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。     

Electrocatalytic oxidation of ascorbic acid and voltammetric determination with a ferrocene-modified platinum electrode

Ferrocene attached to the surface of a platinum electrode catalyses the electrochemical oxidation of ascorbic acid in acidic buffer solutions. The overpotential for ascorbic acid oxidation is decreased by 150 mV at pH 2.2 compared with reaction at bare platinum; and an increase in anodic current and decrease in cathodic current for the redox reaction of ferrocene occurs on addition of ascorbic acid to the solution. The ferrocene-modified electrode is useful for the voltammetric determination of ascorbic acid in natural fruit juices. The advantages result from the electrocatalytic effect and from the prevention of adsorption of inhibitory substances from solution.     

去甲肾上腺素和抗坏血酸在导电聚合物膜修饰电极上的同时测定

采用循环伏安法研究去甲肾上腺素(NE)和抗坏血酸(AA)在4-(2-吡啶偶氮)间苯二酚(PAR)导电聚合膜修饰电极上的电化学行为;以差示脉冲伏安法(DPV)对二者进行测定,发现PAR修饰电极对NE和AA有很强电催化作用,明显增强了电极反应的可逆性及峰电流。在pH 6.0磷酸盐缓冲液(PBS)中,NE氧化峰电流与其浓度在6.25×10-7~6.25×10-5mol/L范围内呈良好的线性关系,AA氧化峰电流与其浓度在1.0×10-6~3.0×10-4mol/L范围内呈良好的线性关系,检出限分别为5.0×10-8mol/L和5.0×10-7mol/L。该PAR膜修饰电极可对NE和AA进行单独或同时的测定,并用于实际样品重酒石酸去甲肾上腺素针剂和维生素C针剂的检测。     

Electrocatalytic oxidation and flow-injection determination of sulfur amino acids on a glassy carbon electrode modified by a nickel(II) polytetrasulfophthalocyanine film

The electrochemical oxidation of sulfur amino acids, i.e., cysteine, cystine, and methionine, is studied on a glassy carbon electrode modified by a film of nickel(II) polytetrasulfophthalocyanine (poly-NiTsPc). Poly-NiTsPc demonstrates a selective mediator activity in the oxidation of sulfur amino acids, depending on the pH of solution. The proper conditions for fabricating a polymer film on the surface of glassy carbon are found and the conditions of registering the maximal electrocatalytic effect on the modified electrode are determined. A procedure is proposed for the voltammetric determination and amperometric detection of cysteine, cystine, and methionine on an electrode coated by a poly-NiTsPc film under the conditions of flow-injection analysis (FIA). The linear relation of the electrocatalytic response of a composite electrode to amino acid concentration is observed to the level n × 10^?6 M in the static mode and n × 10^?9 M under FIA conditions.     

Electrocatalytic determination of ascorbic acid on a glassy carbon electrode chemically modified with cobalt pentacyanonitrosylferrate.

An electrochemically prepared thin film of cobalt pentacyanonitrosylferrate (GC/CoPCNF) was used as a surface modifier for glassy carbon electrodes. The oxidation of ascorbic acid on a glassy carbon electrode modified with GC/CoPCNF as a working electrode was studied using cyclic voltammetry, rotating disk electrode (RDE) voltammetry and chronoamperometry in a 0.25 M KNO3 + 0.25 M phosphate buffer (pH 7) solution. The glassy carbon modified with CoPCNF showed good electrocatalytic activity toward ascorbic acid oxidation. The kinetics of the catalytic reaction was investigated, and the average value of the rate constant (k) for the catalytic reaction and the diffusion coefficient (D) were evaluated by different approaches for ascorbic acid, and were found to be 3.3 +/- 0.3 x 10(2) M(-1) s(-1) and 3.2 +/- 0.3 x 10(-6) cm2 s(-1), respectively.     

Electrochemical oxidation of dopamine and ascorbic acid at a palladium electrode modified with in situ fabricated iodine-adlayer in alkaline solution

The self-assembled iodine-adlayer was fabricated at the palladium (Pd) electrode surface throughout a spontaneous oxidative chemisorption of iodide ions contained in an alkaline supporting electrolyte. It enhances the electron transfer kinetics for the oxidation of dopamine (DA) and ascorbic acid (AA) and was important to separate the peak current of both species with a practical potential difference compared with that occurred at the unmodified electrode. The anodic peak currents of both species were linearly increased with their respective concentrations using linear square stripping voltammetry. The activity of the electrode system was further investigated applying chronoamperometry method. The steady-state amperometric signal for the oxidation of DA in the presence of iodide ions was five times greater than that in its absence. The current-time response was also used to evaluate the diffusion coefficient of DA based on Cottrell plot that results with a value of 4.19 × 10⁻⁸ m² s⁻¹. The proposed method was successfully applied to detect DA and AA in human serum.     

壳聚糖修饰电极上的铁氰根离子对抗坏血酸的电催化氧化作用

在玻碳电极表面滴涂一层壳聚糖膜 ,壳聚糖分子中 -NH2 在酸性溶液中发生质子化 ,靠静电引力作用吸附富集荷负电的电子介体Fe(CN) 63 -,使其固定在电极表面 ,研究了此Fe(CN) 63 - 壳聚糖 GC修饰电极对抗坏血酸的催化氧化作用。抗坏血酸的浓度在 3.0× 1 0 -6～ 5 .0× 1 0 -3 mol L范围内呈很好的线性关系 ,相关系数为 0 .998,检测限达 1 .0× 1 0 -6mol L。该法已用于测定蔬菜中抗坏血酸的含量。     

Electrocatalytic oxidation of uric acid at an electrodeposited redox polymer film-modified gold electrode

A hydrated osmium complex-containing redox polymer film-modified gold electrode based on electrochemical cross-linking was developed. The amount and the characteristics of redox polymer film cross-linked on the gold electrode were investigated by using electrochemical quartz crystal microbalance (EQCM). The redox polymer film exhibited a strong electrocatalytic activity toward the oxidation of uric acid with a lowering of the overpotential by about 230 mV and a large increase in the magnitude of the oxidation peak current. Based on this procedure, an amperometric method for the determination of uric acid concentration was proposed.     

甲醛在脯氨酸膜修饰电极上的电催化氧化

应用电化学法和光谱电化学法研究了脯氨酸膜修饰电极的制备 ,用循环伏安法探讨了该膜的电化学性质及其对甲醛的催化氧化 .该电极催化稳定性良好 ,在NaOH溶液中 ,掺杂Ni (Ⅱ )后的脯氨酸膜修饰电极对甲醛和乙醇的氧化均有一定的催化活性 ,但对甲醛的催化活性更佳     

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。     

Electrocatalytic oxidation of thiosulfate on a modified nickel hexacyanoferrate film electrode

Summary A modified nickel hexacyanoferrate film glassy carbon electrode is prepared by the electrochemical deposition technique. The film is very stable upon voltammetric scanning in the potential range of 1.0 to –0.5 V (vs. SCE) and an oxidation peak occurs at 0.35 V (vs. SCE) (1 mol/l NaNO₃). The effects of electrolyte, solvent, coexisting ions and other variables on the voltammetric behaviour of the modified film have been studied. The thickness of the resulting film can be controlled by changing the number of voltammetric cycles and the concentrations of nickel(II) and hexacyanoferrate(III) ions. The film shows catalytic activity towards electrooxidation of thiosulfate with a peak potential +0.5 V (K^–-containing media). This oxidation potential of thiosulfate on the modified electrode is shifted negatively by about 550 mV as compared to the naked glassy carbon electrode. For practical application, the modified electrode can be used for the determination of thiosulfate in concentrations from 5.0×10^–5 to 1.0×10^–1 mol/l. This method has been successfully applied to the determination of thiosulfate in photographic waste effluents.     

单分子聚苯胺膜电极上抗坏血酸的线性扫描催化氧化波研究

在苯胺浓度为1.0mol.dm^-^3的盐酸溶液中用电化学聚合法制得单分子聚苯胺膜电极。在该修饰电极上, 抗坏血酸在0.01mol.dm^-^3盐酸底液中有一线性扫描催化氧化波, 其峰电位为+0.270V(vs.SCE), 峰电流与抗坏血酸浓度在10^-^2～10^-^5mol.dm^-^3范围内呈线性关系。文中详细地探讨了该波的性质, 证实它是一个不可逆波, 并且测定了αAn, ks, DR值。     

Fabrication of multiwalled carbon nanotubes/polyaniline modified Au electrode for ascorbic acid determination

An ascorbate oxidase (AsOx) (E.C.1.10.3.3) purified from Lagenaria siceraria fruit was immobilized covalently onto a carboxylated multiwalled carbon nanotubes and polyaniline (c-MWCNT/PANI) layer electrochemically deposited on the surface of an Au electrode. The diffusion coefficient of ascorbic acid was determined as 3.05 × 10(-4) cm(2) s(-1). The behavior of different electrolytes on electro-deposition was also studied. An ascorbate biosensor was fabricated using a AsOx/c-MWCNT/PANI/Au electrode as a working electrode, Ag/AgCl (3 M/saturated KCl) as standard and Pt wire as an auxiliary electrode connected through a potentiostat. Linear range, response time and detection limit were 2-206 μM, 2 s and 0.9 μM respectively. The biosensor showed optimum response at pH 5.8 and in a broader temperature range (30-45 °C), when polarized at +0.6 V. The biosensor was employed for determination of ascorbic acid level in sera, fruit juices and vitamin C tablets. The sensor was evaluated with 91% recovery of added ascorbic acid in sera and 6.5% and 11.4% within and between batch coefficients of variation respectively for five serum samples. There was a good correlation (r = 0.98) between fruit juice ascorbic acid values by the standard 2,6-dichlorophenolindophenol (DCPIP) method and the present method. The enzyme electrode was used 200 times over a period of two months, when stored at 4 °C. The biosensor has advantages over earlier enzyme sensors in that it has no leakage of enzyme, due to the covalent coupling of enzyme with the support, lower response time, wider working range, higher storage stability and no interference by serum substances.     

Amperometric determination of ascorbic acid at a novel ‘self-doped’ polyaniline modified microelectrode

A ‘self-doped’ polyaniline modified microelectrode, prepared by cyclic potential sweep on a microdisk gold electrode from –0.2 to 0.85 V in 0.5 mol/L sulfuric acid containing aniline and o-aminobenzoic acid, has been developed. The copolymerized process and the resulting polymer characteristics were investigated in detail. This composite film indicated a good electrochemical activity in a wide pH range even in basic solution. Meanwhile, the redox couple exhibited an excellent electrocatalytic activity for the oxidation of ascorbic acid. The oxidation overpotential of ascorbic acid was decreased over 200 mV at this modified electrode compared with a bare gold one. Moreover, the effects of film thickness and pH on the catalytic efficiency were further studied. The dependence of catalytic currents on the concentration of ascorbic acid was linear in the range of 1.2 × 10^–5∼ 2.4 × 10^–3 mol/L with a correlation coefficient of 0.996. Also, the determination of ascorbic acid in actual samples was evaluated and the results are satisfactory. Received: 7 October 1997 / Revised: 3 February 1998 / Accepted: 7 February 1998     

Amperometric determination of ascorbic acid at a novel ‘self-doped’ polyaniline modified microelectrode

A ‘self-doped’ polyaniline modified microelectrode, prepared by cyclic potential sweep on a microdisk gold electrode from –0.2 to 0.85 V in 0.5 mol/L sulfuric acid containing aniline and o-aminobenzoic acid, has been developed. The copolymerized process and the resulting polymer characteristics were investigated in detail. This composite film indicated a good electrochemical activity in a wide pH range even in basic solution. Meanwhile, the redox couple exhibited an excellent electrocatalytic activity for the oxidation of ascorbic acid. The oxidation overpotential of ascorbic acid was decreased over 200 mV at this modified electrode compared with a bare gold one. Moreover, the effects of film thickness and pH on the catalytic efficiency were further studied. The dependence of catalytic currents on the concentration of ascorbic acid was linear in the range of 1.2 × 10^–5～ 2.4 × 10^–3 mol/L with a correlation coefficient of 0.996. Also, the determination of ascorbic acid in actual samples was evaluated and the results are satisfactory.     

Electrocatalytic oxidation of methanol on Ni modified polyaniline electrode in alkaline medium

Electrolytically deposited Ni on polyaniline film covered carbon paste electrode (Ni/PANI/CPE) was used as anode for the electrooxidation of methanol in alkaline medium. The electrochemical behavior and electrocatalytic activity of the electrode were studied using cyclic voltammetry, impedance spectroscopy, chronomethods, and polarization studies. The morphology and composition of the modified film were obtained using scanning electron microscope and energy dispersive X-ray analysis techniques. The electrooxidation of methanol in NaOH was found to be more efficient on Ni/PANI/CPE than on bare Ni, electrodeposited Ni on Pt, Ni on glassy carbon, and Ni on CPE substrates. Partial chemical displacement of dispersed Ni on PANI with Pt or Pd further improved its performance towards methanol oxidation.     

Electrocatalytic oxidation and sensitive determination of l-cysteine at a poly(aminoquinone)-carbon nanotubes hybrid film modified glassy carbon electrode

A matrix removal procedure has been developed for the determination of trace elements, including As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, Tl, Zn and V, in siliceous materials by inductively coupled plasma mass spectrometry (ICP-MS). Soil and sediment samples were dissolved in a mixture of HNO₃ and HF in sealed vessels by using a microwave oven. Silicon matrix in the solutions was precipitated as sparingly soluble sodium fluorosilicate (Na₂SiF₆) by adding 0.5 mL of 300 mg mL⁻¹ NaCl solution. Simultaneous precipitation of sodium and silicon was achieved in highly acidic solutions containing 30–40% (v/v) HNO₃. A mixture of methanol and nitric acid afforded back-extraction of the trace elements without significant dissolution of the Na₂SiF₆. Samples were analyzed by ICP-MS for trace elements and residual silicon. Calibration was made by aqueous multi-element standard solutions. Up to 95% of the silicon was successfully removed yielding solutions suitable for introduction to ICP-MS. The method was validated by analysis of two NIST certified reference materials; SRM 2711 (Montana Soil) and SRM 2704 (Buffalo River Sediment). Accurate results were obtained for all elements, including those for As, Hg and Se that suffer from losses due to the presence of their volatile species when silicon was converted to volatile SiF₄ via heat-assisted evaporation to dryness. The recoveries from the SRM samples varied between 80% (Cr) and 109% (Hg). No significant interferences were observed from molecular ions of chloride and residual sodium on ⁷⁵As, ⁶³Cu, ⁶⁰Ni, ⁷⁷Se and ⁵¹V. Correspondence: Zikri Arslan, Department of Chemistry, Jackson State University, Jackson, MS 39217, USA     

A glassy carbon electrode modified with a polyaniline doped with silicotungstic acid and carbon nanotubes for the sensitive amperometric determination of ascorbic acid

We report on an electrochemical sensor for the sensitive amperometric determination of ascorbic acid (AA). Aniline containing suspended silicotungstic acid and carbon nanotubes was electropolymerized on the surface of a glassy carbon electrode in a single step which provides a simple and controllable method and greatly improves the electrocatalytic oxidation of AA. The effects of scan rate, solution pH and working potential were studied. A linear relationship exists between the current measured and the concentration of AA in the range from 1 μM to 10 μM and 0.01 mM to 9 mM, with a limit of detection as low as 0.51 μM (S/N?=?3). The sensor is selective, stable and satisfyingly reliable in real sample experiments. In our eyes, it has a large potential for practical applications.

Simultaneous determination of uric acid and ascorbic acid at the film of chitosan incorporating cetylpyridine bromide modified glassy carbon electrode

A glassy carbon electrode (GCE) modified with the film composed of chitosan incorporating cetylpyridine bromide is constructed and used to determine uric acid (UA) and ascorbic acid (AA) by differential pulse voltammetry (DPV). This modified electrode shows efficient electrocatalytic activity and fairly selective separation for oxidation of AA and UA in mixture solution. UA is catalyzed by this modified electrode in phosphate buffer solution (pH 4.0) with a decrease of 80 mV, while AA is catalyzed with a decrease of 200 mV in overpotential compared to GCE, and the peak separation of oxidation between AA and UA is 260 mV, which is large enough to allow the determination of one in presence of the other. Under the optimum conditions, the anodic peak currents (I _pa) of DPV are proportional to the concentration of UA in the range of 2.0 × 10⁻⁶ to 6.0 × 10⁻⁴ M, with the detection limit of 5.0 × 10⁻⁷ M at a signal-to-noise ratio of 3 (S/N = 3) and to that of AA in the range of 4.0 × 10⁻⁶ to 1.0 × 10⁻³ M, with the detection limit of 8.0 × 10⁻⁷ M (S/N = 3).