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Functional and protective hole hopping in metalloenzymes

Gray, Harry B. and Winkler, Jay R. (2021) Functional and protective hole hopping in metalloenzymes. Chemical Science, 12 (42). pp. 13988-14003. ISSN 2041-6520. doi:10.1039/d1sc04286f.

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Electrons can tunnel through proteins in microseconds with a modest release of free energy over distances in the 15 to 20 Å range. To span greater distances, or to move faster, multiple charge transfers (hops) are required. When one of the reactants is a strong oxidant, it is convenient to consider the movement of a positively charged “hole” in a direction opposite to that of the electron. Hole hopping along chains of tryptophan (Trp) and tyrosine (Tyr) residues is a critical function in several metalloenzymes that generate high-potential intermediates by reactions with O₂ or H₂O₂, or by activation with visible light. Examination of the protein structural database revealed that Tyr/Trp chains are common protein structural elements, particularly among enzymes that react with O₂ and H₂O₂. In many cases these chains may serve a protective role in metalloenzymes by deactivating high-potential reactive intermediates formed in uncoupled catalytic turnover.

Item Type:Article
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Gray, Harry B.0000-0002-7937-7876
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© The Royal Society of Chemistry 2021. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Submitted 04 Aug 2021. Accepted 20 Sep 2021. First published 27 Sep 2021. All publication charges for this article have been paid for by the Royal Society of Chemistry. This work was supported by the National Institute of Diabetes and Digestive and Kidney Diseases of the NIH under Award R01DK019038. The content is solely the responsibility of the authors and does not necessarily represent the official views of the NIH. Additional support was provided by the Arnold and Mabel Beckman Foundation. Author contributions. Harry B. Gray: writing – review & editing, Jay R. Winkler: writing – review & editing. There are no conflicts of interest to declare.
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Arnold and Mabel Beckman FoundationUNSPECIFIED
Royal Society of ChemistryUNSPECIFIED
Issue or Number:42
Record Number:CaltechAUTHORS:20211008-224612858
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Official Citation:Functional and protective hole hopping in metalloenzymes. Chem. Sci., 2021, 12, 13988-14003; DOI: 10.1039/d1sc04286f
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:111312
Deposited By: George Porter
Deposited On:12 Oct 2021 20:32
Last Modified:03 Nov 2021 19:33

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