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Extracellular redox-active compounds, flavins and other quinones, have been hypothesized to play a major role in the delivery of electrons from cellular metabolic systems to extracellular insoluble substrates by a diffusion-based shuttling two-electron-transfer mechanism. Here we show that flavin molecules secreted by Shewanella oneidensis MR-1 enhance the(More)
We report the site-specific synthesis of mixed valence TiIV-O-FeII complexes within the pores of ordered mesoporous silica (SBA-15). By using 6-di- tert-butylpyridine as the selective activator of tripodally linked TiIV-OH groups of Ti-grafted SBA-15, the FeCl2.4H2O complexes reacted selectively with the nucleophilic TiIV-O(-) groups. The formation of(More)
Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved(More)
Manganese oxides function as efficient electrocatalysts for water oxidation to molecular oxygen in strongly alkaline conditions, but are inefficient at neutral pH. To provide new insight into the mechanism underlying the pH-dependent activity of the electrooxidation reaction, we performed UV-vis spectroelectrochemical detection of the intermediate species(More)
Pure-culture studies have shown that dissimilatory metal-reducing bacteria are able to utilize iron-oxide nanoparticles as electron conduits for reducing distant terminal acceptors; however, the ecological relevance of such energy metabolism is poorly understood. Here, soil microbial communities were grown in electrochemical cells with acetate as the(More)
Shewanella is an electrogenic microbe that has significant content of c type cytochromes (ca. 0.5 mM). This feature allows the optical absorption spectra of the cell-membrane-associated proteins to be monitored in vivo in the course of extracellular respiratory electron-transfer reactions. The results show significant differences to those obtained in vitro(More)