TY - JOUR
T1 - Protein Dynamics in the Solid State from 2H NMR Line Shape Analysis. II. MOMD Applied to C-D and C-CD3 Probes
AU - Meirovitch, Eva
AU - Liang, Zhichun
AU - Freed, Jack H.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/9/24
Y1 - 2015/9/24
N2 - Deuterium line shape 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 a 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 LKα14 peptide and dimethylammonium tetraphenylborate (C-CD3 and N-CD3 dynamics, respectively), 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, demonstrates the generality of this MOMD-based approach. In this study, C-D and C-CD3 are both found to execute axial diffusion (rates R⊥ and R∥) in the presence of a rhombic potential given by the L = 2 spherical harmonics (coefficients c20 and c22). R⊥ (R∥) 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 120° (consistent with trans-gauche isomerization) or nearly 110.5° (consistent with methyl exchange). Future prospects include extension of the MOMD formalism to include MAS, and application to 15N and 13C nuclei.
AB - Deuterium line shape 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 a 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 LKα14 peptide and dimethylammonium tetraphenylborate (C-CD3 and N-CD3 dynamics, respectively), 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, demonstrates the generality of this MOMD-based approach. In this study, C-D and C-CD3 are both found to execute axial diffusion (rates R⊥ and R∥) in the presence of a rhombic potential given by the L = 2 spherical harmonics (coefficients c20 and c22). R⊥ (R∥) 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 120° (consistent with trans-gauche isomerization) or nearly 110.5° (consistent with methyl exchange). Future prospects include extension of the MOMD formalism to include MAS, and application to 15N and 13C nuclei.
UR - http://www.scopus.com/inward/record.url?scp=84946830885&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.5b07434
DO - 10.1021/acs.jpcb.5b07434
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C2 - 26402431
AN - SCOPUS:84946830885
SN - 1520-6106
VL - 119
SP - 14022
EP - 14032
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 44
ER -