Antivitamins B12 in a Microdrop : The Excited-State Structure of a Precious Sample Using Transient Polarized X-ray Absorption Near-Edge Structure
Polarized transient X-ray absorption near-edge structure (XANES) was used to probe the excited-state structure of a photostable B12 antivitamin (Coβ-2-(2,4-difluorophenyl)-ethynylcobalamin, F2PhEtyCbl). 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 F2PhEtyCbl 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-NDMB bond is elongated in the excited state of F2PhEtyCbl by ca. 10% or more, comparable to the 10% elongation observed for Co-NDMB in CNCbl.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2019 |
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| Erschienen: |
2019 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:10 |
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| Enthalten in: |
The journal of physical chemistry letters - 10(2019), 18 vom: 19. Sept., Seite 5484-5489 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Miller, Nicholas A [VerfasserIn] |
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| Links: |
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| Themen: |
3G0H8C9362 |
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| Anmerkungen: |
Date Completed 25.11.2019 Date Revised 25.11.2019 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/acs.jpclett.9b02202 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM300922256 |
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| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Polarized transient X-ray absorption near-edge structure (XANES) was used to probe the excited-state structure of a photostable B12 antivitamin (Coβ-2-(2,4-difluorophenyl)-ethynylcobalamin, F2PhEtyCbl). 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 F2PhEtyCbl 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-NDMB bond is elongated in the excited state of F2PhEtyCbl by ca. 10% or more, comparable to the 10% elongation observed for Co-NDMB in CNCbl | ||
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| 700 | 1 | |a Britz, Alexander |e verfasserin |4 aut | |
| 700 | 1 | |a Deb, Aniruddha |e verfasserin |4 aut | |
| 700 | 1 | |a DePonte, Daniel P |e verfasserin |4 aut | |
| 700 | 1 | |a Glownia, James M |e verfasserin |4 aut | |
| 700 | 1 | |a Kaneshiro, April K |e verfasserin |4 aut | |
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| 700 | 1 | |a Penner-Hahn, James E |e verfasserin |4 aut | |
| 700 | 1 | |a Sension, Roseanne J |e verfasserin |4 aut | |
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