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J Am Chem Soc. 2013 Dec 18;135(50):18746-9. doi: 10.1021/ja410432f. Epub 2013 Dec 2.

Long-lived nuclear spin states in methyl groups and quantum-rotor-induced polarization.

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School of Chemistry, University of Southampton , SO17 1BJ Southampton, U.K.


Substances containing rapidly rotating methyl groups may exhibit long-lived states (LLSs) in solution, with relaxation times substantially longer than the conventional spin-lattice relaxation time T1. The states become long-lived through rapid internal rotation of the CH3 group, which imposes an approximate symmetry on the fluctuating nuclear spin interactions. In the case of very low CH3 rotational barriers, a hyperpolarized LLS is populated by thermal equilibration at liquid helium temperature. Following dissolution, cross-relaxation of the hyperpolarized LLS, induced by heteronuclear dipolar couplings, generates strongly enhanced antiphase NMR signals. This mechanism explains the NMR signal enhancements observed for (13)C-γ-picoline (Icker, M.; Berger, S. J. Magn. Reson. 2012, 219, 1-3).

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