Can Simulations and Modeling Decipher NMR Data for Conformational Equilibria? Arginine-Vasopressin

Hänsele E, Saleh N, Read CM, Banting L, Whitley DC, Clark T (2016)

Publication Status: Published

Publication Type: Journal article

Publication year: 2016



Book Volume: 56

Pages Range: 1798-1807

Journal Issue: 9

DOI: 10.1021/acs.jcim.6b00344


Arginine vasopressin (AVP) has been suggested by molecular-dynamics (MD) simulations to exist as a mixture of conformations in solution. The H-1 and C-13 NMR chemical shifts of AVP in solution have been calculated for this conformational ensemble of ring conformations (identified from a 23 mu is molecular-dynamics simulation). The relative free energies of these conformations were calculated using classical metadynamics simulations in explicit water. Chemical shifts for representative conformations were calculated using density-functional theory. Comparison with experiment and analysis of the results suggests that the H-1 chemical shifts are most useful for assigning equilibrium concentrations of the conformations in this case. C-13 chemical shifts distinguish less clearly between conformations, and the distances calculated from the nuclear Overhauser effect do not allow the conformations to be assigned clearly. The H-1 chemical shifts can be reproduced with a standard error of less than 0.24 ppm (<2.2 ppm for C-13). The combined experimental and theoretical results suggest that AVP exists in an equilibrium of approximately 70% saddlelike and 30% clinched open conformations. Both newly introduced statistical metrics designed to judge the significance of the results and Smith and Goodman's DP4 probabilities are presented.

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Hänsele, E., Saleh, N., Read, C.M., Banting, L., Whitley, D.C., & Clark, T. (2016). Can Simulations and Modeling Decipher NMR Data for Conformational Equilibria? Arginine-Vasopressin. Journal of Chemical Information and Modeling, 56(9), 1798-1807.


Hänsele, Elke, et al. "Can Simulations and Modeling Decipher NMR Data for Conformational Equilibria? Arginine-Vasopressin." Journal of Chemical Information and Modeling 56.9 (2016): 1798-1807.

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