聚亚甲基蓝修饰金电极对抗坏血酸电催化氧化及其电分析方法研究

研究了亚甲基蓝(methylene blue,MB)聚合物膜修饰金电极(PMB/Au)的制备及其性质,通过电化学阻抗谱图对PMB/Au进行了表征,并对抗坏血酸(ascorbic acid,AA)在PMB/Au上的电化学行为进行了研究。结果表明,PMB/Au对AA的氧化具有良好的电催化作用,使AA的过电位降低约200 mV,氧化峰电流明显增大。测得AA在PMB/Au上的电荷转移系数为0.70,催化反应速率常数为5.99×103mol-1.L.s-1。用方波伏安法(Square Wave Voltammetry,SWV)测得氧化峰电流与AA浓度在2.0×10-5~6.0×10-3mol/L范围内呈良好线性关系,检出限为1.0×10-5mol/L。将PMB/Au应用于Vc片剂和Vc注射液中AA的测定。     

Nickel pentacyanonitrosylferrate film modified aluminum electrode for electrocatalytic oxidation of hydrazine

The electrocatalytic oxidation of hydrazine at the aluminum electrode, modified by electroless deposition of nickel pentacyanonitrosylferrate (NiPCNF) on the surface of the electrode has been studied by cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry and the kinetics of the catalytic reaction were investigated. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. It was found that a one-electron charge-transfer process is rate limiting and that the average values of the rate constant for the catalytic reaction and the diffusion coefficient, evaluated by different approaches, are 5.2×10³ M^–1s^–1 and 8.5×10^–6 cm²s^–1, respectively. Further examinations of the modified electrodes show that the modifying layers (NiPCNF) on the aluminum substrate have reproducible behavior and a high level of stability, after exposing them in air and hydrazine solutions for a long time. Electronic Publication     

Caffeic acid modified glassy carbon electrode for electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH)

A new modified electrode was prepared by electrodeposition of caffeic acid (CFA) at the surface of an activated glassy carbon electrode. Cyclic voltammetry was used to investigate the redox properties of this electrode at various solution pH values and at various scan rates. The pH dependence of the electrode response was found to be 58.5 mV/pH, which is very close to the expected Nernstian value. The electrode was also employed to study electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH), using cyclic voltammetry, chronoamperometry and rotating disk voltammetry as diagnostic techniques. It was found that the modified electrode exhibits potent and persistent electrocatalytic properties toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 450 mV compared to the process at an unmodified electrode. The electrocatalytic current increases linearly with NADH concentration in the range tested from 0.05 to 1.0 mM. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized CFA were calculated as 11.2 s⁻¹ and 0.43, respectively. The heterogeneous rate constant for oxidation of NADH at the CFA-modified electrode surface was also determined and found to be about 3 × 10³ M⁻¹ s⁻¹. Finally, the diffusion coefficient of NADH was calculated as 3.24 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometric results. Received: 6 January 1999 / Accepted: 11 May 1999     

肉桂酸修饰电极同时测定多巴胺和抗坏血酸的研究

用电化学聚合方法制备肉桂酸(CA)修饰的玻碳电极(PCA/GC),研究多巴胺(DA)和抗坏血酸(AA)在修饰电极上的电化学行为.结果表明,在DA和AA共存体系中,DA、AA在PCA/GC电极上氧化峰电流增大且氧化峰电位相差200 mV,据此可同时检测DA和AA.在pH 7.0磷酸盐缓冲液中,DA和AA的氧化峰电流与其浓...     

聚对氨基酚修饰电极的制备及其对尿酸的催化氧化作用

采用循环伏安法制备了聚对氨基酚薄膜修饰玻碳电极, 研究了尿酸在该修饰电极上的电化学行为, 建立了循环伏安法测定尿酸的新方法. 研究发现: 在pH 5.6的磷酸盐缓冲溶液中, 以0.1 mol/L KCl作支持电解质, 聚对氨基酚修饰电极对尿酸存在灵敏的氧化作用, 应用循环伏安法对尿酸进行定量分析, 线性范围为1.0×10-6～4.0×10-5 mol/L, 检出限为8×10-7 mol/L. 对2.0×10-5 mol/L尿酸平行测定5次, 相对标准偏差为4.0%.     

甲苯胺蓝修饰电极的电化学性质及对抗坏血酸的测定

研究了甲苯胺蓝(TB)聚合膜修饰金电极的制备及其电化学性质,并用于抗坏血酸(AA)的测定。在pH 6.5的磷酸盐缓冲溶液中,AA在甲苯胺蓝修饰金电极上产生一灵敏的氧化峰,峰电流与AA的浓度在3.9×10-5~1.0×10-2mol/L范围内呈良好的线性关系,检出限为1.3×10-5mol/L。该电极重现性良好,已用于实际样品中AA的测定。     

抗坏血酸在普鲁士蓝修饰的丝网印刷电极上的电催化氧化

制备了普鲁士蓝修饰的丝网印刷电极,研究了该修饰电极对抗坏血酸的催化氧化作用。在pH5.0的0.2mol/L磷酸盐缓冲溶液中,修饰电极对抗坏血酸显示出快速的电化学响应,较高的稳定性、重现性和催化活性,测定的线性范围为5.0×10-6～8.0×10-3mol/L,相关系数为0.998,检出限为3.0×10-6mol/L(3σ)。已对实际样品进行了测定。     

Simultaneous determination of tryptophan, uric acid and ascorbic acid at iron(III) doped zeolite modified carbon paste electrode

A new chemically modified electrode is constructed based on iron(III) doped zeolite modified carbon paste electrode (Fe(3+)Y/ZCME). The electrode was evaluated as a sensor for sub-micromolar determination of tryptophan (Trp), uric acid (UA) and ascorbic acid (AA) in aqueous solutions. The measurements were carried out by application of the differential pulse voltammetry (DPV) method in phosphate buffer solution with pH 3.5. Iron(III) loaded in zeolite can increase anodic peak currents by adsorption of Trp, UA and AA on electrode surface The analytical performance was evaluated with respect to the carbon paste composition, pH of solution, accumulation time and accumulation potential. The prepared electrode shows voltammetric responses with high sensitivity and selectivity for Trp, UA and AA in optimal conditions, which makes it very suitable for simultaneous determination of these compounds. The linear calibration range for AA in the presence of 50muM UA and 50muM Trp was 0.6muM to 100muM, with a correlation coefficient of 0.9992, and a detection limit of 0.21muM (S/N=3). A linear relationship was found for UA in the range of 0.3-700muM containing 10muM AA and 50muM Trp, with a correlation coefficient of 0.9990 and a detection limit of 0.08muM. The linear calibration range for Trp in the presence of 10muM AA and 50muM UA was 0.2-150muM, with a correlation coefficient of 0.9996, and a detection limit of 0.06muM. The proposed method was successfully applied for determination Trp, UA and AA in biological systems and pharmaceutical samples.     

A simple click generated probe for highly selective sequential recognition of Cu(II) and pyrophosphate

A click generated quinoline derivative (1) has been synthesized and used as a fluorescent probe for sequential recognition of Cu²⁺ and pyrophosphate (PPi) in DMSO/H₂O (1:1, v/v, HEPES 20 mM, pH = 7.4) solution. Probe 1 displays high selectivity to Cu²⁺ ions, and the in-situ prepared probe 1-Cu²⁺ exhibits high selectivity toward pyrophosphate (PPi) with emission recovery of probe 1. Therefore, 1-Cu²⁺ complex can be applied as a fluorescence turn-on probe for PPi with high selectivity and sensitivity.     

An EPR study of Cu doped diaquabis(nicotinamide)bis(o-sulfobenzimidato-N)-cadmium(II) single crystals

The electron paramagnetic resonance spectra of Cu²⁺ doped diaquabis(nicotinamide)bis(o-sulfobenzimidato-N)-cadmium(II) (hereafter, CdNAS) single crystals which were taken at room temperature are discussed. It was found from the analysis of the EPR data that the Cu²⁺ ions substitute for magnetically inequivalent Cd²⁺ ions. Two magnetically inequivalent Cu²⁺sites were observed. The principal values of the g and the hyperfine tensors were determined. The ground state wave functions of the unpaired electron of Cu²⁺ ions in two sites were constructed and type of the distortion was determined.     

Highly selective ratiometric fluorescent sensor for Cu(II) with two urea groups

A new Naphthalene derivative with two urea groups, 1,8-bis[N-(o-methoxyphenyl)ureido]naphthalene (BMPUN), was synthesized for detecting Cu(II) ratiometrically. Complexation between urea groups of BMPUN and Cu(II) with high selectivity gives rise to a great red-shift from 380 to 440 nm in the emission spectra. The introduction of electron donating groups is helpful to increase the electron density of the nitrogen atom of urea groups and then enhance the ability of complexation for Cu(II).     

Construction of a new Cu2+ coated wire ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylidene amino)phenyl)disufanyl)phenylimino)methyl)-4-methoxyphenol Schiff base

In this article a new coated platinum Cu²⁺ ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylideneamino)phenyl)disufanyl)phenylimino) methyl)-4-methoxyphenol Schiff base (L₁) as a new ionophore is described. This sensor has a wide linear range of concentration (1.2 × 10⁻⁷-1.0 × 10⁻¹ mol L⁻¹) and a low detection limit of 9.8 × 10⁻⁸ mol L⁻¹of Cu(NO₃)₂. It has a Nernstian response with slope of 29.54 ± 1.62 mV decade⁻¹ and it is applicable in the pH range of 4.0-6.0 without any divergence in potentioal. The coated electrode has a short response time of approximately 9 s and is stable at least for 3.5 months. The electrode shows a good selectivity for Cu²⁺ ion toward a wide variety of metal ions. The proposed sensor was successfully applied for the determination of Cu²⁺ ion in different real and environmental samples and as indicator electrode for potentiometric titration of Cu²⁺ ion with EDTA.     

嵌入式超薄化学修饰碳糊电极及抗坏血酸的电化学行为研究

以镍铬合金为基体,在其表面构建了嵌入式超薄邻啡口罗啉修饰碳糊电极,以扫描电镜表征电极形貌、电化学技术研究电极的电化学性质。该电极对抗坏血酸(AA)有灵敏的响应,在pH 2.0的B.R.缓冲溶液中,AA的氧化峰电流与其浓度在1.0×10-7~1.0×10-4mol/L范围内呈良好的线性关系,检出限为6.0×10-8mol/L。该电极可用于AA的电化学测量。     

聚中性红/纳米二氧化硅复合修饰电极直接测定抗坏血酸

用滴涂法和电化学聚合法制备了聚中性红/纳米二氧化硅修饰电极(PNR/nano-SiO2/GCE),并用循环伏安法和交流阻抗法研究了修饰电极表面的电化学行为。实验表明,该修饰电极对抗坏血酸(AA)表现出良好的电催化氧化性能,探讨了复合修饰电极协同增效作用的机理。用线性扫描伏安法研究了AA浓度与峰电流之间线性关系,在pH2.0的磷酸盐缓冲溶液中,AA氧化峰电流在1.8×10-6～5.0×10-3mol/L浓度范围内呈良好的线性关系,检出限为5.4×10-7mol/L(S/N=3)。该修饰电极制备简单,可用于药品及果蔬食品中抗坏血酸的直接测定。     

Application of artificial neural network to simultaneous potentiometric determination of silver(I), mercury(II) and copper(II) ions by an unmodified carbon paste electrode

The response characteristics and selectivity coefficients of an unmodified carbon paste electrode (CPEs) towards Ag⁺, Cu²⁺ and Hg²⁺ were evaluated. The electrode was used as an indicator electrode for the simultaneous determination of the three metal ions in their mixtures via potentiometric titration with a standard thiocyanate solution. A three-layered feed-forward artificial neural network (ANN) trained by back-propagation learning algorithm was used to model the complex non-linear relationship between the concentration of silver, copper and mercury in their different mixtures and the potential of solution at different volumes of the added titrant. The network architecture and parameters were optimized to give low prediction errors. The optimized networks were able to precisely predict the concentrations of the three cations in synthetic mixtures.     

A selective voltammetric detection for dopamine using poly (gallic acid) film modified electrode

<正>The electrochemistry behavior of dopamine was investigated by cyclic voltammetry and differential pulse voltammetry at a poly (gallic acid) film modified glassy carbon electrode.Two electrons and two protons participated in the diffusion-controlled electrocatalytic oxidation of dopamine with a diffusion coefficient of 2.186×10~(-5) cm~2/s.The interference of ascorbic acid with the determination of dopamine could be efficiently eliminated.This work provided a simple approach to selectively and sensitively detect dopamine in the presence of high concentration of ascorbic acid.     

Cu(II)-triggered release of paclitaxel from a supramolecular complex

The research on the stimuli-responsive property of biological or synthetic macromolecules in a wide range of scientific fields is a crucial subject for the achievements of the targeted drug release and the precise control of the functions of the supramolecules at a molecular level. We used an anthraquinone-functioned cyclodextrin (1) bridged by an aza-arm to solubilise paclitaxel (PTX) by forming a supramolecular complex (1/PTX). The possible inclusion mode was given based on the experimental results of ultraviolet–visible spectroscopy, Fourier transform infrared, X-ray diffraction, fluorescence spectra, nuclear magnetic resonance, transmission electron microscope, scanning electron microscope and dynamic light scattering characterisations. The controlled release of PTX can be achieved by adding Cu²⁺ to the solution. This study provides useful references in developing stimuli-responsive drug-carrying and drug-releasing materials.     

EPR studies of Cu2+ in tetraaqua-di(nicotinamide) Zn(II)-saccharinate single crystals

Electron paramagnetic resonance (EPR) studies of copper ions, Cu(II), as paramagnetic impurity in tetraaqua-di(nicotinamide) Zn(II)-saccharinates single crystals [Zn(nic)2(H2O)4](sac)2, have been investigated at ambient temperature. The detailed EPR analysis shows the only one site and the copper ion entered the lattice substitutionally in place of Zn(II). The spin-Hamiltonian parameters were obtained from the single crystal EPR analysis. By using the EPR data, molecular bonding coefficient and the Fermi contact interaction terms have been evaluated. Superhyperfine splittings were observed.     

Fabrication of a template-synthesized gold nanorod-modified electrode for the detection of dopamine in the presence of ascorbic acid

Gold nanorods (GNRs) with suitable aspect ratio were synthesized with a template technique and then dispersed in a saturated sodium citrate solution by ultrasonication to form a GNR suspension. A GNR-modified electrode was fabricated using the GNR suspension. The oxidation of dopamine at the GNR/GC electrode exhibited surprisingly high electrocatalytic activity and adsorption-controlled characteristics. Square-wave voltammetry was used to detect dopamine. At the GNR/GC electrode, the linear concentration range of DA is from 1 × 10⁻⁸ M to 1 × 10⁻⁷ M and the detection limit (s/n = 3) is as low as 5.5 × 10⁻⁹ M. The current sensitivity is 3.280 μA/μM, and 1000-fold ascorbic acid (AA) cannot interfere with the determination of DA. All these performances are greatly superior to those of the bare GC electrode.     

Flow-injection analysis of glucose without enzyme based on electrocatalytic oxidation of glucose at a nickel electrode

This paper reports a flow-injection analysis (FIA) of glucose not using enzyme based on the electrocatalytic oxidation of glucose at a nickel electrode. The electrocatalytic mechanism and quantificational method of glucose have been investigated. The current intensity of the electrocatalytic oxidation to glucose at the potential of 550 mV is proportional to the concentration of glucose over the range of 0.10-2.50 mmol l⁻¹, with a 0.04 mmol l⁻¹ detection limit (S/N = 3) and a correlation coefficient of 0.9991. The relative standard deviation (R.S.D.) is less than 4.3% (n = 5) for the determination of practical serum samples. The biologic compounds probably existed in the sample, such as ascorbic acid, uric acid, dopamine and epinephrine, do not disturb the determination of glucose. The result is satisfactory for the determination of glucose in human serum sample as comparison to that from the routine hexokinase method.