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Sensors and Actuators B 193 (2014) 166172

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Simultaneous determination of dopamine, ascorbic acid and uric acid at electrochemically reduced graphene oxide modied electrode
Lu Yang a,b , Dong Liu a,b , Jianshe Huang a , Tianyan You a,
a b

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China University of Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e

i n f o

a b s t r a c t
A facile electrochemical method was applied to prepare electrochemically reduced graphene oxide (ERGO). The morphology and structure of ERGO were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and X-ray diffraction (XRD). Compared with the bare glassy carbon electrode (GCE), ERGO modied GCE (ERGO/GCE) exhibits much higher electrocatalytic activities toward the oxidation of dopamine (DA), ascorbic acid (AA) and uric acid (UA) with increasing of peak currents and decreasing of oxidation overpotentials. Differential pulse voltammetry results show that DA, AA and UA could be detected selectively and sensitively at ERGO/GCE with peak-to-peak separation of 240 mV and 130 mV for AADA and DAUA, respectively. The linear ranges for AA, UA and DA are 5002000 M, 0.560 M and 0.560 M, respectively. Meanwhile, due to the negligible response to physiological level of AA (0.1 mM), ERGO/GCE could be used for the determination of DA in biological sample with high sensitivity and good selectivity. In addition, the presented method was successfully applied for the simultaneous determination of DA, AA and UA in urine sample with reliable recovery. This work provides a simple and green route to construct graphene-based electrochemical sensor, which is promising for the simultaneous determination of DA, AA and UA. 2013 Elsevier B.V. All rights reserved.

Article history: Received 13 May 2013 Received in revised form 15 November 2013 Accepted 26 November 2013 Available online 4 December 2013 Keywords: Electrochemically reduced graphene oxide Simultaneous determination Dopamine Ascorbic acid Uric acid

1. Introduction Ascorbic acid (AA) is a common anti-oxidant, which plays a great role in the metabolic process of human bodies. It inuences essential physiological processes, such as cell division, gene expression and activation of biological defence mechanisms [1]. Dopamine (DA) is an important neurotransmitter in the mammalian central nervous system. Low levels of DA may cause neurological disorders, such as Parkinsons disease and schizophrenia [2]. Uric acid (UA) is the primary product of purine metabolism. Its abnormal concentration levels may lead to several diseases, such as hyperuricemia, gout and pneumonia [3]. DA, AA and UA usually coexist in biological samples. Since the basal DA concentration is very low (0.011 M), while the concentration of AA is generally much higher (about 0.1 mM) [4], it is essential to develop selective and sensitive methods for their simultaneous determination both in analytical application and diagnostic research. Since DA, AA and UA are highly electrochemically active, electrochemical methods for their simultaneous determination possess

Corresponding author. Tel.: +86 431 85262850; fax: +86 431 85262850. E-mail address: (T. You). 0925-4005/$ see front matter 2013 Elsevier B.V. All rights reserved.

the merits of convenience, rapidity and high sensitivity. However, overlaping of the oxidation peaks of these three species at traditional electrodes makes their simultaneous determination highly difcult. To overcome this problem, various chemically modied electrodes have been developed [57]. Due to its wide potential window, relatively inert electrochemistry and high electrocatalytic activity for a variety of redox reactions [8], carbon-based nanomaterials, such as carbon nanober, multi-walled carbon nanotube and hollow nitrogen-doped carbon microspheres, have been widely utilized for the simultaneous determination of DA, AA and UA [911]. As a kind of new carbon material, graphene has attracted tremendous attentions from scientic communities in recent years. Owing to its unique structural and electronic properties, graphene has been widely used for the construction of electrochemical sensors [1214]. Presently, graphene used in electrochemical sensors are mostly prepared by chemical reduction method. This method generally employs toxicity reducing agents result in bringing impurities. Furthermore, partial removal of oxygenated species by chemical reduction method will degrade the electronic properties and weaken the electrochemical performance of graphene [15]. Therefore, a novel green and convenient electrochemical reducing method was proposed by Xias group to

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prepare electrochemically reduced graphene oxide (ERGO). The obtained ERGO showed improved electrochemical performance compared with chemically reduced graphene oxide (CRGO) [16]. Recently, various strategies have been developed to fabricate ERGO lm modied electrodes. Kims group developed a polypyrrole and ERGO composite lm modied electrode by an electrochemical polymerization process. The modied electrode realized the selective determination of DA in presence of AA and UA [17]. Raj et al. fabricated a 1,6-hexanediamine/ERGO (HDA/ERGO) lm modied electrode by a self-assembly method [18]. Despite the HDA/ERGO lm modied electrode realized the separation of the oxidation peaks of DA, AA and UA, the toxicity agent HDA may has adverse effects on the performance of the modied electrode. In this work, we fabricated an ERGO lm modied electrode via drop-casting of graphene oxide (GO) dispersion on the surface of GCE followed by an electrochemical reduction process, which is more convenient than the electrochemical polymerization and selfassembly method. The as-prepared ERGO was characterized with unique structural features and electrochemical properties, which provided it excellent performance as a promising electrode material. Compared with the bare GCE, ERGO modied GCE (ERGO/GCE) exhibited much higher electrocatalytic activities toward the oxidation of DA, AA and UA. Hence, the ERGO-based electrochemical sensor was used for the simultaneous determination of DA, AA and UA with good selectivity and high sensitivity. 2. Experimental 2.1. Apparatus Atomic force microscopy (AFM) images were obtained by using a SPI3800N microscope (Seiko Instruments, Inc.) in tapping mode under ambient conditions. The surface morphologies of GO and ERGO were evaluated by scanning electron microscopy (SEM, PHILIPSXL-30ESEM) at an accelerating voltage of 15 kV. Raman spectra were recorded on a Renishaw Raman microscope (model RM2000) with laser excitation wavelength of 514.5 nm. X-ray diffraction (XRD) patterns were obtained using a D8 ADVANCE (Bruker AXS, Germany) X-ray diffractometer with X-ray photoelectron spectroscopy Cu K radiation ( = 1.5406 A). (XPS) measurements were carried out on an ESCALAB 250 X-ray photoelectron spectrometer (VG Scientic, UK). Electrochemical experiments were performed with a CHI 832 electrochemical workstation (China). A conventional three-electrode system was used for all electrochemical experiments, which consisted of an Ag/AgCl/saturated KCl as reference electrode, a platinum wire as auxiliary electrode, and a bare GCE (2 mm in diameter) or ERGO modied GCE as working electrode. 2.2. Chemicals Natural graphite ake, DA and UA were obtained from Alfa Aesar. AA was obtained from Chemical Reagent Company of Shanghai (China). All other chemicals used were of analytical grade. Double distilled water was used throughout the experiments. 2.3. Preparation of ERGO Graphite oxide was synthesized from natural graphite ake by the modied Hummers method [19]. Then, the as-synthesized graphite oxide was subjected to ultrasonication for 40 min (200 W). Finally, a homogeneous graphene oxide (GO) dispersion was obtained. GO modied GCE (GO/GCE) was prepared by casting 3 L GO dispersion onto the pretreated GCE surface and allowed to dry at room temperature. Then, an electrochemical reduction process

was applied to obtain ERGO/GCE by immersing GO/GCE into 0.1 M pH 7.0 PBS solution with cyclic sweeping in the potential range from 0.0 to 1.4 V at a scan rate of 20 mV/s for 5 cycles. All experiments were conducted at room temperature. 3. Results and discussion 3.1. Morphological characterization Graphite oxide synthesized by the modied Hummers method was exfoliated into single layer graphene oxide, which is conrmed by AFM analysis. As shown in Fig. 1, GO existed as at sheets with a lateral dimension of about 1 m (Fig. 1a), and a thickness of 0.9 nm (Fig. 1b), which matches well with the thickness of an individual layer of GO [20]. The cyclic voltammetry (CV) curves recorded during the reduction process are shown in Fig. S1. There is a large reduction peak at 1.3 V with an onset potential of 0.75 V, which can be attributed to the reduction of surface oxygen groups of GO. The reduction current decrease remarkably and disappear after several cycles later, indicating the reduction process was quick and irreversible. The surface morphologies of GO and ERGO were investigated by SEM. GO displays a relative smooth surface (Fig. 1c). After being electrochemically reduced, ERGO exhibits rough surface with random wrinkles (Fig. 1d). This unique morphology is highly benecial in maintaining large electroactive area on the electrode surface. 3.2. Structural characterization The structure of ERGO was characterized by XPS, XRD and Raman spectra. As shown in Fig. 2, compared with the C1s spectrum of GO, the intensities of C1s peaks assigned to carbon atoms bound to oxygen in ERGO decreased obviously, indicating that most of the oxygen-containing groups were removed after electrochemical reduction. XRD patterns in Fig. 3a show that the sharp diffraction peak in graphite (2 = 26.6 , d = 0.34 nm) disappeared after oxidation and a new one (2 = 10.8 , d = 0.87 nm) appeared in GO, indicating the complete oxidation of graphite [21]. Accordingly, the diffraction peak at 2 = 26.6 does not reappear in ERGO, which means that either all stacking of graphene layers in ERGO is lost, or any remaining stacking is disordered [22]. To further insight into the ordered and disordered crystal structures of carbon in graphite, GO and ERGO, Raman spectra were investigated (Fig. 3b). Graphite displays a strong G band at 1578 cm1 , which is assigned to the E2g phonon of sp2 carbon atoms. While a prominent D band at 1350 cm1 appeared in GO, which corresponds to the breathing mode of -point phonons of A1g symmetry. The emergence of D band indicates the existence of defects in GO caused by oxidation [23]. When GO was electrochemically reduced to ERGO, the D/G intensity ratio increases obviously, suggesting a decrease in the average size of sp2 domains [24]. 3.3. Electrochemical characterization We choose Ru(NH3 )6 3+/2+ , Fe(CN)6 3/4 and Fe3+/2+ as probe molecules to investigate the electrochemical properties of ERGO. In case of Ru(NH3 )6 3+/2+ , a similar redox peak potential difference ( Ep ) was obtained at GCE and ERGO/GCE, indicating that both electrodes can realize the fast electron transfer (Fig. S2a). For Fe(CN)6 3/4 , a probe molecule which is sensitive to the surface state, especially the C sp2 edge plane defects [25], ERGO/GCE shows smaller Ep with response current 1.8 times higher than that at GCE (Fig. S2b), implying that ERGO has more edge plane defects and larger electroactive surface area. As an oxide-sensitive probe of Fe3+/2+ , GCE exhibits a sluggish response, while ERGO/GCE presents a well-dened CV response (Fig. S2c),


L. Yang et al. / Sensors and Actuators B 193 (2014) 166172

Fig. 1. AFM image (a) and the corresponding height prole (b) of GO, SEM images of GO (c) and ERGO (d).

Fig. 2. XPS spectra of GO (a) and ERGO (b).

Fig. 3. Raman spectra (a) and XRD patterns (b) of graphite, GO and ERGO.

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Fig. 4. Cyclic voltammograms at GCE (a) and ERGO/GCE (b) in 0.1 M PBS (pH 7.0) with 5 mM AA, 0.5 mM DA, 0.5 mM UA and their mixture. Scan rate: 50 mV/s.

indicating that the residue oxygen-containing groups at ERGO surface provide much active site for electrochemical reaction. The above results demonstrated that ERGO possess large electroactive surface area, numerous edge plane defects and certain residue oxygen-containing groups, which are favorable for its excellent electrocatalytic performance. 3.4. Electrochemical behaviors of DA, AA, UA and their mixture The CV responses of the bare GCE and ERGO/GCE toward DA, AA and UA are shown in Fig. 4. At the bare GCE, DA, AA and UA show broad oxidation peaks with the peak potentials at 308, 380 and 446 mV, respectively. It is clear that the electrochemical reactions of these three species at bare GCE are irreversible and undergo sluggish electron transfer kinetic process. In contrast, ERGO/GCE can effectively separate the overlapped oxidation peak of these three species and improve the reversibility of DA and UA. For DA, a pair of redox peaks appeared at 224 mV and 166 mV, corresponding to the two electrons oxidation of DA to o-dopaminoquinone and subsequent reduction of o-dopaminoquinone to DA, respectively [26]. The Ep is 58 mV and the oxidation peak current is 8.75 times higher than that obtained at bare GCE, suggesting the excellent electrocatalytic activities of ERGO toward DA. The oxidation peak currents of DA linearly increased with the scan rate in the range of 25500 mV/s (Fig. S3a), indicating the electrode reaction of DA is a surface controlled process at ERGO/GCE. The prominent improved reversibility and sensitivity may due to the electrostatic interaction between positively charged DA (pKa = 8.87) and negatively charged ERGO (remaining COO groups) at pH 7.0, as well as the interaction between phenyl structure of DA and two-dimensional planar hexagonal carbon structure of graphene. In case of UA, a well-dened oxidation peak and a weak reduction peak appear at 396 mV and 315 mV at ERGO/GCE, respectively. Meanwhile, the oxidation peak current increased about 8 times compared to that obtained at bare GCE, indicating much higher electrocatalytic activities of ERGO toward UA. The oxidation peak currents linearly increased with the scan rate in the range of 25500 mV/s (Fig. S3b), suggesting a surface controlled process of UA on the surface of ERGO/GCE. Different from the reaction mechanism in previous studies [7,18], UA shows a sharp reduction peak at ERGO/GCE in our study, which is similar to the reaction mechanism at a mesoporous carbon nanober modied pyrolytic graphite electrode [27]. The result indicates that UA shows a quasi-reversible

process at ERGO/GCE, which can be interpreted as that UA is rst oxidized to its diimine intermediate and then reduced back to uric acid. The improved reversibility can be ascribed to that the diimine intermediate is adsorbed at ERGO/GCE and stabilized in the absorbed state, which may be relevant to the rough surface of ERGO [28]. Regarding AA, the oxidation peak potential negatively shifted about 380 mV compared to that at the bare GCE. Such a large peak potential shift may be caused by the formation of hydrogen bonds between lactone bond of AA and remaining carboxyl of ERGO (Scheme S1), which activates the hydroxyl in the furan nucleus of AA [29]. The oxidation peak currents of AA are linear with the square root of the scan rate in the range of 530 mV/s (Fig. S3c), implying that the electrode reaction of AA at ERGO/GCE is a diffusion controlled process. When the scan rate is above 75 mV/s, two oxidation peaks appear (Fig. S4), which can be attribute to the two consecutive one electron transfer oxidation process of AA at faster scan rate [30]. Although UA and AA are both negatively charged and are repulsed by the negatively charged ERGO, the higher response sensitivity of UA may due to the stronger hydrogen-bond acceptor strength of amide group in UA than ester group in AA. The CV responses of the mixture solution of DA, AA and UA are shown in Fig. 4. One broad overlapped peak at about 390 mV was observed at GCE. While three sharp and well dened oxidation peaks with larger peak separations and higher peak currents corresponding to the oxidation of AA, DA and UA appeared at ERGO/GCE. The large peak separations make it possible to determine DA, AA and UA simultaneously at ERGO/GCE. CV experiment results demonstrate that ERGO possess excellent electrocatalytic activities toward the oxidation of these three species, which can be attributed to its unique structural features and excellent electrochemical properties. 3.5. Effects of pH on the electrochemistry of DA, AA and UA The effect of solution pH on the CV responses of DA, AA and UA was investigated. With the increase of pH from 4.0 to 9.0, the oxidation peak potentials of those three species shift negatively with linear slopes of 57.3, 56.7 and 41.0 mV/pH, respectively. The slops of DA and UA are close to the theory value of 59 mV/pH (25 C), indicating that their oxidation reactions are accompanied by the transfer of an equal number of protons and electrons. While the slop of AA is relatively lower than the theory value, implying that the electrochemical oxidation of AA occurs with less one proton involved [31]. We choose 7.0 as the optimum pH value for their simultaneous determination due to the higher sensitivity. 3.6. Simultaneous determination of DA, AA and UA DPV responses of the mixture of DA, AA and UA at bare GCE and ERGO/GCE are shown in Fig. 5. At the bare GCE, the oxidation peaks of DA, AA and UA completely overlap and show a broad peak at about 300 mV. In contrast, at ERGO/GCE, the overlapped voltammetric peak is resolved into three well-dened peaks at about 35 mV, 195 mV and 325 mV, respectively. The separation of the oxidation peak potentials for AADA and DAUA is 240 mV and 130 mV, respectively, which is larger than that obtained at HDA/ERGO/GCE (160 mV for AADA and 120 mV for DAUA) [18]. The large separation of the peak potentials allows the selective determination of DA, AA, and UA in their mixture. In addition, ERGO/GCE shows good selectivity toward DA detection due to the negligible response to the physiological level of AA (0.1 mM), suggesting this biosensor might be used for the selective determination of DA in biological sample without the interference from AA. Fig. 6 shows the DPV responses of ERGO/GCE toward DA, AA or UA when the concentration of one species changed with the


L. Yang et al. / Sensors and Actuators B 193 (2014) 166172

Fig. 5. DPV proles at (a) GCE and (b) ERGO/GCE in 0.1 M PBS (pH 7.0) containing 5 mM AA, 50 M DA and 50 M UA, (c) ERGO/GCE in 0.1 M PBS (pH 7.0) containing 0.1 mM AA and 1 M DA.

other two species kept constant. The peak current of DA is linear to the DA concentrations in the range of 0.560 M with correlation coefcient of 0.997. Meanwhile, the peak currents of AA and UA almost keep constant during the increase of DA concentration, indicating that the addition of DA does not affect the determination of UA and AA. Similarly, the peak currents of AA and UA are also proportional to their concentration in the range of 0.52 mM for AA and 0.560 M for UA, with correlation coefcients of 0.993 and 0.999, respectively. The detection limits for DA, UA and AA are 0.5, 0.5 and 250 M respectively. We have also investigated the analytical performance at ERGO/GCE for each analyte separately. The detection limit for DA, AA and UA separately was 0.5 M, 0.3 mM and 0.5 M with the linear range of 0.560 M, 0.32 mM and 0.560 M, respectively. Furthermore, the results showed the sensitivity of ERGO/GCE for DA, AA and UA separately was 0.482 A/M, 5.39 A/mM and 0.520 A/M, while the sensitivity for DA, AA and UA in the mixture was 0.511 A/M, 5.98 A/mM and 0.566 A/M. Thus, it is reasonable to conclude that there is ignorable interference of the other analytes in the mixture. In comparison with previously developed graphene-modied electrodes, the proposed electrode exhibits better analytical performance (Table S2). The proposed biosensor showed a larger peak separation for AADA and DAUA than that at graphene/Ptmodied GCE [32] and functionalized-graphene modied graphite electrode [33], suggesting a higher selectivity of this biosensor. Meanwhile, the ERGO/GCE also exhibited much lower response to AA as compared with that at poly (acid chrome blue K) modied GCE [34] and poly (Evans Blue) modied GCE [35], which would benet the selective determination of DA. All above results indicate that the ERGO/GCE could be employed for simultaneous determination of AA, DA, and UA with high sensitivity and selectivity. 3.7. Interference and reproducibility

Fig. 6. DPV proles at ERGO/GCE in 0.1 M PBS (pH 7.0) (a) containing 0.5 mM AA, 10 M UA and different concentrations of DA (from inner to outer): 0.5, 2, 4, 6, 15, 30, 45, 60 M; (b) containing 1 mM AA, 5 M DA and different concentrations of UA (from inner to outer): 0.5, 2, 5, 10, 20, 30, 45, 60 M; (c) containing 5 M DA, 10 M UA and different concentrations of AA (from inner to outer): 0.5, 0.75, 1.0, 1.5, 2.0 mM; Inset: plots of the oxidation peak current as a function of DA, UA and AA concentrations.

determination (signal change below 5%), indicating the proposed electrode has excellent selectivity. The reproducibility of ERGO/GCE was estimated by measuring the responses to the mixture of 0.5 mM AA, 5 M DA and 10 M UA for 10 successive measurements. The relative standard deviations (RSD) are 2.87%, 5.90% and 2.73% for AA, DA and UA, respectively. The good repeatability means that ERGO/GCE is promising for the simultaneous determination of these three species in analytical application. 3.8. Sample analysis

The possible interferences of some inorganic ions were investigated by DPV. It is found that 100-fold K+ , Ca2+ , Na+ , Mg2+ , Zn2+ , NH4 + , Cl , SO4 2 , NO3 and HCO3 do not interfere with the

Human urine sample was selected as the real sample to investigate the reliability of the proposed method. The urine sample was

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diluted 500 times with 0.1 M pH 7.0 PBS before measurement. No other pretreatment process was preformed. The standard addition method was used for testing recovery. The results show that the recovery rates of 20 M UA, 25 M DA and 0.8 mM AA spiked samples are 99.4%, 104.2% and 105.4%, respectively (Table S3), which clearly indicate the applicability and reliability of the proposed method. 4. Conclusions A simple and green electrochemical method was utilized to synthesize ERGO. Owing to its unique structural features and excellent electrochemical properties, ERGO exhibits high electrocatalytic activities toward the oxidation of DA, AA and UA. High selectivity was achieved at the ERGO/GCE that it showed low response to AA, and the as-prepared ERGO/GCE could be used for the simultaneous of DA, AA and UA with high sensitivity. Its analytical performance is superior to some previous developed graphene-based electrodes. The excellent analytical performance and simple fabrication of ERGO make it a promising platform for high sensitive and selective electrochemical biosensors. Acknowledgement This work was nancially supported by the National Nature Science Foundation of China (No. 221222505). Appendix A. Supplementary data Supplementary material related to this article can be found, in the online version, at References
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Lu Yang obtained his B.S. degree in chemistry from Northwest University, China, in 2010. Currently, he is pursuing her M.S. degree in analytical chemistry under the supervision of Prof. Tianyan You at Changchun Institute of Applied Chemistry (CIAC), Chinese Academy of Sciences (CAS), China. His research interest is graphene nanomaterials in electrochemical application. Dong Liu obtained his B.S. degree in chemistry from Ji Lin University, China, in 2008. Currently, he is pursuing his Ph.D. degree in analytical chemistry under the supervision of Prof. Tianyan You at Changchun Institute of Applied Chemistry (CIAC),


L. Yang et al. / Sensors and Actuators B 193 (2014) 166172 Tianyan You obtained her Ph.D. degree in Analytical Chemistry from CIAC, CAS, China, in 1999. During 2000 February2003 December, she worked as a postdoctoral fellow at NTT Microsystem Integration Laboratory (Japan) and the University of Hong Kong, SAR. Since 2004, she has been working in CIAC as a professor. Currently, her research interests are focused on the electrospun nanomaterials in electrochemical application as well as capillary electrophoresis with electrochemical/electrochemiluminescent detection.

Chinese Academy of Sciences (CAS), China. His research interest is electrospun nanomaterials in electrochemical application. Jianshe Huang obtained his Ph.D. degree in Analytical Chemistry from CIAC, CAS, China, in 2009. He worked as a postdoctoral fellow at Hanyang University, Korea, during 2009, August2010, August. Since 2009, he has been employed in CIAC as assistant research fellow. His scientic interest is nanomaterials in electrochemical application.