Residual dipolar coupling TOCSY for direct through space correlations of base protons and phosphorus nuclei in RNA.

Residual dipolar coupling TOCSY for direct through space correlations of base protons and phosphorus nuclei in RNA.
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残余偶极耦合 TOCSY 用于直接通过 RNA 中的基础质子和磷原子核的空间相关性。

DOI:
10.1021/ja005835o
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发表时间:
2001
影响因子:
15
通讯作者:
Williamson,JR
Williamson,JR
中科院分区:
化学1区
文献类型:
--
作者:
Hennig,M;Carlomagno,T;Williamson,JR

文献摘要

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在部分排列的分子中建立的残余偶极耦合测量报告了已知长度的1H-15 N和1H-13 C键矢量相对于分子排列张量的相对取向,1并且越来越多地用于通过NMR确定寡核苷酸的结构。2.最近,介绍了通过各向异性介质中的空间偶极耦合测量Homestrant 1H-1H的方法。3此外,homopolymerTOCSY序列可用于通过非标量耦合的质子之间的偶极耦合来转移磁化。4在这里,我们通过空间相互作用,特别是1H-31 P残留偶极耦合,直接连接磷酸骨架和寡核苷酸中的碱基质子,将部分对齐分子中偶极耦合的观察扩展到异质性。本文介绍了直接观测弱取向分子中通过空间异极偶极耦合的RADAR-TOCSY(剩余偶极耦合全相关光谱)实验。类似于间接标量自旋-自旋耦合相互作用H J,给定的一对自旋为1/2的不同核I,S之间的偶极耦合相互作用由偶极
Established residual dipolar coupling measurements in partially aligned molecules report on the relative orientation of 1H-15N and 1H-13C bond vectors of known lengths with respect to the molecular alignment tensor, 1 and are increasingly used in the structure determination of oligonucleotides by NMR. 2 Recently, methods for the measurement of homonuclear 1H-1H through space dipolar couplings in anisotropic media were introduced. 3 In addition, homonuclear TOCSY sequences can be used to transfer magnetization through dipolar couplings between protons that are not scalar coupled. 4Here we extend the observation of dipolar couplings in partially aligned molecules to heteronuclear through space interactions, specifically 1H-31P residual dipolar couplings, which directly link the phosphate backbone and base protons in oligonucleotides. We introduce the RADAR-TOCSY (residual dipolar coupling total correlation spectroscopy) experiment for the direct observation of through space heteronuclear dipolar couplings in weakly aligned molecules. In analogy to the indirect scalar spin-spin coupling interaction Hˆ J, the dipolar coupling interaction between a given pair of unlike spin-1/2 nuclei I, S is expressed by the dipolar