Conformational Sampling by Ab Initio Molecular Dynamics Simulations Improves NMR Chemical Shift Predictions

0396144 - ÚOCHB 2014 RIV US eng J - Článek v odborném periodiku
Dračínský, Martin - Möller, H. M. - Exner, T. E.
Conformational Sampling by Ab Initio Molecular Dynamics Simulations Improves NMR Chemical Shift Predictions.
Journal of Chemical Theory and Computation. Roč. 9, č. 8 (2013), s. 3806-3815. ISSN 1549-9618. E-ISSN 1549-9626
Grant CEP: GA ČR GA13-24880S
Institucionální podpora: RVO:61388963
Klíčová slova: ab initio molecular dynamics * NMR spectroscopy * DFT calculations * hydration
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 5.310, rok: 2013

Car-Parrinello molecular dynamics simulations were performed for N-methyl acetamide as a small test system for amide groups in protein backbones, and NMR chemical shifts were calculated based on the generated ensemble. If conformational sampling and explicit solvent molecules are taken into account, excellent agreement between the calculated and experimental chemical shifts is obtained. These results represent a landmark improvement over calculations based on classical molecular dynamics (MD) simulations especially for amide protons, which are predicted too high-field shifted based on the latter ensembles. We were able to show that the better results are caused by the solute-solvents interactions forming shorter hydrogen bonds as well as by the internal degrees of freedom of the solute. Inspired by these results, we propose our approach as a new tool for the validation of force fields due to its power of identifying the structural reasons for discrepancies between the experimental and calculated data.
Trvalý link: http://hdl.handle.net/11104/0224058