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天然丰度下的远程¹H-¹⁵N异核位移相关

Long-range (1)H-(15)N heteronuclear shift correlation at natural abundance.

作者信息

Martin G E, Hadden C E

机构信息

Rapid Structure Characterization Group, Pharmaceutical Development, Pharmacia & Upjohn, Kalamazoo, Michigan 49001-0199, USA.

出版信息

J Nat Prod. 2000 Apr;63(4):543-85. doi: 10.1021/np9903191.

Abstract

Despite the inherently low sensitivity of (15)N NMR because of its low gyromagnetic ratio (gamma(N)) and its relatively low natural abundance (0.37%), this important nuclide still has useful potential as a structural probe even at natural abundance. Inverse-detected NMR methods coupled with major advances in NMR probe designs have made it possible to acquire long-range (1)H-(15)N heteronuclear shift correlation data on samples as small as a micromole overnight. Chemical shift referencing schemes for (15)N and the range of (15)N shifts are discussed, followed by a discussion of the currently available pulse sequences, pulse calibration, parametrization and processing of long-range (1)H-(15)N data, and the implications of probe selection. These topics are followed by a review of the applications contained in the literature that have utilized (1)H-(15)N heteronuclear shift correlation experiments at natural abundance, with emphasis placed on the observed long-range coupling pathways.

摘要

尽管由于其低旋磁比(γ(N))和相对较低的天然丰度(0.37%),(15)N NMR本质上灵敏度较低,但即使在天然丰度下,这种重要的核素作为一种结构探针仍具有有用的潜力。反检测NMR方法与NMR探头设计的重大进展相结合,使得在一夜之间就能够从小至微摩尔的样品中获取远程(1)H-(15)N异核位移相关数据。讨论了(15)N的化学位移参考方案和(15)N位移范围,随后讨论了当前可用的脉冲序列、脉冲校准、远程(1)H-(15)N数据的参数化和处理以及探头选择的影响。这些主题之后是对文献中利用天然丰度下(1)H-(15)N异核位移相关实验的应用的综述,重点放在观察到的远程耦合途径上。

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