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。     

靛蓝胭脂红薄层光谱电化学研究(Ⅰ)

采用SnO_2石英玻璃组装的光透薄层电解池,结合紫外可见光谱现场监测技术,研究了靛蓝胭脂红水溶液的电化学还原与氧化过程.测定了不同pH下的式电极电位(E~0)和电子转移数(n).实验结果表明,靛蓝胭脂红在SnO_2电极上的还原为准可逆的两电子转移过程,而它的氧化则为不可逆电极过程.由电解现场检测的光谱,初步探讨了电解还原与氧化的反应机理。     

靛蓝胭脂红波薄层光谱电化学研究(I)

采用SnO_2石英玻璃组装的光透薄层电解池, 结合紫外可见光谱现场监测技术, 研究了靛蓝胭脂红水溶液的电化学还原与氧化过程. 测定了不同pH下的式电极电位(E~0)和电子转移数(n). 实验结果表明, 靛蓝胭脂红在SnO_2电极上的还原为准可逆的两电子转移过程, 而它的氧化则为不可逆电极过程. 由电解现场检测的光谱, 初步探讨了电解还原与氧化的反应机理。     

硝基苯在离子液体BMimBF4-H2O中的电还原

采用循环伏安法和恒电位电解法研究了离子液体BMimBF4-H2O 中硝基苯在微铂电极上的电还原特性. 实验表明, 在BMimBF4中, 随着硝基苯和水的浓度变化, 循环伏安曲线的峰电位和峰电流呈现复杂的变化规律; 硝基苯在铂电极上的电还原反应为双分子8 电子3 步骤电化学过程, 第一步反应为准可逆单分子单电子转移步骤, 产生阴离子自由基, 第二步为2 电子转移步骤, 并伴有随后的双分子不可逆自由基偶合化学反应, 主要产物为氧化偶氮苯, 第三步是2 电子转移产生偶氮苯的过程.     

硝基苯在离子液体EMimBF4中的选择性电还原

采用循环伏安法和恒电位电解法研究了离子液体EMimBF4中硝基苯在微铂电极上的选择性电还原特性. 研究结果表明, 硝基苯在铂电极上的电还原反应为双分子八电子三步骤电化学过程: 第一步反应为准可逆单电子转移步骤, 产生阴离子自由基; 第二步为二电子转移步骤, 并伴有随后的双分子不可逆自由基偶合反应和快速质子化及脱水反应, 主要产物为氧化偶氮苯; 第三步是二电子转移产生偶氮苯的过程. 通过控制电位, 可以选择性地合成氧化偶氮苯和偶氮苯; 在EMimBF4中, 硝基苯和水的浓度变化对电化学行为产生较大影响.     

碱性介质中葡萄糖在铂电极上的阳极氧化

为了进一步探明葡萄糖在铂电极上的氧化机理,用循环伏安法(CV)在-0.9～0.4 V(相对于饱和甘汞参比电极)内研究了葡萄糖在铂电极上催化氧化行为,首次详细报道了葡萄糖在电化学氧化过程中的电位振荡现象,并用电流扫描法表征了葡萄糖的电位振荡情况.电流扫描结果表明,在较慢的电流扫描速度下,电极过程出现了明显的电位振荡.说明电极上产生了毒化中间物,电位振荡是由于毒化中间物在电极上的吸附和在高电位下氧化除去引起的.     

冰醋酸中肾上腺素的现场光谱电化学行为

采用以石墨为工作电极的长光程薄层光谱电化学池, 用循环伏安法、恒电位光谱法和单电位跃计时吸光度法,研究了肾上腺素(AD)在冰醋酸介质中的电子转移反应。结果表明:AD在冰醋酸介质中电氧化反应产物为肾上腺素醌,还原态和氧化态的扩散系数分别为 3. 98×10-6 cm2 /s和 3. 90×10-6 cm2 /s;电极反应的式量电极电位为 0. 632V(vs.SCE),式量异相电子转移速率常数为 7. 30×10-4cm/s;传递系数为 0. 15。     

胆红素胆绿素在铂电极上氧化还原反应的现场光谱电化学研究

本文采用现场光谱电化学技术研究了胆红素(BR Ⅳα)、胆绿素(BV Ⅳα)及其氧化产物胆汁红紫素(Bi-Pu)在铂电极上的电氧化还原行为,并着重对上述过程的动力学进行了探讨。结果表明,在洁净的铂电极上,上述胆汁色素可通过控制电位实现Ⅳ构成的反应循环中,Ⅰ,Ⅱ可达到准可逆电子转移反应,式量非均相速率常数=1.5×10~(-4)cm·s~(-1),而Ⅲ,Ⅳ的氧化还原则为不可逆,=4.8×10~(-5)cm·s~(-1)。     

碳纳米管电极上辣根过氧化物酶的直接电化学

制备了碳纳米管修饰玻碳电极(CNT/GC).将辣根过氧化物酶(HRP)固定在CNT/GC电极表面,形成HRP-CNT/GC电极.研究了HRP的直接电子转移.实验结果表明,HRP在CNT/GC电极表面能进行有效和稳定的直接电子转移反应,其循环伏安曲线上表现出一对良好的、几乎对称的氧化还原峰;式量电位E^0'几乎不随扫速(至少在20～100 mV/s的扫速范围内)而变化,其平均值为(-0.319±0.002) V (vs. SCE, pH 6.9); HRP在CNT/GC电极表面直接电子转移的速率常数为(2.07±0.56) s^-1;式量电位E^0'与溶液pH 的关系表明HRP的直接电化学是(1e+1H⁺)的电极过程.进一步的实验结果显示,固定在CNT/GC电极表面的HRP能保持其对H₂O₂还原的生物电催化活性,而且能快速地响应H₂O₂浓度的变化.本文制备碳纳米管修饰电极和固定酶的方法具有简单和易于操作等优点,可用于获得其它生物氧化还原蛋白质和酶的直接电子转移.     

对再生式光电化学电极的开路电位及其稳定性的探讨

光电化学电极的开路电位及其稳定性与电解质溶液的性质有关。光电极的开路电位与照射在电极上光的强度呈半对数关系。实验表明:对n-型半导体电极,随着溶液中氧化态浓度的增加光电位向正方向移动,而改变溶液中还原态的浓度对光电位影响不大。本文根据电极过程的基本原理解释了这些事实。在某些电解质溶液中还观察到光电极光生电位的滞后现象,文中用费米能级分裂的概念对出现这一现象的原因进行了讨论。     

Dynamic spectroelectrochemical measurement for the conformational transition of cytochrome c induced by bromopyrogal red

The conformational transition of horse heart cytochrome c induced by bromopyrogal red (BPR) in very low concentration has been firstly investigated by dynamic spectroelectrochemical technique, both at the BPR adsorbed platinum gauze electrode and at a bare platinum gauze electrode in a solution containing BPR. The effect of BPR on the structure of cytochrome c was studied by UV-visible and Fourier transform IR spectroscopy. The unfolded cytochrome c behaves simply as an electron transfer protein with a formal potential of −142 mV vs. a normal hydrogen electrode. The difference between the formal potentials of the native and unfolded cytochrome c is coupled to a difference in conformational energy of the two states of about 40 kJ mol⁻¹, which agrees well with the result reported. The stability and slow refolding of the unfolded cytochrome c are discussed.     

Electrochemical investigations of cationictrans-haloarylisocyanidebis(tertiaryphosphino)platinum (II) complexes

Summary The electrochemical behaviour of a series of cationic platinum(II) isocyanide complexes has been studied in acetonitrile. All the tested compounds are oxidized at a platinum electrode via a two-electron process and reduced at a platinum or mercury electrode via two successive one-electron steps. The anodic step involves the formation of platinum(IV) complexes. The main reduction product formed in correspondence to the first cathodic process is a stable dimer platinum(I) containing bridging isocyanide ligands. Platinum(0) species are formed in the subsequent reduction step.     

In situ ESR and UV/vis spectroelectrochemical study of eosin Y upon reduction with and without Zn(II) ions.

The electroreduction of eosin Y on a platinum electrode in deaerated slightly acidic aqueous 0.1 mol L(-1) potassium chloride medium is followed in situ by electron spin resonance (ESR) spectroscopy and UV/Vis spectroscopy. The electrochemical formation of a semiquinone radical is proved by both the appearance of an absorbing band at 408 nm, and a strong ESR signal observed during a negative-going scan. The system is also studied in the presence of Zn(II) ions due to its importance for understanding the growth mechanism of nanostructured ZnO/Eosin Y hybrid films by electrodeposition; under such conditions the ESR and UV/Vis response of the semiquinone radical is not observed. Zinc (II) ions form a complex with the dye, which is reduced by a fast two-electron process.     

Electrochemical modeling of the oxidative dehydrogenation of 4H-thiopyrans

The oxidation of substituted 4H-thiopyrans on a rotating platinum disk electrode with a ring in acetonitrile was accomplished for the first time. It was established that the dehydrogenation of both tri- and pentasubstituted thiopyrans proceeds via a scheme involving the successive transfer of an electron, a proton, and an electron (an EPE process); 4H-thiopyrans are oxidized more readily than the corresponding oxygen analogs.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 318–320, March, 1984.     

The preparation and electrochemistry of manganese(II) complexes of an unsaturated pentadentate macrocyclic ligand

The preparation of a series of six and seven coordinate manganese(II) complexes [Mn^(II)(L)X]⁺, and [Mn^(II)(L)X₂]^2? (X = halide, water, triphenylphosphine oxide, imidazole, 1-methyl imidazole and pyridine) incorporating the pentadentate planar macrocylic ligand L is described. Cyclic voltammetry of these complexes in acetonitrile each shows a reversible one-electron reduction wave near - 1.4 V vs a Ag/AgNO₃ reference electrode. Quantitative reduction of these complexes by controlled potential electrolysis at a platinum gauze at - 1.4 V yields the corresponding one-electron reduction products which have been shown by ESR spectroscopy to be manganese(II)-ligand radical species, the electron being thought to reside on the di-imino pyridine moiety of the macrocyclic ligand. No metal reduced species could be isolated even in the presence of π-acceptor ligands such as CO or phosphines.     

Electrochemical transformations of cycloheptatriene derivatives

Redox reactions of a series of substituted cycloheptatrienes are studied on a platinum electrode in acetonitrile using the cyclic voltammetry method. It was found that heptaphenyl-substituted cycloheptatrienes are irreversibly oxidized in two stages in the range of high anodic potentials to form unstable radical cations and dications. As opposed to the unsubstituted and monosubstituted cycloheptatrienes, they are not reduced at the potentials higher than ?2 V (SCE). A new stable radical anion was found in the reduction of N-cycloheptatrienylphthalimide. Its spin density distribution is studied by ESR spectroscopy.     

Electrochemical characteristics of poly(ophenylendiamine) film electrodes in phosphatic solution

The electrochemical characteristics of poly(o-phenylendiamine) (POPD) film modified electrodes have been investigated using different electrochemical techniques.The main interest is focused on the effect of potential and film thickness on the electrode process.Good agreement has been found for the apparent diffusion coefficient estimated by chronocoulometry and impedance spec-troscopy.The charge transfer process within POPD films is diffusion processes at negative and positive overpotentials and electron hopping mechanism at formal potential.The POPD film conductivity of the oxidized state is better than that of the reduced state.For all electrode processes,the H+ may penetrate the film/electrolyte interface and take part in charge transfer or protonation-deprotonation of phenazine rings.     

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

The reduction of 6-amino-5-nitroso-1,3-dimethyluracil (ANDMU) is a key step in caffeine synthesis. Electroreduction technology is a promising green chemical process. The voltammetric behavior of ANDMU at polycrystalline platinum and nickel cathodes was studied. The Nicholson theory was used to resolve the reduction process semi-quantitatively. The results show that ANDMU mainly undergoes an ECE (electron transfer, chemical reaction, electron transfer) process involving four electrons on the platinum and nickel cathodes in which the two electron-transfer steps occur at almost the same potential and the rate of the coupling chemical reaction between two electron-transfer steps is very fast. Apparent kinetic data and diffusion coefficient were determined for the platinum rotating-disk electrode.     

Alkyl- and aryl-substituted corroles. 5. Synthesis, physicochemical properties, and X-ray structural characterization of copper biscorroles and porphyrin-corrole dyads

The synthesis and characterization of cofacial copper biscorroles and porphyrin-corroles linked by a biphenylenyl or anthracenyl spacer are described. The investigated compounds are represented as (BCA)Cu(2) and (BCB)Cu(2) in the case of the biscorrole (BC) derivatives and (PCA)Cu(2) and (PCB)Cu(2) in the case of porphyrin (P)-corrole (C) dyads, where A and B represent the anthracenyl and biphenylenyl bridges, respectively. A related monomeric corrole (Me(4)Ph(5)Cor)Cu and monomeric porphyrin (Me(2)Et(6)PhP)Cu that comprise the two halves of the porphyrin-corrole dyads were also studied. Electron spin resonance (ESR), (1)H NMR, and magnetic measurements data demonstrate that the copper corrole macrocycle, when linked to another copper corrole or copper(II) porphyrin, can be considered to be a Cu(III) complex in equilibrium with a Cu(II) radical species, copper(III) corrole being the main oxidation state of the corrole species at all temperatures. The cofacial orientation of (BCB)Cu(2), (BCA)Cu(2), and (PCB)Cu(2) was confirmed by X-ray crystallography. Structural data: (BCB)Cu(2)(C(110)H(82)N(8)Cu(2).3CDCl(3)), triclinic, space group P, a = 10.2550(2) A, b = 16.3890(3) A, c = 29.7910(8) A, alpha = 74.792(1) degrees , beta = 81.681(1) degrees , gamma = 72.504(2) degrees , Z = 2; (BCA)Cu(2)(C(112)H(84)N(8)Cu(2).C(7)H(8).1.5H(2)O), monoclinic, space group P 2(1)/c, a = 16.0870(4) A, b = 35.109(2) A, c = 19.1390(8) A, beta = 95.183(3) degrees , Z = 4; (PCB)Cu(2)(C(89)H(71)N(8)Cu(2).CHCl(3)), monoclinic, space group P2(1)/n, a = 16.7071(3) A, b = 10.6719(2) A, c = 40.8555(8) A, beta = 100.870(1) degrees , Z = 4. The two cofacial biscorroles, (BCA)Cu(2) and (BCB)Cu(2), both show three electrooxidations under the same solution conditions. The reduction of (BCA)Cu(2) involves a reversible electron addition to each macrocycle at the same potential of E(1/2) = -0.20 V although (BCB)Cu(2) is reversibly reduced in two steps to give first [(BCB)Cu(2)](-) and then [(BCB)Cu(2)](2)(-), each of which was characterized by ESR spectroscopy as containing a Cu(II) center. These latter electrode reactions occur at E(1/2) = -0.36 and -0.51 V versus a saturated calomel reference electrode. The half-reduced and fully reduced (BCB)Cu(2) show similar Cu(II) ESR spectra, and no evidence of a triplet signal is observed. The two well-separated reductions of (BCB)Cu(2) to give [(BCB)Cu(2)](2)(-) can be attributed to a stronger pi-pi interaction between the two macrocycles of this dimer as compared to those of (BCA)Cu(2). The copper porphyrin-corrole dyads, (PCA)Cu(2) and (PCB)Cu(2), show five reversible oxidations and two reversible reductions, and these potentials are compared with corresponding values for electrochemical reactions of the porphyrin and corrole monomers under the same solution conditions.