Geometry of multiple-spin systems as reflected in 13C-{1H} dipolar spectra measured at Lee-Goldburg cross-polarization

被引:12
作者
Brus, J [1 ]
Jakes, J [1 ]
机构
[1] Acad Sci Czech Republ, Inst Macromol Chem, Pracovnici Oddeleni Strukt Anal, CR-16206 Prague 6, Czech Republic
关键词
solid-state NMR; dipolar couplings; Lee-Goldburg cross-polarization; distance restraints;
D O I
10.1016/j.ssnmr.2004.11.002
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Theoretical calculation and analysis of C-13-{H-1} dipolar spectra of small-size spin clusters is presented. Dipolar spectra simulated using the time-independent average Hamiltonian are compared with the dipolar profiles obtained by 2D and 3D H-1-C-13 correlation experiments employing Lee-Goldburg off-resonance cross-polarization (LG-CP). It is demonstrated that the structural parameters such as interatomic distances as well as mutual orientation of internuclear vectors can be derived from the dipolar profiles of simple spin clusters. Simplified analysis of the dipolar spectra based on isolated-like spin-pair approach can be used only if interacting spin cluster is reduced to the three-spin system in which the angle between both internuclear vectors ranges from 45degrees to 135degrees. For other local arrangements of spin systems the produced dipolar spectra must be analyzed with high caution. Contributions of all interacting spins to dipolar evolution of C-13 magnetization are mutually mixed and cannot be easily separated. However, simplification of the dipolar spectra is achieved by selective excitation. Enhanced selectivity of LG-CP transfer due to the initial H-1 chemical-shiftevolution period makes it possible to construct the dipolar spectra from H-1-C-13 cross-peak intensities for every detected H-1-C-13 spin-pair. Consequently, isolated-like spin pair evolution of the detected H-1-C-13 coherence dominates to the resulting dipolar profile, while the influence of other interacting spins is suppressed. However, this suppression is not quite complete and analysis of the selective dipolar spectra based on isolated-like spin-pair approach cannot be used generally. Especially evolution of long-range H-1-C-13 coherence is still significantly affected by spin states of other coupled hydrogen atoms. (C) 2004 Elsevier Inc. All rights reserved.
引用
收藏
页码:180 / 191
页数:12
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