Electrochemical determination of bisphenol A at Mg-Al-CO3 layered double hydroxide modified glassy carbon electrode

The electrochemical behavior of bisphenol A (BPA) was investigated on Mg-Al layered double hydroxide (LDH) modified glassy carbon electrode (GCE) by cyclic voltammetry (CV), differential pulse voltammetry (DPV), linear sweep voltammetry (LSV) and chronocoulometry (CC). The cyclic voltammogram of BPA on the modified electrode exhibited a well defined anodic peak at 0.454 V in 0.1 M pH 8.0 phosphate buffer solution (PBS). The experimental parameters were optimized and the kinetic parameters were investigated. The probable oxidation mechanism was proposed. Under the optimized conditions, the oxidation peak current was proportional to BPA concentration in the range from 1 × 10⁻⁸ to 1.05 × 10⁻⁶ M with the correlation coefficient of 0.9959. The detection limit was 5.0 × 10⁻⁹ M (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference. The proposed method was successfully applied to determine BPA in plastic products and the results were satisfactory.     

Electrochemical oxidation of benzene at a glassy carbon electrode

Benzene oxidation in sulfuric acid at a glassy carbon electrode was investigated using voltammetric, chronoamperometric, and spectroscopic methods. The results are compared with those at a Pt electrode. Benzene was observed to be oxidized to benzoquinone presumably by active oxygen that was adsorbed on the GC electrode in the oxygen evolution region. It is concluded that oxidation at glassy carbon can produce benzoquinone or quinone-like compounds from an aqueous benzene solution. The applied potential for benzene oxidation should be less than 2.1 V vs RHE in order to prevent glassy carbon electrode damage by oxidation during long operation.     

基于多壁碳纳米管修饰电极的磺胺的电化学检测

运用线性扫描伏安法(LSV)研究了磺胺(SA)在多壁碳纳米管修饰电极(MWNTs/GCE)上的电化学行为,探讨并确定了修饰体积和浓度、支持基质种类、最佳pH值、富集电位和时间等磺胺的最佳检测条件。结果表明,在pH=8.0的Na2HPO4-NaH2PO4缓冲体系中,磺胺在多壁碳纳米管修饰电极上检测到一个不可逆的氧化峰,且在1.0×10-5~2.0×10-4mol/L浓度范围内,磺胺氧化峰电流与其浓度呈现良好的线性关系,线性回归方程为Ip(μA)=0.493 6×C(μmol/L)+9.984 1,相关系数为R=0.996 3,检测下限为8.0×10-6mol/L,平行测定的相对误差(RSD)小于1.463%(n=8),样品平均加标回收率为99.21%~100.93%。     

基于多壁碳纳米管修饰电极的磺胺的电化学检测

运用线性扫描伏安法(LSV)研究了磺胺(SA)在多壁碳纳米管修饰电极(MWNTs/GCE)上的电化学行为,探讨并确定了修饰体积和浓度、支持基质种类、最佳pH值、富集电位和时间等磺胺的最佳检测条件。结果表明,在pH=8.0的Na2HPO4-NaH2PO4缓冲体系中,磺胺在多壁碳纳米管修饰电极上检测到一个不可逆的氧化峰,且在1.0×10-5².0×10-4mol/L浓度范围内,磺胺氧化峰电流与其浓度呈现良好的线性关系,线性回归方程为Ip(μA)=0.493 6×C(μmol/L)+9.984 1,相关系数为R=0.996 3,检测下限为8.0×10-6mol/L,平行测定的相对误差(RSD)小于1.463%(n=8),样品平均加标回收率为99.21%2.0×10-4mol/L浓度范围内,磺胺氧化峰电流与其浓度呈现良好的线性关系,线性回归方程为Ip(μA)=0.493 6×C(μmol/L)+9.984 1,相关系数为R=0.996 3,检测下限为8.0×10-6mol/L,平行测定的相对误差(RSD)小于1.463%(n=8),样品平均加标回收率为99.21%¹00.93%。     

Hydrogen peroxide sensor based on riboflavin immobilized at the nickel oxide nanoparticle-modified glassy carbon electrode

A simple and sensitive electrochemical sensor based on nickel oxide nanoparticles/riboflavin-modified glassy carbon (NiONPs/RF/GC) electrode was constructed and utilized to determine H₂O₂. By immersing the NiONPs/GC-modified electrode into riboflavin (RF) solution for a short period of time (5–300 s), a thin film of the proposed molecule was immobilized onto the electrode surface. The modified electrode showed stable and a well-defined redox couples at a wide pH range (2–10), with surface-confined characteristics. Experimental results revealed that RF was adsorbed on the surface of NiONPs, and in comparison with usual methods for the immobilization of RF, such as electropolymerization, the electrochemical reversibility and stability of this modified electrode has been improved. The surface coverage and heterogeneous electron transfer rate constants (k _s) of RF immobilized on a NiO _x –GC electrode were approximately 4.83 × 10^?11 mol cm^?2, 54 s^?1, respectively. The sensor exhibits a powerful electrocatalytic activity for the reduction of H₂O₂. The detection limit, sensitivity and catalytic rate constant (k _cat) of the modified electrode toward H₂O₂ were 85 nM, 24 nA μM^?1 and 7.3 (±0.2) × 10³ M^?1 s^?1, respectively, at linear concentration rang up to 3.0 mM. The reproducibility of the sensor was investigated in 10 μM H₂O₂ by amperometry, the value obtained being 2.5 % (n = 10). Furthermore, the fabricated H₂O₂ chemical sensor exhibited an excellent stability, remarkable catalytic activity and reproducibility.     

Electrochemical determination of thiamazole at a multi-wall carbon nanotube modified glassy carbon electrode

A simple and convenient method is described for voltammetric determination of thiamazole, a commonly used anti-hyperthyroid drug, based on its electrochemical oxidation at a multi-wall carbon nanotube modified glassy carbon electrode. Under optimized conditions, the proposed method exhibited acceptable analytical performances in terms of linearity (over the concentration range from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁴ mol L⁻¹, r = 0.9983), detection limit (3.0 × 10⁻⁸ mol L⁻¹) and reproducibility (RSD = 2.64%, n = 10, for 5.0 × 10⁻⁵ mol L⁻¹ thiamazole). To further validate its possible application, the method was used for the quantification of thiamazole in pharmaceutical formulations and biological fluids.     

Electrochemical simultaneous determination of nitrophenol isomers at nano-gold modified glassy carbon electrode

A novel method for simultaneous determination of nitrophenol isomers at nano-gold modified glassy carbon electrode has been developed. The gold nanoparticles were directly electrodeposited onto the glassy carbon electrode via a constant potential −0.2 V (vs. SCE) for 60 s from 0.1 mol L⁻¹ KNO₃ containing 0.4 g L⁻¹ HAuCl₄. The resulting electrode (nano-Au/GCE) was characterized with scanning electron microscopy (SEM). The electrochemistry response of nitrophenol isomers at the nano-Au/GCE was studied. The result indicated that o-, m-, and p- nitrophenol are separated entirely at nano-Au/GCE, and a semi-derivative voltammetric technology was adopted to enhance the determination sensitivity. This modified electrode could be applied to direct simultaneous voltammetric determination of nitrophenol isomers in water samples without preseparation with higher sensitivity.     

Electrochemical behavior of o-chloranil in aqueous solution at an activated glassy carbon electrode

A study has been conducted on the effect of specific adsorption of o-chloranil, OCA, at an activated glassy carbon electrode, AGCE, surface on its electrochemical behavior in an aqueous solution. The voltammetric responses of OCA at an AGCE show an anodic prepeak and a cathodic postpeak other than the diffusion main couple in weak acidic and neutral pHs. The anodic prepeak and the cathodic postpeak are ascribed to specific adsorption of OCA. The pK_a value of the adsorbed redox couple of OCA at an AGCE is at least by 4 and 2 pK_a units higher than those of the free redox couple in solution at bare and activated glassy carbon electrodes, respectively. The slop of (I_p)_ads/(I_p)_diff ratio versus ν^1/2 for the cathodic and anodic peaks indicates a stronger adsorption of OCA at AGCE in comparison with OCAH₂. The effects of OCA concentration on its adsorption behavior and applied potential on anodic adsorption of OCA at AGCE have been studied and the surface coverage of OCA (Γ_OCA) has been calculated.     

Electrochemical behavior of cysteine at a CuGeO3 nanowires modified glassy carbon electrode

A CuGeO₃ nanowire modified glassy carbon electrode was fabricated and characterized by scanning electron microscopy. The results of electrochemical impedance spectroscopy reveal that electron transfer through nanowire film is facile compared with that of bare glassy carbon electrode. The modified electrode exhibited a novel electrocatalytic behavior to the electrochemical reactions of l-cysteine in neutral solution, which was not reported previously. Two pairs of semi-reversible electrochemical peaks were observed and assigned to the processes of oxidation/reduction and adsorption/desorption of cysteine at the modified electrode, respectively. The electrochemical response of cysteine is poor in alkaline condition and is enhanced greatly in acidic solution, suggesting that hydrogen ions participate in the electrochemical oxidation process of cysteine. The intensities of two anodic peaks varied linearly with the concentration of cysteine in the range of 1 × 10⁻⁶ to 1 × 10⁻³ mol L⁻¹, which make it possible to sensitive detection of cysteine with the CuGeO₃ nanowire modified electrode. Furthermore, the modified electrode exhibited good reproducibility and stability.     

Electrochemical behavior of phenol in alkaline media at hydrotalcite-like clay/anionic surfactants/glassy carbon modified electrode

The electrochemical behavior of phenol, using glassy carbon (GC) modified electrodes containing a hydrotalcite (HT)-like clay and anionic surfactants such as sodium octyl sulfate (SOS), sodium dodecyl sulfate (SDS), or sodium dodecylbenzenesulfonate (SDBS) in alkaline media, has been examined. Phenol oxidation at the modified electrodes, after a time accumulation under open circuit conditions, promotes increments of the current and shifts the oxidation potential to less positive values, compared to phenol oxidation at HT-GC or GC electrodes. The phenol oxidation is favored by the presence of surfactants in the films. The results suggest that the surfactant molecules intercalate between the HT layers, yielding a hydrophobic clay capable of preconcentrating phenol molecules. X-ray diffraction analyses showed a larger spacing of the HT layers when the surfactant intercalates between them. Cyclic voltammograms have shown that the SOS-HT-GC modified electrode exhibits short-lived activity for phenol oxidation as a consequence of surface fouling, while the SDS-HT-GC and SDBS-HT-GC modified electrodes showed a more stable behavior. The SDBS-HT-GC modified electrode was the most effective adsorbing phenol, since the charge (Q), obtained from the integration of the anodic peak current of the phenol, is higher at this modified electrode. This is probably because the adsolubilization capacity of phenol on the SDBS-HT-GC electrode is higher than on SDS-HT-GC electrode.     

Electrochemical sensors for hemoglobin and myoglobin detection based on methylene blue-multiwalled carbon nanotubes nanohybrid-modified glassy carbon electrode

An effective electrochemical sensors for hemoglobin (Hb) and myoglobin (Mb) detection was firstly developed using a simple procedure of self-assembled methylene blue-multiwalled carbon nanotubes (MB-MWNTs) nanohybrid modified on glassy carbon electrode without using any enzymes immobilization. The direct electrochemical and electrocatalytic behaviors of the modified electrode were studied using cyclic voltammetry (CV) and flow injection analysis (FIA) with amperometry. The performance of the sensor was investigated and optimized and the system was evaluated by monitoring Hb and Mb concentrations. The developed MB-MWNTs nanohybrid modified electrode showed excellent electrocatalytic activity for reduction of Hb and Mb with good stability, sensitivity and reproducibility (RSD = 3.05% and 4.5% for 50 successive injections of Hb and Mb, respectively). Under optimal conditions, the catalytic currents are linearly proportional to the concentrations of Hb and Mb in the wide range from 5 nM to 2 μM and 0.1 to 3 μM, and the corresponding detection limits are 1.5 nM and 20 nM (S/N = 3), respectively. This approach provides improved detection limit over other previous works and may provide a novel and efficient platform for the fabrication of sensors for other heme proteins.     

Electrochemical sensor based on a poly(para-aminobenzoic acid) film modified glassy carbon electrode for the determination of melamine in milk

A novel and simple sensor is developed in this paper for melamine detection, which is based on an electropolymerized molecularly imprinted polymer (MIP) of para-aminobenzoic acid (pABA). The poly(para-aminobenzoic acid) (P-pABA) film was deposited in a pABA solution by potentiodynamic cycling of potential with and without the template (melamine) on a glassy carbon electrode. The surface feature of the modified electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The molecular imprinted sensor was tested by differential pulse voltammetry (DPV) to verify the changes in redox peak currents of hexacyanoferrate. Several important parameters controlling the performance of the P-pABA were investigated and optimized. In the optimal conditions, the relative redox peak currents of hexacyanoferrate were linear. The concentration of melamine ranged from 4.0 μM to 0.45 mM, with a linear correlation coefficient of 0.9992. The detection limit was 0.36 μM (S/N = 3). The MIP sensor was successfully applied to the determination of melamine in milk products and showed high selectivity, sensitivity, and reproducibility. The results of this research demonstrate that it is feasible to use the molecular imprinting methodology when preparing sensing devices for analytes that are electrochemically inactive.     

聚对氨基苯磺酸/石墨烯复合膜修饰玻碳电极测定葡萄糖

制备了对氨基苯磺酸/石墨烯复合膜修饰电极,研究了葡萄糖在该修饰电极上的电化学行为.在0.1 moL/L NaOH溶液中,峰电流与葡萄糖的浓度在1 ×1O-6 ～5 ×1O-4 mol/L的范围内呈良好的线性关系,检出限为2×10-7 mol/L(S/N =3).实验结果表明对氨基苯磺酸/石墨烯复合膜显著提高了方法的检测...     

Electrooxidation of alcohols at a nickel oxide/multi-walled carbon nanotube-modified glassy carbon electrode

Electrocatalytic oxidation of methanol and some other primary alcohols on a glassy carbon electrode modified with multi-walled carbon nanotubes and nano-sized nickel oxide (GCE/MWNT/NiO) was investigated by cyclic voltammetry and chronoamperometry in alkaline medium. The results were compared with those obtained on a nickel oxide-modified glassy carbon electrode (GCE/NiO). Both the electrodes were conditioned by potential cycling in the range of 0.1–0.6 V versus Ag/AgCl in a 0.10 M NaOH solution. The effects of various parameters such as scan rate, alcohol concentration, thickness of NiO film, and real surface area of the modified electrodes were also investigated and compared. It was found that the GCE/MWNT/NiO-modified electrode possesses an improved electrochemical behavior over the GC/NiO-modified electrode for methanol oxidation.     

A sensitive biosensor for cyanide detection using modified glassy carbon electrode with reduced graphene oxide and immobilization of horseradish peroxidase

Cyanide is a highly poisonous and hazardous substance which may release into the environment from natural sources or industrial effluent; therefore, cyanide detection is a fundamental step to prevent environmental pollution and secure health and safety. In this study, we prepared a sensitive amperometric inhibition biosensor for cyanide detection by immobilization of horseradish peroxidase (HRP) enzyme and reduced graphene oxide (rGO) on the surface of glassy carbon electrode (GCE). To do so, we performed the amperometric measurement by modified GCE to test its efficiency in detecting cyanide. The optimum conditions of pH equal to 7.5, −100 mV applied potential, 0.7 μM mediator concentration, and 0.5 mM substrate concentration were found. Then, experiments were performed at different boundary conditions in a range of 0.1 to 10 μM cyanide concentration at optimal conditions and a low detection limit of 0.01 μM was obtained. Also, the possible mechanism of inhibition was analyzed based on the Michalis–Menten equation and non-competitive inhibition was observed. Due to high sensitivity, low detection limit, and low cost, this biosensor is proposed as a useful method for cyanide determination in real samples.     

银掺杂改性蒙脱土修饰电极测定L-色氨酸的电化学行为

以十八烷基三甲基溴化铵(OTAB)、银氨溶液对蒙脱土掺杂改性制得样品,用作电极修饰的材料。采用XRD、SEM、能谱法和交流阻抗法技术对样品表征,以循环伏安法、方波溶出伏安法探究改性蒙脱土修饰电极上L-色氨酸的电化学行为。结果表明,吸附和扩散对该电化学行为均有影响,反应转移的电子数n与质子数m为1,电极有效面积0.11 cm²,扩散系数1.76×10-5cm2,扩散系数1.76×10-5cm²/s。当CL-色氨酸在9.0×10-72/s。当CL-色氨酸在9.0×10-7⁸.0×10-4mol/L时,其浓度与其氧化峰电流呈线性关系,检出限为6.53×10-7mol/L,加标回收率为94.3%8.0×10-4mol/L时,其浓度与其氧化峰电流呈线性关系,检出限为6.53×10-7mol/L,加标回收率为94.3%¹01.9%。     

银掺杂改性蒙脱土修饰电极测定L-色氨酸的电化学行为

以十八烷基三甲基溴化铵(OTAB)、银氨溶液对蒙脱土掺杂改性制得样品,用作电极修饰的材料。采用XRD、SEM、能谱法和交流阻抗法技术对样品表征,以循环伏安法、方波溶出伏安法探究改性蒙脱土修饰电极上L-色氨酸的电化学行为。结果表明,吸附和扩散对该电化学行为均有影响,反应转移的电子数n与质子数m为1,电极有效面积0.11 cm~2,扩散系数1.76×10-5cm~2/s。当CL-色氨酸在9.0×10-7~8.0×10-4mol/L时,其浓度与其氧化峰电流呈线性关系,检出限为6.53×10-7mol/L,加标回收率为94.3%~101.9%。     

Electrochemical determination of methyl parathion using poly(malachite green)/graphene nanosheets–nafion composite film-modified glassy carbon electrode

A novel poly(malachite green)/graphene nanosheets–nafion (PMG/GNs–NF) composite film-modified glassy carbon electrode was developed to indirectly detect methyl parathion (MP). p-nitrophenol, the alkaline hydrolysis product of MP, was successfully determined at a relatively lower potential using this modified electrode due to the excellent electrocatalytic activity of PMG/GNs–NF composite film. The presence of GNs in the composite film enhanced the stability of PMG and increased the electron transfer rate. The kinetic parameters of modified electrodes were studied. What is more, the optimum experimental parameters affecting response were selected in terms of pH, accumulation potential, accumulation time, scanning cycles during polymerization of malachite green, and alkaline hydrolysis conditions. Under optimum conditions, the chronoamperometric response current was proportional to MP concentration over the range from 0.02 to 1.5 μM with a low-detection limit of 2.0 nM. Finally, the sensor was applied for the determination of MP in real samples, and the results were satisfactory with recoveries from 97.20 to 104.53 %. Due to its simple preparation, good reproducibility, and stability, this developed modified electrode provides a new platform for the detection of organophosphate pesticides.     

Voltammetric determination of paracetamol at C60-modified glassy carbon electrode

Voltammetric determination of paracetamol was carried out at C₆₀-modified glassy carbon electrode, which showed stable response with enhanced selectivity and sensitivity. Limitations of conventional methods, viz., hydrolysis time and interference were also overstepped. Common biological and chemical interferents do not show significant interference in a wide concentration range. A linear calibration plot having correlation coefficient 0.985 was obtained in the range 0.05-1.5 mM paracetamol concentration and the sensitivity of the method has been found as 13.04 μA mM⁻¹. Sweep rate studies indicated that electrode reaction is followed by follow-up chemical reactions. Method described is rapid and has been applied for the determination of paracetamol in different tablets and urine samples with several advantages over other analytical methods. The standard deviation (S.D.) was 5.53% for eight determinations.     

Electrochemical study on cobalt film modified glassy carbon electrode and its application

A novel electroactive material for ascorbic acid (AA) determination was successfully prepared by plating/potential cycling method. The cobalt film was first deposited on the surface of glassy carbon electrode (GCE) in CoSO₄ solution by potential cycling, and then a cobalt film on the surface of GCE was activated by potential cycling in 0.1 mol L⁻¹ NaOH. The electrochemical performance of the resulted film (Co/GCE) and factors affecting its electrochemical activity were investigated by cyclic voltammetry and amperometry. This film electrode exhibited good electrocatalytic activity to the oxidation of AA. This biosensor had a fast response of AA less than 3 s and excellent linear relationships were obtained in the concentration range of 3 × 10⁻⁷ to 1 × 10⁻⁴ mol L⁻¹ with a detection limit of 2 × 10⁻⁷ mol L⁻¹ (S/N = 3) under the optimum conditions. Moreover, the selectivity, stability and reproducibility of this biosensor were evaluated with satisfactory results.