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• W1994322673 endingPage "5254" @default.
• W1994322673 startingPage "5245" @default.
• W1994322673 abstract "The one-electron-reduced form of vitamin B12, cob(II)alamin (Co2+Cbl), is found in several essential human enzymes, including the cobalamin-dependent methionine synthase (MetH). In this work, experimentally validated electronic structure descriptions for two “base-off” Co2+Cbl species have been generated using a combined spectroscopic and computational approach, so as to obtain definitive clues as to how these and related enzymes catalyze the thermodynamically challenging reduction of Co2+Cbl to cob(I)alamin (Co1+Cbl). Specifically, electron paramagnetic resonance (EPR), electronic absorption (Abs), and magnetic circular dichroism (MCD) spectroscopic techniques have been employed as complementary tools to characterize the two distinct forms of base-off Co2+Cbl that can be trapped in the H759G variant of MetH, one containing a five-coordinate and the other containing a four-coordinate, square-planar Co2+ center. Accurate spin Hamiltonian parameters for these low-spin Co2+ centers have been determined by collecting EPR data using both X- and Q-band microwave frequencies, and Abs and MCD spectroscopic techniques have been employed to probe the corrin-centered π → π* and Co-based d → d excitations, respectively. By using these spectroscopic data to evaluate electronic structure calculations, we found that density functional theory provides a reasonable electronic structure description for the five-coordinate form of base-off Co2+Cbl. However, it was necessary to resort to a multireference ab initio treatment to generate a more realistic description of the electronic structure of the four-coordinate form. Consistent with this finding, our computational data indicate that, in the five-coordinate Co2+Cbl species, the unpaired spin density is primarily localized in the Co 3dz2-based molecular orbital, as expected, whereas in the four-coordinate form, extensive Co 3d orbital mixing, configuration interaction, and spin−orbit coupling cause the unpaired electron to delocalize over several Co 3d orbitals. These results provide important clues to the mechanism of enzymatic Co2+Cbl → Co1+Cbl reduction." @default.
• W1994322673 created "2016-06-24" @default.
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• W1994322673 creator A5078803587 @default.
• W1994322673 creator A5080715446 @default.
• W1994322673 date "2009-03-19" @default.
• W1994322673 modified "2023-09-27" @default.
• W1994322673 title "Spectroscopic and Computational Characterization of the Base-off Forms of Cob(II)alamin" @default.
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• W1994322673 doi "https://doi.org/10.1021/jp810136d" @default.
• W1994322673 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/3127260" @default.
• W1994322673 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19298066" @default.
• W1994322673 hasPublicationYear "2009" @default.
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