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

Long-lived nuclear spin states in methyl groups and quantum-rotor-induced polarization
Long-lived nuclear spin states in methyl groups and quantum-rotor-induced polarization
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 13C-γ-picoline
0002-7863
18746-18749
Meier, Benno
ed19bfd6-3347-43f1-9e1a-06e6586ee4d1
Dumez, Jean-Nicolas
10fd319d-e42c-42dc-8b2b-34c10475cc27
Stevanato, Gabriele
13f2e0a2-2ce7-4938-a2ac-274a81196a72
Hill-Cousins, Joseph T.
615ef358-b4f3-4736-b5cf-3d05355277f2
Roy, Soumya Singha
fa8b7e87-8477-417a-932e-61e36581c720
Hakansson, Paer
61b6f2aa-81eb-422a-9261-e778a83fc7eb
Mamone, Salvatore
7f4c620f-8bb6-4eea-a95f-1173ce69bf80
Brown, Richard C. D.
21ce697a-7c3a-480e-919f-429a3d8550f5
Pileio, Giuseppe
13f78e66-0707-4438-b9c9-6dbd3eb7d4e8
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Meier, Benno
ed19bfd6-3347-43f1-9e1a-06e6586ee4d1
Dumez, Jean-Nicolas
10fd319d-e42c-42dc-8b2b-34c10475cc27
Stevanato, Gabriele
13f2e0a2-2ce7-4938-a2ac-274a81196a72
Hill-Cousins, Joseph T.
615ef358-b4f3-4736-b5cf-3d05355277f2
Roy, Soumya Singha
fa8b7e87-8477-417a-932e-61e36581c720
Hakansson, Paer
61b6f2aa-81eb-422a-9261-e778a83fc7eb
Mamone, Salvatore
7f4c620f-8bb6-4eea-a95f-1173ce69bf80
Brown, Richard C. D.
21ce697a-7c3a-480e-919f-429a3d8550f5
Pileio, Giuseppe
13f78e66-0707-4438-b9c9-6dbd3eb7d4e8
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3

Meier, Benno, Dumez, Jean-Nicolas, Stevanato, Gabriele, Hill-Cousins, Joseph T., Roy, Soumya Singha, Hakansson, Paer, Mamone, Salvatore, Brown, Richard C. D., Pileio, Giuseppe and Levitt, Malcolm H. (2013) Long-lived nuclear spin states in methyl groups and quantum-rotor-induced polarization. Journal of the American Chemical Society, 135 (50), 18746-18749. (doi:10.1021/ja410432f).

Record type: Article

Abstract

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 13C-γ-picoline

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Published date: 18 December 2013

Identifiers

Local EPrints ID: 414795
URI: https://eprints.soton.ac.uk/id/eprint/414795
ISSN: 0002-7863
PURE UUID: f23cd126-66ab-4df0-8e38-3f6534d19bf2
ORCID for Benno Meier: ORCID iD orcid.org/0000-0003-2258-1507
ORCID for Richard C. D. Brown: ORCID iD orcid.org/0000-0003-0156-7087
ORCID for Giuseppe Pileio: ORCID iD orcid.org/0000-0001-9223-3896
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180

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Date deposited: 11 Oct 2017 16:31
Last modified: 15 Aug 2019 00:52

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Contributors

Author: Benno Meier ORCID iD
Author: Jean-Nicolas Dumez
Author: Gabriele Stevanato
Author: Joseph T. Hill-Cousins
Author: Soumya Singha Roy
Author: Paer Hakansson
Author: Salvatore Mamone
Author: Giuseppe Pileio ORCID iD

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