Abstract
We report the first observation of quadrupole-central-transition (QCT) 59 Co (I=7/2) NMR signals from three cobalamin (Cbl) compounds (CNCbl, MeCbl, and AdoCbl) dissolved in glycerol/water. Measurements were performed at four magnetic fields ranging from 11.7 to 21.1 T. We found that the 59 Co QCT signals observed for cobalamin compounds in the slow motion regime (ω0 τC ≫1) are significantly narrower than those observed from their aqueous solutions where the molecular tumbling is near the condition of ω0 τC ≈1. We demonstrated that an analysis of 59 Co QCT signals recorded over different temperatures and at multiple magnetic fields allowed determination of both the 59 Co quadrupole coupling constant and chemical shift anisotropy for each of the three cobalamins. We successfully applied the 59 Co QCT NMR approach to monitor in situ the transformation of CNCbl to its "base off" form in the presence of KCN. We further discovered that, to obtain the maximum QCT signal intensity with the Hahn-echo sequence, a strong B1 field should be used for the first 90° pulse, but a weak B1 field for the second 180° pulse. The reported 59 Co QCT NMR methodology opens up a new direction for studying structure and function of cobalamin compounds and their roles in biological processes.
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More From: Chemphyschem : a European journal of chemical physics and physical chemistry
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