2，3—二氨基吩嗪的薄层光谱电化学研究

研究了2，3—二氨基吩嗪(DAP)在金圆盘电极、金超微电极上的循环伏安行为 和在金网栅电极上的薄层循环伏安行为．在pH2．0的B—R缓冲溶液中的2，3—二氨 基吩嗪在金圆盘电极上为准可逆氧还过程；以超微电极法求得了2，3—二氨基吩嗪 在pH2．0的B—R缓冲溶液中的扩散系数，由耗竭性库仑电解和循环伏安法求得其电 极反应电子转移数和H+反应级数均为2，实验说明参与电极反应的H+也为2，并用循 环伏安法求得其标准电极反应速率常数．采用紫外—可见薄层光谱电化学方法测得 2，3—二氨基吩嗪的克式量电位和电子转移数，与电化学实验结果一致；双电位阶 跃—计时吸收紫外—可见薄层光谱电化学实验说明，2，3—二氨基吩嗪电还原无随 后化学反应，其在电极上经历了H+eH+e的两步一电子过程，生成产物2，3—二氨基 -5，10-二氢吩嗪．     

Charge transfer across the water/nitrobenzene interface by three-electrode system

A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed. Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.     

Effect of electrode surface microstructure on electron transfer induced conformation changes in cytochrome c monitored by in situ UV and CD spectroelectrochemistry

Electrochemical redox processes of bovine heart cytochrome c were investigated by in situ UV-vis and CD spectroelectrochemistry at bare glassy carbon electrode (GCE) and single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode (SWNTs/GCE) using a long optical path thin layer cell. The spectra obtained at GCE and SWNTs/GCE reflect electrode surface microstructure-dependent changes in protein conformation during redox transition. Potential-dependent conformational distribution curves of cytochrome c obtained by analysis of in situ circular dichroism (CD) spectra using singular value decomposition least square (SVDLS) method show that SWNTs can retain conformation of cytochrome c. Some parameters of the electrochemical reduction process, i.e. the product of electron transfer coefficient and number of electrons (alpha n = 0.3), apparent formal potential (E0' = 0.04 V), were obtained by double logarithmic analysis and standard heterogeneous electron transfer rate constant k0 was obtained by electrochemistry and double logarithmic analysis, respectively.     

Electron transfer between ferrocene-modified Au/octadecanethiol/lipid BLM electrode and redox couples in solution

Bilayers incorporated with ferrocene consisting of self-assembled octadecanethiol and lipid monolayer on gold substrates were fabricated. Its electrochemical behaviors in solutions containing different redox couples were investigated by cyclic voltammetry and ac impedance. The transmembrane electron transfer reaction across octadecanethiol self-assembled film and an adsorbed phospholipid layer mediated by ferrocene have been observed in the solution of Fe(CN)6(3-/4-). The formal potential difference between mediator in bilayer lipid membrane (BLM) and redox couple in solution has a great impact on the transmembrane electron transfer behavior. The ferrocene-modified BLM electrodes might be useful for constructing a bilayer-based electrochemical current rectifying device.     

固载于壳聚糖-纳米金复合膜修饰玻碳电极上的葡萄糖氧化酶的直接电化学研究及其生物传感应用

通过将葡萄糖氧化酶固载于壳聚糖-纳米金复合膜内所构置的传感器,实现了葡萄糖氧化酶的直接电化学,并采用循环伏安法与电化学阻抗法对修饰电极进行了表征。研究表明：在除氧缓冲溶液中,葡萄糖氧化酶-壳聚糖-纳米金复合膜修饰电极表现出一对良好的氧化还原峰,这对峰归因于葡萄糖氧化酶的氧化还原,证明葡萄糖氧化酶被成功固载于复合膜内。电子传递速率常数为15.6 s-1,说明葡萄糖氧化酶的电活性中心与电极之间的电子传递很快。将壳聚糖与纳米金相结合还提高了葡萄糖氧化酶在复合膜内的稳定性并保持其生物活性,并可以用于葡萄糖检测。计算得到其表观米氏常数为10.1 mmol·L-1。而且,该生物传感器可以用于血样中葡萄糖含量的测定。     

Anion-induced adsorption of ferrocenated nanoparticles

Au nanoparticles fully coated with omega-ferrocenyl hexanethiolate ligands, with average composition Au225(omega-ferrocenyl hexanethiolate)43, exhibit a unique combination of adsorption properties on Pt electrodes. The adsorbed layer is so robust that electrodes bearing submonolayer, monolayer, and multilayer quantities of these nanoparticles can be transferred to fresh electrolyte solutions and there exhibit stable ferrocene voltammetry over long periods of time. The kinetics of forming the robustly adsorbed layer are slow; monolayer and submonolayer deposition can be described by a rate law that is first order in nanoparticle concentration and in available electrode surface. The adsorption mechanism is proposed to involve entropically enhanced (multiple) ion-pair bridges between oxidized (ferrocenium) sites and certain specifically adsorbed electrolyte anions on the electrode. Adsorption is promoted by scanning to positive potentials (through the ferrocene wave) and by high concentrations of Bu4N+ X- electrolyte (X- = ClO4(-), PF6(-)) in the CH2Cl2 solvent; there is no adsorption if X- = p-toluenesulfonate or if the electrode is coated with an alkanethiolate monolayer. The electrode double layer capacity is not appreciably diminished by the adsorbed ferrocenated nanoparticles, which are gradually desorbed by scanning to potentials more negative than the electrode's potential of zero charge. At very slow scan rates, voltammetric current peaks are symmetrical and nearly reversible, but exhibit E(fwhm) considerably narrower (typically 35 mV) than ideally expected (90.6 mV, at 298 K) for a one-electron transfer or for reactions of multiple, independent redox centers with identical formal potentials. The peak narrowing is qualitatively explicable by a surface-activity effect invoking large, attractive lateral interactions between nanoparticles and, or alternatively, by a model in which ferrocene sites react serially at formal potentials that become successively altered as ion-pair bridges are formed. At faster scan rates, both deltaE(peak) and E(fwhm) increase in a manner consistent with a combination of uncompensated ohmic resistance of the electrolyte solution and of the adsorbed film, as distinct from behavior produced by slow electron transfer.     

二茂铁基超支化聚氨酯的电化学性能

通过循环伏安法(CV)测定了二茂铁基超支化聚氨酯(HAPE-Fc)的电化学性能.结果表明:HPAE-Fc表现为单对氧化还原峰,在二茂铁接枝到超支化聚氨酯上以后,二茂铁基团依然保持着自身的氧化还原独立性,具有较强的电子转移速率,这是其具有电化学特性和催化作用的前提条件.通过分析扫描速率与HPAE-Fc电化学行为之间的关系,发现HPAE-Fc的电极过程既受扩散控制,同时也受电极反应的控制.     

A comparison between interfacial electron-transfer rate constants at metallic and graphite electrodes

The Fermi golden rule formalism has been used to derive the rate constant for interfacial electron transfer from a semimetallic electrode, such as highly ordered pyrolytic graphite (HOPG), to a redox couple in solution. A simple expression is presented that semiquantitatively relates the electron-transfer rate constant at a semimetallic electrode to that at a metallic electrode. The approach allows for the estimation of the value of the rate constant for interfacial charge transfer to nonadsorbing outer-sphere redox species at semimetallic electrodes. Rate constants for interfacial electron transfer for a variety of one-electron redox couples at semimetallic electrodes have been calculated relative to the rate constant of the ferrocenium/ferrocene redox couple at a gold electrode. Good agreement is found, in general, between the calculated and observed rate constants.     

用分光光度法研究[Fe(H2O)3(NCS)3](18-C-6)在微栅电极上的电化学性质

The electrochemical reduction processes of [Fe(H_2O)_3(NCS)_3] (18-C-6) have been studied in nonaqueous media by method of cyclic voltammetry and spectroelec-trochemistry at an optical transparent thin layer electrode. The formal potential, E°′, electron transfer number, n, diffusion cofficient, D_O, formal heterogeneous electron transfer rate constant, k_S′, and electrochemical transfer coefficient, a, are deter-minated. Significant effect of solvents on the electrochemical behaviors has been observed. The higher the β, the higher the thermodynamic and kinetic stabilities of the coordination compound resulted.     

Direct electrochemistry and electrocatalysis with horseradish peroxidase in Eastman AQ films

Stable films made from ionomer poly(ester sulfonic acid) or Eastman AQ29 on pyrolytic graphite (PG) electrodes gave direct electrochemistry for incorporated enzyme horseradish peroxidase (HRP). Cyclic voltammetry of HRP-AQ films showed a pair of well-defined, nearly reversible peaks at about -0.33 V vs. SCE at pH 7.0 in blank buffers, characteristic of HRP heme Fe(III)/Fe(II) redox couple. The electron transfer between HRP and PG electrode was greatly facilitated in AQ films. The electrochemical parameters such as apparent heterogeneous electron transfer rate constant (k(s)) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry (SWV) with nonlinear regression analysis. Reflectance absorption infrared (RAIR) and UV-Vis absorption spectra demonstrated that HRP retained a near native conformation in AQ films. The embedded HRP in AQ films retained the electrocatalytic activity for oxygen, nitrite and hydrogen peroxide. Possible mechanism of catalytic reduction of H(2)O(2) with HRP-AQ films was proposed.     

血红蛋白在离子液体[BMIM]PF6碳糊电极上的直接电化学

制备了离子液体[BMIM]PF6修饰碳糊电极(CILE), 并对其形貌和电化学行为进行了表征. 采用涂布法利用壳聚糖-皂土有机-无机复合膜将血红蛋白(Hb)固定于CILE电极表面, 利用紫外可见光谱、红外光谱和电化学方法等手段对包埋于膜内的Hb的性质进行了表征. 结果表明, Hb在薄膜内保持了其原始构象与生物活性, 循环伏安实验表明, 在pH=7.0的Britton-Robinson (B-R)缓冲液中, Hb表现出一对峰形良好的准可逆氧化还原峰, 为Hb Fe(III)/Fe(II)电对的特征峰, 对其直接电化学行为进行了研究, 求出式电位为-0.352 V(vs SCE), 电子转移数为0.885, 电荷传递系数为0.578, 表观异相电子转移速率常数为0.149 s-1.     

Nanoparticle films as electrodes: voltammetric sensitivity to the nanoparticle energy gap

Electron-transfer reactions of redox solutes at electrode/solution interfaces are facilitated when their formal potentials match, or are close to, the energy of an electronic state of the electrode. Metal electrodes have a continuum of electronic levels, and redox reactions occur without restraint over a wide span of electrode potentials. This paper shows that reactions on electrodes composed of films of metal nanoparticles do have constraints when the nanoparticles are sufficiently small and molecule-like so as to exhibit energy gaps, and resist electron transfers with redox solutes at potentials within the energy gap. When solute formal potentials are near the electronic states of the nanoparticles in the film, electron-transfer reactions can occur. The electronic states of the nanoparticle film electrodes are reflected in the formal potentials of the electrochemical reactions of the dissolved nanoparticles at naked metal electrodes. These ideas are demonstrated by voltammetry of aqueous solutions of the redox solutes methyl viologen, ruthenium hexammine, and two ferrocene derivatives at films on electrodes of 1.1 nm core diameter Au nanoparticles coated with protecting monolayers of phenylethanethiolate ligands. The methyl viologen solute is unreactive at the nanoparticle film electrode, having a formal potential lying in the nanoparticle's energy gap. The other solutes exhibit electron transfers, albeit slowed by the electron hopping resistance of the nanoparticle film. The nanoparticles are not linked together, being insoluble in the aqueous medium; a small amount of an organic additive (acetonitrile) facilitates observing the redox solute voltammetry.     

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.     

Electrocatalytic reduction of dioxygen on a glassy carbon electrode modified with adsorbed cobaloxime complex.

The preparation and electrochemical properties of a glassy carbon (GC) electrode modified with cobaloxime complex were investigated. The complex of the type [CoIII(DO)(DOH)pn)Cl2] where (DO)(DOH)pn = N2,N2'-propanediylbis-2,3-butanedione-2-imine-3-oxime) was adsorbed irreversibly and strongly on the surface of preanodized glassy carbon electrode. Electrochemical behavior and stability of modified GC electrode were investigated by cyclic voltammetry. The electrocatalytic reduction of dioxygen has been studied using this modified glassy carbon electrode by cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as diagnostic techniques. The modified electrode showed excellent eletrocatalytic ability for the reduction of dioxygen to hydrogen peroxide in acetate buffer (pH 4.0) with overpotential 1.0 V lower than the plain glassy carbon electrode. The formal potential for this modified electrode is not shifted to more negative potentials by repeated reduction-oxidation cycles in oxygen-saturated supporting electrolyte solution. The apparent electron transfer rate constant (kS), the transfer coefficent (alpha) and the catalytic rate constant of O2 reduction at a GC modified electrode were determined by cyclic voltammetry and rotating disk electrode voltammetry and were found to be around 2.6 s(-1), 0.33 and 2.25 x 10(4) M(-1) s(-1). Based on the results, a catalytic mechanism is proposed and discussed.     

肌红蛋白在灿烂甲酚蓝修饰电极上的可逆电子传递反应

利用循环电位吸收法和电位阶跃计时吸收法在薄层电解池中研究了肌红蛋白在灿烂甲酚蓝(BCB)修饰电极上和BCB溶液中的电化学行为。实验表明肌红蛋白可以发生可逆的还原和氧化反应,完全还原和氧化分别需要20和100s, 氧化还原反应的标准速率常数被估算为5.6×10^-^4cm·s^-^1, 并且稳定性很好, 没有蛋白质变性反应发生。用光谱电化学方法测得该反应的标准电极电位和电子转移数与肌红蛋白相符。光电子能谱实验表明肌红蛋白没有吸附在BCB修饰电极上, 对BCB修饰电极促进肌红蛋白的电子转移机理作了初步探讨。     

阿魏酸聚合修饰玻碳电极的制备及其对NADH的催化氧化

研究了阿魏酸修饰电极的制备、性质及对NADH的电催化作用.该电极在0.1mol/L磷酸缓冲溶液(pH=6.60)中,于-0.1～+0.50V(vs.Ag/AgCl)电位范围内呈现一对氧化还原峰,其式量电位E₀为+0.188V(vs.Ag/AgCl),且E₀随pH增加而负向移动.电子转移系数为0.496,表观电极反应速率常数(ks)为6.6s^-1.电极反应的电子数为1且有1个质子参与.该修饰电极对NADH氧化具有很好的催化作用.在NADH存在下,电极过程由扩散控制,扩散系数为1.76×10^-6cm²/s.NADH浓度在0.01～5.0mmol/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6.82×10³mol^-1·L·s^-1.     

血红蛋白在碳纳米管修饰碳糊电极上的直接电化学行为

利用吸附法将血红蛋白(Hb)固定在碳纳米管修饰碳糊电极表面,制成稳定的固载Hb碳纳米管修饰电极,研究了Hb在碳纳米管修饰电极上的直接电化学行为.固载Hb的碳纳米管修饰电极在pH=7.0的PBS（磷酸盐缓冲溶液）中有一对相当可逆的循环伏安氧化还原峰,为Hb血红素辅基Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰.式电位为－0.160 V(vs SCE),随扫描速度变化很小.电子转移数为1.021,近似为一个辅基发生电子转移.Hb在碳纳米管修饰电极表面的电子转移常数为0.0816 s－1,远大于亚甲蓝作媒介体时Hb的电子转移反应速率常数.应用于过氧化氢、三氯乙酸和硝基苯等的电催化还原,固定在碳纳米管修饰碳糊电极的血红蛋白表现出稳定且较高的催化活性.     

血红蛋白在壳聚糖修饰碳纳米管上的电化学特性及对过氧化氢的电催化分析

用壳聚糖对多壁碳纳米管进行修饰,构建了一种用于固定血红蛋白的新型复合材料,并研究了血红蛋白在该碳纳米管上的电化学性质及其对过氧化氢的电催化活性.扫描电镜结果表明,壳聚糖修饰的多壁碳纳米管呈单一的纳米管状,并能均匀分散在玻碳电极表面.紫外光谱分析表明血红蛋白在该复合膜内能很好地保持其原有的二级结构.将该材料固定在玻碳电极上后,血红蛋白能成功地实现其直接电化学.根据峰电位差随着扫描的变化,计算得到血红蛋白在壳聚糖修饰的碳纳米管膜上的电荷转移系数为0.57,表观电子转移速率常数为7.02 s-1.同时,该电极对过氧化氢显示出良好的催化性能,电流响应信号与H2O2浓度在1.0×10-6 ～1.5×10-3 mol/L间呈线性关系,检出限为5.0×10-7 mol/L.修饰电极显示了良好的稳定性.     

Electrochemistry of redox-active self-assembled monolayers

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C₆₀). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.     

Introducing hydrophilic carbon nanoparticles into hydrophilic sol-gel film electrodes

A hydrophilic carbon nanoparticle–sol-gel electrode with good electrical conductivity within the sol-gel matrix is prepared. Sulfonated carbon nanoparticles with high hydrophilicity and of 10–20 nm diameter (Emperor 2000) are co-deposited onto tin-doped indium oxide substrates employing a sol-gel technique. The resulting carbon nanoparticle-sol-gel composite electrodes are characterized as a function of composition and salt (KCl) additive. Scanning electron microscopy and voltammetry in the absence and in the presence of a solution redox system suggest that the composite electrode films can be made electrically conducting and highly porous to promote electron transport and transfer. The effect of the presence of hydrophilic carbon nanoparticles is explored for the following processes: (1) double layer charging, (2) diffusion and adsorption of the electrochemically reversible solution redox system 1,1′-ferrocenedimethanol, (3) electron transfer to the electrochemically irreversible redox system hydrogen peroxide, and (4) electron transfer to the redox liquid tert-butylferrocene deposited into the porous composite electrode film. The extended electrochemically active hydrophilic surface area is beneficial in particular for surface sensitive processes (1) and (3), and it provides an extended solid|organic liquid|aqueous solution boundary for reaction (4). The carbon nanoparticle–sol-gel composite electrodes are optimized to provide good electrical conductivity and to remain stable during electrochemical investigation.