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Photoreduction of Shewanella oneidensis Extracellular Cytochromes by Organic Chromophores and Dye‐Sensitized TiO2
Authors:Emma V. Ainsworth  Dr. Colin W. J. Lockwood  Dr. Gaye F. White  Dr. Ee Taek Hwang  Dr. Tsubasa Sakai  Manuela A. Gross  Prof. David J. Richardson  Dr. Thomas A. Clarke  Dr. Lars J. C. Jeuken  Dr. Erwin Reisner  Prof. Julea N. Butt
Affiliation:1. School of Chemistry, University of East Anglia, Norfolk, UK;2. School of Biological Sciences, University of East Anglia, Norfolk, UK;3. School of Biomedical Sciences, University of Leeds, Leeds, UK;4. Department of Chemistry, University of Cambridge, Cambridge, UK;5. Present address: Suntory Foundation for Life Sciences, Kyoto, Japan
Abstract:The transfer of photoenergized electrons from extracellular photosensitizers across a bacterial cell envelope to drive intracellular chemical transformations represents an attractive way to harness nature's catalytic machinery for solar‐assisted chemical synthesis. In Shewanella oneidensis MR‐1 (MR‐1), trans‐outer‐membrane electron transfer is performed by the extracellular cytochromes MtrC and OmcA acting together with the outer‐membrane‐spanning porin ? cytochrome complex (MtrAB). Here we demonstrate photoreduction of solutions of MtrC, OmcA, and the MtrCAB complex by soluble photosensitizers: namely, eosin Y, fluorescein, proflavine, flavin, and adenine dinucleotide, as well as by riboflavin and flavin mononucleotide, two compounds secreted by MR‐1. We show photoreduction of MtrC and OmcA adsorbed on RuII‐dye‐sensitized TiO2 nanoparticles and that these protein‐coated particles perform photocatalytic reduction of solutions of MtrC, OmcA, and MtrCAB. These findings provide a framework for informed development of strategies for using the outer‐membrane‐associated cytochromes of MR‐1 for solar‐driven microbial synthesis in natural and engineered bacteria.
Keywords:cytochromes  electron transfer  heme proteins  photocatalysis  photoreduction
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