抗坏血酸在聚阿魏酸修饰玻碳电极上的电化学行为研究

研究了抗坏血酸(AA)在聚阿魏酸修饰电极上的电化学性质。在AA存在的条件下,电极过程由扩散控制,测得扩散系数为8.18×10-8cm2/s。AA浓度在0.01~5.0 mmol/L范围内与峰电流呈现良好的线性关系。通过计时安培法测得催化速率常数为8.6×103mol-1.L.s-1。     

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au_nano-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10 nm. Electrochemical behavior of the PAT-Au_nano-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au_nano-ME exhibits two well defined anodic peaks at the potential of 75 and 400 mV for the oxidation of AA and DA, respectively with a potential difference of 325 mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au_nano-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au_nano-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.     

Simultaneous voltammetric determination of ascorbic acid and dopamine at the surface of electrodes modified with self-assembled gold nanoparticle films

Gold nanoparticles (GNs) could be efficiently immobilized on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol and 1-octanethiol (nano-Au/SAMs gold electrode). This GN chemically modified electrode was used for electrochemical determination of ascorbic acid (AA) and dopamine (DA) in aqueous media. The result showed that the GN-modified electrode could clearly resolve the oxidation peaks of AA and DA, with a peak-to-peak separation (∆E _p) of 110 mV enabling determination of AA and DA in the presence of each other. The linear analytical curves were obtained in the ranges of 0.3–1.4 mM for AA and 0.2–1.2 mM for DA concentrations using differential pulse voltammetry. The detection limits (3σ) were 9.0 × 10⁻⁵ M for AA and 9.0 × 10⁻⁵ M for DA.     

Accumulation and stripping behavior of silver ions at dl-dithiothreitol self-assembled monolayer modified gold electrodes

Silver ions can be entrapped at the dl-dithiothreitol (HSCH₂(CHOH)₂CH₂SH, DTT) self-assembled monolayer films modified gold electrodes. When the potential was made moving, an anodic peak was observed at about 0.23 V (vs. SCE). When the electrode Au/DTT was modified with dodecyl mercaptan further, more Ag (I) can be accumulated and the peak grows. Conditions, such as solution pH and supporting electrolyte, were optimized for Ag (I) determination. Under the selected conditions, i.e. 0.010 M pH 4.3 potassium hydrogen phthalate, preconcentration time of 5 min at open circuit, the anodic peak height is linear to the concentration of Ag (I) in the small range of 0.6-2.4 μM. The influence of some ions on the determination of Ag (I) was examined. The Br⁻ ion makes the peak decrease and NCS⁻ makes the peak increase. But the determination is not interfered by 1000-fold Pb²⁺, Cd²⁺, Hg²⁺, Fe³⁺, Ni²⁺, Co²⁺, Cu²⁺ and Sn²⁺ when EDTA was added into the solution. The mechanism involved was discussed.     

纳米铜修饰电极对多巴胺和抗坏血酸的同时测定

用电沉积方法制备了纳米铜修饰电极并将其用于混合溶液中多巴胺(DA)和抗坏血酸的同时测定。在优化的实验条件下,修饰电极对多巴胺和抗坏血酸具有良好的电催化响应,多巴胺的峰电流与浓度在8.0×10-7mol/L~1.0×10-4mol/L范围内成很好的线性关系,抗坏血酸的氧化峰电流与其浓度在8.0×10-6mol/L~1.0×10-3mol/L的范围成良好的线性关系。该修饰电极制备简单、稳定性好,用于样品检测,效果良好。     

抗坏血酸在石墨烯微片修饰玻碳电极上的电化学行为及其测定

基于石墨烯微片修饰玻碳电极对抗坏血酸的电催化作用,建立了测定抗坏血酸的电化学分析方法。石墨烯微片修饰玻碳电极与裸玻碳电极相比,显著提高了抗坏血酸的氧化峰电流,降低了氧化峰电位,提高了测定的灵敏度。该电极测定抗坏血酸的线性范围为5.0×10-5～2.5×10-2mol/L,最低检测限为6.5×10-7mol/L(信噪比=3)。     

多巴胺在咖啡酸修饰电极上的电化学行为

研究了咖啡酸修饰玻碳电极的制备及其电化学性质,测定了电极反应的动力学常数。实验结果表明,在pH7.0的磷酸盐缓冲溶液中,多巴胺(DA)在该修饰电极上产生一灵敏的氧化峰,峰电流与DA浓度在5.0×10-6～1.0×10-4mol/L范围内良好线性关系,检出限为9.0×10-7mol/L。该修饰膜对DA有增敏作用,可望用于DA的测定。     

Electrochemical detection of copper(II) at a gold electrode modified with a self-assembled monolayer of penicillamine

A penicillamine (PCA) self-assembled monolayer (SAM) was prepared on a gold electrode. It has been found that the modified electrode exhibited a selective response to copper ions. As demonstrated by cyclic voltammetric experiments, the SAM-based electrode showed an attractive ability to preconcentrate efficiently traces of copper(II) from solutions. Under optimum conditions, the anodic peak current was proportional to the concentration of Cu(II) in the range from 8.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 4.0 × 10⁻⁷ M. Moreover, this modified gold electrode is also characterized by excellent repeatability, showing a relative standard deviation of 3.2% for nine successive measurements of 1.0 × 10⁻⁵ M Cu(II). The PCA/Au SAM gold electrode was used for the determination of Cu(II) in a tap water sample and the results showed a good agreement with the data obtained by atomic emission spectrometry. The text was submitted by the authors in English.     

Electrochemical behavior of the bis(2,2'-bipyridyl)copper(II) complex immobilized on a self-assembled monolayer modified electrode for L-ascorbic acid detection

Modification of a gold electrode has been achieved by immobilizing a bis(2,2'-bipyridyl)copper(II) complex in a self-assembled monolayer (SAM) of 3-mercaptopropionic acid. The electrostatic interaction of the negatively charged SAM with a di-positive copper complex allowed the attachment. The modified electrode exhibited excellent redox behavior. The dependence of the modified electrode response was investigated in terms of pH, supporting electrolyte and ionic strength. Moreover, it showed good electrocatalytic activity for ascorbic acid oxidation, allowing convenient quantification at levels down to 8.1 x 10(-8) mol l(-1). The [Cu(bipy)2]/SAM modified electrode under optimized operational conditions (PIPES buffer 0.01 mol l(-1) at pH 6.8 and 200 mV vs. SCE) presented a linear response range between 1.0 micromol l(-1) and 100.0 micromol l(-1) for ascorbic acid. This modified electrode also presented an excellent repeatability, showing a relative standard deviation of 2.1% for a series of 12 successive measurements of a 5.0 micromol l(-1) ascorbic acid solution. Furthermore, the electroactivity was maintained over a long period (e.g., 92% after 100 determinations).     

聚5-磺基水杨酸修饰电极上对苯二酚的电化学行为

用循环伏安法将 5 磺基水杨酸修饰于玻碳电极表面 ,制备出对对苯二酚具有电催化作用的聚合物膜修饰电极。研究了对苯二酚 (HQ)在该聚合物薄膜修饰电极上的电化学行为。在 0 5mmol/LH2 SO4底液中 ,HQ在该电极上的线性范围为 2 0× 1 0 - 6～ 1 0× 1 0 - 4 mol/L。该修饰电极可将对苯二酚和邻苯二酚(CC)的氧化峰分开约 1 0 5mV     

尿酸和抗坏血酸在CPB现场修饰碳糊电极上的电化学行为

研究了尿酸(UA)和抗坏血酸(AA)在裸碳糊电极(CPE)和溴化十六烷基吡啶CPB)现场修饰碳糊电极(CPB/CPE)上的电化学行为,研究结果表明在PBS(pH=6.8)缓冲溶液中,UA和AA在CPE和CPB/CPE电极上的氧化均为一不可逆过程,在CPB/CPE上UA和AA的氧化峰电位负移,氧化峰电流增大,CPB/CPE对UA和AA的电化学氧化产生了促进作用。用电化学方法测得了UA和AA在CPE和CPB/CPE上的动力学参数如电荷转移系数α,扩散系数D,反应级数和反应速率常数k1。     

Electrochemical determination of dopamine in the presence of ascorbic acid and uric acid using the synergistic effect of gold nanoflowers and L-cysteamine monolayer at the surface of a gold electrode

This paper describes a facile and effective method to synthesize gold nanoflowers (AuNFs) by a controllable electrodeposition method induced by a L-cysteamine (L-Cys) monolayer self-assembled on the surface of a gold electrode. The AuNFs/L-Cys/Au electrodes were characterized by field emission scanning electron microscopy (FE-SEM), cyclic voltammetry, and AC impedance spectroscopy methods. This obtained AuNFs/L-Cys/Au electrode exhibits excellent electrocatalytic activity towards the oxidation of dopamine (DA) due to the synergistic effect of AuNFs and a L-Cys monolayer. Differential pulse voltammetry (DPV) experiment results show that the oxidation peak of DA is separated from the oxidation peaks of ascorbic acid (AA) and uric acid (UA), which can be used to detect DA in the presence of AA and UA, and the results are satisfactory.     

Simultaneous determination of dopamine and ascorbic acid at a poly(toluidine blue) modified electrode.

A novel polymer modified electrode is discussed in this paper. This resulting electrode can catalyze remarkably toward the electrochemical oxidations of dopamine (DA) and ascorbic acid (AA). Moreover, it can clearly discriminate the electrochemical oxidations of DA from that of AA based on their semi-derivative voltammograms. Hence, a simultaneous determination of DA and AA based on semi-derivative voltammetry at a poly(toluidine blue) modified electrode is suggested. The detection linear range for DA is 0.4 micromol L(-1)-1.5 mmol L(-1), and AA 0.2 micromol L(-1)-2.4 mmol L(-1), respectively. The resulting modified electrode was tentatively used to determine DA and AA in brain tissue.     

Electrochemical sensing and simultaneous determination of ascorbic acid,dopamine and uric acid at nickel nanoparticles/poly (1,2-diaminoanthraquinone) modified electrode

A highly sensitive sensor based on Ni nanoparticles/poly (1,2-diaminoanthraquinone) modified electrode was fabricated at glassy carbon (GC) electrode (Ni/PDAAQ@GC ME) using cyclic voltammetry technique. The incorporation of nickel (II) ions nanoparticles (Ni NPs) followed by anodic polarization process was achieved. Surface morphologies of both PDAAQ@GC ME and Ni/PDAAQ@GC MEs were studied by scanning electron microscope. Ni/PDAAQ@GC ME was tested for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) by square wave voltammetry technique. The ME showed excellent electrocatalytic activity toward electrooxidation of these biomolecules in their single, binary and ternary systems in alkaline 0.1 M NaOH solutions. Experiment revealed that the low detection limits (LOD) for AA, DA and UA were 0.11, 0.072 and 1.2 µM in single system, respectively, and 0.069, 0.29 and 0.12 µM in ternary system, respectively.     

Electrochemical behavior and determination of fluphenazine at multi-walled carbon nanotubes/(3-mercaptopropyl)trimethoxysilane bilayer modified gold electrodes

A novel multi-walled carbon nanotubes/(3-mercaptopropyl)trimethoxysilane (MPS) bilayer modified gold electrode was prepared and used to study the electrochemcial behavior of fluphenazine and determine it. Fluphenazine could effectively accumulate at this electrode and produce two anodic peaks at about 0.78 V and 0.93 V (versus SCE). The peak at about 0.78 V was much higher and sensitive, thus it could be applied to the determination. Various conditions were optimized for practical application. Under the selected conditions (i.e. 0.05 M pH 3.5 HCOOH-HCOONa buffer solution, 5 μl 1 mg ml⁻¹ multi-walled carbon nanotubes for Φ=2.0 mm electrode, accumulation at open circuit for 180 s), the anodic peak current was linear to fluphenazine concentration in the range from 5×10⁻⁸ to 1.5×10⁻⁵ M with correlation coefficient of 0.9984, the detection limit was 1×10⁻⁸ M. For a 1×10⁻⁵ M fluphenazine solution, the relative standard deviation of peak current was 2.51% (n=8). This method was successfully applied to the determination of fluphenazine in drug samples and the recovery was 96.4-104.4%. The electrode could be easily regenerated and exhibited some selectivity, but some surfactants reduced the peak current greatly. The modified electrode was characterized by alternating current impedance and electrochemical probe.     

Electrochemical behavior of acidic acetonitrile solutions at platinum and gold electrodes

Hydrogen evolution reactions from acidic MeCN solutions were studied at Pt and Au electrodes. The acids studied were HCl and HPic in a wide range of concentrations. LiClO₄ and Et₄NClO₄ (0.4 M) were used as supporting electrolytes. Quasi steady state polarization curves show that the reaction is irreversible with a Tafel slope of 2 RT/F after diffusion polarization and pseudo-ohmic drop have been corrected. Non-stationary techniques reveal that the electrochemical reaction is preceded by a chemical reaction attributed to slow dissociation of ACN·2 HCl and ACN·3 HPic species. Equilibria and chemical rate constants for both species were evaluated by chronopotentiometry. The values obtained explain satisfactorily the results accomplished under potentiodynamic conditions. Data at the RDE confirm the existence of a previous chemical reaction. MeCN electroadsorption in the double layer potential region at Pt accounts for the solvent levelling effect towards H adsorption between Pt and Au. Furthermore, an inhibitory effect over hydrogen evolution and hydrogen oxidation is reported at more negative potentials at both Pt and Au electrodes.     

多巴胺在DTNB自组装膜上的电催化研究

在金电极表面制备了DTNB(5,5′ Di thiobis(2 nitrobenzoicacid))自组装单分子层膜(DTNB/AuSAM)。多巴胺在DTNB自组装膜上有一对可逆性良好的氧化还原峰,其氧化峰电流与多巴胺的浓度在5.0×10-6mol/L～1.0×10-4mol/L的范围内呈线性关系,检出限为1.0×10-6mol/L。在pH3.5的缓冲溶液中,在DTNB自组装膜上多巴胺和抗坏血酸的电化学响应可以明显区分,氧化峰电位分离达276mV。可用于抗坏血酸存在下多巴胺的检测。测定了盐酸多巴胺注射液中多巴胺的含量,其平均回收率为104%。     

Electroanalysis of dopamine at a gold electrode modified with N-acetylcysteine self-assembled monolayer

Voltammetric behavior of dopamine (DA) on a gold electrode modified with the self-assembled monolayer (SAM) of N-acetylcysteine has been investigated, and one pair of well-defined redox peaks of dopamine is obtained at the SAM modified gold electrode. The oxidation peak current increases linearly with the concentration of dopamine in the range of  mol l⁻¹. The detection limit is 8.0×10⁻⁷ mol l⁻¹. This method will be applicable to the determination of dopamine in injection of dopamine hydrochloride, and the good recovery of dopamine is obtained. Furthermore, The SAM modified gold electrode can resolve well the voltammetric responses of dopamine and ascorbic acid (AA), so it can also be applied to the determination of dopamine in the presence of ascorbic acid.     

Electrochemical behavior of gold electrodes modified with self-assembled monolayers with an acidic end group for selective detection of dopamine

Gold electrodes modified with monolayers with ionic end groups of different acidity and structure have been evaluated for the detection of dopamine. It has been demonstrated that the selectivity of monolayers depends not only on ionic charge but also on the nature of the ionic end group and defects in the monolayer. Catalytic effects due to the electrocatalytic oxidation of ascorbic acid by dopamine are present at the monolayer modified gold electrode. The angle resolved XPS (X-ray photoelectron spectroscopy) experiments demonstrate that the sulfonate group do not compete with thiol on binding the gold electrode. The capacitance measurements demonstrate that the capacitance depends on the length, end group type and defects present in monolayers.     

Simultaneous determination of ascorbic acid,dopamine and serotonin at poly(phenosafranine) modified electrode

The oxidation of phenosafranine at glassy carbon electrode gives rise to stable redox active electropolymerized film containing a polyazine moiety (poly(phenosafranine)). The redox response of the poly(phenosafranine) film was observed at the modified electrode at different pH and the pH dependence of the peak potential is 60 mV/pH, which is very close to the expected Nernstian behavior. The apparent diffusion coefficient (D_app) of poly(phenosafranine) film was measured as 2.51 × 10⁻⁹ cm²/s. This film exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards ascorbic acid (AA), dopamine (DA) and serotonin with activation overpotential, which is 200 mV lower than that of the bare electrode for AA oxidation. Using differential pulse voltammetry (DPV) studies, the limit of detection of DA in the presence of AA is estimated to be in the submicromolar regime. This method has been used for determining DA and AA concentrations in real samples with satisfactory results.