Complete 13C NMR Chemical Shifts Assignment for Cholesterol Crystals by Combined CP-MAS Spectral Editing and ab Initio GIPAW Calculations with Dispersion Forces

We report here the first fully ab initio determination of 13C NMR spectra for several crystal structures of cholesterol, observed in various biomaterials. We combine Gauge-Including Projector Augmented Waves (GIPAW) calculations at relaxed structures, fully including dispersion forces, with Magic An...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2012-04, Vol.116 (14), p.3765-3769
Main Authors: Küçükbenli, Emine, Sonkar, Kanchan, Sinha, Neeraj, de Gironcoli, Stefano
Format: Article
Language:English
Subjects:
Carbon Isotopes
Cholesterol - chemistry
Crystallization
Crystallography, X-Ray
Models, Molecular
Molecular Structure
Nuclear Magnetic Resonance, Biomolecular
Quantum Theory
Water - chemistry
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Summary:We report here the first fully ab initio determination of 13C NMR spectra for several crystal structures of cholesterol, observed in various biomaterials. We combine Gauge-Including Projector Augmented Waves (GIPAW) calculations at relaxed structures, fully including dispersion forces, with Magic Angle Spinning Solid State NMR experiments and spectral editing to achieve a detailed interpretation of the complex NMR spectra of cholesterol crystals. By introducing an environment-dependent secondary referencing scheme in our calculations, not only do we reproduce the characteristic spectral features of the different crystalline polymorphs, thus clearly discriminating among them, but also closely represent the spectrum in the region of several highly overlapping peaks. This, in combination with spectral editing, allows us to provide a complete peak assignment for monohydrate (ChM) and low-temperature anhydrous (ChAl) crystal polymorphs. Our results show that the synergy between ab initio calculations and refined experimental techniques can be exploited for an accurate and efficient NMR crystallography of complex systems of great interest for biomaterial studies. The method is general in nature and can be applied for studies of various complex biomaterials.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp3019974