Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

Pham, Cindy C.; Mulder, David W.; Pelmenschikov, Vladimir; King, Paul W.; Ratzloff, Michael W.; Wang, Hongxin; Mishra, Nakul; Alp, Esen E.; Zhao, Jiyong; Hu, Michael Y.; Tamasaku, Kenji; Yoda, Yoshitaka; Cramer, Stephen P.

doi:10.1002/ange.201805144

Title: Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

Journal Article · 23 July 2018 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201805144 · OSTI ID:1461220

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^[2]; Ratzloff, Michael W. ^[2];

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^[4]; Tamasaku, Kenji ^[5]; Yoda, Yoshitaka ^[5];

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Department of Chemistry UC Davis One Shields Ave Davis CA 95616 USA
National Renewable Energy Laboratory 15013 Denver W. Pkwy. Golden CO 80401 USA
Institut für Chemie Technische Universität Berlin Straße des 17. Juni 135 10623 Berlin Germany
Building 401 Argonne National Laboratory 9700 Cass Ave Lemont IL 60439 USA
JASRI SPring-8 1-1-1 Kouto, Mizauki-cho Sayo-gun Hyogo 679-5198 Japan

Abstract A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe−H/D bending modes in Cr HydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native Cr HydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe−H/D normal modes. We observed a significant shift to higher frequency in an Fe−H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted Cr HydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme.

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Sponsoring Organization:: USDOE

OSTI ID:: 1461220

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 33; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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