Sensitive Voltammetric Determination of Baicalein at Thermally Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of the flavonoid baicalein by using a thermally reduced graphene oxide (TRGO) modified glassy carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology and structure of TRGO investigated by atomic force microscopy, FT‐IR spectroscopy and Raman spectroscopy reveal that the TRGO prepared maintained as single or bilayer sheets and with significant edge‐plane‐like defect sites. The TRGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE and GO/GCE electrodes. The electrochemical behaviors of baicalein at the TRGO/GCE were investigated by cyclic voltammetry, suggesting that the TRGO/GCE exhibits excellent electrocatalytic activity to baicalein. Under physiological conditions, the modified electrode showed linear voltammetric response from 10 nM to 10 µM for baicalein, with a detection limit of 6.0 nM. This work demonstrates that the graphene‐modified electrode is a promising tool for electrochemical determination of flavonoid drugs.     

Polyfurfural-Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode for the Direct Determination of Nitrofurazone

An electrochemical sensor based on a polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode has been developed for the sensitive and rapid determination of nitrofurazone. The morphologies and properties of the sensor were characterized by electrochemical impedance spectroscopy, scanning electron microscopy, cyclic voltammetry, and differential pulse voltammetry (DPV). In pH 7.0 Britton–Robinson buffer solution, the as-prepared polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode shows excellent electrocatalytic performance for the electrochemical reduction of nitrofurazone, and the reduction peak current is about 9.45, 1.31, and 1.25 times higher than that of the bare glassy carbon electrode, polyfurfural modified glassy carbon electrode, and electrochemically reduced graphene oxide modified glassy carbon electrode, respectively. The DPV determination of nitrofurazone indicates that the linear range and detection limit of nitrofurazone are 1–50 and 0.25?µmol/dm³, respectively. In addition, this sensor exhibits high selectivity, reproducibility, stability, and also was successfully used to directly determine nitrofurazone in the commercial antibacterial lotion with comparative sensitivity to high-performance liquid chromatography, showing its promising application prospects.     

Electrochemical Behavior and Voltammetric Determination of Curcumin at Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of curcumin by using a electrochemically reduced graphene oxide (ERGO) modified glass carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The electrochemical behaviors of curcumin at ERGO/GCE were investigated by cyclic voltammetry, suggesting that the ERGO/GCE exhibits excellent electrocatalytic activity towards curcumin, compared with bare GCE and GO/GCE electrodes. The electrochemical reaction mechanisms of curcumin, demethoxycurcumin and bisdemethoxycurcumin at the ERGO/GCE were also investigated and discussed systematically. Under physiological condition, the modified electrode showed linear voltammetric response from 0.2 μM to 60.0 μM for curcumin, with the detection limit of 0.1 μm. This work demonstrates that the graphene‐modified electrode is a promising strategy for electrochemical determination of biological important phenolic compounds.     

Electrochemical Determination of Hydrogen Peroxide Using a Glassy Carbon Electrode Modified with Three-Dimensional Copper Hydroxide Nanosupercages and Electrochemically Reduced Graphene Oxide

Three-dimensional copper hydroxide nanosupercages and electrochemically reduced graphene oxide were used to modify the glassy carbon electrode for the selective determination of hydrogen peroxide. The morphology and electrochemistry properties of copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode were characterized using transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra, Raman spectra, cyclic voltammetry, and electrochemical impedance spectroscopy. The resulting copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode showed favorable performance for the electrocatalytic reduction of hydrogen peroxide. The amperometric current–time curve of the electrochemical sensor exhibited a wide linear range from 0.5 to 1030?µM with a limit of detection of 0.23?µM at a signal-to-noise ratio of three. Moreover, the sensor provided favorable selectivity, reproducibility, and stability and was used for the determination of H₂O₂ in tap water.     

Capacitive Properties of the Binder‐Free Electrode Prepared from Carbon Derived from Cotton and Reduced Graphene Oxide

The binder‐free composite films of reduced graphene oxide (rGO ) and activated carbon derived from cotton (aCFC ) have been fabricated and used as electrodes for electrochemical capacitors (ECs ) to avoid the decrease of capacitive performance in traditional process caused by the additional binder. The optimal aCFC is prepared at 850 °C when the mass ratio of carbon and potassium hydroxide is 1 to 4. The optimal composite film prepared from the mass ratio of aCFC /GO =2/1 exhibits porous structure, and has a specific surface area of 849.6 m²•g⁻¹ and a total pore volume of 0.61 mL •g⁻¹. Based on the two‐electrode system testing in 6.0 mol/L KOH electrolyte, the optimal composite has specific capacitance of about 202 F•g⁻¹, 374 mF •cm⁻² and 116 F•cm⁻³ in terms of mass, area and volume, and shows excellent rate capability and good cyclic stability (91.7% retention of the initial capacitance after 5000 cycles). Furthermore, the assembled solid‐state ECs by using KOH /polyvinyl alcohol as electrolyte show good mechanical stability and capacitive performances after repeated bending cycles. It is proved that this method is effective to fabricate binder‐free electrodes for ECs and will open up a novel route for the reuse of waste cotton.     

Indirect Electrochemical Determination of Ribavirin Using Boronic Acid-Diol Recognition on a 3-Aminophenylboronic Acid-Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode (APBA/ERGO/GCE)

A novel method for the indirect electrochemical determination of ribavirin based on boronic acid-diol recognition was developed using the platform as the sensing element. The device was constructed using a 3-aminophenylboronic acid (APBA)-electrochemically reduced graphene oxide (ERGO) modified electrode. When the electrode was immersed in a solution of ribavirin, complexation of boronic acid groups of APBA with ribavirin occurred at the surface of the electrode and simultaneously caused steric hindrance, resulting in a current decrease because the ferricyanide redox probe was unable access the surface. Under the optimized conditions, a linear relationship was obtained between the relative change in current (%Δi) of [Fe(CN)₆]^3?/4?and the concentration of ribavirin at levels from 10.0 to 7.50?×?10²?ng mL^?1. The proposed electrochemical sensor performed with acceptable sensitivity and reproducibility and was successfully used to determine the content of ribavirin in an injection with satisfactory results.     

Voltammetric Determination of Methylparaban in Cosmetics Using a Multi-Wall Carbon Nanotubes/Nafion Composite Modified Glassy Carbon Electrode

A novel voltammetric sensor using multi-wall carbon nanotubes (MWNTs) coupled with Nafion modified glassy carbon electrode (GCE) was developed for the detection of methylparaben (MP). The sensor exhibited good electrocatalytic activity toward the oxidation of MP in the phosphate buffer solution (PBS, pH 6.5). It displayed good sensitivity, repeatability, reproducibility, and long-term stability. Under the optimized conditions, the anodic peak current was linear with the concentration of MP in the range of 3 × 10^?6 mol L^?1 to 1 × 10^?4 mol L^?1. The detection limit was 1 × 10^?6 mol L^?1. The proposed method was successfully applied to determine MP in cosmetics with satisfactory results.     

Voltammetric Determination of Sophoridine Based on Gold Nanoparticles/L‐cysteine/ Graphene Modified Glassy Carbon Electrode

A new strategy to make the electrochemical sensor was presented, through combining gold nanoparticles (GNPs) with reduced graphene oxide (rGO) via L‐cysteine (L‐cys) as crosslinker. The resulting electrodes were characterized by scanning electron microscopy (SEM) and electrochemical methods. And it was applied to develop a high‐sensitive electrochemical sensor for determination of sophoridine. Compared with the bare GCE and reduced graphene oxide modified electrode, the resulting electrodes exhibited excellent response toward the oxidation of sophoridine by significantly enhancing the oxidation peak currents and decreasing the overpotential of sophoridine. Under the selected conditions, there exist the linear relation between the oxidation peak currents and sophoridine concentration in the range of 1.0 x 10^‐6～1.0 x 10^‐4 mol L^‐1, with detection limit of 4.0 x 10^‐7 mol L^‐1. At the same time, the method can be successfully applied to the quantitative determination of sophoridine in injection samples and its result is satisfactory.     

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.     

Voltammetric Determination of Isoniazid Drug in Various Matrix by Using CuOx Decorated MW‐CNT Modified Glassy Carbon Electrode

Copper oxide decorated multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) was prepared for determination of isoniazid (INZ) in various matrices. The electrochemical behavior of INZ was tested with the aid of Cyclic Voltammetry (CV) and quantitative experiments were performed by using Linear Sweep Voltammetry (LSV). Morphological and structural characterization of the modified electrode was performed by utilizing Scanning Electron Microscopy (SEM), X‐Ray Photoelectron Spectroscopy (XPS) while electrochemical characterization was performed by using CV and Electrochemical Impedance spectroscopy (EIS). The proposed sensor exhibited well defined anodic peak at 0.30 V for INZ at pH 6.0 medium. Under the optimum conditions, a linear relation between INZ concentration and peak current was observed in the range of 2.0×10^?7 to 5.0×10^?5 M. Limit of detection was calculated as 1.0×10^?8 M and repeatability and accuracy was found as 5.60 % and 91.0 % for 5.0 10^?7 M INZ by using 3 successive measurement, respectively. Then, the analytic performance of the electrode developed was tested by analyzing commercial tablets, artificial human serum and urine samples. The results indicated that satisfactory recoveries was observed for all issue.     

A Laser Reduced Graphene Oxide Grid Electrode for the Voltammetric Determination of Carbaryl

Laser-reduced graphene oxide (LRGO) on a polyethylene terephthalate (PET) substrate was prepared in one step to obtain the LRGO grid electrode for sensitive carbaryl determination. The grid form results in a grid distribution of different electrochemically active zones affecting the electroactive substance diffusion towards the electrode surface and increasing the electrochemical sensitivity for carbaryl determination. Carbaryl is electrochemically irreversibly oxidized at the secondary amine moiety of the molecule with the loss of one proton and one electron in the pH range from 5 to 7 by linear scan voltammetry (LSV) on the LRGO grid electrode with a scan rate of 300 mV/s. Some interference of the juice matrix molecules does not significantly affect the LSV oxidation current of carbaryl on the LRGO grid electrode after adsorptive accumulation without applied potential. The LRGO grid electrode can be used for LSV determination of carbaryl in fruit juices in the concentration range from 0.25 to 128 mg/L with LOD of 0.1 mg/L. The fabrication of the LRGO grid electrode opens up possibilities for further inexpensive monitoring of carbaryl in other fruit juices and fruits     

Fabrication of Electrochemical Reduced Graphene Oxide Films on Glassy Carbon Electrode by Pulsed Potentiostatic Methods and Its Electrochemical Application

A graphene‐based electrochemical sensing platform for sensitive determination of baicalein was constructed by means of pulsed potentiostatic reduction of graphene oxide (GO) on a glassy carbon electrode (GCE). The resulting electrode (ERGO/GCE) was characterized by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The electrochemical behaviors of baicalein at the ERGO/GCE were investigated in detail by CV, chronoamperometry (CA) and chronocoulometry (CC). The experimental results demonstrated that the ERGO/GCE exhibited excellent response toward the redox of baicalein as evidenced by the significant enhancement of redox peak currents (i_p) and the decreased peak‐to‐peak separation (ΔE_p) in comparison with a bare GCE. Under the optimum experimental conditions, the reduction peak cureent was proportioanal to the baicalein concentration in the range of 5.0 × 10^‐9 ～ 5.0 × 10^‐7 mol L^‐1 with the detection limit of 2.0 × 10^‐9 mol L^‐1. The proposed method was also applied successfully to determine baicalein in spiked human blood serum samples.     

Electroanalytical Determination of Paracetamol Using Pd Nanoparticles Deposited on Carboxylated Graphene Oxide Modified Glassy Carbon Electrode

The study presents a novel paracetamol (PA) sensor based on Pd nanoparticles (PdNPs) deposited on carboxylated graphene oxide (GO?COOH) and nafion (Nf) modified glassy carbon electrode (GCE). The morphologies of the as prepared composites were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR). The experimental results demonstrated that Nf/GO?COOPd displayed excellent electrocatalytic response to the oxidation PA. The linear range was 0.04–800 μM for PA with limit of detection of 0.012 μM and excellent sensitivity of 232.89 μA mM^?1 cm^?2. By considering the excellent performance of Nf/GO?COOPd composite such as wider linear range, lower detection, better selectivity, repeatability, reproducibility, and storage stability, the prepared composite, especially GO?COOH support, with satisfactory electrocatalytic properties was a promising material for the modification of electrode material in electrochemical sensor and biosensor field.     

聚吡咯/还原氧化石墨烯复合物的合成及电容性能

通过原位聚合方法制备不同配比的聚吡咯/氧化石墨（PPy/GO）复合物,将其用NaBH4还原得到聚吡咯/还原氧化石墨烯(PPy/RGO)复合物,采用X射线衍射、红外光谱和场发射扫描电子显微镜（FESEM）对其结构和形貌进行物理表征。 采用循环伏安、恒电流充放电和交流阻抗等电化学方法系统研究了所制备样品的电化学性能。 实验结果表明,在电流密度为0.5 A/g、吡咯（Py）与GO质量比为95∶5时,得到的复合物还原前后比电容分别可达401.5和314.5 F/g,远高于单纯的GO（34.8 F/g）和PPy（267.5 F/g）。 经过1200圈循环稳定性测试后,PPy/RGO复合物比电容保持了原来的62.5%,与PPy和PPy/GO（电容保持率分别为16.8%和46.4%）相比,PPy/RGO表现出更好的循环稳定性能,有望成为超级电容器电极材料。     

铜纳米粒子/聚丙烯酸/石墨烯纳米复合材料修饰玻碳电极检测水中的4-硝基苯酚

采用一种温和且简单的原位生长法将铜纳米粒子和石墨烯非共价键合,得到铜纳米粒子/聚丙烯酸/石墨烯(CuNPs/PAA/GR)纳米复合材料,对4-硝基苯酚(4-NP)表现出良好的电催化活性.用扫描电镜对此纳米复合材料的形貌进行了表征.以此材料修饰的玻碳电极受吸附控制,4-NP在该电极表面的反应机理为两电子转移过程,电子转移数n=2.3,修饰电极的有效面积为0.6275 cm2,是裸电极的2.22倍,电极吸附量Гs为1.6×10-11 mol/cm2,催化速率常数kcat的平均值为1.15×104 L/(mol/s).修饰电极的响应电流与4-NP的浓度在1 ～ 150 μmol/L范围内呈良好的线性关系,线性方程为:Ipa(μA)=-0.015C(μmol/L)-0.98,(R2 =0.9951),检出限为0.23 μmol/L(S/N=3).此传感器制备简单、灵敏性高、稳定性和重现性好.使用此传感器检测实际水样中4-NP的回收率为88.6％～ 100.7％,相对标准偏差为2.6％ ～5.9％.     

Covalent Modification of Glassy Carbon Electrode with L-Cysteine for the Determination of Acetaminophen

A novel L-cysteine film modified electrode has been fabricated by means of an electrochemical oxidation procedure, and it was successfully applied to the electrochemical determination of acetaminophen. This method utilizes the electrooxidation of amines to their analogous cation radicals to form a chemically stable covalent linkage between the nitrogen atom of the amine and edge plane sites at the glassy carbon electrode surface. The electrochemical behaviour of acetaminophen at the film electrode was investigated in 0.1 mol L⁻¹ phosphate buffer (pH 6.20). It was found that the redox peak current of acetaminophen was enhanced greatly on the film electrode. Linearity between the oxidation peak current and the acetaminophen concentration was obtained in the range of 1.0 × 10⁻⁴–2.0 × 10⁻⁷ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁸ mol L⁻¹. For seven parallel detections of 1.0 × 10⁻⁵ mol L⁻¹ acetaminophen, the relative standard deviation (RSD) was 1.46%, suggesting that the film electrode has excellent reproducibility. Application to the determination of acetaminophen in drug tablets and human urine demonstrated that the film electrode has good stability and high sensitivity.     

Electrocatalysis of Hemoglobin in ZnO Nanoparticle/Ionic Liquid Composite Film Modified Glassy Carbon Electrode

A nanobiocompatible composite containing hemoglobin (Hb), ZnO nanoparticles (nano‐ZnO) and ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) was fabricated and further modified on the glassy carbon electrode (GCE). The electrochemical behaviours of Hb in the composite film were carefully studied and a pair of quasi‐reversible redox peaks appeared in pH 7.0 phosphate buffer solution, which was attributed to the electrode reaction of Hb heme Fe(III)/Fe(II) redox couple. The presences of nano‐ZnO and BMIMPF₆ in the film can retain the bioactivity of Hb and greatly enhance the direct electron transfer of Hb. The immobilized Hb showed high stability and good electrocatalytic ability to the reduction of hydrogen peroxide and O₂.     

Graphene Oxide/ZnO Nano Composite for Sensitive and Selective Electrochemical Sensing of Levodopa and Tyrosine Using Modified Graphite Screen Printed Electrode

Determination of levodopa and tyrosine as two important species for treatment of Parkinson's disease is described. A novel electrochemical sensor involving graphene oxide/ZnO nanorods (GR/ZnO) nano composite and the graphite screen‐printed electrodes (GSPE) was developed for the simultaneous detection of levodopa and tyrosine. The screen‐printed electrodes with several advantages, including low cost, versatility and miniaturization were employed. On the other hand, the graphene oxide/ZnO nanorods nano composite was casted on the surface of GSPE to obtain GR/ZnO/SPE. The proposed nano sensor has excellent performance such as high sensitivity, good selectivity and analytical application in real samples. The combination of graphene oxide/ZnO nanorods nano composite with the screen‐printed electrode is favorable for amplifying electrochemical signals. Under optimized conditions square wave voltammetry (SWV) exhibited linear dynamic ranges from 1.0×10^?6 to 1.0×10^?3 M and 1.0×10^?6 to 8.0×10^?4 M with detection limits of 4.5×10^?7 M and 3.4×10^?7 M for levodopa and tyrosine respectively.     

Fabrication of Bismuth/Multi-walled Carbon Nanotube Composite Modified Glassy Carbon Electrode for Determination of Cobalt

A bismuth/multi‐walled carbon nanotube (Bi/MWNT) composite modified electrode for determination of cobalt by differential pulse adsorptive cathodic stripping voltammetry is described. The electrode is fabricated by potentiostatic pre‐plating bismuth film on an MWNT modified glassy carbon (GC) electrode. The Bi/MWNT composite modified electrode exhibits enhanced sensitivity for cobalt detection as compared with the bare GC, MWNT modified and bismuth film electrodes. Numerous key experimental parameters have been examined for optimum analytical performance of the proposed electrode. With an adsorptive accumulation of the Co(II)‐dimethylglyoxime complex at ?0.8 V for 200 s, the reduction peak current is proportional to the concentration of cobalt in the range of 4.0×10^?10?1.0×10^?7 mol/L with a lower detection limit of 8.1×10^?11 mol/L. The proposed method has been applied successfully to cobalt determination in seawater and lake water samples.     

Permselectivity of Electrodeposited Polydopamine/Graphene Composite for Voltammetric Determination of Dopamine

A novel permselective film of electrodeposited polydopamine (PDA) on electrochemical reduced graphene oxide (erGO) surface was prepared. The obtained composite films were characterized by atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The influences of permselectivity with different electropolymerized cycles and concentration of dopamine on electrochemical responses of biomolecules on electrode were investigated. It was found that the composite film held high cationic permeable to dopamine (DA) and good suppression of ascorbic acid (AA) and uric acid (UA) using CV. The anodic peak currents were proportional to dopamine concentration. The significant permselectivity suggested that the PDA/graphene‐modified electrode has opened a new route to high selective dopamine biosensor.