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Axial Ligation of Heme in c‐Type Cytochromes of Living Shewanella oneidensis : A New Insight into Enhanced Extracellular Electron Transfer
Author(s) -
Yuan Yong,
Li Laicai,
Zhou Shungui
Publication year - 2015
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201500234
Subject(s) - shewanella oneidensis , heme , electron transfer , imidazole , chemistry , shewanella , redox , biochemistry , photochemistry , bacteria , biology , inorganic chemistry , enzyme , genetics
The controlled axial ligation reaction of the heme Fe in c‐type cytochromes (c‐Cyts) is a valid approach to regulating the redox activity of c‐Cyts, but it is mainly revealed in purified c‐Cyts. Herein, we demonstrate the first example of regulating the redox activity of c‐Cyts in a living microorganism through heme axial ligation to target high extracellular electron transfer (EET). The direct electrochemistry of Shewanella oneidensis amended with an axial ligand (imidazole) delivered a 1.5‐fold increase in the biocurrent, demonstrating enhanced EET. In vivo UV/Vis and Raman spectra confirmed the axial ligation of imidazoles to the c‐Cyts. Density functional calculations revealed the optimized electronic structure and lowered reorganization energy values of the imidazole‐ligated heme, which benefited EET. These findings provide, not only a better understanding of the mechanism underlying the EET, but also new insights into the enhanced EET.