pp 117ndash166 2007

[13] J Livage M Henry and C Sanchez ldquoSol-gel chemistry oftransition metal oxides Solid Staterdquo Progress in Solid StateChemistry vol 18 no 4 pp 259ndash341 1988

[14] N Y Turova E P Turevskaya V G Kessler and M IYanovskaya The Chemistry of Metal Alkoxides Kluwer Aca-demic Publishers Boston Mass USA 2002

[15] D C Bradley R C Mehrotra I P Rothwell and A SinghAlkoxo and Aryloxo Derivatives of Metals Academic PressLondon UK 2001

[16] J Yang ldquoAharsh environmentwireless pressure sensing solutionutilizing high temperature electronicsrdquo Sensors vol 13 no 3 pp2719ndash2734 2013

[17] P R Bergquist and J J Bedford ldquoThe incidence of antibacterialactivity in marine demospongiae systematic and geographicconsiderationsrdquoMarine Biology vol 46 no 3 pp 215ndash221 1978

[18] J EThompson R PWalker and D J Faulkner ldquoScreening andbioassays for biologically-active substances from forty marinesponge species from San Diego California USArdquo MarineBiology vol 88 no 1 pp 11ndash21 1985

[19] K Govender D S Boyle P B Kenway and P OrsquoBrienldquoUnderstanding the factors that govern the deposition andmorphology of thin films of ZnO from aqueous solutionrdquoJournal of Materials Chemistry vol 14 no 16 pp 2575ndash25912004

[20] S Maiti U N Maiti A Chowdhury and K K ChattopadhyayldquoAmbient condition oxidation of zinc foil in supersaturated

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 20: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

20 Bioinorganic Chemistry and Applications

solution for shape tailored ZnO nanostructures low costcandidates for efficient electron emitter and UV-detectorrdquoCrystEngComm vol 16 no 9 pp 1659ndash1668 2014

[21] Z Liu J Li J Ya Y Xin and Z Jin ldquoMechanism andcharacteristics of porous ZnOfilms by sol-gelmethodwith PEGtemplaterdquoMaterials Letters vol 62 no 8-9 pp 1190ndash1193 2008

[22] S S NathM Choudhury D Chakdar G Gope and R K NathldquoAcetone sensing property of ZnO quantum dots embedded onPVPrdquo Sensors and Actuators B Chemical vol 148 no 2 pp353ndash357 2010

[23] H Shokry Hassan A B Kashyout I Morsi A A A Nasserand A Raafat ldquoFabrication and characterization of gas sensormicro-arraysrdquo Sensing and Bio-Sensing Research vol 1 pp 34ndash40 2014

[24] Y Saddeek H Shokry Hassan and G Abd Elfadeel ldquoFabri-cation and analysis of new bismuth borate glasses containingcement kiln dustrdquo Journal of Non-Crystalline Solids vol 403 pp47ndash52 2014

[25] M F Elkady and H Shokry Hassan ldquoEquilibrium and dynamicprofiles of Azo dye sorption onto innovative nano-zinc oxidebiocompositerdquo Current Nanoscience vol 11 no 6 pp 805ndash8142015

[26] F Liu J Wu K Chen and D Xue ldquoMorphology study by usingscanning electron microscopyrdquo inMicroscopy Science Technol-ogy Applications and Education pp 1781ndash1792 Formatex 2010

[27] QQWangG L Zhao andG RHan ldquoSynthesis of single crys-talline CdS nanorods by a PVP-assisted solvothermal methodrdquoMaterials Letters vol 59 no 21 pp 2625ndash2629 2005

[28] N R Yogamalar and A C Bose ldquoTuning the aspect ratio ofhydrothermally grown ZnO by choice of precursorrdquo Journal ofSolid State Chemistry vol 184 no 1 pp 12ndash20 2011

[29] J Zhang H Liu Z Wang N Ming Z Li and A SBiris ldquoPolyvinylpyrrolidone-directed crystallization of ZnOwith tunable morphology and bandgaprdquo Advanced FunctionalMaterials vol 17 no 18 pp 3897ndash3905 2007

[30] J H Zhang H Y Liu Z L Wang and N B Ming ldquoLow-temperature growth of ZnO with controllable shapes and bandgapsrdquo Journal of Crystal Growth vol 310 no 11 pp 2848ndash28532008

[31] S F Wei J S Lian and Q Jiang ldquoControlling growth ofZnO rods by polyvinylpyrrolidone (PVP) and their opticalpropertiesrdquo Applied Surface Science vol 255 no 15 pp 6978ndash6984 2009

[32] AK ZakM E AbrishamiWHAMajid R Yousefi and SMHosseini ldquoEffects of annealing temperature on some structuraland optical properties of ZnO nanoparticles prepared by amodified sol-gel combustion methodrdquo Ceramics Internationalvol 37 no 1 pp 393ndash398 2011

[33] C Panatarani I W Lenggoro and K Okuyama ldquoSynthesisof single crystalline ZnO nanoparticles by salt-assisted spraypyrolysisrdquo Journal of Nanoparticle Research vol 5 no 1-2 pp47ndash53 2003

[34] S B Kulkarni U M Patil R R Salunkhe S S Joshi and C DLokhande ldquoTemperature impact onmorphological evolution ofZnO and its consequent effect on physico-chemical propertiesrdquoJournal of Alloys and Compounds vol 509 no 8 pp 3486ndash34922011

[35] S M Pawar K V Gurav S W Shin et al ldquoEffect of bathtemperature on the properties of nanocrystalline ZnO thinfilmsrdquo Journal of Nanoscience and Nanotechnology vol 10 no5 pp 3412ndash3415 2010

[36] S Cho S-H Jung and K-H Lee ldquoMorphology-controlledgrowth of ZnO nanostructures using microwave irradiationfrom basic to complex structuresrdquo Journal of Physical ChemistryC vol 112 no 33 pp 12769ndash12776 2008

[37] E Arca K Fleischer K Fleischer and I V Shvets ldquoInfluence ofthe precursors and chemical composition of the solution on theproperties of zno thin films grown by spray pyrolysisrdquo Journalof Physical Chemistry C vol 113 no 50 pp 21074ndash21081 2009

[38] R-Q Chen C-W Zou X-D Yan and W Gao ldquoZinc oxidenanostructures and porous films produced by oxidation ofzinc precursors in wet-oxygen atmosphererdquo Progress in NaturalScience Materials International vol 21 no 2 pp 81ndash96 2011

[39] L Wu Y Wu W Lu H Wei and Y Shi ldquoMorphologydevelopment and oriented growth of single crystalline ZnOnanorodrdquoApplied Surface Science vol 252 no 5 pp 1436ndash14412005

[40] D Vernardou G Kenanakis S Couris et al ldquoThe effect ofgrowth time on the morphology of ZnO structures depositedon Si (1 0 0) by the aqueous chemical growth techniquerdquo Journalof Crystal Growth vol 308 no 1 pp 105ndash109 2007

[41] R A McBride J M Kelly and D E McCormack ldquoGrowth ofwell-defined ZnO microparticles by hydroxide ion hydrolysisof zinc saltsrdquo Journal of Materials Chemistry vol 13 no 5 pp1196ndash1201 2003

[42] H J Fan U Gosele andM Zacharias ldquoFormation of nanotubesand hollow nanoparticles based on kirkendall and diffusionprocesses a reviewrdquo Small vol 3 no 10 pp 1660ndash1671 2007

[43] R Krithiga and G Chandrasekaran ldquoSynthesis strucutral andoptical properties of vanadium doped zinc oxide nanograinsrdquoJournal of Crystal Growth vol 311 no 21 pp 4610ndash4614 2009

[44] Z Emami-Karvani and P Chehrazi ldquoAntibacterial activityof ZnO nanoparticle on Gram-positive and Gram-negativebacteriardquo African Journal of Microbiology Research vol 5 no12 pp 1368ndash1373 2011

[45] K M Reddy K Feris J Bell D G Wingett C Hanley andA Punnoose ldquoSelective toxicity of zinc oxide nanoparticles toprokaryotic and eukaryotic systemsrdquo Applied Physics Lettersvol 90 no 21 Article ID 213902 3 pages 2007

[46] T D Malevu and R O Ocaya ldquoEffect of annealing temperatureon structural morphology and optical properties of ZnO nano-needles prepared by zinc-air cell system methodrdquo InternationalJournal of Electrochemical Science vol 10 no 2 pp 1752ndash17612015

[47] M F Elkady M A Alrafaa and N A El Essawy ldquoMorpho-logical and electrical properties of zirconium vanadate dopedwith cesiumrdquo Beni-Suef University Journal of Basic and AppliedSciences vol 3 no 3 pp 229ndash237 2014

[48] M Soosen Samuel J Koshy A Chandran and K CGeorge ldquoDielectric behavior and transport properties of ZnOnanorodsrdquo Physica B Condensed Matter vol 406 no 15-16 pp3023ndash3029 2011

[49] J M Yousef and E N Danial ldquoIn vitro antibacterial activityandminimum inhibitory concentration of zinc oxide and nano-particle zinc oxide against pathogenic strainsrdquo Journal of HealthSciences vol 2 no 4 pp 38ndash42 2012

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 21: Research Article Construction of Zinc Oxide into Different ...downloads.hindawi.com/journals/bca/2015/536854.pdf · Construction of Zinc Oxide into Different Morphological Structures

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of