Accurate prediction of proton chemical shifts. II. Peptide analogues
- 25 January 2002
- journal article
- research article
- Published by Wiley in Journal of Computational Chemistry
- Vol. 23 (4), 492-497
- https://doi.org/10.1002/jcc.10044
Abstract
Proton chemical shifts of eight cyclic amide molecules were measured in DMSO and D2O solutions. The magnetic shieldings of the corresponding aliphatic, aromatic, and amide protons were calculated by Hartree-Fock and DFT, using the 6-311G**, 6-311++G**, and TZVP basis sets. For aliphatic protons, all of these methods reproduce the experimental values in DMSO solutions excellently after linear regression. The Hartree-Fock method tends to give slightly better agreement than DFT. The best performance is given by the HF/6-311G** method, with an rms deviation of 0.068 ppm. The deviations from experimental chemical shifts in D2O solutions are only slightly larger than those in DMSO solutions. This suggests that we can use the calculated gas phase proton chemical shifts directly to predict experimental data in various solvents, including water. For amide protons, which exchange with water and form hydrogen bonds with DMSO, only modest agreement is obtained, as expected. The present studies confirm that the GIAO approach can reach high accuracy for the relative chemical shifts of aliphatic and aromatic protons at a low cost. Such calculations may provide constraints for the conformational analysis of proteins and other macromolecules. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 492–497, 2002; DOI 10.1002/jcc.10044Keywords
This publication has 15 references indexed in Scilit:
- Accurate prediction of proton chemical shifts. I. Substituted aromatic hydrocarbonsJournal of Computational Chemistry, 2001
- Toward direct determination of conformations of protein building units from multidimensional NMR experiments I. A theoretical case study of For-Gly-NH2 and For-L-Ala-NH2Journal of Computational Chemistry, 2000
- A Comparison of Density Functional Methods for the Estimation of Proton Chemical Shifts with Chemical AccuracyThe Journal of Physical Chemistry A, 1999
- Density Functional Calculations of Proton Chemical Shifts in Model PeptidesJournal of the American Chemical Society, 1997
- Secondary and Tertiary Structural Effects on Protein NMR Chemical Shifts: an ab Initio ApproachScience, 1993
- Density-functional thermochemistry. III. The role of exact exchangeThe Journal of Chemical Physics, 1993
- Relationship between nuclear magnetic resonance chemical shift and protein secondary structureJournal of Molecular Biology, 1991
- Empirical correlation between protein backbone conformation and C.alpha. and C.beta. 13C nuclear magnetic resonance chemical shiftsJournal of the American Chemical Society, 1991
- Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculationsJournal of the American Chemical Society, 1990
- Self-consistent perturbation theory of diamagnetismMolecular Physics, 1974