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二维¹H核磁共振交叉弛豫光谱揭示小囊泡中的磷脂堆积和构象

Phospholipid packing and conformation in small vesicles revealed by two-dimensional 1H nuclear magnetic resonance cross-relaxation spectroscopy.

作者信息

Xu Z C, Cafiso D S

出版信息

Biophys J. 1986 Mar;49(3):779-83. doi: 10.1016/S0006-3495(86)83705-5.

Abstract

Two-dimensional 1H-NMR spectroscopy has been used to examine cross-relaxation in sonicated phospholipid vesicle systems. The observed pattern of proton cross-relaxation reveals several important features of these vesicle systems. For example, cross-relaxation rates on each monolayer of the vesicle system can be resolved and reflect the expected geometric packing constraints of the vesicle system. Small but significant magnetization-exchange is also seen to develop between the headgroup N-methyl resonance and the terminal methyl resonance. Spectra taken with deuterated lipids indicate that this exchange is not mediated by spin-diffusion down the length of the alkyl chains. Since spin-diffusion is the only process that is expected to facilitate magnetization-exchange over distances of 15-20 A, a close proximity of headgroup and terminal methyl protons in a fraction of the membrane lipid is indicated by these results. This could occur by events such as lipid interdigitation or alkyl chain bends that terminate lipid alkyl chain ends near the membrane surface.

摘要

二维¹H-NMR光谱已用于研究超声处理的磷脂囊泡系统中的交叉弛豫。观察到的质子交叉弛豫模式揭示了这些囊泡系统的几个重要特征。例如,囊泡系统每个单层上的交叉弛豫率可以分辨出来,并反映了囊泡系统预期的几何堆积限制。在头基N-甲基共振和末端甲基共振之间也观察到小但显著的磁化交换。用氘代脂质获得的光谱表明,这种交换不是由沿着烷基链长度的自旋扩散介导的。由于自旋扩散是预期在15 - 20 Å距离上促进磁化交换的唯一过程,这些结果表明在一部分膜脂质中头基和末端甲基质子紧密相邻。这可能是由脂质相互交叉或烷基链弯曲等事件引起的,这些事件使脂质烷基链末端在膜表面附近终止。

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