Ab initio electronic structure calculations on model cations containing a disulfide linkage and a protonated amine site are carried out to examine ow the rate of electron transfer from a Rydberg orbital on the amine site to the S S * orbital depends upon the distance between these two rbitals. These simulations are relevant to both electron-capture and electron-transfer dissociation mass spectr...

The aim of this work was to investigate the effect of oxygen limitation on whole­ cell oxygenases, and to determine how the physiochemical properties of oils affect their ability to enhance the oxygen transfer rate. Whole-cell oxygenase biocatalysts require oxygen as a substrate for the reaction and for the electron transport chain. The productivity of these bioconversions is therefore influenc...

Previous ENDOR studies on reaction centers from Rhodopseudomonas sphaeroides have shown the presence of two hydrogen-bonded protons associated with the primary, ubiquinone, acceptor Q(A). These protons exchange with deuterons from solvent (2)H(2)O. The effect of this deuterium substitution on the charge-recombination kinetics (BChl)(2) (+)Q(A) (-) --> (BChl)(2)Q(A) has been studied with a sensi...

We study the energy-transfer rate for electrons in a double-quantum-well structure, where the layers are coupled through screened Coulomb interactions. The energy-transfer rate between the layers (similar to the Coulomb drag effect in which the momentum transfer rate is considered) is calculated as functions of electron densities, interlayer spacing, the temperature difference of the 2DEGs, and...

The electron shuttle heme protein Cyt-c(6) from the photosynthetic cyanobacterium Nostoc sp. PCC 7119 was immobilized on nanostructured Ag electrodes coated with SAMs that mimic different possible interactions with its natural reaction partner PSI. The structure, redox potential, and electron-transfer dynamics of the SAM-Cyt-c(6) complexes were investigated by TR-SERR spectroelectrochemistry. I...

Charge transfer through biological macromolecules is essential for many biological processes such as, for instance, photosynthesis and respiration. Protons or electrons are transferred between titratable residues or redox-active cofactors, respectively. Transfer rates between these sites depend on the current charge configuration of neighboring sites. Here, we formulate the kinetics of charge-t...

Thermal intramolecular electron transfer from the ferrocene (Fc) to naphthoquinone (NQ) moiety occurs efficiently by the addition of metal triflates (M(n)()(+): Sc(OTf)(3), Y(OTf)(3), Eu(OTf)(3)) to an acetonitrile solution of a ferrocene-naphthoquinone (Fc-NQ) linked dyad with a flexible methylene and an amide spacer, although no electron transfer takes place in the absence of M(n)()(+). The r...

Bovine heart cytochrome c oxidase is an electron-current driven proton pump. To investigate the mechanism by which this pump operates it is important to study individual electron- and proton-transfer reactions in the enzyme, and key reactions in which they are kinetically and thermodynamically coupled. In this work, we have simultaneously measured absorbance changes associated with electron-tra...

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6-4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the ...