We report a novel caffeic acid (CA) electrochemical sensor using reduced graphene oxide and polydopamine composite modified glassy carbon electrode. Electrochemical method was applied on graphene oxide (GO) and PDA composite modified electrode for the preparation of RGO@PDA composite. The RGO@PDA composite was used as an electrocatalyst for the oxidation of CA. Cyclic voltammetry (CV) was used to investigate the electrochemical behavior of different modified electrodes toward oxidation of CA and the CV results show that RGO@PDA composite has high electrocatalytic activity to CA than other modified electrodes. Optimization studies such as effect of catalyst loading and pH are investigated and discussed. Differential pulse voltammetry was used for determination of CA, and shows that the response of CA was linear over the concentration ranging from 5.0 nM to 450.55 μM with the low detection limit of 1.2 nM. The selectivity of the sensor was elevated in the presence of potentially active interfering species, and the results reveal that the composite modified electrode has acceptable selectivity in the presence of interfering species. The practical applicability of the composite was evaluated in wine samples and the obtained recovery of CA in wine samples authenticates its potential for practical applications. Caffeic acid (CA) is known as natural phenolic antioxidant and major representative of hydroxycinnamic acids in wine. 1,2 CA is present in the range of products, including fruits, vegetables, wine, olive oil, and coffee. 1 CA is primary and abundant compound in red wines, and improved the color stability and prevent the oxidation of wines. 3 Therefore, the accurate determination of CA in wines has received significant interest to the analytical community. To date, different analytical methods have been used for determination of CA in real samples, such as, high performance liquid chromatography, 4 capillary electrophoresis 5 and electrochemical methods. 6,7 Compared to liquid chromatography and capillary electrophoresis methods, electrochem-ical methods are simple, cost-effective, and provides high sensitivity for determination of CA. 8 Redox active based biosensors have also been exhibited a high selectivity toward CA 9–13 however, it has critical drawbacks such as complicated immobilization procedures, high cost and low stability. 14 Recently, the nanomaterial-modified electrodes have been used as an alternative for the sensitive and selective determination of CA in human fluids and beverages. 15–19 Compared with other nanomaterials, reduced graphene oxide (RGO) is a promising material for wide range of applications including electrochemical sensors and biosensors. In addition, the composites of reduced graphene oxide (RGO) with conducting polymers, biomolecules, metal and metal oxide nanoparticles have found high catalytic behavior toward oxidation of CA. 8,19–22 On the other hand, polydopamine (PDA) is an oxidative polymer of dopamine and served as a functional material to incorporate specific groups on the electrode surface. 23,24 Recent studies found that PDA can be easily incorporated with graphene oxide (GO), and exhibited a high catalytic activity in electrochemical sensors when compared with pristine GO. 25–29 However, only few papers have focused on the preparation of GO and RGO based PDA composites and their application in electrochemical sensors. 26–30 More recently, we have electrochemically prepared RGO@PDA composite and used for the electrochemical sensing of chlorpromazine. 30 Herein, we have used electrochemically prepared RGO@PDA composite for the electro-chemical oxidation of CA for the first time. In the present work, a simple electrochemical method was used for the fabrication of RGO@PDA composite and used as a novel sensing probe for the determination of CA. The RGO@PDA composite shows an enhanced catalytic activity toward the oxidation of CA than other z E-mail:
smchen78@ms15.hinet.net;
v.velusamy@mmu.ac.uk modified electrodes. The selectivity of the developed sensors was evaluated in the presence of range of potentially active interfering species, and are critically discussed. The practical applicability of the sensor has also been investigated in two different wine samples. Experimental Materials and method.—Natural graphite was purchased from Sigma Aldrich. Dopamine and caffeic acid were obtained from Sigma and used as received. All other compounds purchased from Sigma Aldrich was used without any purification. The supporting electrolyte, phosphate buffer (pH 7.0) was prepared using 0.1 M Na 2 PO 4 and NaH 2 PO 4 with ultrapure doubly distilled water, and pH were adjusted using diluted H 2 SO 4 and NaOH solutions. All other solutions were prepared with ultrapure doubly distilled water (resistivity > 18.2 M at 25 • C) using a LOTUN Ultrapure Water System. All the electrochemical measurements were carried out using an electrochemical work station of CH 750A from CH instruments. Typical three-electrode configuration was used for electrochemical experiments , where the saturated Ag/AgCl as reference electrode, platinum wire (diameter = 0.5 mm) as a counter electrode and BAS glassy carbon electrode as working electrode (apparent surface area = 0.079 cm 2). Scanning electron microscopic images of different materials were taken using Hitachi S-3000H Scanning Electron Microscope. FT-IR spectra were obtained using Thermo SCIENTIFIC Nicolet iS10 instruments. All electrochemical experiments were performed in room temperature unless otherwise stated. The GO@PDA composite was prepared by our previously reported method. 29 To prepare RGO@PDA composite, about 10 μL (optimum) of GO@PDA composite dispersion was drop coated on pre-cleaned GCE, and dried in an air oven. The resulting GO@PDA composite electrode was electrochemically reduced at –1.4 V for 200 s in pH 5, as reported previously. 30 The schematic representation for preparation of RGO@PDA composite and its electro-oxidation behavior toward CA is shown in Scheme 1. The fabricated RGO@PDA composite electrode was dried in room temperature and stored under dry conditions when not in use. The optimization of catalyst loading toward detection of CA is shown in Fig. 3A, and the optimum about 10 μL drop coated GO@PDA composite was used for preparation of RGO@PDA composite and the resulting electrode was further used for electrochemical experiments.