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Electron-transfer Rate (electron-transfer + rate)
Selected AbstractsDramatic Effects of Ionic Liquid on Platinum Electrode Surface and Electron-Transfer Rates of meso -TetraphenylporphyrinsELECTROANALYSIS, Issue 12 2006Afsaneh Safavi Abstract The effect of addition of a room temperature ionic liquid, 1-butyl-3-methyl imidazolium hexafluorophosphate [bmim][PF6], on the electrochemical behavior of different free-base para-substituted meso -tetraphenylporphyrins in dichloromethane solution has been studied using cyclic voltammetric technique. It has been found that the ionic liquid has the ability to regenerate platinum electrode surface and improves the reversibility of electrode processes. This has been true for the case of all the porphyrins studied. [source] Comparison of the Electrochemical Reactivity of Carbon Nanotubes Paste Electrodes with Different Types of Multiwalled Carbon NanotubesELECTROANALYSIS, Issue 17 2008Xueling Li Abstract Carbon nanotubes (CNTs) are widely used in electrochemical studies. It is reported that CNTs with different source and dispersed in different agents [1] yield significant difference of electrochemical reactivity. Here we report on the electrochemical performance of CNTs paste electrodes (CNTPEs) prepared by multiwalled carbon nanotubes (MWNTs) with different diameters, lengths and functional groups. The resulting electrodes exhibit remarkable different electrochemical reactivity towards redox molecules such as NADH and K3[Fe(CN)6]. It is found that CNTPEs prepared by MWNTs with 20,30,nm diameter show highest catalysis to NADH oxidation, while CNTPEs prepared by MWNTs with carboxylate groups have best electron-transfer rate (The peak-peak separation (,Ep) is +0.108,V for MWNTs with carboxylate groups, +0.155,V for normal MWNTs, and +0.174,V for short MWNTs) but weak catalysis towards oxidation of NADH owing to the hydrophilicity of carboxylate groups. The electrochemical reactivity depends on the lengths of CNTs to some extent. The ,long' CNTs perform better in our study (The oxidation signals of NADH appear below +0.39,V for ,long' CNTs and above +0.46,V for the ,short' one totally). Readers may get some directions from this article while choose CNTs for electrochemical study. [source] Effects of heterogeneous electron-transfer rate on the resolution of electrophoretic separations based on microfluidics with end-column electrochemical detectionELECTROPHORESIS, Issue 19 2009Joseph Wang Abstract We demonstrate here that the electrode kinetics of an electrochemical detector contributes greatly to the resolution of the analyte bands in microchip electrophoresis systems with amperometric detection. The separation performance in terms of resolution and theoretical plate number can be improved and tailored by selecting or modifying the working electrode and/or by controlling the detection potential. Such improvements in the separation performance reflect the influence of the heterogeneous electron-transfer rate of electroactive analytes upon the post-channel band broadening, as illustrated for catechol and hydrazine compounds. The electrode kinetics thus has a profound effect not only on the sensitivity of electrochemical detectors but on the separation efficiency and the overall performance of microchip electrochemistry systems. [source] Modified Microperoxidases Exhibit Different Reactivity Towards Phenolic SubstratesCHEMBIOCHEM, Issue 12 2004Corrado Dallacosta Dr. Abstract The reactivity of several microperoxidase derivatives with different distal-site environments has been studied. The distal-site environments of these heme peptides include a positively charged one, an uncharged environment, two bulky and doubly or triply positively charged ones, and one containing aromatic apolar residues. The reactivity in the catalytic oxidation of two representative phenols, carrying opposite charges, by hydrogen peroxide has been investigated. This allows the determination of the binding constants and of the electron-transfer rate from the phenol to the catalyst in the substrate/microperoxidase complex. The electron-transfer rates scarcely depend on the redox and charge properties of the phenol, but depend strongly on the microperoxidase. Information on the disposition of the substrate in the adducts with the microperoxidases has been obtained through determination of the paramagnetic contribution to the1H NMR relaxation rates of the protons of the bound substrates. The data show that the electron-transfer rate drops when the substrate binds too far away from the iron and that the phenols bind to microperoxidases at similar distances to those observed with peroxidases. While the reaction rate of microperoxidases with peroxide is significantly smaller than that of the enzymes, the efficiency in the one-electron oxidation of phenolic substrates is almost comparable. Interestingly, the oxyferryl form of the triply positively charged microperoxidases shows a reactivity larger than that exhibited by horseradish peroxidase. [source] Interaction of Flavin Adenine Dinucleotide (FAD) with a Glassy Carbon Electrode SurfaceCHEMISTRY & BIODIVERSITY, Issue 8 2008Haizhen Wei Abstract The interaction of flavin adenine dinucleotide (FAD) with a glassy carbon electrode (GCE) surface was investigated in terms of the FAD adsorption thermodynamics and kinetics, the subsequent electroreduction mechanism, and the corresponding electron-transfer rate. The kinetics of FAD electroreduction at the GCE was found to be an adsorption-controlled process. A set of electroreduction kinetic parameters was calculated: the true number of electrons involved in the FAD reduction, n=1.76, the apparent transfer coefficient, ,app=0.41, and the apparent heterogeneous electron-transfer rate constant, kapp=1.4,s,1. The deviation of the number of exchanged electrons from the theoretical value for the complete reduction of FAD to FADH2 (n=2) indicates that a small portion of FAD goes to a semiquinone state during the redox process. The FAD adsorption was well described by the Langmuir adsorption isotherm. The large negative apparent Gibbs energy of adsorption (,Gads=,39.7 ±0.4,kJmol,1) indicated a highly spontaneous and strong adsorption of FAD on the GCE. The energetics of the adsorption process was found to be independent of the electrode surface charge in the electrochemical double-layer region. The kinetics of FAD adsorption was modeled using a pseudo -first-order kinetic model. [source] Distance dependence of long-range electron transfer through helical peptides,JOURNAL OF PEPTIDE SCIENCE, Issue 2 2008Minako Kai Abstract Helical peptides of 8mer, 16mer, and 24mer carrying a disulfide group at the N -terminal and a ferrocene moiety at the C -terminal were synthesized, and they were self-assembled on gold by a sulfur,gold linkage. Infrared reflection,absorption spectroscopy and ellipsometry confirmed that they formed a monolayer with upright orientation. Cyclic voltammetry showed that the electron transfer from the ferrocene moiety to gold occurred even with the longest 24mer peptide. Chronoamperometry and electrochemical impedance spectroscopy were carried out to determine the standard electron transfer rate constants. It was found that the dependence of the electron-transfer rates on the distance was significantly weak with the extension of the chain from 16mer to 24mer (decay constant , = 0.02,0.04). This dependence on distance cannot be explained by an electron tunneling mechanism even if increased hydrogen-bonding cooperativity or molecular dynamics is considered. It is thus concluded that this long-range electron transfer is operated by an electron hopping mechanism. Copyright © 2007 European Peptide Society and John Wiley & Sons, Ltd. [source] Advances in Photoelectrocatalysis with Nanotopographical PhotoelectrodesCHEMPHYSCHEM, Issue 8 2010A. G. Muñoz Dr. Abstract The design of photoelectrodes for high efficiency solar fuel energy conversion devices is based on the search for adequate surface conditioning to achieve efficient light harvesting, stability, minimized surface recombination losses and high electron-transfer rates at the electrolyte interface. An overview on established and novel approaches is given. A recent viable solution is provided by electroplating of nanoscale catalytic metals on passivated semiconductor surfaces, thereby forming reactive centers and avoiding contact between the semiconductor surface and the electrolyte. At these nano-dimensioned Schottky-type junctions, light-induced excess minority carriers are scavenged and transferred to the electrolyte. Various possible device configurations are outlined and envisaged systems for hydrogen or oxygen evolution and carbon dioxide reduction are presented. The role of ultrathin passivating films is emphasized and methods to fabricate open as well as compact conformal films are described. [source] | ||||||||||