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Water‐Based Hydrogen‐Atom Wires as Mediators in Long‐Range Proton‐Coupled Electron Transfer in Enzymes: A New Twist on Water Reactivity
Author(s) -
Cárdenas Diego J.,
Cuerva Juan M.,
Alías Miriam,
Buñuel Elena,
Campaña Araceli G.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100964
Subject(s) - electron transfer , hydrogen atom , reactivity (psychology) , proton , chemistry , proton coupled electron transfer , ligand (biochemistry) , range (aeronautics) , electron , cofactor , chemical physics , atom (system on chip) , twist , combinatorial chemistry , enzyme , photochemistry , materials science , physics , computer science , biochemistry , receptor , organic chemistry , quantum mechanics , alternative medicine , mathematics , pathology , composite material , embedded system , alkyl , geometry , medicine
Water is a conducting ligand between metal complexes! Water mediates the long‐range proton‐coupled electron transfer between two Cu complexes separated by 11 Å in the peptidylglycine α‐hydroxylating monooxygenase (PHM) cofactor (see scheme). The proposed mechanism, which involves three H‐atom exchanges, accounts for long‐range electron transfer in metalloenzymes, and may be ubiquitous in nature.

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