DOI: 10.36686/Ariviyal.GR.2021.02.05.021 Green Rep., 2021, 2(5),
15-21.
Role of Carbon Nanotubes in Extraction and Detection of Pesticides
Al-kazafy Hassan Sabry
Pests and Plant Protection Department, National Research Centre,
Cairo, Egypt.
*Corresponding author E-mail address:
[email protected]
Ariviyal Publishing Journals
ISSN: 2582-6239 Abstract: Pesticides residues and food
contamination by pesticides is considered one of the most threat
which faces
the food production. Extraction and detection of pesticides can be
reduced the hazard of pesticides contamination. Many traditional
methods were used to extract and detect of pesticides such as using
of organic solvents in pesticides extraction and thin layer
chromatograph. With the beginning of the nanotechnology era a new
method to extract and detect pesticides was discovered. This method
carried out by carbon-nanotubes as a solid phase. Carbon-nanotubes
play the main role in this method as adsorbent material.
Carbon-nanotubes have many advantages in extraction and detection
of pesticides. These advantages are including using of solid phase
extraction, high surface area, high stability, good thermal
conductivity and high mechanical strength in tension. This review
throws some light on the use of carbon-nanotubes in the extraction
and detection of pesticides.
Keywords: Carbon nanotubes; pesticides residues; extraction;
detection
Publication details
1. Introduction
Carbon discovered for 6000 years and used in the reduction of
metal
oxides. [1]
branch was discovered after the synthesis of fullerenes,
especially
the buckminsterfullerene C60, in 1985. [2]
Iijima S. [3]
nanoparticles of carbon by using of an arc-discharge
evaporation
method. Under an electronic microscope these particles appear
as
tiny tubes or tiny cylinders ranged between 4 to 30 nm
diameters
and can be reached to 100 nm. These nanotubes cab be extract
pesticides by adsorption force. So, these nanotubes can be in
the
detection and extraction of pesticides in crops or
vegetables.
Pesticide residues play an important role in the quality and
acceptable fruits to export. Pesticide residues are defined as
any
substance or mixture of substances in food for man or animals
resulting from the use of a pesticide and include any
specified
derivatives, such as degradation and conversion products,
metabolites, reaction products, and impurities that are considered
to
be of toxicological significance.
Therefore, the main objective of this chapter is to briefly
discuss
the role of carbon-nanotubes as a new method, cheap, sensitive
and,
fast in the extraction and detection of pesticides in water,
crops,
vegetables and, humans.
2. Extraction and Detection of Pesticides
Pesticides are toxic substances for plants, animals and, humans.
So, it
needs to determine the residues of these pesticides in plants to
avoid
exceeding of maximum residue limit of these materials. To
determine
the residues of these toxic substances; detection and extraction
must
be done. In the near, past there were many conventional methods
to
extract pesticides
2.1.1. Liquid liquid extraction (LLE)
Pesticides were extracted by many conventional methods such
as
using of organic solvents. So, this method called liquid
liquid
extraction (LLE). [4]
carried out in aqueous samples. This method needs simple
constituent. Many organic solvents can be used in this method
such
as hexane, dichloromethan (DCM) and acetonitrile. These
solvents
called less polar organic solvents. So, this method was suitable
with
polar pesticides. To uses this method for polar pesticides it must
be
mixed with polar solvents such as acetone. Lacassie E. et al.
[5]
used a
mixture of polar and less polar solvents. This mixture consists
of
acetone/DCM/ hexane as 5: 2: 3, respectively. This mixture was
used
in the extraction of pesticides from apples and pears. With
polar
pesticides other organic solvents were used in liquid
chromatography. These solvents were such as ethyl acetate and
ethanol. [6]
The disadvantage of this method was it needs a large
volume of toxic solvents. [7]
2.1.2. Supercritical fluid extraction
This method was suitable for the extraction of pesticides
from
relatively drayed materials without any solvent. [4]
This method was
used in extraction of imazalil, tebuconazole, triadimefon,
chlorpyrifos
and, cypermethrin under temperature condition 70 °C,
extraction
.
This method mostly was used with solid materials. Extraction
of
pesticides with pressurized liquid extraction was faster than
any
methods. Organic solvents were used in pesticide extraction
whether
alone or as a mixture. This method needs a high temperatures
and
pressure (upto 2000C, 20 MPa respectively). Pesticide extraction
can
be degraded by high temperatures. [8]
2.2. Analytical methods for pesticides detection
2.2.1. Liquid chromatography (LC)
Liquid chromatography (LC) is a separation process used to
separate the individual components of a combination. This
process
consists of two steps. The first one is mass transfer of a
sample
through a non-polar mobile phase and the second through
non-polar
stationary phase. Liquid chromatography uses conventional
detectors in pesticide analysis. These detectors include UV
detector,
fluorescence detector and diode-array detector (DAD). [9]
The column
of LC involved porous medium such as silica as a stationary
phase
(Fig. 1). The sample is injected into this medium (stationary
phase).
The organic solvent passes into the medium and sample. After
the
sample injected it's adsorbed in a medium phase (silica). The
solvent
carried this sample and separate all components according to
relative
affinity to the packing materials and the solvent.
2.2.2. Gas chromatography (GC)
solvents. The tested compound is dissolved in the organic
solvent
and vaporized to separate the components of the tested material
by
distributing the sample between two phases: a stationary phase
and
a mobile phase (Fig. 2). (FID Gas chromatography uses many
detectors especially with pesticide detection. [7]
These detectors
detector).
detection of pesticides
3.1. Supercritical fluid extraction (SFE)
In this method carbon dioxide (Co2) is the best extraction
medium.
This method is used with nonpolar pesticides and moderate
polar
such as Organophosphorus compounds and chlorinated
hydrocarbon. An organic solvent such as acetone and methanol
also
can be used Ono et al. [10]
Pereira et al. [11]
extraction (SFE) to extract the lignans phyllanthin and niranthin
from
Phyllanthus amarus plant. The authors used Co2 as a medium in
extraction. The obtained lignans phyllanthin and niranthin were
ten
times pure compared with other extraction methods.
3.2. Solid phase extraction
There are many methods for solid phase extraction. Carbon
nanotubes are considered one of the most effective methods as
a
solid phase extraction. [12]
3.3. Carbone nanotubes
The main advantage of the use of carbon nanotubes in
pesticide
extraction is the high surface area of this material. [13]
Du et al. [14]
used the multiwalled carbon nanotubes as a solid phase in the
extraction of Organophosphours pesticide (Methyl parathion)
from
garlic. Using of carbon nanotubes in pesticide extraction is
fast,
selective and sensitive.
with primary secondary amine as a solid phase in pesticides
extraction from berry samples.
Carbon nanotubes (CNTs) are the cylindrical allotrope
nanostructures of carbon that consist of rolled-up sheets of
single-
layer carbon atoms (graphene). [16]
These cylinders are folded to
create the sphere. These materials can be conjugated easily
with
biomaterials such as nucleic acids or proteins.
Fig. 1. The simple liquid chromatography
Fig. 2. Gas chromatography
The structure of carbon nanotubes is arranged in hexagonal
shapes such as honeycomb. This means that six carbons atoms
are
arranged in a hexagonal structure (Fig. 3).
3.3.3. Features of carbon nanotubes [17,18]
Carbon nanotubes have a longer inner volume compared
with the diameter of nanotubes entrapment
The carbon nanotubes have an inner and outer surface
Some types of nanotubes have the open end in both sides
and other are closed
Non-Biodegradable, immunogenic nature and
delivery
Carbon nanotubes cab be extracted by urine (96%) and 4%
only survived in faeces
of carbon nanotubes can be ten times thinner and lighter
than amorphous carbon electrodes)
Due to the tumbler shape of carbon nanotubes it is easily
penetrated cells by spontaneous mechanisms
Extraordinary electrical conductivity, heat conductivity
(their conductivity is more than one thousand times
greater than amorphous carbon), and mechanical
properties.
There are two types of carbon nanotubes; single walled carbon
nanotubes (SWCNT) and multi walled carbon nanotubes (MWCNT).
3.3.4.1. Single walled carbon nanotubes (SWCNT)
The single walled carbon nanotubes composite of one layer of
graphene rolled as a small cylinder with a range between 0.5 to
1.5
nm diameters (Fig. 4). The thickness of this layer is depending on
the
temperature to which it exposed. [19]
The surface area of this layer
reached 1300 m 2 /g.
[20] The single layers of carbon atoms in the
hexagonal shape are arranged in three types [21]
(Fig. 5); Zig-zag
shape, Armchair shape and Chiral shape. The single walled
carbon
nanotubes have faster permeability. So, it can be used in
blood
against some human diseases such as antitumor drugs. [22]
The single
3.3.4.2. Multiwalled carbon nanotubes
The multi walled carbon nanotubes are flatulent tubes with a
cylinder shapes. These nanotubes consist of many rolled
layers
depending on their properties. [23]
These layers ranged between 6-25
layers (Fig. 6). The diameter of these nanotubes ranged between 1-
3
nm compared with 0.7 to 2 nm in single walled carbon nanotubes.
[24]
MWCNTs are relatively novel in pesticide multi-residue analysis,
and
due to their large surface area and strong absorbing capability,
the
amount of MWCNTs required for cleanup is only 5.0 mg for fruits
and
vegetables. [25]
material and others by chemical materials. Zhang et al. [26]
prepared
carbon-nanotubes from natural materials such as sunflower
seed
shells and sago. The authors were pyrolyzing this mixture at
800°C.
On the other hand, Liang et al. [27]
prepared the carbon-nanotubes by
Fig. 4. Single walled carbon nanotubes
Fig. 5. Types of hexagonal shapes of carbon atoms in carbon
nanotubes
Fig. 6. Multiwalled carbon nanotubes (Cited by Madani et al.,
2013)
18
Al-kazafy Hassan Sabry Green Reports
Green Rep., 2021, 2(5), 15-21.
heating methane at 680 °C for 120 min. The authors used mixture
of
nickel oxide–silica as a catalyst. The diameter of
carbon-nanotubes
obtained ranged between 40-60 nm. The arc-discharge technique
method also was used for carbon-nanotubes production. This
method used high temperature (1700 °C). [28]
Finally, there three main methods for carbon-nanotubes
preparation
Arc discharge
Laser ablation
This method is the easiest method for carbon-nanotubes
preparation. This method needs a high temperature exceeded
1700
C. This method produced C60 fullerenes. In this method the
vapor
was obtained by an arc discharge between two carbon
electrodes
with or without. Electric arc was initiated between two
carbon
electrodes with high temperature to synthesis an arc by
digital
current (DC). Gas also used to increase the carbon
nanoparticle
deposition. In this way the high temperature convert carbon
particles
to nanoparticles and sublimate carbon nanoparticles. After
these
particles were cooling in the specific chamber in presence of
helium,
argon or methane. Carbon nanoparticles were converted to the
single walled carbon-nanotubes and multiwalled
carbon-nanotubes.
The single-walled carbon nanotubes (SWCNT) were produced by
using catalysts such as Fe, Ni, or Co. But the multiwalled
carbon-
nanotubes (MWCNT) didn't need any catalysts. The diameters of
SWCNTs are ranger between 0.6 to 1.4 nm and MWCNTs 10 nm.
[29]
3.3.5.2. Laser ablation method for carbon-nanotubes
preparation
Kuo et al. [30]
preparation. The obtained carbon-nanotubes diameter was
ranged
between 5 to 10 nm. In this method graphite are exposed to
the
laser. The graphite was vaporized by laser at a high temperature.
The
main advantage of this method is pure carbon-nanotubes
produced.
These pure carbon-nanotubes were also depending on the
temperature used. Mubarak et al. [29]
found that the best
temperature used in the laser method was 1200 °C. Nickel and
cobalt
were used as catalysts.
deposition (CVD)
In this method mixture of hydrocarbon, catalyst (iron, nickel,
or
cobalt put in ceramic boat) and inert gas (hydrogen and argon)
were
used in the reaction chamber at temperatures 700–900º C and
atmospheric pressure. A huge quantity of carbon-nanotubes can
be
produced by catalytic chemical vapor deposition of acetylene
over
iron catalysts and cobalt. The obtained carbon-nanotubes were
collected in the preheating zone with the ceramic boat.
3.3.7. Using of carbon-nanotubes in extraction and detection
of
pesticides
used paper strip method in pesticides
detection. In this method iodine and silver nitrate were used
as
chromogenic reagent. This method was used in detection of
some
organophosphours pesticides in vegetable samples.
Now, carbon-nanotubes can be used in detection and extraction
of pesticides in crops and vegetables. [32]
Chromatographic
applications of carbon-nanotubes (CNTs) were used as
stationary
phases in gas chromatography (GC)(Yuan et al. 2006) or liquid
gas
chromatography (LC). [33]
and extraction
There are four main steps in using carbon-nanotubes as a
solid
phase electrode in pesticide detection and extraction [34]
(Fig. 7):-
Conditioning of the solid phase by using organic solvents or
water to pass through the column to increase the activity of
the
surface area and decrease the interference. [35]
After that drying
materials used
reduced the interference between materials used. The sample
must be extracted well, cleanup and concentrated of analytes
before determination. The volume of the sample depending on
the persistency of this sample.
Washing, to obtain good determination it must be used
selective
cleaner. Using selective washing is accomplished when the
target
analytes and the impurities are retained on the sorbent bed.
Elution, using selective elution decreases the impurities in
the
sample. So, it must elute unwanted materials by strongly
polar
solvent. But elute weakly persistent materials by using a
less
polar solvent. The elution must be involved different
solvents.
Carbon nanotubes whether single-walled or multiwalled carbon-
nanotubes play an important role as sorbent in solid phase.
[36]
In pesticide extraction especially it prefers use of
solid-phase
because it has high extraction efficiency and little amount of
organic
solvent used Ravelo-Pérez et al. [37,38]
used dry carbon nanotubes as
solid-phase extraction sorbents at 80–120C for a few hours.
Before
using carbon-nanotubes in pesticides detection and extraction
it
must be treated to eliminate the metallic impurities. This
pre-
treatment improves the electron transfer properties in
carbon-
nanotubes. This treatment was carried out by using solutions
of
sulfuric, nitric, and hydrochloric acids. Treatments of
carbon-
Fig. 7. The main steps in solid phase electrode
19
nanotubes before use in analysis increase the activity of
these
materials. [39]
carbon-nanotubes such as dispersing of CNTs in some solvents
with
sonication after purification and activation pre-treatments
followed
by dropping the resultant suspensions on the electrode surfaces
and
allowing them to dry. These solvents include
N,Ndimethylformamide, [40]
acetone, [41]
ethanol, [42]
toluene [43]
during the analysis some additives must be added. These
additives
include surfactants, polymers, proteins and cyclodextrins.
3.3.8. Role of carbon-nanotubes in pesticides detection and
extraction
As mention before there were many methods to detect and
extract pesticides such as using high- performance liquid
chromatography (HPLC), [45]
fluorescence spectrophotometry, [46]
....etc. Although all these methods before, all of
them were expensive and require skilled labor. So, there is
badly
need to develop a new method of simple, cheap, sensitive,
selective,
and portable sensing platforms for pesticide determination. This
new
method is using of carbon-nanotubes as a solid phase in
pesticide
detection and extraction. It's difficult to detect pesticide
residues in a
low concentration. Using Carbon-nanotubes are solving this
problem.
Using carbon nanotubes mixed with graphene can be detecting
low
concentrations of pesticides. [48]
detection were used as an electrode. These carbon-nanotubes
were
mixed with a hydrophobic organic liquid (mineral oil, paraffin oil,
or
silicone oil). [49]
detection and extraction of carbendazim (Fungicide widely
used
against plant diseases in cereals and fruits, Fig. 8). The authors
found
that when multiwalled carbon nanotubes were used in glassy
carbon
electrodes the numbers of fungicide peaks were increased
fifteen
times compared with other detection methods. The percentage
of
determination of this pesticide in both soil and water were
ranged
between 84.5% and 93.7%. This means that the high sensitivity
of
this method in pesticide detection and extraction. Mani et al.
[48]
used
a glassy carbon electrode with graphene oxide and
multi-walled
carbon nanotubes (GO–MWCNT) in the detection of diuron (Fig.
9)
and fenuron (Fig. 10) (Herbicides widely used against
pre-emergent
and post-emergent control of broadleaved and grass weeds).
Both
diuron and fenuron were oxidized perfectly by GO–MWCNT. By
this
method the percentage detection of both herbicides in lake
water
and arrogation were 95.1% to 104.3%. Sundari et al. [50]
used also
glassy carbon electrode with multiwalled carbon- nanotubes
and
poly(3-methyl thiophene (P3MT) film as a polymer in the detecting
of
cypermethrin, deltamethrin, dicofol, fenvalerate isoproturon,
and
spiromesifan (All of them are insecticides). Musameh et al.
[51]
recorded that the carbon nanotubes used as sensors and
biosensors
in detecting pesticides in water. The physical and chemical
properties
of carbon nanotubes are more effective in detecting pesticides
than
other conventional detectors such as high-performance liquid
chromatography or gas chromatography because the carbon-
nanotubes give rapid detection and low cost. By this method it
can
be used biosensors such as acetylcholinesterase with carbon-
nanotubes. The authors used acetylcholinesterase with carbon-
nanotubes to detect organophosphours compound. Due to the
huge
surface area of carbon-nanotubes it can be used in the extraction
of
organophosphours compound. Zhou et al. [52]
compared the
of atrazine and simazine (widely used herbicides). The
obtained
results showed that the MWCN was better and faster than the
other
detection method (HPLC). Al-Degs et al. [53]
used multiwalled carbon-
nanotubes for extraction of atrazine, methidathion, and
propoxur
(widely used herbicides) in the tap water samples. Xu et al.
[54]
used
magnetic multiwalled carbon-nanotubes (Fe3O4-MWCNTs) as
adsorbents for the extraction of pesticides in eggs. Total of 48
eggs
were used as sample and mixed with NaCl and Na2SO4 (Fig. 11). 5,
10,
15, 20 and 25 mg of Fe3O4-MWCNTs for 2 ml of the extract was
optimized. The obtained results showed that 50% of selected
eggs
were contaminated by fipronil-sulfone (Insecticide) and
aflatoxin
(Fungal toxin). Zhu et al. [55]
using of multiwalled carbon nanotubes as
an adsorbent agent in pesticides detection in tea leaves. This
method
was very fast, sensitive and simple. To achieve this method 4 g of
tea
sample were added to 10 ml of acetonitrile. After that the
sample
was extracted by homogenate method at 12,000 r/min for 1 min.
Reinholds et al. [56]
Fig. 8. Carbendazim structure
Fig. 9. Diuron structure
Fig. 10. Fenuron structure
Fig. 11. Atrazine structure
Al-kazafy Hassan Sabry Green Reports
Green Rep., 2021, 2(5), 15-21.
to extract pesticides from food. This method was very rapid
and
advanced. Song et al. [57]
used multiwalled carbon-nanotubes mixed
with Primary Secondary Amine (PSA) and salts (NaCl and MgSo4)
functioned as absorbents to determine the residues of
forty-seven
different pesticides in pepper, chilli peppers and chilli sauce.
The
authors found that this method was rapid, safe, easy cheap
and
suitable for determining multi residues pesticides at the same
time
compared with other methods. Zhang et al. [58]
tested the different
weights of multiwalled carbon nanotubes (MWCNTs) to determine
60 pesticide residues in the cinnamon samples; 5.0, 7.5, and 10 mg
of
MWCNTs were used in combination with MgSO4, PSA + C18. The
obtained results showed that no difference in most pesticide
residues (44 pesticides of 60) with all tested weights. Lei et al.
[59]
determined the residues of three pesticides (epoxiconazole,
tebuconazole, and metalaxyl) in lettuce, cabbage and apple.
The
authors used multiwalled carbon-nanotubes as adsorbent. The
obtained results showed that the multiwalled carbon-nanotubes
were effective as sorbent agent.
4. Conclusions
Carbon nanotubes are currently one of the most promising groups
of
materials with interesting properties such as lightness, rigidity,
high
surface area, and high mechanical strength in tension, good
thermal
conductivity or resistance to mechanical damage. These unique
properties make CNTs a competitive alternative to
conventional
sorbents used in analytical chemistry, especially in
extraction
techniques. The amount of work that discusses the usefulness
of
CNTs as a sorbent in a variety of extraction techniques has
increased
significantly in recent years. In this review article the most
important
features and different applications of SPE including classical
solid-
phase extraction and dispersive solid-phase extraction using CNTs
for
pesticides isolation from different matrices.
Conflicts of Interest
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