Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment
Abstract
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.
- Authors:
-
[1];
[2];
[3];
[2];
[1];
[1];
[4];
[4];
[4];
[1]
- 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
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1461220
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 33; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
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, and Cramer, Stephen P. Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment. Germany: N. p., 2018.
Web. doi:10.1002/ange.201805144.
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. Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment. Germany. https://doi.org/10.1002/ange.201805144
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, and Cramer, Stephen P. Mon .
"Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment". Germany. https://doi.org/10.1002/ange.201805144.
@article{osti_1461220,
title = {Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment},
author = {Pham, Cindy C. and Mulder, David W. and Pelmenschikov, Vladimir and King, Paul W. and Ratzloff, Michael W. and Wang, Hongxin and Mishra, Nakul and Alp, Esen E. and Zhao, Jiyong and Hu, Michael Y. and Tamasaku, Kenji and Yoda, Yoshitaka and Cramer, Stephen P.},
abstractNote = {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.},
doi = {10.1002/ange.201805144},
journal = {Angewandte Chemie},
number = 33,
volume = 130,
place = {Germany},
year = {Mon Jul 23 00:00:00 EDT 2018},
month = {Mon Jul 23 00:00:00 EDT 2018}
}
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