Diffusion Ordered Nuclear Magnetic Resonance Spectroscopy: Principles and Applications

Diffusion Ordered Nuclear Magnetic Resonance Spectroscopy: Principles and Applications
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DOI:
10.1002/chin.199933338
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发表时间:
1999-05
期刊:
ChemInform
影响因子:
--
通讯作者:
Charles S. Johnson
Charles S. Johnson
中科院分区:
其他
文献类型:
--
作者:
Charles S. Johnson

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术语表ALS(计算机程序)方舟 * 先验知识BPP* 双极脉冲对CONTIN(计算机程序)CORE COSY-DOSY CTP DECRA DEPT DISCRETE DLS DSTE DOSY* Diffusion Ordered NMR Spectroscopy EXSY FID FIDLE(计算机程序)GCSTE GCSTESL GPC-NMR(计算机算法)HDL(脂蛋白)HMQC-DOSY HR-DOSY HSQC INEPT ILT(逆拉普拉斯变换)低密度脂蛋白(lipoprotein)LED* 纵向涡流延迟或纵向编码-解码MaxEnt MCR(计算机算法)MOSY* 迁移率有序NMR光谱(计算机程序)NLREG(计算机程序)NOESY-DOSY PFG-NMR PVA(计算机算法)RDCON SE SPLMOD STE STEP(计算机程序)VLDL(脂蛋白)VMAX(计算机算法)CSJ负责LED、DOSY和MOSY以及包含它们的一些连字符形式。他可能是第一个使用缩写BPP和APK的人。其他的在正文中定义。NMR光谱学中最富有成果的想法之一是引入第二频率维度[1]。这是通过使用具有两个独立的进动周期的脉冲序列而实现的。在一类二维NMR(2D-NMR)实验中,哈密顿量在演化周期和检测周期之间切换。作为进化周期的结果,共振被传播到第二维中以揭示它们的起源。这种2D“分辨”光谱的例子包括J分辨,其中哈密顿量通过自旋去耦[2]和NMR成像来切换,其中磁场梯度方向被切换[3]。这些想法的一个逻辑延伸是引入额外的NMR维度,这些维度取决于分子的性质,如大小,形状,质量和电荷,这些都没有明确包括在自旋哈密顿量中。这些整体的分子性质在常规NMR中没有很好地表示,因为自旋相互作用往往是相当局部的。因此,基于这些性质的分散可以提供新的信息以及用于编辑NMR谱的手段。问题是确定分子性质影响NMR谱或可以影响NMR谱的方式。核弛豫时间是明显的候选者,因为它们取决于分子运动的相关时间,而相关时间又取决于分子的大小和形状。然而,弛豫时间可以是完全不同的不同的核在同一个分子,因为网站特定的磁相互作用,因为局部或节段运动可能会掩盖整体分子运动。在纵向松弛的情况下,高频局部节段运动可能提供主要的松弛机制,导致T1...
Nomenclature GLOSSARY ALS (computer program) ARK* a priori knowledge BPP* Bipolar Pulse Pairs CONTIN (computer program) CORE COSY-DOSY CTP DECRA DEPT DISCRETE DLS DSTE DOSY* Diffusion Ordered NMR SpectroscopY EXSY FID FIDDLE (computer program) GCSTE GCSTESL GPC-NMR GRAM (computer algorithm) HDL (lipoprotein) HMQC-DOSY HR-DOSY HSQC INEPT ILT (inverse Laplace tranform) LDL (lipoprotein) LED* Longitudinal Eddy current Delay or Longitudinal Encode–Decode MaxEnt MCR (computer algorithm) MOSY* Mobility Ordered NMR SpectroscopY MWD NIPALS (computer program) NLREG (computer program) NOESY-DOSY PFG-NMR PVA (computer algorithm) RDCON SE SPLMOD STE STEP (computer program) VLDL (lipoprotein) VMAX (computer algorithm) CSJ is responsible for LED, DOSY, and MOSY and some of the hyphenated forms containing them. He may have been the first to use the abbreviations BPP and APK. The others are defined in the text. One of the most fruitful ideas in NMR spectroscopy was the introduction of a second frequency dimension [1]. This was made possible through the use of pulse sequences having two independent precession periods. In one class of two-dimensional NMR (2D-NMR) experiments, the Hamiltonian is switched between the evolution period and the detection period. As a consequence of the evolution period, resonances are spread into a second dimension to reveal their origins. Examples of such 2D 'resolved' spectro-scopies include J-resolved where the Hamiltonian is switched through spin decoupling [2] and NMR imaging where magnetic field gradient directions are switched [3]. A logical extension of these ideas is the introduction of additional NMR dimensions that depend on molecular properties such as size, shape, mass, and charge that are not explicitly included in spin Hamil-tonians. These overall molecular properties are not well represented in conventional NMR as spin interactions tend to be quite local. Therefore, dispersion on the basis of such properties can provide new information as well as a means for editing NMR spectra. The problem is to identify ways that molecular properties influence NMR spectra or can be made to affect NMR spectra. Nuclear relaxation times are obvious candidates because they depend on correlation times for molecular motion, and the correlation times in turn depend on molecular sizes and shapes. However, relaxation times can be quite different for different nuclei in the same molecule because of site specific magnetic interactions and because local or segmental motions may obscure overall molecular motions. In the case of longitudinal relaxation, high frequency local segmen-tal motion may provide the dominant relaxation mechanism, leading to T 1 …