TODAY SCIENCE TOMORROW INDUSTRY PROCEEDINGS · 2015. 7. 8. · Anamarija Šter, Martina Medvidović-Kosanović , Tomislav Balić, Iva Ćurić, Paula Mihaljević-Jurić Josip Juraj

Croatian Society of Chemical Engineers

Josip Juraj Strossmayer University of Osijek, Faculty of Food Technology Osijek

European Federation of Food Science and Technology

European Association for Chemical and Molecular Sciences

European Hygienic Engineering & Design Group

International Scientific and Professional Conference

15th Ružička days

“TODAY SCIENCE – TOMORROW INDUSTRY”

11th and 12th September 2014

Vukovar, Croatia

PROCEEDINGS

Hrvatsko društvo kemijskih inženjera i tehnologa

Sveučilište Josipa Jurja Strossmayera u Osijeku, Prehrambeno-tehnološki fakultet Osijek

European Federation of Food Science and Technology

European Association for Chemical and Molecular Sciences

European Hygienic Engineering & Design Group

međunarodni znanstveno-stručni skup

XV. Ružičkini dani

“DANAS ZNANOST – SUTRA INDUSTRIJA”

11. i 12. rujna 2014.

Vukovar, Hrvatska

ZBORNIK RADOVA

Osijek i Zagreb, 2015.

PROCEEDINGS 15th

Ružička days

TODAY SCIENCE – TOMORROW INDUSTRY

ZBORNIK RADOVA XV. Ružičkini dani

DANAS ZNANOST - SUTRA INDUSTRIJA

Published by/Izdavači Josip Juraj Strossmayer University of Osijek

Faculty of Food Technology Osijek

Croatian Society of Chemical Engineers

Sveučilište Josipa Jurja Strossmayera u Osijeku

Prehrambeno-tehnološki fakultet Osijek

Hrvatsko društvo kemijskih inženjera i tehnologa (HDKI)

Editors/Urednici Drago Šubarić, Ante Jukić

Executive Editors/Izvršne urednice Mirela Planinić, Đurđica Ačkar

Technical Editor/Tehnička urednica Ivana Lauš

Proceedings Reviewers/

Recenzenti Zbornika

Igor Jerković, Darko Kiš, Maja Molnar, Ivica Strelec,

Rezica Sudar, Elvira Vidović

Proofreaders/Lektori Lidija Obad, Antonija Šarić

Cover page design/Dizajn naslovnice Ivana Lauš

Printing and Binding/Tisak i uvez Grafoprojekt, Virovitica, Hrvatska

Number of Copies/Naklada 200

Scientific and Organizing Committee

Znanstveno-organizacijski odbor

Drago Šubarić (predsjednik/chairman),

Ante Jukić (dopredsjednik/vice-chairman),

Srećko Tomas (dopredsjednik/vice-chairman),

Đurđica Ačkar, Jurislav Babić, Ljubica Glavaš-Obrovac, Vlado

Guberac, Mirjana Hruškar, Ivan Hubalek, Stela Jokić, Stjepan

Leaković, Ivanka Miličić, Slavko Marjančević, Jadranka

Mustapić-Karlić, Vesna Ocelić Bulatović, Ivana Lauš, Mirela

Planinić, Milan Sak-Bosnar, Nataša Srnić, Zvonimir Zdunić

Honorary Committee

Počasni odbor

Vladimir Andročec, Božo Galić, Marin Hraste, Zvonimir

Janović, Leo Klasinc, Filip Kljajić, Gordan Kolundžić, Ruža

Marić, Sandra Mrvica Mađarac, Ivan Penava, Vlasta Piližota,

Damir Skender, Nenad Trinajstić, Željko Turkalj, Ivan Vrdoljak

Osijek i Zagreb, 2015.

ISBN (PTF): 978-953-7005-36-8

ISBN (HDKI): 978-953-6894-53-6

A CIP catalogue record of this publication is available from the

City and University Library Osijek under 140114084

CIP zapis dostupan u računalnom katalogu

Gradske i sveučilišne knjižnice Osijek pod brojem 140114084

Publication of the Proceedings was approved by the Senate of the Josip Juraj Strossmayer University of

Osijek at the fifth session of the academic year 2014/2015 held on the 31st March 2015 numbered 12/15.

Objavljivanje ovog Zbornika odobrio je Senat Sveučilišta Josipa Jurja Strossmayera u Osijeku na 5.

sjednici u akademskoj godini 2014./2015. održanoj 31. ožujka 2015. godine, pod brojem 12/15.

International Scientific and Professional Conference 15th

Ružička days


11th

and 12th September 2014

Vukovar, Croatia

Kemijska analiza i sinteza / Chemical analysis and synthesis

32

Electrochemical characterization of (1E)-1-N-{[4-(4-{[(E)-N-(4- aminophenyl)

carboxyimidoyl] phenoxy}butoxy) phenyl]methylidene} benzene-1,4-diamine

UDC: 543.55 : 547.532

Anamarija Šter, Martina Medvidović-Kosanović, Tomislav Balić,

Iva Ćurić, Paula Mihaljević-Jurić

Josip Juraj Strossmayer University of Osijek, Department of Chemistry, Cara Hadrijana 8/A,

HR-31000 Osijek, Croatia

Summary

Oxido-reduction properties of a novel synthesized Schiff base were studied by cyclic and differential

pulse voltammetry. The results of electrochemical study have shown that the oxidation of the

investigated Schiff base is reversible, diffusion controlled process and that the oxidation products

are adsorbed on the glassy carbon electrode surface.

Keywords: Schiff base, electrochemistry, voltammetry

Introduction

Schiff bases have been widely studied due to their pronounced biological and

pharmacological activity (Liang et al., 2014), optical (Fang et al., 2014), photochromical

(Zhao et al., 2001), thermochromical (Minkin et al., 2011) properties and other outstanding

material properties. Furthermore, they can easily form different types of polydentate

ligands and because their diversified donor groups (or atoms) are suitable as chelating

agents. Complex compounds of Schiff bases are considered to be a transition state between

simple coordination compounds and metalloproteins (Chandra et al., 2008).

Untill now, Schiff bases and their metal complexes were studied by XRD (Kianfar et al.,

2014a), EDX (Kianfar et al., 2014a), TGA/DTA (Kianfar et al., 2014a), SEM (Kianfar et

al., 2014a), TEM (Kianfar et al., 2014a), FT-IR spectroscopy (Booysen et al., 2014;

Grivani et al., 2014; Kianfar et al., 2014a; Novoa et al., 2014; Shafaatian et al., in press). 1H NMR (Grivani et al., 2014; Shafaatian et al., 2014), elemental analysis (Novoa et al., in

press; Shafaatian et al., 2014), fluorescence (Shafaatian et al., 2014), conductometry

(Booysen et al., 2014; Shafaatian et al., 2014) and EPR (Novoa et al., in press). Their

structure was determined by X-ray diffraction (Booysen et al., 2014; Grivani et al., 2014;

Novoa et al., in press; Shafaatian et al., 2014) and ab initio calculations (Novoa et al., in

press) and electrochemical characterization was conducted by cyclic voltammetry

Corresponding author: [email protected]


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(Booysen et al., 2014; Kianfar et al., 2013b, 2011c; Menati et al., 2012; Shafaatian et al.,

2014) and square wave voltammetry (Booysen et al., 2014). Biological activity and use of

Schiff bases as potentiometric sensors for metal cation determination was also studied

(Afkhami et al., 2013; Bandi et al., 2013).

In this study we have examined oxido-reduction properties of (1E)-1-N-{[4-(4-{[(E)-N-(4-

aminophenyl) carboxyimidoyl] phenoxy} butoxy) phenyl] methylidene} benzene-1,4-

diamine (Fig. 1) by cyclic and differential pulse voltammetry. Preliminary information

obtained from this research is very useful as indicator of potential application of this

compound (i.e. organic semiconductor, liquid crystal, potentiometric sensor etc.).

Fig. 1. Structure of synthesized Schiff base (1E)-1-N-{[4-(4-{[(E)-N-(4- aminophenyl)

carboxyimidoyl] phenoxy}butoxy) phenyl]methylidene} benzene-1,4-diamine

Materials and methods

All commercially available chemicals were of reagent grade and used as purchased from

commercial sources. Dialdehyde 4-[4-(4-formylphenoxy) butoxy]benzaldehyde was

prepared by previously reported method. All solvents were purchased commercially. N,N-

dimethylformamide (DMF) was purchased from Fischer Chemical and Lithium Chloride

(LiCl) from BDH Prolabo and were used without further purification.

Shiff base synthesis: Dialdehyde (0.6 g, 2 mmol) was dissolved in 40 ml of methanol and 2-

3 drops of acetic acid were added to this solution. The solution was brought to brisk reflux

and 0.49 g (4.5 mmol) of p-phenylendiamine dissolved in 25 ml of methanol was gradually

added. The mixture was heated at reflux temperature for 3 hours. After the reaction was

completed, the resulting mixture was left at room temperature for 24 hours. The red powder

product was filtered and washed with cold ethanol and diethyl ether. Yield: 76 %

IR spectrum was recorded on a Shimadzu FTIR 8400S spectrophotometer using the DRS

8000 attachment, in the 4000-400 cm−1

region. Thermogravimetric analysis was performed

using a simultaneous TGA-DSC analyser (Mettler-Toledo TGA/DSC 1). The compound


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was placed in aluminium pan (100 L) and heated in nitrogen atmosphere (200 mL min−1

)

up to 550 °C at a rate of 10 °C min−1

. The data collection and analysis was performed using

the program package STARe Software 10.0. The

1H NMR and

13C NMR were recorded on

NMR (300 MHz) Bruker instrument, using deuterated dimethyl sulfoxide as solvent at

NMR Laboratory of the Ruđer Bošković Institute, Zagreb.

Electrochemical experiments were performed on PalmSens potentiostat/galvanostat

(PalmSens BV, Utrecht, The Netherlands) driven by PSTrace 4.2 software. A conventional

three-electrode cell was used with a glassy carbon as a working electrode, non-aqueous

Ag/Ag+ (and aqueous Ag/AgCl) as a reference electrode and a platinum wire as a counter

electrode. The glassy carbon working electrode was polished with coarse diamond polish

(1 µm, ALS, Japan) and with polishing α-Al2O3 (0.05µm, ALS, Japan) before each

measurement. Cyclic voltammetry scan rate was 100 mV s–1

. The differential pulse

voltammetry conditions were: scan increment 5 mV, pulse amplitude 25 mV, pulse width

70 ms and scan rate 5 mV s–1

.

Results and discussion

Cyclic voltammetry studies

A cyclic voltammogram of the investigated Schiff base is shown in Fig. 2. One anodic (A1)

peak at a potential of 0.4562 V and one cathodic (K1) peak at a potential 0.3962 V appeared

when the potential was scaned from -0.2 V to 0.8 V vs. Ag/Ag+ reference electrode. Obtained

Ep value was 60 mV, indicating that the oxidation reaction is reversible.

Fig. 2. Cyclic voltammogram of title compound (c = 1.1·10-4

mol dm-3

) at a glassy carbon electrode

(Ic = 0.1 M LiCl in DMF). Scan rate: 100 mV/s. A1 (anodic peak), K1 (cathodic peak)


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The influence of concentration of the investigated Schiff base on anodic peak current and

anodic peak potential was examined and the obtained data are given in Table 1. The effect

of scan rate on the oxidation of the Shiff base has been investigated as well (Fig. 3). The

obtained results have shown that both anodic peak potential and anodic peak current

increase with the increase in Schiff base concentration and scan rate.

Fig. 3. Cyclic voltammograms of title compound (c = 1.1·10-4

mol dm-3

) at a glassy carbon electrode (Ic = 0.1 M LiCl in DMF) obtained with: a) Ag/Ag

+ and b) Ag/AgCl reference electrode, at different

scan rates ( = 25, 75, 150, 200, 250 and 300 mV/s)

Table 1. Anodic peak potential (Ep,a) and anodic peak current (Ip,a) of the title compound as the

function of its concentration obtained with Ag/Ag+ and Ag/AgCl reference electrode.

Scan rate: 100 mV/s.

non-aqueous Ag/Ag+ electrode aqueous Ag/AgCl electrode

104 c / mol dm-3 Ep,a / V Ip,a / A Ep,a / V Ip,a / A

0.31 0.4164 0.1636 0.6314 0.2033

0.59 0.4184 0.1853 0.6383 0.2120

1.10 0.4509 0.2146 0.6579 0.2435

1.25 0.4519 0.2149 0.6692 0.2543


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Fig. 4 shows that at lower concentrations of Schiff base (bellow c ~ 1.1 10-4

mol dm–3

)

anodic peak current is a linear function of the Schiff base concentration (the adsorption of

the investigated Schiff base oxidation products on the electrode surface occurs). At higher

concentrations of Schiff base (above c ~ 1.1 10 –4

mol dm–3

), the increase of peak current

slows down, which could be explained by increase of interactions between molecules

adsorbed on the electrode surface and by diffusion current (Medvidović-Kosanović et al.,

2010). The Schiff base oxidation is controlled by diffusion (Fig. 5) since linear dependence

was found between anodic peak current and the square root of scan rate (Medvidović-

Kosanović et al., 2010; Yagmur et al., 2013).

Fig. 4. Anodic peak current as a function of title compound concentration (Ic = 0.1 M LiCl in DMF). Scan rate: 100 mV/s

Fig. 5. Anodic peak current, I, as a function of the square root of scan rate, 1/2

, at a glassy carbon

electrode in solution of title compound (c = 1.1·10-4

mol dm-3

, Ic = 0.1 M LiCl in DMF)


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Differential pulse voltammetry studies

Differential pulse voltammogram in Fig. 6 revealed one oxidation peak of the investigated

Schiff base at the potential 0.415 V. The oxidation peak decreases with successive scans

which confirms adsorption of the Schiff base oxidation products on the glassy carbon

electrode surface.

Fig. 6. Differential pulse voltammogram of title compound (c = 1.1·10-4

mol dm-3

) at a glassy

carbon electrode (Ic = 0,1 M LiCl in DMF). Scan rate: 5 mV/s. First scan (a),

second scan, third scan, forth scan

Peak current and peak potential also increase with increasing Schiff base concentration

(Fig. 7) which could be explained by kinetic limitation in the reaction between the redox

sites of a glassy carbon electrode and the investigated Schiff base (Bandi et al., 2013). A

linear relationship could be established between peak current and Schiff base concentration

in the range of 0.3110-4

mol dm-3

to 1.25 10-4

mol dm-3

(the inset of Fig. 7). A linear

regression equation, Ip = 1.3592 c + 2.4628 with a correlation coefficient R2 = 0.9823, can

be obtained, where Ip is the oxidation peak current (10-2

A) and c is the Schiff base

concentration (10-4

mol dm-3

). It can also be seen from Fig. 8 that the results obtained by

non-aqueous Ag/Ag+ reference electrode show higher R

2 values compared to aqueous

Ag/AgCl electrode. Therefore, non-aqueous Ag/Ag+ reference electrode should be used for

experiments in non-aqueous medium.


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Fig. 7. Differential pulse voltammograms in the solutions of title compound with concentrations (c =

3.1 ·10-5

; 5.9 ·10-5

; 1.1 ·10-4

and 1.25 ·10-4

(d) mol dm-3

) at a glassy carbon electrode (Ic = 0.1 M

LiCl in DMF). Scan rate: 5 mV/s. The inset of figure 7: Anodic peak current, I, as a function of the

Schiff base concentration, c (data taken from Fig. 7)

Fig. 8. Anodic peak current, I, as a function of the title compound concentration, c,

at a glassy carbon electrode obtained with: a) non-aqueous Ag/Ag+ () and b)

aqueous Ag/AgCl (●) reference electrode (Ic = 0.1 M LiCl in DMF)


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Conclusions

The electrochemical results have shown that the oxidation of the Schiff base title

compound is reversible and controlled by diffusion at the investigated experimental

conditions. Adsorption of the oxidation products on the glassy carbon electrode occurs and

this process is kinetically limited. A linear relationship between peak current and Schiff

base concentration in the range of 0.3110-4

mol dm-3

to 1.25 10-4

mol dm-3

was established.

Comparison of the results obtained by non-aqueous Ag/Ag+ and aqueous Ag/AgCl

reference electrode has shown that for experiments in non-aqueous medium non-aqueous

Ag/Ag+ reference electrode should be used.

Acknowledgements

The authors thank J. J. Strossmayer University of Osijek, Croatia for financial support.

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Documents

TODAY SCIENCE TOMORROW INDUSTRY PROCEEDINGS · 2015. 7. 8. · Anamarija Šter, Martina Medvidović-Kosanović , Tomislav Balić, Iva Ćurić, Paula Mihaljević-Jurić Josip Juraj