Matches in SemOpenAlex for { <https://semopenalex.org/work/W2945641181> ?p ?o ?g. }
- W2945641181 endingPage "4672" @default.
- W2945641181 startingPage "4663" @default.
- W2945641181 abstract "Derivatives of vitamin B12 are six-coordinate cobalt corrinoids found in humans, other animals, and microorganisms. By acting as enzymatic cofactors and photoreceptor chromophores, they serve vital metabolic and photoprotective functions. Depending on the context, the chemical mechanisms of the biologically active derivatives of B12-methylcobalamin (MeCbl) and 5'-deoxyadenosylcobalamin (AdoCbl)-can be very different from one another. The extent to which this chemistry is tuned by the upper axial ligand, however, is not yet clear. Here, we have used a combination of time-resolved Fourier transform-electron paramagnetic resonance (FT-EPR), magnetic field effect experiments, and spin dynamic simulations to reveal that the upper axial ligand alone only results in relatively minor changes to the photochemical spin dynamics of B12. By studying the photolysis of MeCbl, we find that, similar to AdoCbl, the initial (or geminate) radical pairs (RPs) are born predominantly in the singlet spin state and thus originate from singlet excited-state precursors. This is in contrast to the triplet RPs and precursors proposed previously. Unlike AdoCbl, the extent of geminate recombination is limited following MeCbl photolysis, resulting in significant distortions to the FT-EPR signal caused by polarization from spin-correlated methyl-methyl radical f-pairs formed following rapid diffusion. Despite the photophysical mechanism that precedes photolysis of MeCbl showing wavelength dependence, the subsequent spin dynamics appear to be largely independent of excitation wavelength, again similar to AdoCbl. Our data finally provide clarity to what in the literature to date has been a confused and contradictory picture. We conclude that, although the upper axial position of MeCbl and AdoCbl does impact their reactivity to some extent, the remarkable biochemical diversity of these fascinating molecules is most likely a result of tuning by their protein environment." @default.
- W2945641181 created "2019-05-29" @default.
- W2945641181 creator A5001077244 @default.
- W2945641181 creator A5010822875 @default.
- W2945641181 creator A5018819443 @default.
- W2945641181 creator A5036164033 @default.
- W2945641181 creator A5058507488 @default.
- W2945641181 creator A5059752371 @default.
- W2945641181 creator A5076493204 @default.
- W2945641181 creator A5079635985 @default.
- W2945641181 creator A5087807433 @default.
- W2945641181 creator A5090926581 @default.
- W2945641181 date "2019-05-13" @default.
- W2945641181 modified "2023-10-03" @default.
- W2945641181 title "Photochemical Spin Dynamics of the Vitamin B<sub>12</sub> Derivative, Methylcobalamin" @default.
- W2945641181 cites W1194791285 @default.
- W2945641181 cites W1748868217 @default.
- W2945641181 cites W1855881744 @default.
- W2945641181 cites W1963761005 @default.
- W2945641181 cites W1969897800 @default.
- W2945641181 cites W1971953901 @default.
- W2945641181 cites W1974652308 @default.
- W2945641181 cites W1976185935 @default.
- W2945641181 cites W1979750870 @default.
- W2945641181 cites W1987468043 @default.
- W2945641181 cites W2008164563 @default.
- W2945641181 cites W2013036895 @default.
- W2945641181 cites W2014018678 @default.
- W2945641181 cites W2015530277 @default.
- W2945641181 cites W2020527704 @default.
- W2945641181 cites W2020968990 @default.
- W2945641181 cites W2024848805 @default.
- W2945641181 cites W2034648318 @default.
- W2945641181 cites W2042212940 @default.
- W2945641181 cites W2042987546 @default.
- W2945641181 cites W2048941941 @default.
- W2945641181 cites W2050350740 @default.
- W2945641181 cites W2050810652 @default.
- W2945641181 cites W2052126905 @default.
- W2945641181 cites W2056282212 @default.
- W2945641181 cites W2059709867 @default.
- W2945641181 cites W2063783087 @default.
- W2945641181 cites W2073294006 @default.
- W2945641181 cites W2074123089 @default.
- W2945641181 cites W2080056789 @default.
- W2945641181 cites W2083400700 @default.
- W2945641181 cites W2084596334 @default.
- W2945641181 cites W2085460615 @default.
- W2945641181 cites W2105573265 @default.
- W2945641181 cites W2112066266 @default.
- W2945641181 cites W2119116665 @default.
- W2945641181 cites W2135173167 @default.
- W2945641181 cites W2135695843 @default.
- W2945641181 cites W2141247247 @default.
- W2945641181 cites W2142280021 @default.
- W2945641181 cites W2165790578 @default.
- W2945641181 cites W2170614560 @default.
- W2945641181 cites W2310814904 @default.
- W2945641181 cites W2313187531 @default.
- W2945641181 cites W2323024216 @default.
- W2945641181 cites W2323898916 @default.
- W2945641181 cites W2329748352 @default.
- W2945641181 cites W2335424814 @default.
- W2945641181 cites W2386990068 @default.
- W2945641181 cites W2406215274 @default.
- W2945641181 cites W2463368123 @default.
- W2945641181 cites W2582751793 @default.
- W2945641181 cites W2602977838 @default.
- W2945641181 cites W2611712440 @default.
- W2945641181 cites W2619320260 @default.
- W2945641181 cites W2796912840 @default.
- W2945641181 cites W2949410724 @default.
- W2945641181 doi "https://doi.org/10.1021/acs.jpcb.9b01969" @default.
- W2945641181 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/31081330" @default.
- W2945641181 hasPublicationYear "2019" @default.
- W2945641181 type Work @default.
- W2945641181 sameAs 2945641181 @default.
- W2945641181 citedByCount "9" @default.
- W2945641181 countsByYear W29456411812019 @default.
- W2945641181 countsByYear W29456411812020 @default.
- W2945641181 countsByYear W29456411812021 @default.
- W2945641181 countsByYear W29456411812022 @default.
- W2945641181 countsByYear W29456411812023 @default.
- W2945641181 crossrefType "journal-article" @default.
- W2945641181 hasAuthorship W2945641181A5001077244 @default.
- W2945641181 hasAuthorship W2945641181A5010822875 @default.
- W2945641181 hasAuthorship W2945641181A5018819443 @default.
- W2945641181 hasAuthorship W2945641181A5036164033 @default.
- W2945641181 hasAuthorship W2945641181A5058507488 @default.
- W2945641181 hasAuthorship W2945641181A5059752371 @default.
- W2945641181 hasAuthorship W2945641181A5076493204 @default.
- W2945641181 hasAuthorship W2945641181A5079635985 @default.
- W2945641181 hasAuthorship W2945641181A5087807433 @default.
- W2945641181 hasAuthorship W2945641181A5090926581 @default.
- W2945641181 hasBestOaLocation W29456411812 @default.
- W2945641181 hasConcept C121332964 @default.
- W2945641181 hasConcept C181500209 @default.
- W2945641181 hasConcept C184779094 @default.