title: 15N solid-state NMR as a probe of flavin H-bonding.
abstract: Flavins mediate a wide variety of chemical reactions in biology. To learn how one cofactor can be made to execute different reactions in different enzymes, we are developing solid-state NMR (SSNMR) to probe the flavin electronic structure, via the (15)N chemical shift tensor principal values (δ(ii)). We find that SSNMR has superior responsiveness to H-bonds, compared to solution NMR. H-bonding to a model of the flavodoxin active site produced an increase of 10 ppm in the δ(11) of N5, although none of the H-bonds directly engage N5, and solution NMR detected only a 4 ppm increase in the isotropic chemical shift (δ(iso)). Moreover SSNMR responded differently to different H-bonding environments, as H-bonding with water caused δ(11) to decrease by 6 ppm, whereas δ(iso) increased by less than 1 ppm. Our density functional theoretical (DFT) calculations reproduce the observations, validating the use of computed electronic structures to understand how H-bonds modulate the flavin's reactivity.
authors: Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, United States.
authors: Dongtao
authors: D
authors: Cui
authors: Ronald L
authors: RL
authors: Koder
authors: P Leslie
authors: PL
authors: Dutton
authors: Anne-Frances
authors: AF
authors: Miller
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