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Antivitamins B 12 in a Microdrop: The Excited-State Structure of a Precious Sample Using Transient Polarized X-ray Absorption Near-Edge Structure.
- Source :
-
The journal of physical chemistry letters [J Phys Chem Lett] 2019 Sep 19; Vol. 10 (18), pp. 5484-5489. Date of Electronic Publication: 2019 Sep 04. - Publication Year :
- 2019
-
Abstract
- Polarized transient X-ray absorption near-edge structure (XANES) was used to probe the excited-state structure of a photostable B <subscript>12</subscript> antivitamin (Coβ-2-(2,4-difluorophenyl)-ethynylcobalamin, F <subscript>2</subscript> PhEtyCbl). A drop-on-demand delivery system synchronized to the LCLS X-ray free electron laser pulses was implemented and used to measure the XANES difference spectrum 12 ps following excitation, exposing only ∼45 μL of sample. Unlike cyanocobalamin (CNCbl), where the Co-C bond expands 15-20%, the excited state of F <subscript>2</subscript> PhEtyCbl is characterized by little change in the Co-C bond, suggesting that the acetylide linkage raises the barrier for expansion of the Co-C bond. In contrast, the lower axial Co-N <subscript>DMB</subscript> bond is elongated in the excited state of F <subscript>2</subscript> PhEtyCbl by ca. 10% or more, comparable to the 10% elongation observed for Co-N <subscript>DMB</subscript> in CNCbl.
Details
- Language :
- English
- ISSN :
- 1948-7185
- Volume :
- 10
- Issue :
- 18
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry letters
- Publication Type :
- Academic Journal
- Accession number :
- 31483136
- Full Text :
- https://doi.org/10.1021/acs.jpclett.9b02202