Acceleration of Extracellular Electron Transfer by Alternative Redox-Active Molecules to Riboflavin for Outer-Membrane Cytochrome c of Shewanella oneidensis MR-1

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• 作者：Yoshihide Tokunou ; Kazuhito Hashimoto ; Akihiro Okamoto
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：July 28, 2016
• 年：2016
• 卷：120
• 期：29
• 页码：16168-16173
• 全文大小：316K
• 年卷期：0
• ISSN：1932-7455

文摘

Extracellular electron transfer (EET) between outer membrane c-type cytochromes (OM c-Cyts) of Shewanella oneidensis MR-1 and anodic and cathodic electrodes is markedly enhanced by the presence of riboflavin that operates as a redox active center in OM c-Cyt protein OmcA. Here, to obtain insight into the EET mechanism via bound riboflavin in OmcA, we replaced riboflavin with two flavin-like polycyclic molecules, safranin (Saf) and anthraquinone-1-sulfonate (α-AQS), and examined the influence of the interaction with OmcA and the potential of these redox molecules for the rate of cathodic EET by MR-1 in vivo. The results of electrochemical assays with wild-type and mutant strains of MR-1 lacking OmcA showed that both Saf and α-AQS increased the cathodic current production for fumarate reduction at −0.45 V versus SHE as a bound cofactor in OmcA. Dissociation constant and enhancement factor analyses of Saf and α-AQS suggested that the N(5) atom in the isoalloxazine ring of riboflavin is important for the affinity with OmcA and that a positive redox potential is critical for a high rate of EET. The present results suggest that the molecular design of the redox-active center in OM c-Cyts may allow control of the rate of EET in EET-capable bacteria.