用碳黑微电极伏安法测定多巴胺

研究了多巴胺(DA)在碳黑微电极上的电化学行为,试验结果表明,在pH 4.5(pH 3.8~5.2)的磷酸盐缓冲介质(PBS)中,多巴胺在伏安图0.21 V处的二阶导数峰高与其浓度在6×10-6~2×10-5mol.L-1之间保持线性关系,其检出限(3σ)为1×10-6mol.L-1;将此方法应用于多巴胺针剂试样的分析,测定结果的RSD值(n=5)均小于2.4%,用标准加入法做回收率试验,结果在96%~102%之间。此方法所测得结果与碘量法测得的结果之间无显著差异。     

二茂铁修饰碳黑微电极同时测定多巴胺和抗坏血酸

研究了神经递质多巴胺(DA)和抗坏血酸(AA)在二茂铁修饰碳黑微电极上的电化学行为。实验结果表明,在pH4.5的磷酸盐中,DA在该电极上的线性范围为2.0×10-6～4.0×10-3mol/L,检出限(3σ)为1.0×10-6mol/L;AA在该电极上的线性范围为6.0×10-6～1.0×10-3mol/L,检出限(3σ)为2.0×10-6mol/L;用这种电极可以同时测定多巴胺,抗坏血酸。     

普鲁士兰修饰碳黑微电极同时微分伏安法测定多巴胺和抗坏血酸

将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系DA为4.0×10-6～8.0×10-4mol·L-1,VC为6.0×10-5～1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%～101.0%及95.0%～102.5%.     

硫辛酸修饰碳纤维微电极在抗坏血酸共存下选择性测定神经递质多巴胺

本研究了硫辛酸修饰电化学活化碳纤维电极。此电极在测定脑神经递质多巴胺（ＤＡ）时，具有较高的灵敏度和较好的选择性，它能够有效地消除抗坏血酸（ＡＡ）的干扰。该电极测定多巴胺的线性范围为１×１０＾－８－１×１０＾－５ｍｏｌ／Ｌ；检出下限为５×１０＾－９ｍｏｌ／Ｌ。     

新型电流型传感器——双柱碳纤维微电极

本文报道了双柱碳纤维微电极的研究及应用.分别用循环伏安法,计时电流法考察了该电极的性能,并用实验验证了双柱微电极的稳态电流理论公式,探讨了理论曲线与实验结果偏离的原因.采用发生-收集模式,提出间接测定维生素B_1的方法,并取得了满意的结果,维生素B_1的检测限为1.0×10~(-6)mol·dm~(-3),线性范围为7.5×10~(-6)～7.5×10~(-4)mol·dm~(-3).     

多壁碳纳米管修饰碳黑微电极同时测定多巴胺和抗坏血酸

制备了多壁碳纳米管修饰碳黑微电极,研究了多巴胺(DA)和抗坏血酸(AA)在该修饰电极上的电化学行为.实验表明,在pH 7.0的PBS缓冲溶液中,该修饰电极对DA和从均具有显著的催化氧化作用,AA与DA的氧化电位分别为30 mV和280 mV(vs.SCE).利用二次导数线性扫描伏安法测定,DA与AA的线性范围分别为6.0×10-9～2.0×10-4 mol/L和2.0×10-7～1.0×10-3mol/L,检出限为2.0×10-9mol/L 和1.0×10-7mol/L.方法已用于人工合成样品的分析.     

碳纤维微电极恒电位活化及测定金属离子的研究

碳纤维微电极已被广泛应用于电化学研究和分析测定,该电极尺寸极小,在分析性能上与常规电极有显著不同,在不镀汞的情况下,用碳纤维电极直接测定金属离子几乎没有明显的伏安响应,本文提出用+2.5 V恒电位预先活化碳纤维电极,使测定灵敏度大为提高,在双电极体系和静止溶液中,采用溶出伏安法可测定10~(-9)级金属离子,以同样的方法清洗电极,测定结果重现性良好,由于分析过程中不使用汞,该电极的测定范围大大增加,特别是用于氧化还原电位较正的金属离子测试,根据循环伏安法、扫描电镜和电子能谱的研究,发现碳纤维表面状况在处理前后有很大变化,并与测定灵敏度密切相关。     

普鲁士兰修饰碳黑微电极同时微分伏安法测定多巴胺和坑坏血酸

将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系:DA为4.0×10-6～8.0×10-4mol·L-1,VC为6.0×10-5～1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%～101.0%及95.0%～102.5%.     

Electropolymerization of Thin Film Conducting Polymer and Its Application for Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid

In this paper electropolymerization of a thin film of para‐phenylenediamine (PPD) is studied at glassy carbon electrode (GCE) in sulfuric acid media by cyclic voltammetry. The results showed that this polymer was conducting and had a reproducible redox couple in the potential region from 0.0 to 0.4 V in phosphate buffer solution. This modified GCE (p‐PPD‐GCE) was applied for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) using differential pulse voltammetry (DPV). The p‐PPD‐GCE in 0.1 M phosphate buffer solution (pH 5.0) separated the DPV signals of AA, DA and UA with sufficient potential differences between AA–DA and DA–UA and also enhanced their oxidation peak currents. The oxidation currents were increased from 2.0 to 2000.0 µM for AA, 10.0 to 1250.0 µM for DA and 50.0 to 1600.0 µM for UA. The detection limits were evaluated as 0.4, 1.0 and 2.5 µM for AA, DA and UA, respectively (S/N=3).     

Ultrathin Carbon Nanoparticle Composite Film Electrodes: Distinguishing Dopamine and Ascorbate

Ultrathin carbon nanoparticle–poly(diallyldimethylammonium chloride) films (CNP‐PDDAC films) are formed on tin‐doped indium oxide (ITO) electrodes in a layer‐by‐layer electrostatic deposition process employing 9–18 nm diameter carbon particles. Transparent and strongly adhering films of high electrical conductivity are formed and characterized in terms of their electrochemical reactivity. When immersed in aqueous 0.1 M phosphate buffer pH 7, each layer of CNP‐PDDAC (of ca. 5–6 nm average thickness) is adding an interfacial capacitance of ca. 10 μF cm^?2. Absorption into the CNP–PDDAC nanocomposite film is dominated by the sites in the PDDAC cationomer and therefore anionic molecules such as indigo carmine are strongly bound and retained within the film (cationic binding sites per layer ca. 150 pmol cm^?2). In contrast, cationic redox systems such as ferrocenylmethyltrimethyl‐ammonium⁺ fail to bind. For solution phase redox systems such as hydroquinone, the rate of electron transfer is dramatically affected by the CNP‐PDDAC film and switched from completely irreversible to highly reversible even with a single layer of carbon nanoparticles. For the mixed redox system ascorbate–dopamine in 0.1 M phosphate buffer pH 7 cyclic voltammograms suggest a rapid and selective temporary poisoning process which causes the ascorbate oxidation to be suppressed in the second potential cycle. This effect is exploited for the detection of micromolar concentrations of dopamine in the presence of millimolar ascorbate.     

Electrochemical Behaviour of Carbamazepine in Acetonitrile and Dimethylformamide Using Glassy Carbon Electrodes and Microelectrodes

The electrochemical reduction of carbamazepine in acetonitrile (ACN) and dimethylformamide (DMF) using a glassy carbon electrode and microelectrodes has been studied. The reduction process is consistent with an electrochemical‐chemical mechanism (EC) involving a two electron transfer followed by a first order reaction, as shown by the cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Half‐wave potential, number of electron transferred, diffusion coefficient and rate constant of the associated chemical reaction are reported. Limits of detection (LOD) for DPV are 0.92 and 0.76 µg mL^?1 (3.89×10^?6 mol L^?1 and 3.21×10^?6 mol L^?1) in ACN and DMF, respectively. Precision (%RSD) and recovery (%) values when pharmaceutical compounds (200mg carbamazepine tablets) and spiked plasma samples were tested ranged from 1.09 to 9.04 % and % recoveries ranged from 96 to 104.1 %.     

Studies on the Electrochemistry of Dopamine at a Pyrocatechol Sulfonephthalein Modified Glassy Carbon electrode

IntroductionThere has been a considerable interest in developing the methods to measure the secretionneurotransmitters. Electrochemical teChniques have proven to be significantly advantageous tothe biosciencesLlj. The application of ultramicroelectrodes to neuroscien.ce, which has been pioneered by Adams[2], to monitor the concentration of neurotransmitters in the central nervesystem has had a special impact. Several neurotransmitters, e. g., dopamine(DA) are electroactlve and therefore can …     

Some Properties of Sodium Dodecyl Sulfate Functionalized Multiwalled Carbon Nanotubes Electrode and Its Application on Detection of Dopamine in the Presence of Ascorbic Acid

A sodium dodecyl sulfate (SDS) functionalized multiwalled carbon nanotubes (MWNTs) electrode (SDS/MWNTs) was successfully constructed in this study. The electrochemical property of the SDS/MWNTs electrode has been characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Nyquist plots suggest that the immersion time of SDS affects the resistances of the MWNTs electrodes. The thickness of adsorbed SDS on MWNTs surface is estimated to be 1.23 nm, which is close to the value of SDS monolayer. CV results demonstrate a 5‐fold enhanced response for dopamine (DA) at the SDS/MWNTs electrode compared to the bare MWNTs one. DPV results illustrate that DA can be selectively determined in the presence of high concentration ascorbic acid (AA) with a linear range from 20 μM to 0.20 mM and a sensitivity of 0.024 μA μM^?1 at the SDS/MWNTs electrode.     

Electrochemical Properties of Different Carbon‐Fiber Microelectrodes Using Fast‐Scan Cyclic Voltammetry

In this study, fast‐scan cyclic voltammetry (FSCV) was used to compare responses to neurochemicals of various carbon fibers, with different conductivities and carbon precursors. Pitch‐based P‐25 and P‐55 fibers were compared to polyacrylonitrile‐based T‐650 and HM fibers. Highly conductive fibers such as P‐55s or HMs have larger background charging currents than lower conductivity fibers. Using a standard waveform, PAN‐based fibers and less conductive fibers experience faster kinetics. With a more positive switching potential, higher conductivity fibers show faster kinetics for catecholamines and larger oxidation peak currents for anions such as ascorbic acid and 3,4‐dihydroxyphenylacetic acid (DOPAC). Conductivity was found to have the greatest impact on fiber performance, but the nature of its effect depends on the waveform used and the analyte detected.     

纳米金修饰玻碳电极在抗坏血酸共存下选择性测定多巴胺

利用电沉积的方式制备了纳米金 ( Nano- gold,NG)修饰玻碳电极 ( GCE)。该电极对多巴胺 ( DA)和抗坏血酸 ( AA)均有催化作用 ,且多巴胺在纳米金修饰玻碳电极上有较强的吸附作用。同时研究了磷酸缓冲溶液的 p H值和离子强度对 DA的电化学行为的影响。纳米金修饰玻碳电极在 DA和 AA的混合溶液中的循环伏安图上可观察到两个明显分开的氧化峰 ,峰电位差达到 1 5 0 m V。据此 ,提出了两种利用该电极在抗坏血酸共存下选择性测定多巴胺的方法 ,线性范围分别为 3.0× 1 0 - 6 ～1 .0× 1 0 - 4mol/ L和 1 .2 5× 1 0 - 6 ～ 1 .0× 1 0 - 4mol/ L。     

Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid at Pt Nanoparticles Decorated Multiwall Carbon Nanotubes Modified GCE

A modified electrode was fabricated by electrochemically deposition of Pt nanoparticles on the multiwall carbon nanotube covered glassy carbon electrode (Pt nanoparticles decorated MWCNT/GCE). A higher catalytic activity was obtained to electrocatalytic oxidation of ascorbic acid, dopamine, and uric acid due to the enhanced peak current and well‐defined peak separations compared with both, bare and MWCNT/GCE. The electrode surfaces were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). Individual and simultaneous determination of AA, DA, and UA were studied by differential pulse voltammetry. The detection limits were individually calculated for ascorbic acid, dopamine, and uric acid as being 1.9×10^?5 M, 2.78×10^?8 M, and 3.2×10^?8 M, respectively. In simultaneous determination, LODs were calculated for AA, DA, and UA, as of 2×10^?5 M, 4.83×10^?8 M, and 3.5×10^?7 M, respectively.     

Catalytic Oxidation of Ascorbic Acid at a Polyhistidine Modified Electrode and Its Application to the Voltammetric Resolution of Ascorbic Acid and Dopamine

Abstract

A new polymer (polyhistidine) modified electrode has been fabricated and was applied to the catalytic oxidation of ascorbic acid (AA), reducing the overpotential by 400 mV. The catalytic rate constant of the modified electrode for the oxidation of AA was determined using a rotating electrode. The catalytic current was linearly dependent on the ascorbic acid concentration between 5×10^?5 and 2×10^?3 M. The catalytic effect on the AA resulted in the separation of the overlapping voltammograms of AA and dopamine (DA) in a mixture. This allowed the determination of AA in the presence of DA. The electrode was rather stable even after several months; a reproducible response of AA was obtained.     

在抗坏血酸存在下用L-赖氨酸修饰玻碳电极测定多巴胺

采用电化学氧化法制备了L-广赖氮酸单分子层修饰玻碳电极,研究了多巴胺（DA）和抗坏血酸（AA）在该电极上的电化学行为。结果表明,L-广赖氨酸单分子层修饰玻碳电极不仅能改善多巴胺和抗坏血酸的电化学行为,而且能将多巴胺和抗坏血酸二者在裸电极上的完全重叠的单氧化峰分开成为两个完全独立的氧化峰,循环伏安（CV）图上峰间距为507mV,差分脉冲伏安（DPV）图上峰间距为460mV,由此可实现在AA的共存下对样品中的DA进行选择性测定。