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通过可变角度样品旋转(VASS)确定场取向双分子层中偶极耦合的符号

Sign determination of dipolar couplings in field-oriented bicelles by variable angle sample spinning (VASS).

作者信息

Tian F, Losonczi J A, Fischer M W, Prestegard J H

机构信息

Complex Carbohydrate Research Center, University of Georgia, Athens 30602-4712, USA.

出版信息

J Biomol NMR. 1999 Oct;15(2):145-50. doi: 10.1023/a:1008356210291.

Abstract

Residual dipolar couplings are being increasingly used as structural constraints for NMR studies of biomolecules. A problem arises when dipolar coupling contributions are larger than scalar contributions for a given spin pair, as is commonly observed in solid state NMR studies, in that signs of dipolar couplings cannot easily be determined. Here the sign ambiguities of dipolar couplings in field-oriented bicelles are resolved by variable angle sample spinning (VASS) techniques. The director behavior of field-oriented bicelles (DMPC/DHPC, DMPC/CHAPSO) in VASS is studied by 31P NMR. A stable configuration occurs when the spinning angle is smaller than the magic angle, 54.7 degrees, and the director (or bicelle normal) of the disks is mainly distributed in a plane perpendicular to the rotation axis. Since the dipolar couplings depend on how the bicelles are oriented with respect to the magnetic field, it is shown that the dipolar interaction can be scaled to the same order as the J-coupling by moving the spinning axis from 0 degree toward 54.7 degrees. Thus the relative sign of dipolar and scalar couplings can be determined.

摘要

剩余偶极耦合越来越多地被用作生物分子核磁共振研究的结构约束条件。当给定自旋对的偶极耦合贡献大于标量贡献时,就会出现问题,这在固态核磁共振研究中很常见,因为偶极耦合的符号不容易确定。在这里,通过可变角度样品旋转(VASS)技术解决了场取向双分子层中偶极耦合的符号模糊问题。通过31P核磁共振研究了VASS中场取向双分子层(DMPC/DHPC、DMPC/CHAPSO)的指向矢行为。当旋转角度小于魔角54.7度时会出现稳定构型,圆盘的指向矢(或双分子层法线)主要分布在垂直于旋转轴的平面内。由于偶极耦合取决于双分子层相对于磁场的取向方式,结果表明,通过将旋转轴从0度移向54.7度,偶极相互作用可以按与J耦合相同的量级进行缩放。因此,可以确定偶极耦合和标量耦合的相对符号。

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