Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets

Autor: Vincent Reboul, Johannes F. P. Colell, Guannan Zhang, Warren S. Warren, Thomas Theis, Jacob R. Lindale, Thomas Glachet
Přispěvatelé: Duke University [Durham], Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), North Carolina State University [Raleigh] (NC State), University of North Carolina System (UNC)
Jazyk: angličtina
Rok vydání: 2019
Předmět:
Zdroj: Angewandte Chemie International Edition
Angewandte Chemie International Edition, Wiley-VCH Verlag, 2019, 58 (32), pp.11118-11124. ⟨10.1002/anie.201904026⟩
ISSN: 1433-7851
1521-3773
DOI: 10.1002/anie.201904026⟩
Popis: International audience; Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The 15N2 labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long‐lived lifetimes. The (‐CH15N2) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (‐CH15N2) moiety to 1H, thus combining the advantages of long lifetimes of 15N polarization with superior sensitivity of 1H detection. Despite the proximity of 1H to 15N nuclei in the diazirine moiety, 15N T1 times of up to (4.6±0.4) min and singlet lifetimes Ts of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized 1H2 singlet states in CH2 groups of chiral molecules. The singlet lifetime of 1H singlets is up to (9.2±1.8) min, thus exceeding 1H T1 relaxation time (at 8.45 T) by a factor of ≈100.
Databáze: OpenAIRE