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高分辨率 NMR 研究 T1 磁弛豫分散。III. 自旋 1/2 杂核对强耦合质子间自旋弛豫和极化转移的影响。

High resolution NMR study of T1 magnetic relaxation dispersion. III. Influence of spin 1/2 hetero-nuclei on spin relaxation and polarization transfer among strongly coupled protons.

机构信息

Institut für Experimentalphysik, Freie Universität Berlin Arnimallee 14, 14195 Berlin, Germany.

出版信息

J Chem Phys. 2012 Sep 7;137(9):094503. doi: 10.1063/1.4746780.

Abstract

Effects of spin-spin interactions on the nuclear magnetic relaxation dispersion (NMRD) of protons were studied in a situation where spin ½ hetero-nuclei are present in the molecule. As in earlier works [K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, J. Chem. Phys. 129, 234513 (2008); S. E. Korchak, K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, ibid. 133, 194502 (2010)], spin-spin interactions have a pronounced effect on the relaxivity tending to equalize the longitudinal relaxation times once the spins become strongly coupled at a sufficiently low magnetic field. In addition, we have found influence of (19)F nuclei on the proton NMRD, although in the whole field range, studied protons and fluorine spins were only weakly coupled. In particular, pronounced features in the proton NMRD were found; but each feature was predominantly observed only for particular spin states of the hetero-nuclei. The features are explained theoretically; it is shown that hetero-nuclei can affect the proton NMRD even in the limit of weak coupling when (i) protons are coupled strongly and (ii) have spin-spin interactions of different strengths with the hetero-nuclei. We also show that by choosing the proper magnetic field strength, one can selectively transfer proton spin magnetization between spectral components of choice.

摘要

自旋-自旋相互作用对含有自旋为½的异核的分子中质子的核磁共振弛豫弥散(NMRD)的影响进行了研究。与早期的工作[K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, J. Chem. Phys. 129, 234513 (2008); S. E. Korchak, K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, ibid. 133, 194502 (2010)]一样,自旋-自旋相互作用对弛豫率有显著影响,一旦自旋在足够低的磁场下强烈耦合,就会趋向于使纵向弛豫时间相等。此外,我们发现(19)F 核对质子 NMRD 有影响,尽管在所研究的整个磁场范围内,质子和氟自旋只是弱耦合。特别是,我们发现了质子 NMRD 中的明显特征;但每个特征主要仅在异核的特定自旋态下观察到。这些特征从理论上进行了解释;表明即使在弱耦合的极限下,当(i)质子强烈耦合和(ii)与异核具有不同强度的自旋-自旋相互作用时,异核也会影响质子 NMRD。我们还表明,通过选择适当的磁场强度,可以在选择的谱分量之间选择性地转移质子自旋磁化强度。

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