SYNERGISTIC EFFECT OF GRAPHENE AND MULTI-WALLED CARBON NANOTUBES ON GLASSY CARBON ELECTRODE FOR SIMULTANEOUS DETERMINATION OF URIC ACID AND DOPAMINE IN THE PRESENCE OF ASCORBIC ACID Sijing He, Yanyan Yu, Zuanguang Chen,* Qiujia Shi, and Lin Zhang School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China *Corresponding author. Tel.: +86 20 3994 3044, Fax: +86 20 3994 3071 E-mail address: chenzg@mail.sysu.edu.cn (Z. Chen) SUPPLEMENTAL INFORMATION Preparation of poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotubes suspension 1.5 mg graphene oxide, 1 mL poly(diallyldimethylammonium chloride) (0.2 wt %), 1 mL hydrazine hydrate (4 wt %), and 4 mL H2O were mixed and sonicated for 5 minutes to form a homogeneous dispersion. After stirring for 30 minutes at room temperature, the mixture was heated to 100 °C with a reflux condenser for 30 minutes. The black poly(diallyldimethylammonium chloride)-graphene dispersion was 1 obtained at a concentration of 0.25 mg mL-1. Centrifugation (15,000 rpm, 10 min) was used to collect poly(diallyldimethylammonium chloride)-graphene and remove the excess reagents. For the preparation of the poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube modified electrode, 0.5 mg of multiwalled carbon nanotubes were dispersed in 3 mL poly(diallyldimethylammonium chloride)-graphene solution (0.5 mg mL-1) and sonicated for 1 h to form a homogenous mixture. 2 Table S1. Analytical figures of merit for modified electrodes reported in the literature. Linear dynamic range Limit of detection Electrode Reference -1 -1 (µmol L ) (µmol L ) uric acid dopamine uric acid dopamine 31.0-172.0 29.0-167.0 1.19 0.51 Tsierkezos et al. (2014) 2.0-200.0, 0.4-10.0 1.00 0.20 Yang et al. (2011) Nitrogen-doped multiwalled carbon nanotubes/gold nanoparticles Methylene blue/multiwalled nanotubes/glassy carbon electrode (GCE) Multi walled carbon nanotube Habibia and 0.55-90.0 0.5-100.0 0.42 0.31 /carbon-ceramic electrode (CCE) Nitrogen doped graphene/GCE Pournaghi-Azar (2010) 0.1-20.0 0.5-170.0 0.045 0.25 Sheng et al. (2012) 0.5-60.0 0.5-60.0 0.50 0.50 Yang et al. (2014) 2.0-45.0 1.0-24.0 2.00 1.00 Han et al. (2010) 10.0-130.0 10.0-170.0 0.45 0.25 Xu et al. (2014) 2.5-65.0 - 0.10 - Zhang et al. (2013) 5.0-350.0 10.0-400.0 0.13 0.55 This work Electrochemically reduced graphene oxide/GCE Chitosan/graphene/GCE Pt/reduced graphene oxide/GCE Graphene/singlewalled carbon nanotube/GCE Poly(diallyldimethylammonium chloride)/graphene/multiwalled carbon nanotube/GCE 3 REFERENCES Habibia, B., and M. H. Pournaghi-Azar. 2010. Simultaneous determination of ascorbic acid, dopamine and uric acid by use of a MWCNT modified carbon-ceramic electrode and differential pulse voltammetry. Electrochim. Acta. 55: 5492–5498. Han, D. X., T. T. Han, C. S. Shan, A. Ivaska, and L. Niu. 2010. Simultaneous Determination of Ascorbic Acid, Dopamine and Uric Acid with Chitosan-Graphene Modified Electrode. Electroanalysis. 22: 2001-2008. Sheng, Z. H., X. Q. Zheng, J. Y. Xu, W. J.B ao, F. B. Wang, and X. H. Xia. 2012. Electrochemical sensor based on nitrogen doped graphene: Simultaneous determination of ascorbic acid, dopamine and uric acid. Biosens. Bioelectron. 34: 125-131. Tsierkezos, N. G., P. Szroeder, and U. Ritter. 2014. Voltammetric study on pristine and nitrogen-doped multi-walled carbon nanotubes decorated with gold nanoparticles. Microchim. Acta. 181: 329–331. Xu, T. Q., Q. L. Zhang, J. N. Zheng, Z. Y. Lv, J. Wei, A. J. Wang, and J. J. Feng. 2014. Simultaneous determination of dopamine and uric acid in the presence of ascorbic acid using Pt nanoparticles supported on reduced graphene oxide. Electrochim. Acta 115: 109–115. Yang, L., D. Liu, J. S. Huang, T, and Y. You. 2014. Simultaneous determination of 4 dopamine, ascorbic acid and uric acid at electrochemically reduced graphene oxide modified electrode. Sens. Actuators B 193: 166-172. Yang, S. L., G. Li, R. Yang, M. M. Xia, and L.B. Qu. 2011. Simultaneous voltammetric detection of dopamine and uric acid in the presence of high concentration of ascorbic acid using multi-walled carbon nanotubes with methylene blue composite film-modified electrode. J.Solid State Electrochem. 15: 1909–1918. Zhang, F. F., J. Tang, Z. H. Wang, and L. C. Qin. 2013. Graphene–carbon nanotube composite aerogel for selective detection of uric acid. Chem. Phys. Lett. 590: 121–125. 5 Fig. S1. Influence of the mass ratio of poly(diallyldimethylammonium chloride)-graphene and multiwalled carbon nanotubes on the oxidation peak currents of 100 µmol L-1 uric acid and 100 µmol L-1 dopamine in 0.1 mol L-1 phosphate buffer (pH 7.0) at a scan rate of 50 mV s-1. 6 Fig. S2. Cyclic voltammograms of 1 mmol L-1 ascorbic acid, 1 mmol L-1 dopamine, and 1 mmol L-1 uric acid at a (A) bare glassy carbon electrode, (B) poly(diallyldimethylammonium chloride)-graphene-glassy carbon electrode, (C) multi-walled carbon nanotube-glassy carbon electrode, and (D) poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube-glassy carbon electrode in 0.1 mol L-1 phosphate buffer (pH 7.0) at a scan rate of 50 mV s-1. 7 Fig. S3. (A) Cyclic voltammograms of 1 mmol L-1 uric acid at the poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube glassy carbon electrode at various scan rates (a-r: 20, 60, 120, 180, 220, 260, 300, 340, 380, 460, 500, 560, 640, 680, 720, 760, 800, and 850 mV s-1) in 0.1 mol L-1 phosphate buffer (pH 7.0); (B) Cyclic voltammograms of 1 mmol L-1 dopamine at poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube glassy carbon electrode at various scan rates (a-i: 10, 30, 40, 70, 100, 120, 140, 200, and 250 mV s-1) in 0.1 mol L-1 phosphate buffer solution (pH 7.0); (C) anodic and cathodic peak currents versus scan rate of uric acid; (D) anodic and cathodic peak currents versus scan rate of dopamine. 8 Fig. S4. Differential pulse voltammograms at the poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube glassy carbon electrode in 0.1 mol L-1 phosphate buffer (pH 7.0): (A) 500 µmol L-1 ascorbic acid, 100 µmol L-1 dopamine, and various concentrations of uric acid (a-q = 5, 10, 20, 40, 60, 80, 100, 130, 150, 180, 200, 230, 250, 280, 300, 320, and 350 µmol L-1) and (B) 500 µmol L-1 ascorbic acid, 100 µmol L-1 uric acid, and various concentrations of dopamine (a-g=10, 30, 50, 100, 200, 300, and 400 µmol L-1). Plots of peak current versus concentration for (C) uric acid and (D) dopamine. 9