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异核各向同性混合分离局部场核磁共振光谱法。

Heteronuclear isotropic mixing separated local field NMR spectroscopy.

作者信息

Dvinskikh Sergey V, Yamamoto Kazutoshi, Ramamoorthy Ayyalusamy

机构信息

Biophysics Research Division, University of Michigan, Ann Arbor, MI 48109-1055, USA.

出版信息

J Chem Phys. 2006 Jul 21;125(3):34507. doi: 10.1063/1.2212939.

Abstract

This paper presents a theoretical, numerical, and experimental study of a new class of separated local field (SLF) techniques. These techniques are based on the heteronuclear isotropic mixing leading to spin exchange via the local field (HIMSELF). It is shown that highly efficient and robust SLF experiments can be designed based on double channel windowless homonuclear decoupling sequences. Compared to rotating frame techniques based on Hartmann-Hahn cross polarization, the new approach is less susceptible to the frequency offset and chemical shift interaction and can be applied in the structural studies of macromolecules that are uniformly labeled with isotopes such as (13)C and (15)N. Furthermore, isotropic mixing sequences allow for transfer of any magnetization component of one nucleus to the corresponding component of its dipolar coupled partner. The performance of HIMSELF is studied by analysis of the average Hamiltonian and numerical simulation and is experimentally demonstrated on a single crystalline sample of a dipeptide and a liquid crystalline sample exhibiting motionally averaged dipolar couplings.

摘要

本文介绍了一类新型分离局部场(SLF)技术的理论、数值和实验研究。这些技术基于异核各向同性混合,通过局部场实现自旋交换(HIMSELF)。结果表明,基于双通道无窗口同核去耦序列可以设计出高效且稳健的SLF实验。与基于Hartmann-Hahn交叉极化的旋转框架技术相比,新方法对频率偏移和化学位移相互作用的敏感度较低,可应用于用诸如(13)C和(15)N等同位素均匀标记的大分子的结构研究。此外,各向同性混合序列允许将一个核的任何磁化分量转移到其偶极耦合伙伴的相应分量。通过平均哈密顿量分析和数值模拟研究了HIMSELF的性能,并在二肽单晶样品和表现出运动平均偶极耦合的液晶样品上进行了实验验证。

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