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  Five-coordinate MnIV intermediate in the activation of nature’s water splitting cofactor

Chrysina, M., Heyno, E., Kutin, Y., Reus, M., Nilsson, H., Nowaczyk, M. M., et al. (2019). Five-coordinate MnIV intermediate in the activation of nature’s water splitting cofactor. Proceedings of the National Academy of Sciences of the United States of America, 116(34), 16841-16846. doi:10.1073/pnas.1817526116.

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Chrysina, Maria1, Author           
Heyno, Eiri2, Author
Kutin, Yuri3, Author           
Reus, Michael1, Author           
Nilsson, Håkan4, Author
Nowaczyk, Marc M.2, Author
DeBeer, Serena1, Author           
Neese, Frank5, Author           
Messinger, Johannes4, 6, Author
Lubitz, Wolfgang7, Author           
Cox, Nicholas8, Author
Affiliations:
1Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
2Plant Biochemistry, Faculty of Biology and Biotechnology, Ruhr-Universität Bochum, D-44780 Bochum, Germany, ou_persistent22              
3Research Department Lubitz, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023873              
4Department of Chemistry, Chemical Biological Centre, Umeå University, S-90187 Umeå, Sweden, ou_persistent22              
5Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
6Department of Chemistry–Ångström Laboratorium, Uppsala University, 75120 Uppsala, Sweden, ou_persistent22              
7Research Department Lubitz, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023878              
8Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia, ou_persistent22              

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 Abstract: Nature’s water splitting cofactor passes through a series of catalytic intermediates (S0-S4) before O-O bond formation and O2 release. In the second last transition (S2 to S3) cofactor oxidation is coupled to water molecule binding to Mn1. It is this activated, water-enriched all MnIV form of the cofactor that goes on to form the O-O bond, after the next light-induced oxidation to S4. How cofactor activation proceeds remains an open question. Here, we report a so far not described intermediate (S3') in which cofactor oxidation has occurred without water insertion. This intermediate can be trapped in a significant fraction of centers (>50%) in (i) chemical-modified cofactors in which Ca2+ is exchanged with Sr2+; the Mn4O5Sr cofactor remains active, but the S2-S3 and S3-S0 transitions are slower than for the Mn4O5Ca cofactor; and (ii) upon addition of 3% vol/vol methanol; methanol is thought to act as a substrate water analog. The S3' electron paramagnetic resonance (EPR) signal is significantly broader than the untreated S3 signal (2.5 T vs. 1.5 T), indicating the cofactor still contains a 5-coordinate Mn ion, as seen in the preceding S2 state. Magnetic double resonance data extend these findings revealing the electronic connectivity of the S3' cofactor is similar to the high spin form of the preceding S2 state, which contains a cuboidal Mn3O4Ca unit tethered to an external, 5-coordinate Mn ion (Mn4). These results demonstrate that cofactor oxidation regulates water molecule insertion via binding to Mn4. The interaction of ammonia with the cofactor is also discussed.

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Language(s): eng - English
 Dates: 2018-10-112019-07-102019-08-072019-08-20
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1073/pnas.1817526116
 Degree: -

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Title: Proceedings of the National Academy of Sciences of the United States of America
  Other : Proc. Acad. Sci. USA
  Other : Proc. Acad. Sci. U.S.A.
  Other : Proceedings of the National Academy of Sciences of the USA
  Abbreviation : PNAS
Source Genre: Journal
 Creator(s):
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Publ. Info: Washington, D.C. : National Academy of Sciences
Pages: - Volume / Issue: 116 (34) Sequence Number: - Start / End Page: 16841 - 16846 Identifier: ISSN: 0027-8424
CoNE: https://pure.mpg.de/cone/journals/resource/954925427230