Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B12

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto; Garabato, Brady D.; Glownia, James M.; Kiefer, Laura M.; Koralek, Jake; Sikorski, Marcin; Spears, Kenneth G.; Wiley, Theodore E.; Zhu, Diling; Kozlowski, Pawel M.; Kubarych, Kevin J.; Penner-Hahn, James E.; Sension, Roseanne J.

doi:10.1021/jacs.6b11295

Title: Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B₁₂

Journal Article · Mon Jan 30 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b11295· OSTI ID:1353170

Miller, Nicholas A. ^[1]; Deb, Aniruddha ^[1]; Alonso-Mori, Roberto ^[2]; Garabato, Brady D. ^[3]; Glownia, James M. ^[2]; Kiefer, Laura M. ^[1]; Koralek, Jake ^[2]; Sikorski, Marcin ^[2]; Spears, Kenneth G. ^[1]; Wiley, Theodore E. ^[1]; Zhu, Diling ^[2]; Kozlowski, Pawel M. ^[4];

^[1];

^[1]

Univ. of Michigan, Ann Arbor, MI (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Louisville, Louisville, KY (United States)
Univ. of Louisville, Louisville, KY (United States); Medical Univ. of Gdansk, Gdansk (Poland)

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B₁₂, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributions and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N_Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: CHE 1150660; CHE 1300239; CHE 1464584; AC02-76SF00515

OSTI ID:: 1353170

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 5; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 52 works

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