期刊
PROGRESS IN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
卷 123, 期 -, 页码 1-50出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.pnmrs.2020.12.001
关键词
Liquid-state NMR; Small molecules in mixture; Viscous solvents; Spin diffusion; Nuclear Overhauser effet (NOE); ViscY
资金
- CNRS
- Conseil Regional Champagne Ardenne
- Conseil General de la Marne
- EUprogramme FEDER
- MESR
The nuclear Overhauser effect (NOE) is a result of cross-relaxation between nuclear spins mediated by dipolar coupling, becoming increasingly important in determining through-space atom proximity relationships within molecules. The efficiency of NOE depends on the molecular rotational correlation time, and increasing solution viscosity can reveal otherwise unobservable NOEs.
The nuclear Overhauser effect (NOE) is a consequence of cross-relaxation between nuclear spins mediated by dipolar coupling. Its sensitivity to internuclear distances has made it an increasingly important tool for the determination of through-space atom proximity relationships within molecules of sizes ranging from the smallest systems to large biopolymers. With the support of sophisticated FT-NMR techniques, the NOE plays an essential role in structure elucidation, conformational and dynamic investigations in liquid-state NMR. The efficiency of magnetization transfer by the NOE depends on the molecular rotational correlation time, whose value depends on solution viscosity. The magnitude of the NOE between H-1 nuclei varies from +50% when molecular tumbling is fast to -100% when it is slow, the latter case corresponding to the spin diffusion limit. In an intermediate tumbling regime, the NOE may be vanishingly small. Increasing the viscosity of the solution increases the motional correlation time, and as a result, otherwise unobservable NOEs may be revealed and brought close to the spin diffusion limit. The goal of this review is to report the resolution of structural problems that benefited from the manipulation of the negative NOE by means of viscous solvents, including examples of molecular structure determination, conformation elucidation and mixture analysis (the ViscY method). (C) 2020 Elsevier B.V. All rights reserved.
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