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通过一维和二维（1）H-NMR光谱法及有机分子力学方法研究双链d(pTGTTTGGC) d(pCCAAAC)A在水溶液中的空间结构

[Study of the spatial structure of the duplex d(pTGTTTGGC) d(pCCAAAC)A in aqueous solution by methods of uni- and two-dimensional (1)H-NMR spectroscopy and organic molecular mechanics].

作者信息

Bichenkova E V, Vorob'ev Iu N, Kutiavin I V, Lebedev A V, Mal'tseva T V, Ténné E Iu

出版信息

Bioorg Khim. 1990 Sep;16(9):1236-58.

PMID:2080930
Abstract

Structure of the complementary complex d(pTGTTTGGC) d(pCCAAAC)A in the aqueous solution has been investigated by one- and two-dimensional 1H NMR spectroscopy. The resonances of nonexchangeable protons of bases as well as methyl and deoxyribose 1', 2'a, 2'b, 3' and 4' protons have been assigned by means of two-dimensional J-correlated spectroscopy (COSY) and two-dimensional nuclear Overhauser enhancement spectroscopy (NOESY). Using one-dimensional NOE measurements, 62 interproton distances (intranucleotide: (H6/H8)i--(H1')t, (H6/H8)i--(H2'a)i, (H1')i--(H2'a)i, (H1')i--(H2'b)i; internucleotide: (H6/H8)i--(H1')i-1, (H6/H8)i--(H2'a)i-1, (H6/H8)i--(H2'b)i-1, (H5/CH3)i--(H6/H8)i-1, (H5/CH3)i--(H2'a/H2'b)i-1) have been determined for nearest-neighbour protons. Spin-coupling constant values for some sugar protons have been obtained from COSY spectra. The restrained molecular mechanics calculations have yielded the possible solution structures of duplex fitting the experimental set of interproton distances and coupling constants.

摘要

通过一维和二维¹H NMR光谱研究了水溶液中互补复合物d(pTGTTTGGC) d(pCCAAAC)A的结构。借助二维J相关光谱（COSY）和二维核Overhauser增强光谱（NOESY），对碱基不可交换质子以及甲基和脱氧核糖1'、2'a、2'b、3'和4'质子的共振进行了归属。利用一维NOE测量，确定了62个最近邻质子间的质子间距离（核苷酸内：(H6/H8)i--(H1')t、(H6/H8)i--(H2'a)i、(H1')i--(H2'a)i、(H1')i--(H2'b)i；核苷酸间：(H6/H8)i--(H1')i-1、(H6/H8)i--(H2'a)i-1、(H6/H8)i--(H2'b)i-1、(H5/CH3)i--(H6/H8)i-1、(H5/CH3)i--(H2'a/H2'b)i-1）。从COSY光谱中获得了一些糖质子的自旋耦合常数。受限分子力学计算得出了符合实验质子间距离和耦合常数集的双链体可能的溶液结构。

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