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Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets
Author(s) -
Zhang Guannan,
Colell Johannes F. P.,
Glachet Thomas,
Lindale Jacob R.,
Reboul Vincent,
Theis Thomas,
Warren Warren S.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904026
Subject(s) - diazirine , moiety , chemistry , singlet state , hyperpolarization (physics) , stereochemistry , molecule , photochemistry , nuclear magnetic resonance spectroscopy , organic chemistry , atomic physics , excited state , physics
Abstract Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The 15 N 2 labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long‐lived lifetimes. The (‐CH 15 N 2 ) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (‐CH 15 N 2 ) moiety to 1 H, thus combining the advantages of long lifetimes of 15 N polarization with superior sensitivity of 1 H detection. Despite the proximity of 1 H to 15 N nuclei in the diazirine moiety, 15 N T 1 times of up to (4.6±0.4) min and singlet lifetimes T s of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized 1 H 2 singlet states in CH 2 groups of chiral molecules. The singlet lifetime of 1 H singlets is up to (9.2±1.8) min, thus exceeding 1 H T 1 relaxation time (at 8.45 T) by a factor of ≈100.

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