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Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B12 Coenzymes Controlled by the Axial Base
Abstract
Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B12 coenzymes.
- Authors:
-
- University of Michigan, Ann Arbor, MI (United States)
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 2322465
- Grant/Contract Number:
- AC02-76SF00515; CHE 1836435; CHE 2154157; P41GM139687
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B
- Additional Journal Information:
- Journal Volume: 128; Journal Issue: 6; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chung, Taewon, McClain, Taylor P., Alonso-Mori, Roberto, Chollet, Matthieu, Deb, Aniruddha, Garcia-Esparza, Angel T., Huang Ze En, Joel, Lamb, Ryan M., Michocki, Lindsay B., Reinhard, Marco, van Driel, Tim B., Penner-Hahn, James E., and Sension, Roseanne J. Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B12 Coenzymes Controlled by the Axial Base. United States: N. p., 2024.
Web. doi:10.1021/acs.jpcb.3c07779.
Chung, Taewon, McClain, Taylor P., Alonso-Mori, Roberto, Chollet, Matthieu, Deb, Aniruddha, Garcia-Esparza, Angel T., Huang Ze En, Joel, Lamb, Ryan M., Michocki, Lindsay B., Reinhard, Marco, van Driel, Tim B., Penner-Hahn, James E., & Sension, Roseanne J. Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B12 Coenzymes Controlled by the Axial Base. United States. https://doi.org/10.1021/acs.jpcb.3c07779
Chung, Taewon, McClain, Taylor P., Alonso-Mori, Roberto, Chollet, Matthieu, Deb, Aniruddha, Garcia-Esparza, Angel T., Huang Ze En, Joel, Lamb, Ryan M., Michocki, Lindsay B., Reinhard, Marco, van Driel, Tim B., Penner-Hahn, James E., and Sension, Roseanne J. Thu .
"Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B12 Coenzymes Controlled by the Axial Base". United States. https://doi.org/10.1021/acs.jpcb.3c07779.
@article{osti_2322465,
title = {Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B12 Coenzymes Controlled by the Axial Base},
author = {Chung, Taewon and McClain, Taylor P. and Alonso-Mori, Roberto and Chollet, Matthieu and Deb, Aniruddha and Garcia-Esparza, Angel T. and Huang Ze En, Joel and Lamb, Ryan M. and Michocki, Lindsay B. and Reinhard, Marco and van Driel, Tim B. and Penner-Hahn, James E. and Sension, Roseanne J.},
abstractNote = {Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B12 coenzymes.},
doi = {10.1021/acs.jpcb.3c07779},
journal = {Journal of Physical Chemistry. B},
number = 6,
volume = 128,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2024},
month = {Thu Feb 01 00:00:00 EST 2024}
}
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