聚色氨酸膜电极相敏交流伏安法测定肾上腺素

研究了聚色氨酸膜电极的制备及其肾上腺素在该修饰电极上的相敏交流伏安特性,建立了相敏交流伏安法测定肾上腺素的电化学分析法。在pH 6.0的磷酸盐缓冲溶液中,肾上腺素的相敏交流伏安氧化峰电位在298 mV,线性响应范围为1.05×10-6~3.98×10-5mol/L,检出限为8.40×10-7mol/L。用于药剂中肾上腺素的测定,相对标准偏差小于3.84%,加标回收率为99%~104%,多巴胺、抗坏血酸和尿酸不干扰。     

聚吡咯尿酸酶电极的生物电化学活性

聚吡咯尿酸酶电极具有快速的生牧电化学响应.在5.9×10^-6mol·dm^-3至1.5×10^-3mol·dm^-3的尿酸浓度范围内,酶电极的响应电流与底物浓度之间呈线性关系.固定酶的催化反应活化能为34.81kJ ·mol^-1.与可溶性的尿酸酶相比,聚吡咯尿酸酶电极的一些生物活性,如与溶液的pH和温度的关系,发生了有利的变化.     

聚L-白氨酸修饰电极伏安法测定痕量多巴胺的研究

用循环伏安法制备了聚L-白氨酸修饰玻碳电极,研究了多巴胺在聚L-白氨酸修饰玻碳电极上的电化学行为,建立了循环伏安法测定痕量多巴胺的新方法。实验结果表明,在pH 6.0的磷酸盐缓冲溶液中,多巴胺在聚L-白氨酸修饰玻碳电极上产生一对灵敏的氧化还原峰,峰电位分别为Epa=0.281V,Epc=0.170 V(相对Ag/AgCl电极)。峰电流与多巴胺的浓度在5.0×10-8~5.0×10-4mol/L的范围内有线性关系,检出限为5.0×10-9mol/L。对1.0×10-5mol/L多巴胺溶液平行测定9次,其相对标准偏差为4.0%。已用于针剂中多巴胺的测定。     

多巴胺在聚2,4,6-三甲基吡啶修饰电极上的电化学行为

用循环伏安法制备了聚 2 ,4 ,6 三甲基吡啶修饰玻碳电极 ,研究了神经递质多巴胺在该聚合物薄膜修饰电极上的电化学行为。实验结果表明 :在pH 7.4磷酸盐缓冲溶液中 ,多巴胺在该修饰电极上的线性范围为4 .0× 10 -6～ 1.0× 10 -5mol/L。该修饰电极对抗坏血酸无响应 ,从而可有效消除其对多巴胺测定的干扰     

多巴胺在聚硫堇和Nafion双层修饰玻碳电极上的电化学行为

用电化学聚合法在玻碳电极上制备聚硫堇,然后涂渍一层Nafion膜,采用循环伏安法研究其制备和电化学性质。该电极峰电流与多巴胺(DA)在2.00×10-7~1.43×10-3mol/L浓度范围内呈良好的线性关系,检出限为6.67×10-8mol/L,相关系数为0.995。该修饰电极有效排除了抗坏血酸(AA)的干扰。并且具有良好的灵敏度、重现性、稳定性,可用于实际样品中DA的测定。     

碳纳米管修饰电极对多巴胺和肾上腺素的电分离及同时测定

研究了多巴胺 (DA)和肾上腺素 (EP)在多壁碳纳米管 (MWNT)修饰电极上的电化学性质 ,发现该修饰电极对神经递质DA和EP有显著的增敏和电分离作用。还原峰电位差达ΔEp=390mV ,可同时测定DA和EP。DA和EP的还原峰电流与其浓度分别在 2 .0× 10 -6～ 1.0× 10 -3 mol/L和 1.0× 10 -6～ 1.0× 10 -3 mol/L浓度范围内呈良好的线性关系 ;方法的检出限分别为 1× 10 -6mol/L和 5× 10 -7mol/L。由于抗坏血酸 (AA)在MWNT修饰电极上的氧化是不可逆的 ,因此利用还原峰进行测定 ,消除了AA对DA和EP的干扰     

单重态氧化学VII. 迷迭香中主要抗氧化成分对单重态氧的猝灭作用

本文研究了迷迭香酚和鼠尾草酚对单重态氧的猝灭作用。实验证明迷迭香酚和鼠尾草酚在甲醇中猝灭单重态氧的总速率常数K~A分别为2.51×10^7和7.19×10^6mol^1.dm^-3.s^-1, 其中化学猝灭的速率常数k~r分别为1.27×10^7和9.82×10^5mol.dm^-3.s^-1, 相应的半猝灭浓度β值为4.6×10^-3和1.6×10^-2mol.dm^-3。这是一类有实用价值的高效抗氧化剂。     

聚L-苏氨酸修饰电极对多巴胺和肾上腺素的电催化氧化

利用循环伏安法将L-苏氨酸聚合修饰在玻碳电极表面, 制成聚L-苏氨酸修饰电极. 实验表明, 该电极对多巴胺和肾上腺素都有较好的催化氧化效果. 运用循环伏安法详细研究了修饰电极的电化学性质. 在pH 2.5的磷酸盐缓冲溶液(PBS)中, 肾上腺素的电子传递系数为0.51, 表观反应速率常数为1.33 s-1; 在pH 7.5的PBS中, 多巴胺在电极上产生一对氧化还原峰, 多巴胺在电极上的电子传递系数为0.60, 表观反应速率常数为0.92 s-1. 该修饰电极对多巴胺和肾上腺素能够进行同时测定, 还原峰电流与多巴胺和肾上腺素浓度分别在1.0×10-6-5.0×10-4 mol·L-1和3.0×10-6-1.0×10-4 mol·L-1范围内呈现良好的线性关系.     

聚甲基蓝修饰电极的制备及对多巴胺的测定

研究了聚甲基蓝修饰电极的制备及其多巴胺在聚甲基蓝修饰电极上的循环伏安特性,建立了循环伏安法测定多巴胺的新方法。在pH7.0磷酸盐缓冲溶液中,峰电流与多巴胺浓度在8.0×10-7～5.0×10-4mol L范围内呈良好的线性关系,检出限为5.0×10-8mol L。已用于药剂中多巴胺的测定。     

抗坏血酸在β-环糊精/二茂铁甲酸修饰电极上的电化学行为及测定

利用主客体化学反应将二茂铁甲酸包络在β-环糊精聚合物的空穴中,用新鲜蛋清作交联剂制成β-环糊精聚合物/二茂铁甲酸化学修饰玻碳电极,用电化学阻抗法和循环伏安法研究了修饰电极的电化学性能。在pH 7.0的磷酸盐缓冲溶液中,该修饰电极对抗坏血酸的电化学氧化有很好的催化活性,氧化峰电流与其浓度在6.2×10-6~5.0×10-3mol/L范围内呈良好的线性关系,线性回归方程为ip=0.4375+0.0301C(ip:μA,C:μmol/L),相关系数r=0.9982,检出限为1.0×10-6mol/L。抗坏血酸和多巴胺在修饰电极上于不同的电位(ΔE=490 mV)被氧化,可用于多巴胺存在下选择性测定抗坏血酸。     

蒙脱土修饰碳纤维电极的制备及其应用于活体测定脑神经递质

制备了蒙脱土修饰碳纤维电极,研究了其对神经递质多巴胺(DA)及5羟色胺(5HT)的富集作用,以及对负电性的代谢产物3,4二羟基苯乙酸(DOPAC)、5羟吲哚乙酸(5HIAA)及脑内大量存在的抗坏血酸(AA)排斥性能.该电极具有很高的灵敏度、分辨率和抗干扰性,对DA的检测下限达16×10^-8mol/L,优于传统的Nafion修饰电极,对5HT的检测下限为1×10^-7mol/L.在动物活体分析中,使用该电极成功地检测了大鼠双侧颈总动脉结扎再灌损伤时,脑纹状体中神经递质DA浓度的变化.     

Electrochemical determination of dopamine using a poly(2-picolinic acid) modified glassy carbon electrode

A poly(2-picolinic acid) chemically modified electrode (CME) for the determination of dopamine (DA) by cyclic voltammetry is described. Compared with a bare glassy carbon electrode, the CME exhibits a 200 mV shift of the oxidation potential of DA in the cathodic direction and a marked enhancement of the current response. In pH 7.0 buffer solution, a linear calibration graph is obtained over the range from 2.5 x 10(-7) to 1.0 x 10(-5) mol dm-3 with a correlation coefficient of 0.998. The detection limit is 3.0 x 10(-8) mol dm-3. The modified electrode eliminated efficiently the interference from ascorbic acid (AA) when present in a 150-fold concentration ratio. It also showed excellent stability and reproducibility.     

A chitosan-multiwall carbon nanotube modified electrode for simultaneous detection of dopamine and ascorbic acid.

A chemically modified electrode based on a chitosan-multiwall carbon nanotube (MWNT) coated glassy carbon electrode (GCE) is described, which exhibits an attractive ability to determine dopamine (DA) and ascorbic acid (AA) simultaneously. The modified electrode exhibited a high differential pulse voltammetry (DPV) current response to DA at 0.144 V and AA at -0.029 V (vs. SCE) in a 0.1 mol l(-1) phosphate buffer solution (pH = 7.2). The properties and behaviors of the chitosan-multiwall carbon nanotube modified electrode (MC/GCE) were characterized using cyclic voltammetry (CV) and DPV methods. The mechanism for the discrimination of dopamine from ascorbic acid at MC/GCE is discussed. The linear calibration range for DA and AA were 5 x 10(-7) mol l(-1) to 1 x 10(-4) mol l(-1) (r = 0.997), and 5 x 10(-6) mol l(-1) to 1 x 10(-3) mol l(-1) (r = 0.996), respectively. The MC/GCE showed good sensitivity, selectivity and stability.     

Covalent modification of glassy carbon electrodes with beta-alanine for voltammetric separation of dopamine and ascorbic acid.

beta-Alanine was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) proved the immobilization of beta-alanine monolayer on GCE. The electrode shows strong electrocatalytic functions to dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by 0.20 V and 0.23 V, respectively. Due to its different catalytic effects toward DA and AA, the modified electrode resolved the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by CV or differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentrations in the ranges of 4.0 x 10(-6)-5.0 x 10(-4) mol/L and 2.0 x 10(-5)-6.0 x 10(-3) mol/L with correlation coefficients of 0.997 and 0.995, respectively. The detection limits (3 sigma) for DA and AA were 2.4 x 10(-6) mol/L and 1.2 x 10(-5) mol/L, respectively. The electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Cu(II)氧化抗坏血酸的动力学和机理

本文在总离子强度I=1.00mol.dm^-^3、[Cu^2^+]>>[H2A]、[H^+]>>[H2A]、无氧及无缓冲剂存在的条件下, 研究Cu(II)氧化抗坏血酸(H2A)的动力学和机理. 发现Cu(II)与H2A不发生配位反应, 但以Cl^-存在的情况下, 确有Cu(II)的H2A配合物生成, Cu(II)氧化H2A反应的速率方程为r={a+b[Cl^-]}[Cu^2^+]{[H+]+Ka}^-^2, 25℃时a和b值分别为4.08×10^-^4s^-^1和0.555dm^3.s^-^1.mol^-^1. Cu(II)氧化H2A反应的表观活化能为68.1KJ.mol^-^1. 根据动力学结果, 提出了反应机理, 并给出了配合物ClCuHA的结构形式.     

Synthesis of magnetic molecularly imprinted polymer particles for selective adsorption and separation of dibenzothiophene

We are presenting an electrochemical sensor for the simultaneous determination of dopamine (DA) and uric acid (UA) in the presence of even high concentrations of ascorbic acid (AA). It based on a glassy carbon electrode modified with an electroactive film of polymerized dibromofluorescein. The electrochemical behaviors of DA and UA were studied by cyclic voltammetry using the modified electrode. It exhibits excellent electrocatalytic activity towards the oxidation of the two analytes. Most notably, the oxidation potentials differ by 180 and 200?mV between AA-DA and DA-UA, respectively. Thus, excellent selectivity towards the oxidation of DA and UA in the presence of even high concentrations of AA is accomplished. Under the optimum conditions, the anodic peak currents are linearly related to the concentrations of DA and UA in the range from 0.2 to 200?μmol?L^-1 and from 1.0 to 250?μmol?L^-1, respectively. The detection limits for DA and UA are 0.03?μmol?L^-1 and 0.2?μmol?L^-1, respectively (at an S/N of 3). The method has good selectivity and sensitivity and was successfully applied to the simultaneous determination of DA and UA in spiked human serum.

锗(IV)-茜素红-VOSO4-EDTA体系极谱吸附催化波研究

报导了在酸性缓冲液中锗(IV)-茜素红-VOSO4-EDTA体系的配合吸附平行催化波的研究.锗的最低检出量为1.0x10^-^9mol.dm^-^3.研究了催化波的机理.     

聚三聚氰胺-石墨烯复合膜修饰电极对多巴胺与尿酸的同时测定

采用循环伏安法制备了聚三聚氰胺-石墨烯复合膜修饰电极(poly-(MA)-ERGO/GCE)。研究了抗坏血酸(AA)、尿酸(UA)和多巴胺(DA)在该修饰电极上的电化学行为。结果表明,该修饰电极对AA、UA和DA均有良好的电化学响应,且三者的氧化峰在该修饰电极上可完全分离。据此建立了在大量AA存在下同时测定UA和DA的新方法。在优化条件下,微分脉冲伏安法(DPV)测定UA和DA的线性范围均为1.0×10~(-8)~5.0×10-6mol·L~(-1),检出限(3sb)均为5.0×10~(-9)mol·L~(-1)。     

Attachment of DNA to the carbon fiber microelectrode via gold nanoparticles for simultaneous determination of dopamine and serotonin.

A novel biochemical sensor was fabricated on a carbon fiber microelectrode, which consisted of an inner layer of electrodeposited gold nanoparticles, as a nano-array electrode, and an outer layer of electrodeposited calf thymus ds-DNA at +1.5 V vs. SCE. This modified electrode was characterized by X-ray photoelectron spectroscopy, scanning electron microscope, atomic force microscopy, cyclic voltammetry and differential pulse voltammetry (DPV). It was found that this electrochemical sensor exhibits a strong catalytic activity toward the oxidation of dopamine (DA), serotonin (5-HT) and ascorbic acid (AA), as a result of resolving the anodic voltammetric peaks of DA, 5-HT and AA into three well-defined peaks. Simutaneous DPV determination of DA and 5-HT can be achieved in the presence of 2000-fold AA. The modified electrode shows good sensitivity, selectivity and stability.     

Microchip capillary electrophoresis with a cellulose-DNA-modified screen-printed electrode for the analysis of neurotransmitters

A microfluidic chip based on capillary electrophoresis coupled with a cellulose-single-stranded DNA (cellulose-ssDNA) modified electrode was used for the simultaneous analysis of dopamine (DA), norepinephrine (NE), 3,4-dihydroxy-L-phenylalanine (L-DOPA), 3,4-dihydroxyphenylacetic acid (DOPAC), and ascorbic acid (AA). The modification of the electrode improved the electrophoretic analysis performance by lowering the detection potential and enhancing the signal-to-noise characteristic without surface poisoning of the electrode. The sensitivity of the modified electrode was about 12 times higher than those of the bare ones. The test compounds were separated using a 62 mm long separation channel at the separation field strength of +200 V/cm within 220 s in a 10 mM phosphate buffer (pH 7.4). The most favorable potential for the amperometric detection was 0.7 V (vs. Ag/AgCl). A reproducible response (relative standard deviation of 1.3, 1.3, 2.1, 3.1, 3.4% for DA, NE, L-DOPA, DOPAC, and AA, respectively, for n = 9) for repetitive sample injections reflected the negligible electrode fouling at the cellulose-ssDNA modified electrode. Square-wave voltammetric analyses reflected the sensitivities of the modified electrode for DA, NE, L-DOPA, DOPAC, and AA which were 1.78, 0.82, 0.69, 2.45, and 1.23 nC/microM with detection limits of 0.032, 0.93, 1.13, 0.31, and 0.62 microM, respectively. The applicability of this microsystem to real sample analysis was demonstrated.