Exceptional Photochemical Stability of the Co-C Bond of Alkynyl Cobalamins, Potential Antivitamins B12 and Core Elements of B12-Based Biological Vectors
Alkynylcorrinoids are a class of organometallic B12 derivatives, recently rediscovered for use as antivitamins B12 and as core components of B12-based biological vectors. They feature exceptional photochemical and thermal stability of their characteristic extra-short Co-C bond. We describe here the synthesis and structure of 3-hydroxypropynylcobalamin (HOPryCbl) and photochemical experiments with HOPryCbl, as well as of the related alkynylcobalamins: phenylethynylcobalamin and difluoro-phenylethynylcobalamin. Ultrafast spectroscopic studies of the excited state dynamics and mechanism for ground state recovery demonstrate that the Co-C bond of alkynylcobalamins is stable, with the Co-N bond and ring deformations mediating internal conversion and ground state recovery within 100 ps. These studies provide insights required for the rational design of photostable or photolabile B12-based cellular vectors.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
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| Enthalten in: |
Inorganic chemistry - 59(2020), 9 vom: 04. Mai, Seite 6422-6431 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Salerno, Elvin V [VerfasserIn] |
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| Links: |
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| Themen: |
3G0H8C9362 |
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| Anmerkungen: |
Date Completed 24.11.2020 Date Revised 10.01.2021 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/acs.inorgchem.0c00453 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM308957504 |
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| 500 | |a Date Revised 10.01.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Alkynylcorrinoids are a class of organometallic B12 derivatives, recently rediscovered for use as antivitamins B12 and as core components of B12-based biological vectors. They feature exceptional photochemical and thermal stability of their characteristic extra-short Co-C bond. We describe here the synthesis and structure of 3-hydroxypropynylcobalamin (HOPryCbl) and photochemical experiments with HOPryCbl, as well as of the related alkynylcobalamins: phenylethynylcobalamin and difluoro-phenylethynylcobalamin. Ultrafast spectroscopic studies of the excited state dynamics and mechanism for ground state recovery demonstrate that the Co-C bond of alkynylcobalamins is stable, with the Co-N bond and ring deformations mediating internal conversion and ground state recovery within 100 ps. These studies provide insights required for the rational design of photostable or photolabile B12-based cellular vectors | ||
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| 700 | 1 | |a Miller, Nicholas A |e verfasserin |4 aut | |
| 700 | 1 | |a Konar, Arkaprabha |e verfasserin |4 aut | |
| 700 | 1 | |a Salchner, Robert |e verfasserin |4 aut | |
| 700 | 1 | |a Kieninger, Christoph |e verfasserin |4 aut | |
| 700 | 1 | |a Wurst, Klaus |e verfasserin |4 aut | |
| 700 | 1 | |a Spears, Kenneth G |e verfasserin |4 aut | |
| 700 | 1 | |a Kräutler, Bernhard |e verfasserin |4 aut | |
| 700 | 1 | |a Sension, Roseanne J |e verfasserin |4 aut | |
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