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DOI: 10.1002/elan.201400302

Poly-(Alizarin Red S)-Modified Glassy Carbon Electrode
for Simultaneous Electrochemical Determination of
Levodopa, Homovanillic Acid and Ascorbic Acid
Abdolhamid Hatefi-Mehrjardi,*[a, b] Nasrin Ghaemi,[b] Mohammad Ali Karimi,[a, b] Masoumeh Ghasemi,[b]
and Somaieh Islami-Ramchahi[b]

Abstract: A polymeric film of Alizarin Red S was formed
on a glassy carbon electrode and used for electrochemical
detection of Levodopa (l-DOPA) and homovanillic acid
(HVA) in the presence of ascorbic acid (AA). The sensor
represented excellent electrocatalytic activity for their oxidations. The resultant differential pulse voltammograms
show well defined and fully resolved anodic oxidation

peaks for determination of the analytes. Anodic oxidation
currents of l-DOPA, HVA, and AA showed linearity
with good correlation coefficient (> 0.996), high sensitivity, and low detection limits (6, 17, and 30 nM respectively). The sensor was used for recovery of analytes in
human plasma samples.

Keywords: Alizarin Red S · Modified glassy carbon electrode · Electrocatalysis · Levodopa · Homovanillic acid · Ascorbic acid ·
Simultaneous determination.

1 Introduction
Parkinsons disease (PD) is the most common neurodegenerative movement disorder. It arises owing to the premature death of dopamine-containing neurons in the part
of the midbrain called the substantia nigra, leading to debilitating problems with tremor, muscular rigidity and
slowness of movement [1, 2]. PD can not be cured, but
medications can help control the symptoms, often dramatically by increasing brains supply of dopamine. However, dopamine cannot be given directly, since it cannot
enter the brain. Levodopa (l-DOPA or l-3,4-dihydroxyphenylalanine), the most effective PD medication, is
a natural chemical that passes into brain and then converted to dopamine. l-DOPA is the precursor to the neurotransmitters dopamine, norepinephrine (noradrenaline),
and epinephrine (adrenaline) collectively known as catecholamines. Dopamine is formed by the decarboxylation
of l-DOPA. The main metabolite of dopamine by catechol-O-methyl transferase is homovanillic acid (4-hydroxy-3-methoxyphenylacetic acid, HVA) that can be
used as a marker of dopamine functioning and metabolism. Thus, simultaneous determination of l-DOPA and
HVA in the presence of interferences mainly Ascorbic
acid (AA) in plasma is important [2–12]. There are very
limited analytical methods for simultaneous determination of l-DOPA and HVA including spectrophotfluorometry [8–10] and HPLC [4–7]. However, these techniques
require expensive equipment as well as complicated and
time-consuming solvent cleanup steps. Electroanalytical
techniques have been shown to provide a selective and
sensitive approach, based on electrooxidation of catecholamines, for the detection of dopamine and its derivatives.
Unfortunately, because of the large overpotential of lwww.electroanalysis.wiley-vch.de

DOPA and HVA at conventional electrodes, it is not well
suited for quantitation via conventional electrochemical
approaches. Also, the voltammetric sensing of neurotransmitter metabolites usually suffers from the interference of
AA, which usually coexists in vivo as anions at high concentrations and possesses an oxidation potential close to
that of neurotransmitter metabolites at unmodified glassy
carbon (GC) electrode [13]. Moreover, the direct redox
reactions of these species at the bare electrodes take
place at very similar potentials and often suffer from
a pronounced fouling effect, which results in rather poor
selectivity and reproducibility [14]. One promising approach for minimizing overvoltage effects and facilitating
the determination is through the use of an electrocatalytic
process at chemically modified electrodes.
Anthraquinone-2-sulfonates display an interesting electrochemical behavior due to their quinonoid structure
[15]. The most important feature of quinones is the reversible reduction via a one-electron-transfer to semiquinone
species, which has a radical structure [16]. Alizarin Red S
(ARS) is a dye derived from anthraquinone-2-sulfonate
which is known as one of the most widely used and popu[a] A. Hatefi-Mehrjardi, M. A. Karimi
Department of Chemistry, Payame Noor University
PO Box 19395-4697 Tehran, Iran
tel: + 98-345-5233541, fax: + 98-345-5233540
[b] A. Hatefi-Mehrjardi, N. Ghaemi, M. A. Karimi, M. Ghasemi,
S. Islami-Ramchahi
Department of Chemistry & Nanoscience and
Nanotechnology Research Laboratory (NNRL), Payame
Noor University (PNU)
Sirjan, Iran
*e-mail: hhatefy@pnu.ac.ir
hhatefy@Yahoo.com 

2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Electroanalysis 2014, 26, 1 – 11

&1&

These are not the final page numbers! ÞÞ

carbon nanotube/ARS [21. high sensitivity and selectivity. Levodopa. the glassy carbon working electrode (nominal area of 0.1 M PBS (pH 3) at a scan rate of 100 mV s 1.1 M NaOH.4 Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) Imaging The topological characteristics of the sensor were examined by AFM using Nanosurf Easy Scan 2 AFM (Nanosurf AG. consisting of bare or poly-ARS modified GC electrode as working. Because the thickness of non-conducting polymers is only 10–100 nm. 2. Urmia.8 V on a glassy carbon electrode. the anodic peak current decreases until a steady state after about ten cycles. The modified electrode was characterized and used for simultaneous electrochemical determination of l-DOPA and HVA in the presence of AA. Therefore. The consecutive cyclic voltammetric curves (the first fifteen cycles) are plotted in Figure 1 for the GCE in a solution containing 1 mM of ARS in 0. It has been used as a redox homogeneous mediator in different electrochemical configurations [22–25] A few strategies based on chemical modification of carbon electrodes by ARS.1 Fabrication and Characterization of Poly-ARS Modified GCE The nonconducting polymers are those with high resistivity that have been prepared by electropolymerization. 26] and electrochemically preanodized modification of GCE [27]. fast response time and high selectivity could also be expected for non-conducting polymers modified GCE. electroactive species diffuse rapidly to the including electrode surface [28]. The Netherlands). Increasing the potential scan rate resulted in the cathodic wave being more well-defined and the peak becoming narrower (data not shown). and AA in complex matrix as blood plasma and shows wide linear range.05 mm) on polishing cloth.2 to 1. Utrecht. which might be useful in preventing interfering species from approaching or contaminating the electrode surface. Then electropolymerization of ARS on the clean surface of the GCE was performed in PBS (pH 3) containing 1 mM ARS by cyclic potential sweep in the range of 0. HVA. As the number of cycles increases. 1 – 11 &2& These are not the final page numbers! ÞÞ .1 M KCl and 0. Phosphate buffer saline solutions (PBS) were prepared by mixing the stock solutions of 0. Switzerland) and Field Emission Scanning Electron Microscope (FESEM) from Tescan Inc (MIRA\\TESCAN. All experiments were carried out at room temperature.de 3. The irreversibility of this anodic process resulted from the insta-  2014 Wiley-VCH Verlag GmbH & Co. the ARS was electropolymerized on GCE by successive cycling the potentials by cyclic voltammetry method. the nonconducting films are permselective. All potentials mentioned in this paper refer to this reference electrode.2 Electrode Modification Before electrode modification. Cyclic voltammetry was used to form electropolymerized film and the redox behavior of ARS was investigated between 0. KGaA.0314 cm2 Azar electrode Co.9 software (Eco Chemie BV.2 and 1. Metrohm) as reference. The measurements were carried out using Potentiostat/Galvanostat Autolab 12 interfaced with a personal computer. 2. Weinheim Electroanalysis 2014. 26.Full Paper lar analytical reagents for preconcentration and analysis of metal ions [17. AFM images were taken in air in the contact/tapping mode and were examined at least in three different sites in given samples. was used for electrochemical measurements. thoroughly rinsed with distilled water and sonicated in water/ethanol/water each for 3 min. Also. Germany) and used without any further purification. KCl (saturated.electroanalysis. The growth of such polymers is self-limited and the film that is formed is much thinner than typical conducting polymer films. Double-distilled water was used for solutions preparation. USA). This indicated that the electrode surface was completely covered by the polymer. and controlled by GPES 4.wiley-vch.8 V at a scan rate of 100 mV s 1. An anodic peak currents corresponding to the oxidation of ARS is observed at about + 0. All other reagents were of analytical grade from Merck (Darmstadt. 2 Experimental 3 Results and Discussion 2. After electropolymerization.1 Materials and Reagents Alizarin Red S was purchased from Sigma. and a platinum bar (Metrohm) as auxiliary electrode. the modified electrode was rinsed thoroughly with distilled water and used for electrochemical measurements. At much higher scan rates. indicating the behavior of a quasi-reversible reaction. which remained constant after further cycling. was observed. 18]. and ascorbic acid were obtained from Fluka (Switzerland). and then adjusting the pH with 0.01 M H3PO4. are reported including gold nanoparticles/ ARS) [19].72 V with a small cathodic wave on the reverse scan. In this paper. Iran) was polished using aqueous slurries of alumina (0.2-quinone derivative [29]. A Metrohm 691 pH/Ion Meter was used for pH adjustments. Previous studies on ARS suggested that the side dihydroxyl functionality underwent a two-electron two-proton irreversible oxidation to give the corresponding 1. 2. Homovanillic acid. peak currents for the cathodic wave were comparable to the corresponding anodic current. Ag/AgCl.3 Electrochemical Measurements A conventional three electrode cell. The potential was continuously cycled until a minimum value of current. www. The proposed sensor can be used for electrochemical determination of l-DOPA. ARS also is useful for the electrochemical detection of different biological samples [19– 21].

Figure 2 represents the topography SEM and AFM images acquired from the surface of bare GC and poly-ARS-GC electrodes.Full Paper Fig. It has been reported that the reversible reduction of the oxidized product could be observed only at high scan rates. It is important to mention that the entire electrode surface was densely covered by polymer films in a homogenous way.2 Electrochemical Behavior of l-DOPA. while at the modified poly-ARS-GCE surface. Weinheim Electroanalysis 2014. and 234 mV. bility of the fully oxidized quinone derivative. The comparison of these two curves for each analyte shows the peak potential of lDOPA. The anodic peak potentials for l-DOPA (a). KGaA. at which the following chemical transformation had no time to take place [27]. 1. Successive cyclic voltammograms of GCE in 0. HVA and AA In order to study the electrocatalytic effect of the polyARS-GC electrode. 21].1 M PBS (pH 3) containing 1 mM ARS in the potential range of for first 15 cycles. which are formed via layer-by-layer deposition. These electron rich groups result in that the poly-ARS-GC modified elec-  2014 Wiley-VCH Verlag GmbH & Co. it can be seen that the surface morphology is considerably changed in the presence of poly-ARS on the surface of the bare GC substrate. While the modified GCE micrographs reveal different patterns. and AA in pH 3 phosphate buffer using cyclic voltammetry. substantial increases in the peak currents were observed due to the improvements in the reversibility of the electron transfer processes which suggests an efficient oxidation-reduction reaction of l-DOPA. the cyclic voltammogram of mixture of three analytes on the bare GC electrode are not well defined with overlapped peaks. HVA (b). and 224 mV respectively toward negative values compared with that at the bare electrode. and AA at the modified poly-ARS-GC electrode. The oxidized product underwent chemical transformation. the anodic peaks are clearly separated. and AA (c) oxidation at the bare GC electrode are about 625. 26.electroanalysis. 100 mV s 1. Images (b) obviously show that the electrode surface is layer by layer fully covered electrochemically by poly-ARS. show sluggish and small responses. the bare and modified electrodes were used for electrochemical behavior of l-DOPA. www. HVA. Scan rate.de 0. 53. the topography AFM images were acquired in contact mode from the surface of bare GC and poly-ARS-GC electrodes. while the corresponding potentials at the poly-ARS-GC electrode are 446. 716. HVA. The SEM images of smooth and homogeneous surface correspond to the unmodified glassy carbon electrode (a). Also as is shown in Figure 3A (d). Also. suggests much larger homogeneity catalysis that affects the electrode surface properties toward diffusing electroactive species. 662. The highly uniform microporous structure of poly-ARS films.wiley-vch. while.8 V 3. Moreover. the related peak currents on the surface of bare GC. HVA. From these images. This high electrocatalytic activity of poly-ARS modified GCE because of formation of high concentration of negative charged SO3 group and electron rich oxygen atoms on the electrode surface. and AA oxidation at the surface of modified electrode shifts by about 179.2 and 1. 1 – 11 &3& These are not the final page numbers! ÞÞ . It is further illustrated that a polymeric product of the orthoquinone is formed on the electrode surface [20. The morphological characteristics of the modified electrode were studied by SEM and AFM. and 458 mV respectively (Figure 3A).

1 – 11 &4& These are not the final page numbers! ÞÞ .electroanalysis. Figure 4A shows the first and second CV scans of the poly-ARS-GCE in the solution of 0. 26. peak 1). the electrosynthesis of 3. there is a complication with the electrochemistry of HVA which could seriously affect on www. trode shows a well affinity towards the l-DOPA positive ions by exchanging the electrons and enhanced the oxidation of l-DOPA. KGaA.0 V. This process is represented in Figure 3B.025 mM HVA at the scan rate 20 mV s 1 and potential range of 0.3 to 1. This is an evidence for the ability of the poly-ARS-GC sensor to determine catechols simultaneously in the presence of AA in biological samples after optimization of the conditions. 2.1 M PBS containing 0. SEM images in two scales (above) and AFM images (below) of bare GC (a) and poly-ARS-GC (b) electrodes.e. with an Ep value of  2014 Wiley-VCH Verlag GmbH & Co. A typical electrooxidation response is clearly observed through the anodic sweep of scan 1 (Figure 4A. i.4-dihydroxyphenyl acetic acid (DOPAC) from HVA on the electrode surface.Full Paper Fig.wiley-vch. However.de its quantification. Weinheim Electroanalysis 2014.

The suggestion that peaks 2 and 3 correspond to electrogenerated DOPAC is reported in literature [30].-) electrodes. the cathodic sweep of scan 1 showed a reduction response (peak 2) with Ep value of about 0.0). However. In the scan 2. Fig.1 M phosphate buffer solution (pH 3. l-DOPA was selected because of well-defined responses. 3.36 V unexpected for an irreversible process (Figure 4B. (B) Electrochemical mechanism for generation of a reversible redox couple (DOPAC/4-aceto-o-quinone) from the irreversible oxidation of HVA in aqueous solution (step 1). On the subsequent scan.Full Paper Fig. on the surface of poly-ARS-GCE. and its peak potentials position. (A) Cyclic voltammograms of 0. cyclic  2014 Wiley-VCH Verlag GmbH & Co.15 mM l-DOPA (a). 1 – 11 &5& These are not the final page numbers! ÞÞ . on the first scan.1 M PBS containing 0. step 1). and AA on the surface of the modified poly-ARS-GC electrode.60 V. (A) Two subsequent CVs in the solution of 0.wiley-vch. Weinheim Electroanalysis 2014. on the surface of poly-ARS-GCE at the scan rate 20 mV s 1. The product of step 1 is the oxidized form of DOPAC and thus on the backward scan reduced to DOPAC (step 2) to produce peak 2. (B) Related redox mechanisms for electrochemical oxidation of l-DOPA. The reaction scheme in Figwww.15 mM HVA (b). about 0. 4. Therefore. the current intensity continued to increase on subsequent scans.3 Effect of pH In order to find the optimum pH in the electrochemical studies of l-DOPA. 3. HVA.025 mM HVA. electrochemical reversibility.. and modified polyARS-GC (. Potential sweep rate was 20 mV s 1 and supporting electrolyte was 0. the formed DOPAC is oxidized to regenerate 4aceto-o-quinone (step 3) results in peak 3. Also.de ure 4B is consistent with the CV data shown in Figure 4A. Obviously. a new peak has appeared in the anodic sweep (peak 3) with Ep value of about 0. indicating adsorption of one or more electroactive species. 0. The reversible couple involves the addition of 2H + and 2e for the formation of DOPAC (step 2) and its removal upon oxidation (step 3). only HVA is present in the cell and its electrooxidation results in peak 1 corresponding to the step 1. 0.15 mM AA (c) and the mixture of the three analytes (d) on the surface of bare GC (—). KGaA.electroanalysis.43 V followed by increased HVA oxidation and DOPAC reduction peaks. 26.

15 mM of each of l-DOPA (A). HVA. where np (number of protons) = ne (number of electrons) [31]. and AA (C) with a sweep rate of 20 mV s 1 which were obtained on the surface of bare (a) and poly-ARS-GC (b) electrodes.a) are pH dependent and decreased by increasing the pH values at the working pH range. Figure 6 shows the linear sweep voltammograms in buffered solutions (0. Scan rate = 20 mV s 1. and (e) 7. exchange current (I0) and  2014 Wiley-VCH Verlag GmbH & Co.wiley-vch. So pH 3.0. the formal potential (E8’) and anodic peak current (Ip. pH in the range of pH 4–7. (c) 5. Also according to the linear plot of E8’ vs. (b) 4.1 M PBS. the best result with respect to sensitivity accompanied with sharper response was obtained with pH 3.de 3. The regression equations are mentioned on the respected figure.0.Full Paper Fig. 1 – 11 &6& These are not the final page numbers! ÞÞ .0 was selected for further experiments. Cyclic voltammograms of 0. voltammograms in various buffer solutions (pH 3–7) containing 0. pH (Figure 5) it is obvious that.1 M PBS at pH (a) 3. Weinheim Electroanalysis 2014. However. As can be seen in the Inset of Figure 5.electroanalysis. and AA The linear sweep voltammetry (LSV) which is a useful technique for electroactive substances was used to extract the kinetic parameters.a and E8’ vs. (d) 6. Insets). 26.15 mM l-DOPA was recorded (Figure 5). www. 5.054 V/pH is obtained which is close to the expected Nernstian value of 0.0. pH 3) containing 0. HVA (B).4 Kinetic Studies of Electrode Interaction by l-DOPA. the slope 0. KGaA. The plots of the extracted Ip. From the plot of Ipa vs.0. that clearly shows protons are involved in the oxidation process.0.0. transfer coefficient (a). Table 1 reveals the regression equations and extracted parameters including equilibrium potential (Eeq).059 mV at 25 8C. peak currents are affected by the pH values.15 mM l-DOPA at the poly-ARS-modified GCE in 0. The points from the rising part of voltammograms which is known as Tafel region and is affected by the electron transfer kinetics was derived for three analytes and the Tafel plots based on them were drawn (Figure 6. pH are shown above.

1 M PBS. k0 (cm s 1) 1. 26. as Eeq for l-DOPA. (f) 150. (e) 150.096 0.1 10.95  10 11 11 8 9 9 8 a Eeq (V) Tafel equation 0. 6. (f) 600. (b) 100. and AA (C) obtained on the surface of bare (a) and poly-ARS-GC (b) electrodes with a sweep rate of 20 mV s 1.40  10 2. Weinheim Electroanalysis 2014. HVA (B). the DPVs of various concentrations of Fig.53 8.64 0.170 0.1 l-DOPA. (d) 500. and AA (C) at poly-ARS-GCE in 0. (c) 120. 0.229. Under the optimized solution conditions (0.26  10 2.66 h logI (A) = 15.20  10 5 6 3 4 4 3 I0 (A) 7.wiley-vch. The insets show the respected Tafel plots and equations.95  10 1.001 logI (A) = 5.44 h logI (A) = 7.76 0.27  10 1.2 h logI (A) = 8.89 8. Table 1.171 V respectively to the more anodic potentials which showed widely movement in Eeq and peak potential.80  10 5.5 Analytical Application 3. (V) (V) (V) (V) (V) (V) 10.21 h intrinsic rate constant (k0).428. (e) 140. (b) 400.94  10 1.99 7.84 0.1 M PBS (pH 3). Electrochemical and kinetic parameters extracted from the linear sweep voltammograms (Figure 6). and AA shift 0.02  10 2. 1 – 11 &7& These are not the final page numbers! ÞÞ .de  2014 Wiley-VCH Verlag GmbH & Co.95 0. column 4).54 0.electroanalysis.22  10 5. (b) 100. www. pH 3). pH 3) containing 0.29  10 1. The results confirm excellent improvement on the kinetic parameters by the modification of GCE. This is another evidence for ability of the polyARS-GC sensor for simultaneous determination of lDOPA and HVA in the presence of AA.15 mM of each of l-DOPA (A). and 0. HVA concentrations (nM): (a) 90. HVA and AA Determination on the Modified Electrode Since differential pulse voltammetry (DPV) has a much higher current sensitivity. it was used in study of l-DOPA.4 h logI (A) = 12.9 7.53 Analyte Electrode l-DOPA HVA AA l-DOPA HVA AA GC ARS GCE 3. Linear sweep voltammograms in buffered solutions (0. (f) 160.1 M PBS. KGaA. HVA. and better resolution than cyclic voltammetry.20  10 2. and AA concentration at the poly-ARS-GC modified electrode. (e) 550.332 0.012 0. HVA (B).5. (c) 450. 7. Differential pulse voltammograms of l-DOPA (A). (d) 130.76 0. (c) 110.98 h logI (A) = 1.Full Paper Fig. HVA. (d) 140.217 0. Insets: Related calibration plots of extracted anodic peak currents and equations. l-DOPA concentrations (nM): (a) 75. and AA concentrations (nM): (a) 300. It is worthy to mention that Eeq also significantly improved after electrode modification (Table 1. (g) 160.

07 0.5. 90–160 nM.6 Interference Study The ability of the modified electrode for simultaneous determination of each analyte was examined by addition of various concentrations of the species in the presence of the constant concentration of others (Figure 8). the results show that the poly-ARS-GCE is an appropriate sensor for simultaneous determination of three analytes at low concentrations.09 0.24. PNB: poly(Nile blue-A). and AA.006 – Cabergoline AA.16 0. and 1. HVA.12 0. Weinheim Electroanalysis 2014. CP-TNMCPEs: cobalt porphyrin-TiO2 nanoparticles modified carbon paste electrode. The limits of detection (3s) for determination of l-DOPA. the peak current of l-DOPA increased linearly with increasing l-DOPA concentration at the range of 63–120 nM and the related regression calibration is I (mA) = 0.7-bis(ferrocenyl ethyl) fluoren-9-one. SCE. AA [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] This work [a] [b] [b] [b] [b] [b] [b] [b] [b] [b] [b] [b] [a] Potential vs. a lower limit of detection can be achieved using the proposed method.160 0.7–100 0. the peak current of HVA grows linearly by increasing HVA concentration at the range of 100– 300 nM and the related regression calibration is I (mA) = 0. and AA on the Modified Electrode 3. HVA and AA were separately recorded (Figure 7).25–225 0.360 0. different concentrations of HVA in the presence of 300 nM AA and 50 nM l-DOPA illustrate excellent DPVs responses (Figure 8B).electroanalysis.25 0.25–200 0.11 (Figure 8B. Q/fMWCNT: quercetin/functionalized multi-wall carbon nanotube. LU/fMWCNT: luteolin (LU) immobilized on the functionalized multi-wall carbon nanotubes.90–85. Comparison of the analytical performance for the electroanalysis of l-DOPA using different modified electrodes.04 0. UA: uric acid.006 C (nM) + 1. (Nafion/Co(OH)2 MWCNTs/CILE): carbon ionic liquid electrode modified with multi-walled carbon nanotubes and cobalt hydroxide nanoparticles.015 1.4.13 0. HVA at 110 nM and AA at 410 nM were obtained 1. Inset) and the linear ranges of 75–160 nM.10-dihydroxy-6H-benzofuro[3. and AA was investigated.06 0.a (V) Linear range (mM) LOD (mM) Concomitant Ref. These results indicate that the electrochemical determination of three analytes in the presence of each other on the poly-ARS-modified GCE surface is possible independently. TY: tyramine. Ag/AgCl. [b] Potential vs.wiley-vch.2-c]chromen-6-on).38 0. HVA. HVA. but the peak current of AA in the concentration range of 400–750 nM increased linearly with calibration regression equation of I (mA) = 0.05–800 2–100 0. which caused an approximately  5 % relative error in the determinations of each  2014 Wiley-VCH Verlag GmbH & Co.15 mM l-DOPA. The respected calibration curves of the anodic peak currents for solutions containing different amounts of each analyte were plotted (Figure 7. Folic acid Carbidopa Folic acid HVA.2 Simultaneous Determination of l-DOPA. and AA respectively.1–700 0.997 were obtained for l-DOPA. 26.151 0. 3. TY UA. by increasing of various concenwww.120 0.450 0. 0.993. TY Serotonin UA.994. HVA. FMCNPE: ferrocenemonocarboxylic acid modified carbon nanotubes paste electrode.500 0.105 C (nM) + 5.1–100 0.2.03 (Figure 8C. rGO: reduced graphene oxide. UA Carbidopa Carbidopa Acetaminophen.254 0.100 0. There is no serious variation observed in the peak current of HVA and l-DOPA. DC/IL CTP: (7(1. and 30 nM respectively. l-DOPA. It is observable that the oxidation peaks related to HVA and AA are approximately steady.09–850 0.4-BBFT)/carbon paste electrode. Also.285 0. Furthermore. the influence of various interfering species on the determination of 0. 17.0 0. We also observed oxidation peaks of various amount of AA in the presence of constant concentration of HVA (100 nM) and l-DOPA (50 nM) (Figure 8C).4-BBFT/CPE: 1-(4-bromobenzyl)-4-ferrocenyl-1H-[1.de Under the optimum experimental conditions. and 300–600 nM and correlation coefficients (r2) 0.Full Paper Table 2.3]-triazole (1. trations of l-DOPA in the presence of 100 nM HVA and 250 nM AA (Figure 8A). The tolerance limit was taken as the maximum concentration of the foreign substances.446 1–60 0. 0. and coated with Nafion.320 0. 1. Electrode Ep. Inset) which shows simultaneous determination of HVA in the presence of AA and l-DOPA on the surface of poly-ARS-modified GCE.5 % respectively for 6 measurements which reveals that the sensor had good reproducibility.026 C (nM) + 3. and 0. 1 – 11 &8& These are not the final page numbers! ÞÞ . Under the optimum conditions.290 0. Inset). The relative standard deviations (RSDs) for l-DOPA at 90 nM. (5AEB/CNPE): 5-amino-2’-ethyl-biphenyl-2-ol/carbon nanotubes paste electrode. KGaA.075–0. 2. These values are comparable with values reported by other research groups for electrocatalytic oxidation of l-DOPA at the surface of chemically modified electrodes by other modifiers (Table 2). (DC) titanium dioxide nanoparticles (TiO2) and ionic liquid (IL) modified carbon paste electrode. There is no previous report on the simultaneous electrochemical determination of lDOPA. Also.4-BBFT/CPE rGO/GCE 5AEB/CNPE DC/IL CTP LU/fMWCNT/GCE Co(OH)2 MWCNTs/CILE Q/fMWCNT/GCE 2.7-BFCNPE CP-TNMCPEs FMCNPE poly-ARS/GCE 0. on the modified electrode surface were found to be 6.3-dithiolan-2-yl)-9.195 0. From the data shown. HVA and AA. Inset).7BFCNPE: 2. the modified electrode presented good repeatability. PNB/MWCNT/GCE 1.1–900 0.07 0.86 (Figure 8A.

5 – 102. and. Ni2 + .032 0. KGaA.106  0.92 – 97. Cl . different concentrations of HVA (B): (a) 100. and AA respectively.03 M for Mg2 + .012 183. CO23 .63 1. (b) 125.2 – 101. (f) 300 in the presence of 50 nM l-DOPA and 300 nM AA.5 0 7.28  0. www. which leads to a significant increase in the peak current and a great decrease in peak over-potential as 0.5 – 100.012 52. HVA and AA. NO3 . l-cysteine. (d) 200.1 M PBS.012 180.69  0.648  0. 1 – 11 &9& These are not the final page numbers! ÞÞ .86 1. and uric acid.5  4.630  0.de In this study. it was shown that poly-ARS film on the GCE can be considered as a sensitive and selective sensing element in simultaneous voltammetric determination of l-DOPA. The tolerated concentration of foreign substances was 0.98 – 102. pH 3 containing different concentrations (nM) of l-DOPA (A): (a) 63.3 – 101. 0. (b) 450. Cd2 + . folic acid.10  0.2 M for Na + .97 – 104. K + .93 – 100.017  0. F . Ba2 + . (f) 750 in the presence of 50 nM l-DOPA and 100 nM HVA.012 52. (e) 110. S2 . Differential pulse voltammograms of poly-ARS-modified GCE in 0.006 7.03 1. (d) 100. glucose.4 2 3 HVA 1 2 3 AA 1 2 3 analytes.007 7. l-glycine. 4 Conclusions Fig. Analyte Serum sample Added (nM) Found (nM) Recovery (%) l-DOPA 1 0 7.034 179.Full Paper Table 3. direct determination of l-DOPA.028 0. 26.wiley-vch. Insets: Related calibration plots of extracted anodic peak currents and equations.458  0.123  0.109  0.224 V for l-DOPA.01 M for l-lysine. (e) 650.8  2. 8.142  0. sensor produc-  2014 Wiley-VCH Verlag GmbH & Co.053.352 1.179.7 Real Sample Analysis In order to evaluate the analytical applicability of the proposed method. The recoveries of these three analytes in blood serum were determined by the standard addition method (Table 3) and satisfactory results were obtained.1 M PBS solution (pH 3) without any treatment. HVA and AA.77  0.5 0 7.9  3. and Ca2 + . and different concentrations of AA (C): (a) 400. and 0. 0.16  0. Weinheim Electroanalysis 2014.006 7. Determination and recovery tests of l-DOPA. The human blood plasma samples were collected from clinical laboratory and diluted to 5 times with 0. (e) 250. 0. These results show that the poly-ARS-GC modified electrode is an excellent sensitive tool for simultaneous determination of the analytes in physiological samples. (d) 550. (c) 88. (b) 75. 3. HVA and AA in three human blood serum samples obtained using poly-ARS-GC modified electrode.5 0 175 0 175 0 175 0 50 0 50 0 50 0. (c) 150. The modified electrode showed an effective electrocatalytic activity toward the anodic oxidation of l-DOPA.382 1. tryptophan. lglutamic acid. This method is financially more reasonable than chromatographic separation methods. Pb2 + . Furthermore. (f) 120 in the presence of 250 nM AA and 100 nM HVA.86 – 100. (c) 500.68  0.116  0.electroanalysis. Cu2 + .543 2.015 52. HVA. HVA and AA was applied for three physiological samples (human blood serum).

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M.wiley-vch. Weinheim Electroanalysis 2014. Homovanillic Acid and Ascorbic Acid www. Islami-Ramchahi && – && Poly-(Alizarin Red S)-Modified Glassy Carbon Electrode for Simultaneous Electrochemical Determination of Levodopa. 1 – 11 &11& These are not the final page numbers! ÞÞ . M.de  2014 Wiley-VCH Verlag GmbH & Co. 26. S. A.Full Paper FULL PAPERS A. Ghaemi. Ghasemi. Karimi.electroanalysis.* N. KGaA. Hatefi-Mehrjardi.