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Understanding Sterol–Membrane Interactions Part I: Hartree–Fock versus DFT Calculations of 13 C and 1 H NMR Isotropic Chemical Shifts of Sterols in Solution and Analysis of Hydrogen‐Bonding Effects
Author(s) -
Jolibois Franck,
Soubias Olivier,
Réat Valérie,
Milon Alain
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400245
Subject(s) - chemical shift , chemistry , hydrogen bond , density functional theory , molecule , chemical bond , hydrogen , computational chemistry , membrane , organic chemistry , biochemistry
Abstract 1 H and 13 C NMR chemical shifts are exquisitely sensitive probes of the local environment of the corresponding nuclei. Ultimately, direct determination of the chemical shifts of sterols in their membrane environment has the potential to reveal their molecular interactions and dynamics, in particular concerning the hydrogen‐bonding partners of their OH groups. However, this strategy requires an accurate and efficient means to quantify the influence of the various interactions on chemical shielding. Herein the validity of Hartree–Fock and DFT calculations of the 13 C and 1 H NMR chemical shifts of cholesterol and ergosterol are compared with one another and with experimental chemical shifts measured in solution at 500 MHz. A computational strategy (definition of basis set, simpler molecular models for the sterols themselves and their molecular complexes) is proposed and compared with experimental data in solution. It is shown in particular that the effects of hydrogen bonding with various functional groups (water as a hydrogen‐bond donor and acceptor, acetone) on NMR chemical shifts in CDCl 3 solution can be accurately reproduced with this computational approach.