[NMR paper] Protein Dynamics in the Solid-State from 2H NMR Lineshape Analysis. II: MOMD Applied to C-D, and C-CD3 Probes.

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Protein Dynamics in the Solid-State from 2H NMR Lineshape Analysis. II: MOMD Applied to C-D, and C-CD3 Probes.

Related Articles Protein Dynamics in the Solid-State from 2H NMR Lineshape Analysis. II: MOMD Applied to C-D, and C-CD3 Probes.

J Phys Chem B. 2015 Sep 24;

Authors: Meirovitch E, Liang Z, Freed JH

Abstract
Deuterium lineshape analysis from mobile C?-D and C-?CD3 groups has emerged as a particularly useful tool for studying dynamics in the solid-state. The theoretical models devised so far consist typically of sets of independent dynamic modes. Each such mode is simple and usually case-specific. In this scenario model-improvement entails adding yet another mode (thereby changing the overall model), comparison of different cases is difficult, and ambiguity is unavoidable. We recently developed the microscopic order macroscopic disorder (MOMD) approach as single-mode alternative. In MOMD the local spatial restrictions are expressed by an anisotropic potential, the local motion by a diffusion tensor, and the local molecular geometry by relative (magnetic and model-related) tensor orientations, all of adjustable symmetry. This approach provides a consistent method of analysis, thus resolving the issues above. In this study we apply MOMD to PS-adsorbed LK?14 peptide and dimethyl ammonium tetraphenylborate (C?-CD3 dynamics), as well as HhaI methyltransferase target DNA and Phase III of benzene-6-hexanoate (C-?D dynamics). The success with fitting these four disparate cases, as well as the two cases in the previous report, demonstrate the generality of this MOMD-based approach. In this study C-?D and C?-CD3 are both found to execute axial diffusion (rates Rperp and Rpar) in the presence of a rhombic potential given by the L = 2 spherical harmonics (coefficients c20 and c22). Rperp (Rpar) is in the 102?-103 (104?-105) s?-1 range, and c20 and c22 are on the order of 2-?3 kBT. Specific parameter values are determined for each mobile site. The diffusion and quadrupolar tensors are tilted at either 120o (consistent with trans-gauche isomerization) or nearly 110.5o (consistent with methyl exchange). Future prospects include extension of the MOMD formalism to include MAS, and application to 15N and 13C nuclei.


PMID: 26402431 [PubMed - as supplied by publisher]



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