PMID- 25156475 OWN - NLM STAT- MEDLINE DCOM- 20150528 LR - 20161125 IS - 1521-3773 (Electronic) IS - 1433-7851 (Linking) VI - 53 IP - 41 DP - 2014 Oct 6 TI - Flavin redox bifurcation as a mechanism for controlling the direction of electron flow during extracellular electron transfer. PG - 10988-91 LID - 10.1002/anie.201407004 [doi] AB - The iron-reducing bacterium Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). While the mechanism for electron export from the OM c-Cyts to an anode is well understood, how the redox centers in OM c-Cyts take electrons from a cathode has not been elucidated at the molecular level. Electrochemical analysis of live cells during switching from anodic to cathodic conditions showed that altering the direction of electron flow does not require gene expression or protein synthesis, but simply redox potential shift about 300 mV for a flavin cofactor interacting with the OM c-Cyts. That is, the redox bifurcation of the riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell-electrode interface to drive bacterial metabolism as either anode or cathode catalysts. CI - (c) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. FAU - Okamoto, Akihiro AU - Okamoto A AD - Department of Applied Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan). okamoto@light.t.u-tokyo.ac.jp. FAU - Hashimoto, Kazuhito AU - Hashimoto K FAU - Nealson, Kenneth H AU - Nealson KH LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20140826 PL - Germany TA - Angew Chem Int Ed Engl JT - Angewandte Chemie (International ed. in English) JID - 0370543 RN - 0 (Benzoquinones) RN - 0 (Flavins) RN - 0 (Hydroquinones) RN - 9007-43-6 (Cytochromes c) RN - EC 1.3.99.1 (Succinate Dehydrogenase) RN - XV74C1N1AE (hydroquinone) SB - IM MH - Benzoquinones/chemistry MH - Cytochromes c/chemistry/metabolism MH - Electrodes MH - Electron Transport MH - Electrons MH - Flavins/*chemistry MH - Geobacter/metabolism MH - Hydroquinones/chemistry MH - Oxidation-Reduction MH - Succinate Dehydrogenase/chemistry/metabolism OTO - NOTNLM OT - cytochromes OT - electron transfer OT - in vivo studies OT - microbial electrosynthesis OT - riboflavins EDAT- 2014/08/27 06:00 MHDA- 2015/05/29 06:00 CRDT- 2014/08/27 06:00 PHST- 2014/07/08 00:00 [received] PHST- 2014/08/27 06:00 [entrez] PHST- 2014/08/27 06:00 [pubmed] PHST- 2015/05/29 06:00 [medline] AID - 10.1002/anie.201407004 [doi] PST - ppublish SO - Angew Chem Int Ed Engl. 2014 Oct 6;53(41):10988-91. doi: 10.1002/anie.201407004. Epub 2014 Aug 26.