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Journal of Molecular Liquids 219 (2016) 63–67

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Determination of hydroquinone in food and pharmaceutical samples

using a voltammetric based sensor employing NiO nanoparticle and
ionic liquids
Hoda Soltani, Abbas Pardakhty, Saeid Ahmadzadeh ⁎
Pharmaceutics Research Center, Institute of Neuropharmacology, Kerman University of Medical Sciences, Kerman, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A sensitive modified carbon paste electrode (MCPE) employing NiO nanoparticle (NiO/NPs) and 1-butyl-3-
Received 20 December 2015 methylimidazolium tetrafluoroborate (BMITFB) ionic liquid was used for trace level analysis of hydroquinone
Received in revised form 29 February 2016 (HQ) in aqueous solution. Compared to bare electrode, the electro-oxidation signal of HQ was greatly improved.
Accepted 4 March 2016
The obtained result shows that, the electro-oxidation signal was increased to about 2.5 times at the surface of
Available online xxxx
(NiO/NPs/BMITFB/MCPE) compared to CPE. The linear response range and detection limit were found to be
Keywords:
0.1–500 μM and 0.05 μM by square wave voltammetry (SWV), respectively. NiO/NPs/BMITFB/MCPE was effec-
Hydroquinone analysis tively applied for the determination of HQ in real samples such as Liposomes carrier containing HQ and water
Liposomes sample.
Modified electrode © 2016 Elsevier B.V. All rights reserved.
Ionic liquid

1. Introduction So far, numerous analytical procedures including high performance

liquid chromatography [13,14], fluorescence [15,16], chemilumines-
Hydroquinone (HQ, 1,4-dihydroxybenzene) is an isomer of phenolic cence [17,18], spectrophotometry [19,20] and electrochemical methods
compounds which extensively used in several fields such as cosmetics, [21–23] has been reported for determination of HQ in various matrices.
medicines, dye, photostabilizer, plastic, petroleum refinery, antioxidant, Electrochemical methods in comparison to other strategies received
pesticides, and photography [1–3]. HQ works by inhibiting the enzyme more interest because the mentioned techniques mostly involve expen-
tyrosinase, which is essential in the production of the pigment melanin sive instruments, lengthy sample preparation and complicated analysis
and lead to bleaching of the skin [4]. Hydroquinone blocks a step in a procedures which has limited their application in the rapid and quanti-
specific enzymatic pathway that involves tyrosinase as an enzyme in tative analysis of electroactive compounds [24–28]. On the other hand,
the procedure of converting dopamine to melanin [5]. HQ is used as a electrochemical sensors as an efficient approach offering advantages
topical application for skin whitening for reducing the color of the such as low cost, fast analysis, high sensitivity and selectivity in compare
skin. However, numerous studies revealed that if HQ taken orally may to instrumental analysis [29–31].
cause exogenous ochronosis, a disfiguring disease in which blue-black Room temperature ionic liquids (RTILs) which composed entirely of
pigments are deposited onto the skin [6]. HQ is difficult to degrade in ions received increasing interest over the last decade due to their char-
the ecological environment and highly toxic to human health even at acteristics of negligible vapor pressure and good solubility and chemical
low concentrations [7,8]. High concentration of HQ can lead to acute stability. RTILs due to their unique electrochemical properties such as
myeloid leukemia, tinnitus, headache, fatigue, dizziness, nausea, considerable high ionic conductivity, broad electrochemical window
edema of internal organs, skin irritation and cause kidney damage in and fast ion mobility have been applied in various fields such as electro-
humans [9–11]. HQ considered as an environmental pollutant by the lytes in batteries, binder, electrochemical cells, and electroplating. As a
US Environmental Protection Agency (EPA) and the European Union new green medium, RTILs have also been newly used in construction
(EU) [12]. Therefore, development of sensitive and reliable analytical of electrochemical modified sensors. The obtained results revealed
methods with high accuracy has been greatly demanded in the field of that the use of RTILs could increase the sensitivity of electrochemical
environmental pollutant analysis. response and facilitate efficient direct electron transfer of various bio-
logical, environmental and pharmaceutical compounds [32–34].
Nanomaterials and especially metal oxide nanoparticles of a variety of
⁎ Corresponding author.
shapes, sizes and compositions benefited the electrochemical measure-
E-mail addresses: chem_ahmadzadeh@yahoo.com, saeid.ahmadzadeh@kmu.ac.ir ment of electroactive materials because of their unique electrical, ther-
(S. Ahmadzadeh). mal, chemical and physical properties [35–40]. This kind of materials

http://dx.doi.org/10.1016/j.molliq.2016.03.014
0167-7322/© 2016 Elsevier B.V. All rights reserved.
64 H. Soltani et al. / Journal of Molecular Liquids 219 (2016) 63–67

can be improved sensitivity and selectivity voltammetric sensors in Standard addition method was used to determine the percentage of
analysis filed [41–43].Metal oxide nanoparticles with high surface non-trapped HQ using proposed sensor.
area show valuable electrocatalytic activity and high conductivity to Water sample was used without any pretreatment for spike HQ
modify the surface of electrodes. Metal oxide nanoparticles due to analysis as a real sample.
their good biocompatibility are remarkably applied in preparation of
biosensors [44–46]. It can be concluded that combination of metal 3. Results and discussion
oxide nanomaterials and RTILs could reveal awesome and novel fea-
tures in preparation of new electrochemical sensors for pharmaceutical, 3.1. SEM investigation for used nanoparticles
biological and environmental compound analysis.
Surface morphology of NiO nanoparticles was characterized by SEM
2. Materials and methods method (Fig. 1). The dark spots correspond to NiO nanoparticles, which
were only synthesized in our synthesis condition. Nanoparticles with
2.1. Chemical and reagents near-spherical shapes were synthesized.

Hydroquinone, 1-butyl-3-methylimidazolium tetrafluoroborate

3.2. Electrochemical analysis
were purchased from Sigma-Aldrich. Lecithins, NaOH, cholesterol, min-
eral oil, and methanol and graphite powder were obtained from Merck.
According to previous published paper, the electro-oxidation signal
Phosphate buffer solution (PBS) with various pH was prepared by
of HQ is closely related to the pH value of buffer solution [47]. According
mixing the stock solution of 0.1 M H3PO4. The doubly distilled water
to the mentioned paper, optimization of pH is a very important factor
was used in all solution preparations. All of the other chemicals were
for trace analysis of it in real samples. The obtained results show that
purchased in analytical grade from Merck.
the electro-oxidation current increased gradually from pH 6.0 to 7.0,
and then the oxidation signal conversely decreased when the pH
2.2. Apparatus
value increased from 7.0 to 9.0 (Fig. 2). So pH 7.0 was selected as a
best condition in analytical procedure in further steps. The relationship
Voltammetric measurements were performed on a Sama-500 elec-
between the electro-oxidation potential and pH was also investigated. A
trochemical workstation (Isfahan, Iran). A three-electrode system was
linear shift of Epa towards negative potential with an increasing pH can
employed with a modified or unmodified carbon paste electrode as
be obtained, which indicates that protons are directly involved in the
working electrode, a Pt wire as counter electrode, and a Ag/AgCl/
oxidation of HQ (Fig. 3). A slope of 0.064 V/pH suggests that the number
KClsaturated electrode as reference electrode.
of electron transfer is equal to the proton number involved in the elec-
Microstructure and surface morphology of nanoparticles were iden-
trode reaction.
tified by a scanning electron microscope (SEM, Philips).
The current density for oxidation signal of HQ derived from the cy-
clic voltammogram responses of 500 μM HQ (pH 7.0) at the surface of
2.3. Preparation of BMITB/NiO/NPs/CPE
different electrodes is shown in Fig. 4 (inset).
The cyclic voltammograms of HQ at NiO/NPs/BMITFB/MCPE are also
NiO/NPs/BMITFB/MCPE was prepared by mixing 0.2 g of BMITFB,
compared with that at bare carbon paste electrode (CPE), NiO/NPs/
0.8 g of paraffin, 0.1 g of nanoparticles and 0.9 g of graphite powder.
MCPE and BMITFB/MCPE at a scan rate of 100 mV/s in 0.1 M PBS
Then the mixture was mixed well for 1 h until a uniformly wetted
(pH 7.0) (Fig. 4). At the bare electrode, the electro-oxidation of HQ
paste was obtained. A portion of the paste was filled firmly into a glass
tube as described above to prepare NiO/NPs/BMITFB/MCPE. When nec-
essary, a new surface of NiO/NPs/BMITFB/MCPE was obtained by push-
ing an excess of the paste out of the tube and polishing it on a white
paper.

2.4. Recommended procedure

NiO/NPs/BMITFB/MCPE was polished with a white and clean paper.

To prepare a blank solution, 10.0 mL of the buffer solution (PBS, pH 7.0)
was transferred into an electrochemical cell. The initial and final poten-
tials were adjusted to − 0.4 and 0.8 V vs. Ag/AgCl, respectively. Cyclic
voltammogram was recorded with a scan rate of 100 mV/s to record
the electrochemical signal at pH = 7.0.

2.5. Real sample preparation

Liposomes containing HQ were prepared using film hydration meth-

od. Lecithin and cholesterol were dissolved in chloroform solvent with
three different compositions of 50:50, 60:40 and 70:30, respectively.
Rotary evaporator was used to evaporate the solvent, until an oily con-
centrated mixture was obtained and then a known amount of HQ which
is dissolved in di-water, was added to the mixture and for 30 min rotary
evaporating process was continued until milky color suspensions con-
taining liposomes were formed. To prevent the oxidation of lecithin
the procedure was carried out under inert atmosphere. To determine
the amount of HQ loading in all formulations, the non-entrapped com-
pounds were separated from encapsulated ones by centrifuge. The su-
pernatant phase which contains the non-trapped HQ was separated. Fig. 1. SEM image of synthesized NiO nanoparticles.
 H. Soltani et al. / Journal of Molecular Liquids 219 (2016) 63–67 65

Fig. 2. Current–pH curve for electrooxidation of 500 μM HQ at NiO/NPs/BMITFB/MCPE.

Inset) influence of pH on cyclic voltammograms of HQ at the surface of the modified
electrode, (pH 6.0, 7.0, 8.0 and 9.0, respectively).

has a low current with high overvoltage. After modification with NiO/
NPs or BMITFB ionic liquid oxidation signal for HQ improved and over-
voltage reduce for it. Therefore, we found that NiO/NPs and BMITFB are Fig. 4. Cyclic voltammograms of (a) NiO/NPs/BMITFB/MCPE, (b) BMITFB/MCPE, (c) NiO/
NPs/CPE and (d) BCPE in the presence of 500 μM HQ pH 7.0, respectively.
two conductive compounds and can be used as a mediator for carbon
paste modification. Fig. 4 (curve a) shows better condition for electro-
oxidation of HQ. The result confirms that modification of electrode
with NiO/NPs or BMITFB is increasing quality of sensor for trace analysis 3.3. Interference of coexisting substances
of HQ. So, we selected NiO/NPs/BMITFB/MCPE as a suitable sensor in
this work. The influence of some compounds on the determination of 50.0 μM
Electrochemical mechanisms and kinetic characteristics of an HQ was also studied. It was found that 100-fold concentration of fruc-
electroactive compound (HQ in this case) can be investigated by scan tose, lactose, glucose, urea, thiourea, sucrose, phenol, and Na+, SO2− 4 ,
rate study of it. Fig. 5 insets showed the cyclic voltammograms of HQ Cl−, Mg2+, Ca2+, Pb2+, Zn2+, NO− 3 , and Ni
+2
and 75 fold concentration
on NiO/NPs/BMITFB/MCPE between − 0.3 and 0.60 V at various scan of histidine, methionine, cysteine, lysine, phenyl alanine, and glycine do
rates. Fig. 5 shows the electro-oxidation peak currents (Ip) increased lin- not affect the determination of HQ (signal change ≤ 5% in current and
early vs. ν1/2 from 300 to 800 mV/s indicating that the electro-oxidation potential).
of HQ on NiO/NPs/BMITFB/MCPE was a diffusion controlled process.
Chronoamperometric analysis of HQ at NiO/NPs/BMITFB/MCPE was
carried out by setting the working electrode potential at 900 mV for 3.4. Dynamic range
the 100 μM, 200 μM, 300 μM, 400 μM and 500 μM of HQ in buffered
aqueous solutions (pH 7.0) (Fig. 6A). Experimental plots of I vs. t−1/2 Square wave voltammetry curves showed that as the concentration
were employed, with the best fits for different concentrations of HQ of HQ increased, the current signal gradually increased. During the HQ
(Fig. 6B). The slopes of the resulting straight lines were then plotted concentration range 0.1–500 μM, the concentration and the current re-
vs. HQ concentration. From the resulting slope and Cottrell equation sponse of HQ exhibited a linear relationship with equation: I = 0.3425
the mean value of the D was found to be 4.14 × 10−5 cm2/s. CHQ + 1.9640; R2 = 0.9913, where C is μM concentration of HQ and Ip
is the peak current. The detection limit was determined at 0.05 μM HQ
according to the definition of YLOD = YB + 3σ.

Fig. 3. Plot of potential, E, vs. pH for the electro-oxidation of 500 μM HQ at a surface of NiO/ Fig. 5. Plot of Ipa versus ν1/2 for the oxidation of HQ at NiO/NPs/BMITFB/MCPE. Inset shows
NPs/BMITFB/MCPE. Inset: influence of pH on cyclic voltammograms of HQ at a surface of cyclic voltammograms of HQ at NiO/NPs/BMITFB/MCPE at different scan rates of (a) 300,
the modified electrode (pH 6–9, respectively). (b) 400, (c) 500, (d) 600 and (e) 800 mV/s in 0.1 M phosphate buffer, pH 7.0.
66 H. Soltani et al. / Journal of Molecular Liquids 219 (2016) 63–67

with the detection limit of 0.05 μM. The excellent properties of the
NiO/NPs/BMITFB/MCPE make them promising for application to real
sample analysis.

Acknowledgments

The authors express their appreciation to Kerman University of

Medical Sciences, Kerman, Iran for supporting the current dissertation.

References
[1] F.A. Andersen, W.F. Bergfeld, D.V. Belsito, R.A. Hill, C.D. Klaassen, D.C. Liebler, J.G.
Marks, R.C. Shank, T.J. Slaga, P.W. Snyder, Final amended safety assessment of hy-
droquinone as used in cosmetics, Int. J. Toxicol. 29 (2010) 274S–287S.
[2] H. Zhang, X. Bo, L. Guo, Electrochemical preparation of porous graphene and its elec-
trochemical application in the simultaneous determination of hydroquinone, cate-
Fig. 6. (A) Chronoamperograms obtained at NiO/NPs/BMITFB/MCPE in the presence of chol, and resorcinol, Sensors Actuators B Chem. 220 (2015) 919–926.
(a) 100; (b) 200; (c) 300; (d) 400 and (e) 500 μM HQ in the buffer solution (pH 7.0). [3] Y. Zhang, S. Xiao, J. Xie, Z. Yang, P. Pang, Y. Gao, Simultaneous electrochemical deter-
(B) Cottrell's plot for the data from the chronoamperograms. mination of catechol and hydroquinone based on graphene–TiO2 nanocomposite
modified glassy carbon electrode, Sensors Actuators B Chem. 204 (2014) 102–108.
[4] J.K. No, M.S. Kim, Y.J. Kim, S.J. Bae, J.S. Choi, H.Y. Chung, Inhibition of tyrosinase by
3.5. Stability and reproducibility protocatechuic aldehyde, Am. J. Chin. Med. 32 (2004) 97–103.
[5] E.V. Curto, C. Kwong, H. Hermersdörfer, H. Glatt, C. Santis, V. Virador, V.J. Hearing,
The reproducibility of the NiO/NPs/BMITFB/MCPE was evaluated by T.P. Dooley, Inhibitors of mammalian melanocyte tyrosinase: in vitro comparisons
of alkyl esters of gentisic acid with other putative inhibitors, Biochem. Pharmacol.
determination of HQ with four sensors prepared using the same proce- 57 (1999) 663–672.
dure. The relative standard deviation (RSD) is 1.9% for HQ, which indi- [6] H.S. Han, J.-M. You, H. Seol, H. Jeong, S. Jeon, Electrochemical sensor for hydroqui-
cated the suitable reproducibility of the fabricated sensor. none and catechol based on electrochemically reduced GO–terthiophene–CNT, Sen-
sors Actuators B Chem. 194 (2014) 460–469.
The stability of the novel modified electrode is also a major issue for [7] X. Yuan, D. Yuan, F. Zeng, W. Zou, F. Tzorbatzoglou, P. Tsiakaras, Y. Wang, Prepara-
the practical implementation of electrochemical analysis. Therefore, the tion of graphitic mesoporous carbon for the simultaneous detection of hydroqui-
stability of the NiO/NPs/BMITFB/MCPE was studied over 65 days. The none and catechol, Appl. Catal. B Environ. 129 (2013) 367–374.
[8] F.J. Enguita, A.L. Leitão, Hydroquinone: Environmental Pollution, Toxicity, and Mi-
proposed sensor was stored dry at room temperature for 10 days and
crobial Answers, BioMed Research International, 2013, 2013.
still retained about 97.0% of its original response for HQ, revealing that [9] Y. Liu, H. Liao, Y. Zhou, Y. Du, C. Wei, J. Zhao, S. Sun, J.S. Loo, Z.J. Xu, Fe2O3 nanopar-
the as-prepared electrode had excellent stability. ticle/SWCNT composite electrode for sensitive electrocatalytic oxidation of hydro-
quinone, Electrochim. Acta 180 (2015) 1059–1067.
[10] T. McDonald, N. Holland, C. Skibola, P. Duramad, M. Smith, Hypothesis: phenol and
3.6. Real sample analysis hydroquinone derived mainly from diet and gastrointestinal flora activity are causal
factors in leukemia, Leukemia 15 (2001) 10–20.
[11] A.P. DeCaprio, The toxicology of hydroquinone—relevance to occupational and envi-
In order to assess the ability of the NiO/NPs/BMITFB/MCPE as a novel ronmental exposure, Crit. Rev. Toxicol. 29 (1999) 283–330.
sensor, it used for direct analysis of HQ in real samples such as tap water [12] S. Erogul, S.Z. Bas, M. Ozmen, S. Yildiz, A new electrochemical sensor based on Fe3O4
functionalized graphene oxide-gold nanoparticle composite film for simultaneous
and waste water. The results are listed in Table 1 and shows feasibility of determination of catechol and hydroquinone, Electrochim. Acta 186 (2015)
the NiO/NPs/BMITFB/MCPE in the direct analysis of HQ in real samples. 302–313.
Moreover, the encapsulation efficiency of formed liposome contain- [13] C.-H. Lin, J.-Y. Sheu, H.-L. Wu, Y.-L. Huang, Determination of hydroquinone in cos-
metic emulsion using microdialysis sampling coupled with high-performance liquid
ing HQ was calculated by determination of the non-entrapped HQ chromatography, J. Pharm. Biomed. Anal. 38 (2005) 414–419.
which is remaining in supernatant phase by proposed fabricated sensor. [14] J. Wittig, S. Wittemer, M. Veit, Validated method for the determination of hydroqui-
According the the obtained results using standard addition method, the none in human urine by high-performance liquid chromatography–coulometric-
array detection, J. Chromatogr. B Biomed. Sci. Appl. 761 (2001) 125–132.
composition of 70:30 (Lecithin:cholesterol) liposome revealed the best
[15] M.F. Pistonesi, M.S. Di Nezio, M.E. Centurión, M.E. Palomeque, A.G. Lista, B.S.F. Band,
encapsulation efficiency of 76.7% in compare to the other prepared Determination of phenol, resorcinol and hydroquinone in air samples by synchro-
composition. nous fluorescence using partial least-squares (PLS), Talanta 69 (2006) 1265–1268.
[16] F.-r. Zeng, Y.-q. Xi, S.-q. Zhang, H.-o. Qiu, Z.-y. Tang, Determination of phenol and hy-
droquinone in environmental water by fluorescence spectrometry, Chin. J. Anal, Lab.
4. Conclusion 26 (2007) 76.
[17] B.G.-T. Corominas, M.C. Icardo, L.L. Zamora, J.G. Mateo, J.M. Calatayud, A tandem-
flow assembly for the chemiluminometric determination of hydroquinone, Talanta
This work demonstrated the application of a NiO/NPs and 1-butyl-3- 64 (2004) 618–625.
methylimidazolium tetrafluoroborate as a modifier in carbon paste ma- [18] W. Shu-hao, DU, Ling Yun, W.E.I. Xin-ting, Zhuang Hui-sheng, (1. Institute of Chem-
istry and Chemical Engineering, Liaocheng University, Liaocheng 252059, China; 2.
trix for the determination of HQ. The proposed sensor showed good College of Environmental Science and Engineering, Donghua University, Shanghai
electrocatalytic activity towards the electro-oxidation response of HQ 200051, China); FI-chemiluminescence determination of hydroquinone in river
with the enhancement of the electro-oxidation signal. Under the opti- water [J], Phys. Test. Chem. Anal. Part B: Chem. Anal. 3 (2007).
[19] M.I. Bhanger, A. Niaz, A. Shah, A. Rauf, Ultra-trace level determination of hydroqui-
mum conditions in cyclic voltammetric investigation, the peak current none in waste photographic solutions by UV–vis spectrophotometry, Talanta 72
was proportional to the HQ concentration in the range of 0.1–500 μM (2007) 546–553.
[20] L. Lianwei, Determination of trace hydroquinone by inhibition kinetic-spectropho-
tometry [J], Chin. J. Anal. Chem. 9 (2000) 007.
Table 1 [21] Y. Zhang, R. Sun, B. Luo, L. Wang, Boron-doped graphene as high-performance
Determination of HQ in real samples. electrocatalyst for the simultaneously electrochemical determination of hydroqui-
none and catechol, Electrochim. Acta 156 (2015) 228–234.
Sample HQ Recovery % RSD [22] H. Yin, Q. Zhang, Y. Zhou, Q. Ma, L. Zhu, S. Ai, Electrochemical behavior of catechol,
resorcinol and hydroquinone at graphene–chitosan composite film modified glassy
Added (μM) Found (μM)
carbon electrode and their simultaneous determination in water samples,
Tap water 10.00 9.87 ± 0.45 98.7 2.2 Electrochim. Acta 56 (2011) 2748–2753.
20.00 20.55 ± 0.75 102.8 2.8 [23] S. Radhakrishnan, K. Krishnamoorthy, C. Sekar, J. Wilson, S.J. Kim, A promising elec-
Waste water 50.00 50.85 ± 1.11 101.7 3.2 trochemical sensing platform based on ternary composite of polyaniline–Fe2O3–
reduced graphene oxide for sensitive hydroquinone determination, Chem. Eng. J.
80.00 79.45 ± 1.32 99.3 3.8
259 (2015) 594–602.
 H. Soltani et al. / Journal of Molecular Liquids 219 (2016) 63–67 67

[24] T. Eren, N. Atar, M.L. Yola, H. Karimi-Maleh, A sensitive molecularly imprinted poly- [37] T. Jamali, H. Karimi-Maleh, M.A. Khalilzadeh, A novel nanosensor based on Pt:Co
mer based quartz crystal microbalance nanosensor for selective determination of nanoalloy ionic liquid carbon paste electrode for voltammetric determination of vi-
lovastatin in red yeast rice, Food Chem. 185 (2015) 430–436. tamin B9 in food samples, LWT Food Sci. Technol. 57 (2014) 679–685.
[25] M.L. Yola, N. Atar, T. Eren, H. Karimi-Maleh, S. Wang, Sensitive and selective deter- [38] M.A. Khalilzadeh, H. Karimi-Maleh, V.K. Gupta, A nanostructure based electrochem-
mination of aqueous triclosan based on gold nanoparticles on polyoxometalate/re- ical sensor for square wave voltammetric determination of L-cysteine in the pres-
duced graphene oxide nanohybrid, RSC Adv. 5 (2015) 65953–65962. ence of high concentration of folic acid, Electroanalysis 27 (2015) 1766–1773.
[26] H. Karimi-Maleh, F. Tahernejad-Javazmi, N. Atar, M.L.t. Yola, V.K. Gupta, A.A. Ensafi, [39] B. Nikahd, M.A. Khalilzadeh, Liquid phase determination of bisphenol A in food sam-
A novel DNA biosensor based on a pencil graphite electrode modified with polypyr- ples using novel nanostructure ionic liquid modified sensor, J. Mol. Liq. 215 (2016)
role/functionalized multiwalled carbon nanotubes for determination of 6- 253–257.
mercaptopurine anticancer drug, Ind. Eng. Chem. Res. 54 (2015) 3634–3639. [40] A.A. Ensafi, H. Karimi-Maleh, Modified multiwall carbon nanotubes paste electrode
[27] N. Atar, M.L. Yola, T. Eren, Sensitive determination of citrinin based on molecular as a sensor for simultaneous determination of 6-thioguanine and folic acid using
imprinted electrochemical sensor, Appl. Surf. Sci. 362 (2016) 315–322. ferrocenedicarboxylic acid as a mediator, J. Electroanal. Chem. 640 (2010) 75–83.
[28] M.L. Yola, T. Eren, N. Atar, Molecularly imprinted electrochemical biosensor based [41] M.R. Shahmiri, A. Bahari, H. Karimi-Maleh, R. Hosseinzadeh, N. Mirnia,
on Fe@ Au nanoparticles involved in 2-aminoethanethiol functionalized multi- Ethynylferrocene–NiO/MWCNT nanocomposite modified carbon paste electrode
walled carbon nanotubes for sensitive determination of cefexime in human plasma, as a novel voltammetric sensor for simultaneous determination of glutathione
Biosens. Bioelectron. 60 (2014) 277–285. and acetaminophen, Sensors Actuators B Chem. 177 (2013) 70–77.
[29] H. Du, J. Ye, J. Zhang, X. Huang, C. Yu, A voltammetric sensor based on graphene- [42] R. Moradi, S. Sebt, H. Karimi-Maleh, R. Sadeghi, F. Karimi, A. Bahari, H. Arabi, Synthe-
modified electrode for simultaneous determination of catechol and hydroquinone, sis and application of FePt/CNT nanocomposite as a sensor and novel amide ligand
J. Electroanal. Chem. 650 (2011) 209–213. as a mediator for simultaneous determination of glutathione, nicotinamide adenine
[30] T. Gan, J. Sun, K. Huang, L. Song, Y. Li, A graphene oxide–mesoporous MnO2 nano- dinucleotide and tryptophan, Phys. Chem. Chem. Phys. 15 (2013) 5888–5897.
composite modified glassy carbon electrode as a novel and efficient voltammetric [43] H. Beitollah, M. Goodarzian, M.A. Khalilzadeh, H. Karimi-Maleh, M. Hassanzadeh, M.
sensor for simultaneous determination of hydroquinone and catechol, Sensors Actu- Tajbakhsh, Electrochemical behaviors and determination of carbidopa on carbon
ators B Chem. 177 (2013) 412–418. nanotubes ionic liquid paste electrode, J. Mol. Liq. 173 (2012) 137–143.
[31] S.-J. Li, Y. Xing, G.-F. Wang, A graphene-based electrochemical sensor for sensitive [44] H. Karimi-Maleh, F. Tahernejad-Javazmi, A.A. Ensafi, R. Moradi, S. Mallakpour, H.
and selective determination of hydroquinone, Microchim. Acta 176 (2012) Beitollahi, A high sensitive biosensor based on FePt/CNT nanocomposite/N-(4-
163–168. hydroxyphenyl)-3, 5-dinitrobenzamide modified carbon paste electrode for simul-
[32] M. Najafi, M.A. Khalilzadeh, H. Karimi-Maleh, A new strategy for determination of taneous determination of glutathione and piroxicam, Biosens. Bioelectron. 60
bisphenol A in the presence of Sudan I using a ZnO/CNTs/ionic liquid paste electrode (2014) 1–7.
in food samples, Food Chem. 158 (2014) 125–131. [45] H. Karimi-Maleh, P. Biparva, M. Hatami, A novel modified carbon paste electrode
[33] M. Elyasi, M.A. Khalilzadeh, H. Karimi-Maleh, High sensitive voltammetric sensor based on NiO/CNT nanocomposite and (9, 10-dihydro-9, 10-ethanoanthracene-11,
based on Pt/CNTs nanocomposite modified ionic liquid carbon paste electrode for 12-dicarboximido)-4-ethylbenzene-1, 2-diol as a mediator for simultaneous deter-
determination of Sudan I in food samples, Food Chem. 141 (2013) 4311–4317. mination of cysteamine, nicotinamide adenine dinucleotide and folic acid, Biosens.
[34] H. Karimi-Maleh, S. Rostami, V.K. Gupta, M. Fouladgar, Evaluation of ZnO nanoparti- Bioelectron. 48 (2013) 270–275.
cle ionic liquid composite as a voltammetric sensing of isoprenaline in the presence [46] M. Bijad, H. Karimi-Maleh, M.A. Khalilzadeh, Application of ZnO/CNT nanocomposite
of aspirin for liquid phase determination, J. Mol. Liq. 201 (2015) 102–107. ionic liquid paste electrode as a sensitive voltammetric sensor for determination of
[35] N. Atar, T. Eren, M.L. Yola, H. Karimi-Maleh, B. Demirdögen, Magnetic iron oxide and ascorbic acid in food samples, Food Anal. Methods 6 (2013) 1639–1647.
iron oxide@ gold nanoparticle anchored nitrogen and sulfur-functionalized reduced [47] L. Zheng, L. Xiong, Y. Li, J. Xu, X. Kang, Z. Zou, S. Yang, J. Xia, Facile preparation of
graphene oxide electrocatalyst for methanol oxidation, RSC Advances 5 (2015) polydopamine-reduced graphene oxide nanocomposite and its electrochemical ap-
26402–26409. plication in simultaneous determination of hydroquinone and catechol, Sensors Ac-
[36] B.J. Sanghavi, A.K. Srivastava, Adsorptive stripping voltammetric determination of tuators B Chem. 177 (2013) 344–349.
imipramine, trimipramine and desipramine employing titanium dioxide nanoparti-
cles and an amberlite XAD-2 modified glassy carbon paste electrode, Analyst 138
(2013) 1395–1404.