微生物燃料电池

结合最近几年来微生物燃料电池研究进展情况，对微生物燃料电池的电子转移机理，影响电子转移的主要因素和解决方法，以及微生物燃料电池实用化过程中所面临的问题和应用前景进行了综述。  

聚苯胺用作乙醇脱氢反应中的电子传递介质

脱氢酶（ADH）在电化学氧化还原反应中是很重要的一种酶，但它在催化有机分子脱氢反应时需烟酰胺腺嘌呤二核苷酸（NAD＋）参与，后者从底物接收电子生成还原形NADH.脱氢酶电极是根据NADH的电化学氧化产生的阳极电流构成的[1－3].然而NADH与裸体炭电极和铂金电极之间的直接电子传递是非常困难的，往往需一个相当高的过电位[4].另一个问题是生成物易将电极玷污[5，6].克服这些问题的方法是使用均相电子传递介质，例如在底物溶液中加入Meldola蓝、Nile蓝A和NMP＋甲替硫酸盐等[7－9]，及复相电子传递介质，例如将镍六氰基高铁酸盐固…  

Unusual microstructures formed during the mediated electrodeposition of polypyrrole on Al 2024-T3 at low current densities

We have recently described the direct electrodeposition of polypyrrole on aluminum alloy 2024-T3 using electron transfer mediation. While studying the nucleation and growth phases of this deposition process using atomic force microscopy, we observed the formation of unusual polypyrrole structures. These structures formed only at low current density (10–100 A/cm²), only in the presence of the mediator (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt), and only in cells employing a small-area counter electrode (relative to the working electrode area). In this report, we present some of these interesting polypyrrole structures and the conditions of their formation.  

Surface effects of monolayer-protected gold nanoparticles on the redox reactions between ferricyanide and thiosulfate

The intense research interest in nanosized particle materials is mainly fueled by their unique physical, chemical, electronic, and magnetic properties[1]. Among these, they have shown great application po-tentialities in the catalytic regulation of elec-t…  

Direct and mediated electron transfer catalyzed by anionic tobacco peroxidase

The properties of anionic tobacco peroxidase (TOP) adsorbed on graphite electrode have been studied in direct and mediated electron transfer in a wall-jet flow injection system. The percentage of tobacco peroxidase molecules active in directelectron transfer is about 83%, which is higher than that for horeradish peroxidase (40–50%). This observation is explained in terms of the lower degree of glycosylation of TOP compared with horseradish peroxidase and, therefore, a reduced in terference from the oligosaccharide chains with direct electron transfer. Calcium ions cause an 11% drop in the reaction rate constant toward hydrogen peroxide. The detection limit of calcium chloride has been estimated as 5 m M. The results obtained by means of bioeletrochemistry, stopped-flow kinetics, and structural modeling provide evidence for the interaction between calcium cations and negatively charged residues at the distal domain (Glu-141, heme propionates, Asp-79, Asp-80) blocking the activesite. The observation that both soluble and immobilized enzyme under go conformational changes resulting in the blockade of the active site indicates that the immobilized enzyme preserves conformational flexibility. An even stronger suppressing effect of calcium ions on the rate constant for mediated electron transfer was observed. In the case of direct electron transfer, this couldmean that there is nodirect contact between the electrode and the active site of TOP. The electrons are shuttled from the active site to the surface of the electrode through electron transfer pathways in the protein globule that are sensitive to protein conformational changes.  

Catecholamine release from cultured bovine adrenal medullary chromaffin cells in the presence of 60-Hz magnetic fields

Effects of powerline frequency (50/60 Hz) electric and magnetic fields on the central nervous system may involve altered neurotransmitter release. This possibility was addressed by determining whether 60-Hz linearly polarized sinusoidal magnetic fields (MFs) alter the release of catecholamines from cultured bovine adrenal chromaffin cells, a well-characterized model of neural-type cells. Dishes of cells were placed in the center of each of two four-coil Merritt exposure systems that were enclosed within mu-metal chambers in matched incubators for simultaneous sham and MF exposure. Following 15-min MF exposure of the cells to flux densities of 0.01, 0.1, 1.0 or 2 mT, norepinephrine and epinephrine release were quantified by high-performance liquid chromatography (HPLC) coupled with electrochemical detection. No significant differences in the release of either norepinephrine or epinephrine were detected between sham-exposed cells and cells exposed to MFs in either the absence or presence of Bay K-8644 (2 microM) or dimethylphenylpiperazinium (DMPP, 10 microM). Consistent with these null findings is the lack of effect of MF exposure on calcium influx. We conclude that catecholamine release from chromaffin cells is not sensitive to 60-Hz MFs at magnetic flux densities in the 0.01-2 mT range.  

Enzymatic mechanisms and electron transfer mediation in chronoamperometric biosensors

Electron transfer mediation to an anode, whose potential is judiciously controlled, provides the conceptual basis for the development of novel chronoamperometric biosensors. The mediators are appropriately selected redox couples (Ox/Red) which are amenable to recycling in the following type of enzyme E catalyzed reaction sequence

Electron-transfer mediation on poly-aryl dendrimer-modified electrodes

Electrochemical properties of a dendrimer-modified electrode that was prepared by immobilization of ferrocenyl-terminated dendrimers on a poly-phenyl acetate anchoring layer were investigated in CH₂Cl₂. The anchoring layer was made by electro-grafting of the corresponding diazonium salt on a glassy carbon surface. The method allows the fabrication of a robust interface where the properties of the dendrimers are well-preserved. Moreover, the control of the layer properties as the permeation of molecules from the solution to the surface could be tuned up from only limited to totally blocked through the electrochemical conditions used during the electro-grafting of the anchoring layer. Detailed investigations performed with cyclic voltammetry and on different types of layers show that the modified electrode catalyses the oxidation of redox substrates. The process depends on the standard potential of the redox couple compared to that of the adsorbed dendrimer molecules. Experiments indicate that the electron exchange with molecules in solution takes place mainly at the dendrimer film–solution interface as the dendrimers inside the film permit the charge-transfer through the modified film to the carbon substrate. The interest of using robust electrode dendrimer relies on the possibility of large structural variations allowing the careful introduction of specific properties in the layer.  

Evaluation of Some Redox Mediators in the Design of Reagentless Amperometric Glucose Biosensor

The influence of redox mediators (tetrathiafulvalene (TTF), tetrathiafulvalene‐tetracyanoquinodimethane complex (TTF‐TCNQ), phenazine methosulfate (PMS), 5,6‐diamino‐1,10‐phenonthroline (5,6‐DAP), potassium ferrocyanide (K4[Fe(CN)6]), methylene blue (MB) and toluidine blue (TB)) on the response of amperometric glucose biosensor was investigated in this research. Graphite rod electrode (GRE) modified by adsorbed mediator and glucose oxidase (GOx) cross‐linked with glutaraldehyde was served as working electrode. The highest amperometric signals were observed by using TTF and TTF‐TCNQ as mediators. The impact of amount of immobilized GOx, an optimal pH region for operation, stability and reproducibility of the analytic signal of designed biosensor using these mediators were investigated and discussed.