细胞色素C在单糖修饰金电极上的直接电化学

Hill等发现在4,4′-联吡啶存在时,细胞色素C在金电极上能进行准可逆的电化学反应。在研究细胞色素C的直接电化学过程中,人们又发现一些生物小分子如氨基酸、嘌呤等对细胞色素C的电化学反应有促进作用,但迄今未见有关糖类分子对细胞色素C电化学反应促进作用研究的报道。本文研究了5种单糖对细胞色素C电化学反应的促进作用。     

细胞色素c在咔唑修饰的金电极上的直接电化学

在生物体内,细胞色素c是一种电子载体,它能进行可逆的氧化还原反应,但在金属电极上的电化学反应却不可逆。1977年,Hill研究组发现,在4,4′-联吡啶存在时,细胞色素c在金电极上能进行准可逆的电化学反应。4,4′-联吡啶在细胞色素c电化学反应的过程中不起氧化还原反应而被称为促进剂。Hill等对50多种有机化合物的促进作用进行评价后提出,能加速细胞色素c电化学反应速率的促进剂分子至少应具有两个功能团。表面增强拉曼光     

细胞色素C电化学反应的静电作用模型

首次发现,简单的阴离子Ⅰ~-是细胞色素c电化学反应的良好促进剂。在碘离子修饰的金电极上能观察到细胞色素c的准可逆电化学反应。根据细胞色素c的结构特点和碘离子的吸附特性,提出了一个以静电作用为基础的细胞色素c的电化学反应的模型。     

磷灰石通道离子替换对细胞色素C直接电化学的影响

采用沉淀法合成了以OH^-、F^-、Cl^-为通道离子的磷灰石纳米晶体。利用其独特的多位点吸附特性,研究了磷灰石不同通道离子替换对细胞色素c直接电化学的影响。在pH7．0的磷酸盐缓冲溶液中,细胞色素C在磷灰石修饰玻碳电极表面于0．074V(us．Ag／AgCl)附近有一对准可逆的氧化还原峰,为细胞色素C血红素辅基Fe(Ⅲ）／Fe(Ⅱ)电对的特征峰。细胞色素C与磷灰石之间的静电作用使深藏在细胞色素C内部的电活性中心靠近电极表面,加速了细胞色素C在玻碳电极表面扩散控制的准可逆单电子转移过程。其中氟磷灰石对细胞色素C直接电化学的促进作用最显著,羟基磷灰石次之,氯磷灰石最弱。     

细胞色素C在吡啶、聚吡啶修饰的金电极上的直接电化学

研究了细胞色素C在吡啶修饰的金电极上的电化学反应,结果表明,只具有一个功能团的吡啶分子和它的聚合物对细胞色素C电化学反应也有促进作用,讨论了影响促进剂促进作用的主要因素。     

细胞色素c在羟基磷灰石修饰玻碳电极上的直接电化学

采用沉淀法合成羟基磷灰石纳米晶体，由于具有独特的多吸附位点特征，羟基磷灰石可作为一种新型电子传递促进剂用于细胞色素c的直接电化学研究．在pH7．0的磷酸盐缓冲溶液中，细胞色素c在羟基磷灰石修饰玻碳电极表面于0．074V(vs．Ag/AgC1)处有一对准可逆的氧化还原峰，为细胞色素c血红素辅基Fe(Ⅲ)／Fe(Ⅱ)电对的特征峰．实验结果表明细胞色素c与羟基磷灰石之间的静电作用．促进了细胞色素c在玻碳电极表面扩散控制的准可逆单电子转移过程．讨论了电位扫描速度、溶液离子强度对细胞色素c直接电化学的影响．     

细胞色素C在聚乙烯氧化物修饰的金电极上的直接电化学反应

本文报道了细胞色素Ｃ在聚乙烯氧化物修饰的金电极上的直接电化学行为，发现ＰＥＯ是细胞色素Ｃ电化学反应的促进剂，ＰＥＯ修饰膜的形态对细胞色素Ｃ电化学反应的可逆性有较大的影响。     

脲对细胞色素c同步荧光光谱和电化学行为的影响

研究了细胞色素C溶液的同步荧光光谱和电化学性质随加入的脲的浓度而发生的变化,发现随着脲浓度的增加,细胞色素c分子在溶液中发生降聚、细胞色素c分子中卟啉环对溶剂暴露程度的增加和卟啉环上Fe-S键的断裂等过程和相应的电化学行为的变化.提出细胞色素c在金属电极上电化学反应不可逆可能是在较浓细胞色素c的溶液中,其分子大都以电化学活性较差的多聚体的形式存在而造成的.     

细胞色素C在吡啶,聚吡啶修饰的金电极上的直接电化学

研究了细胞色素Ｃ在吡啶修饰的金电极上的电化学反应，结果表明，只具有一个功能团的吡啶分子和它的聚合物对细胞色素Ｃ电化学反应也有促进作用，讨论了影响促进剂促进作用的主要因素。     

维生素B1对细胞色素C电化学反应的影响

本文探讨了细胞色素Ｃ在维生素Ｂ１修饰金电极上的电化学反应，结果表明维生素Ｂ１是细胞色素Ｃ电化学反应很好的促进剂而且它的促进作用与金电极表面维生素Ｂ１分子数量相关。     

铁氰化钆修饰电极的制备及表征

应用电化学循环扫描法于玻碳电极表面沉积并形成铁氰化钆修饰电极(GdHCF/GC),扫描电镜(SEM)显示,有两种大小和外形明显不同的颗粒状GdHCF附着在电极表面.红外光谱表明,GdCHF的C≡N弯曲振动吸收峰出现在2062.5 cm-1处.循环伏安法测试表明,在0.2 mol/L NaC l溶液中,GdHCF/GC电极出现两对氧化还原峰,扫速为20 mV/s时,其氧化还原峰的式量电位分别为E0’(I)=192.5 mV和E0’(II)=338.5 mV.研究了不同支持电解质对GdHCF/GC电极电化学性能的影响,GdHCF对Na+离子有优先选择性.     

Oxidation of some cage hydrocarbons by dioxiranes. Nature of the transition structure for the reaction of C-H bonds with dimethyldioxirane: a comparison of B3PW91 density functional theory with experiment

Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1',7-cyclopropan-(E)-2-methylbicyclo[2.2.1]heptane} (), tricyclo[3.2.2.0(2,4)]nonane (), exo-endo-endo- () and exo-exo-exo- () heptacyclo[9.3.1.0(2,10).0(3,8).0(4,6).0(5,9).0(12,14)]pentadecane, yielding tertiary alcohols as the main products. The rate constants for oxidation of by DMD were measured and the Arrhenius parameters determined. The DFT theory (B3LYP and B3PW91) using restricted and unrestricted methods was employed to study the oxidation reaction of the C-H bond of cage hydrocarbons , adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agreed with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs. the radical part is discussed.     

Catalytic photooxidation of alcohols by an unsymmetrical tetra(pyridyl)pyrazine-bridged dinuclear Ru complex

The dinuclear complexes [(tpy)Ru(tppz)Ru(bpy)(L)](n+) (where L is Cl(-) or H(2)O, tpy and bpy are the terminal ligands 2,2':6',2'-terpyridine and 2,2'-bipyridine, and tppz is the bridging backbone 2,3,5,6-tetrakis(2-pyridyl)pyrazine) were prepared and structurally and electronically characterized. The mononuclear complexes [(tpy)Ru(tppz)](2+) and [(tppz)Ru(bpy)(L)](m+) were also prepared and studied for comparison. The proton-coupled, multi-electron photooxidation reactivity of the aquo dinuclear species was shown through the photocatalytic dehydrogenation of a series of primary and secondary alcohols. Under simulated solar irradiation and in the presence of a sacrificial electron acceptor, the photoactivated chromophore-catalyst complex (in aqueous solutions at room temperature and ambient pressure conditions) can perform the visible-light-driven conversion of aliphatic and benzylic alcohols into the corresponding carbonyl products (i.e., aldehydes or ketones) with 100% product selectivity and several tens of turnover cycles, as probed by NMR spectroscopy and gas chromatography. Moreover, for aliphatic substrates, the activity of the photocatalyst was found to be highly selective toward secondary alcohols, with no significant product formed from primary alcohols. Comparison of the activity of this tppz-bridged complex with that of the analogue containing a back-to-back terpyridine bridge (tpy-tpy, i.e., 6',6'-bis(2-pyridyl)-2,2':4',4':2',2'-quaterpyridine) demonstrated that the latter is a superior photocatalyst toward the oxidation of alcohols. The much stronger electronic coupling with significant delocalization across the strongly electron-accepting tppz bridge facilitates charge trapping between the chromophore and catalyst centers and therefore is presumably responsible for the decreased catalytic performance.     

Rhodium-benzimidazolidin-2-ylidene catalyzed addition of arylboronic acids to aldehydes

Six rhodium–carbene complexes (2a–f) have been prepared and the new compounds characterized by C, H, N analyses, ¹H-n.m.r. and ¹³C-n.m.r. Phenylboronic acid reacts with aldehydes in the presence of a catalytic amount of rhodium(I)–carbene complex, RhCl(COD)(1,3-dialkylbenzimidazolidin-2-ylidene), (2a–f), to give the corresponding aryl secondary alcohols in good yields.     

细胞色素C在离子液体修饰电极上的电化学行为

分别合成了疏水和亲水性咪唑类离子液体,并制备了相应的两种离子液体修饰的玻碳电极。循环伏安法测量结果显示,细胞色素C在离子液体修饰的玻碳电极上的电子传递过程为一扩散控制的准可逆反应,表明咪唑类离子液体也可用作细胞色素C电子传递的有效促进剂。电化学交流阻抗谱的测量结果得到了与循环伏安相同的结论。     

The role of neutral coligands on the stabilization of mono-Tp(i)Pr2 U(III) complexes

The reaction of [UI(3)(THF)(4)] with 1 equiv of KTp()i(Pr)()2 in toluene in the presence of several neutral coligands allowed the synthesis of a novel family of mono-Tp()i(Pr)()2 complexes, [UI(2)Tp()i(Pr)()2(L)(x)()] [L = OPPh(3), x = 1 (3); L = C(5)H(5)N, x = 2 (4); L = Hpz()t(Bu,Me), x = 2 (5); and L = bipy, x = 1 (6)]. The adduct with THF, [UI(2)Tp()i(Pr)()2(THF)(2)(-)(3)] (1), could also be isolated by reacting [UI(3)(THF)(4)] with 1 equiv of KTp()i(Pr)()2 in tetrahydrofuran. However, complex 1 is not a good starting material to enter into the mono-Tp()i(Pr)()2 U(III) complexes as it decomposes in solution, leading to mixtures of U(III) species coordinated with Hpz()i(Pr)()2. The solid-state structures of 3, 4, and 6 were determined by single-crystal X-ray diffraction and revealed that this family of mono-Tp()i(Pr)()2 complexes can be six- (3) or seven-coordinated (4 and 6), depending on the nature of the neutral coligand. Complex 3 displays distorted octahedral coordination geometry, while 4 and 6 display distorted pentagonal bipyramid and capped octahedral geometries, respectively. Complexes 3 and 6 are static in solution, and the patterns of the (1)H NMR spectra are consistent with the C(s)() symmetry found in the solid state. The other complexes (1, 4, and 5) are fluxional, but the dynamic processes involved can be slowed by decreasing the temperature.     

Metal electrodes for continuous amperometric measurement of free hydrofluoric acid in acidic solutions containing complexing ions

Titanium-based electrodes have been demonstrated to be useful for measuring free HF concentration in the range 0.01-0.07M at temperatures between 19 and 61 degrees C in acidic, complexed HF solutions, by measurement of the current density resulting when the electrode potential is approximately +0.6 V with respect to an inert electrode. The current density, i, is linearly related to the HF concentration when the solution is adequately stirred to remove diffusion effects at the electrode, and is independent of HNO(3) concentration up to 1.75M. The dependence on the absolute temperature is ln i = - A/T + B + C ln T, and the activation energy at an absolute temperature T(r) is R(A + T(r)C), where A,B and C are constants and R is the gas constant. For a Ti-2% Pd electrode, the activation energy for anodic dissolution is found to be 43.7 +/- 0.2 kJ/mole at 312 K. The equations relating the current density to HF concentration at different temperatures can be combined to give a single equation for [HF] as a function of both i and T.     

Large-bite bis(phosphite) ligand containing mesocyclic thioether moieties: synthesis, reactivity, group 11 (Cu(I), Au(I)) metal complexes and anticancer activity studies on a human cervical cancer (HeLa) cell line

The large-bite bis(phosphite) ligand [{(-OC(10)H(6)(mu-S)C(10)H(6)O-)P{mu-(-OC(10)H(6)(mu-S)C(10)H(6)O-)}P(-OC(10)H(6)(mu-S)C(10)H(6)O-)}] (Pinsertion markP) () was obtained by the reaction of PCl(3) and thiobis(2,2'-naphthol) (). The stoichiometric reactions of with elemental sulfur and selenium afforded the corresponding chalcogenide derivatives [(E)Pinsertion markP(E)] (, E = S; , E = Se) in good yield. Treatment of two equivalents of [ClAu(SMe(2))] with afforded a dinuclear complex [ClAu(Pinsertion markP)AuCl] (), whereas the 1 : 1 reaction with CuI yielded the [(Pinsertion markP)CuI] () complex. The copper(i) complex on treatment with various pyridyl derivatives, produced mixed-ligand complexes [(Pinsertion markP)CuI(NC(5)H(5))] (), [(Pinsertion markP)Cu(2,2'-bpy)]I (), [(Pinsertion markP)Cu(1,10-phen)]I () and {[(Pinsertion markP)Cu(4,4'-bpy)]I}(infinity) (). The compounds were tested for their cytotoxic activity on the human cervical cancer (HeLa) cell line. Compounds and were found to inhibit proliferation of HeLa cells significantly. These agents also induced apoptotic cell death in cancer cells. Evidence presented in this study indicated that the compounds and activate the tumor suppressor protein p53 in the colon adenocarcinoma (HCT-116) cell line.     

离子交换介孔分子筛DEAE-SBA-15的制备及其用于分离纯化粉尘螨主要变应原Derf2

通过3-含氧缩水甘油基-丙基-三甲氧基硅烷(GPTS)将二乙胺基乙基(DEAE)嫁接在介孔分子筛SBA-15的表面,制得弱阴离子交换层析剂DEAE-SBA-15,使其既具有分子筛作用,又具有离子交换作用的特点.经DEAE-SBA-15层析后,从粉尘螨代谢培养基中获得单一的洗脱峰,SDS-PAGE显示一条谱带,其相对分子质量为14000,表明经分离纯化所得到的蛋白质是粉尘螨主要变应原Derf2.对螨性哮喘患者皮肤点刺试验表明,所得Derf2仍具有变应原活性,且仅通过一次柱色谱即得Derf2,表明DEAE-SBA-15是一种较好的离子交换层析剂.     

Novel kinetic and background current selectivity in the even harmonic components of fourier transformed square-wave voltammograms of surface-confined azurin

Fourier transform analysis of ramped square-wave voltammograms indicates the availability of a novel form of kinetic selectivity for surface-confined electron-transfer processes. Thus, for all the even harmonic components, quasi-reversible processes are sensitive to the surface coverage, the reversible potential, the electron-transfer rate constant (k(0')), and the electron-transfer coefficient (alpha), as well as to the amplitude (DeltaE) and frequency (f) of the square wave and dc scan rate. Additionally, it is insensitive to background capacitance current. In contrast, reversible processes and background currents are predicted to be absent from the even harmonics and only detectable in the odd harmonic components. The square-wave voltammetry of the surface-confined quasi-reversible azurin process azurin[Cu(II)] + e(-) right arrow over left arrow azurin[Cu(I)] at a paraffin-impregnated graphite electrode has been employed as a model system to test theoretical predictions. Most voltammetric characteristics of the even harmonic components obtained from the Fourier analysis are consistent with electrode kinetic values of k(0') = 90 s(-1) and alpha = 0.48, although some nonideality possibly due to kinetic dispersion also is apparent. Conditions also have been determined under which a readily generated waveform constructed from the Fourier series of sine waves produces voltammograms that are essentially indistinguishable from those predicted when an ideal square wave is employed.