Systematic Evaluation of Polarizing Agents for Dynamic Nuclear Polarization Enhanced NMR

R Ran Wei (Institut des Sciences et Ingénierie Chimiques) G Gilles Casano (Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire (UMR 7273), Av. Esc. Normandie Niemen, 13013 Marseille, France) Y Yuxuan Zhang (College of Chemistry) I Ivanska M. Gierbolini‐Colón (National High Magnetic Field Laboratory Florida State University Tallahassee FL 32301 USA) Y Yu Rao (Institut des Sciences et Ingénierie Chimiques) S Shubha S. Gunaga (National High Magnetic Field Laboratory) F Faith J. Scott (National High Magnetic Field Laboratory) J Jiaxin Zhou (Tianjin Key Laboratory of Biosensing and Molecular Recognition, Research Center for Analytical Science, Frontiers Science Center for New Organic Matter, College of Chemistry) S Satyaki Chatterjee (Department of Chemistry, Science Institute, University of Iceland) S Sanyog Kumari (Department of Chemistry University of Iceland Science Institute Reykjavik 107 Iceland) H Hakim Karoui (Aix‐Marseille Univ., CNRS Institut de Chimie Radicalaire UMR 7273 Marseille 13013 France) M Mang Huang (Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics, School of Pharmacy Tianjin Medical University Tianjin 300070 P.R. China) S Snorri Th. Sigurdsson (Science Institute, University of Iceland, Dunhaga 5, Reykjavik 107, Iceland) G Gaël De Paëpe (Univ. Grenoble Alpes, CEA, CNRS, IRIG, MEM) Y Yangping Liu F Frederic Mentink‐Vigier (National High Magnetic Field Laboratory Florida State University Tallahassee FL USA) A Amrit Venkatesh (Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL)) O Olivier Ouari (Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire (UMR 7273), Av. Esc. Normandie Niemen, 13013 Marseille, France) L Lyndon Emsley (Laboratory of Magnetic Resonance, Institut des Sciences et Ingénierie Chimiques)

Abstract

Abstract Dynamic nuclear polarization (DNP) can significantly enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy, via the transfer of polarization from unpaired electrons to nuclei. As a result, there is considerable interest in improving DNP efficiency, particularly through the development of new polarizing agents (PAs). Here, a series of 32 PAs, including 26 dinitroxide and 6 hetero biradicals, of which 11 are introduced for the first time, were evaluated for their performance in DNP NMR experiments at magnetic field strengths of 9.4 T, 14.1 T, and 21.1 T. The PAs that are soluble in aqueous media were compared for different proton concentrations. A detailed comparison of the enhancement factors, polarization build‐up times, contribution factors, and the resulting overall sensitivity factors is provided. We find that the class of narrow‐line‐broad‐line biradicals not only yield the best performance at high field (21.1 T and 14.1 T) but remain among the best at intermediate fields (9.4 T). Specifically, SNAPol‐1 and HyTEK2 are consistently among the best performing radicals at any field. Among the dinitroxides, notably at 9.4 T, the AsymPol‐POK and M‐TinyPol families stand out in proton‐dense aqueous matrices, and a newly developed dinitroxide, NaphPolCbo, is found to provide the best overall sensitivity factor in organic solvent.

Article Details

Volume / Issue Vol. 64, Issue 31
Published July 28, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (19)

R

Ran Wei

Institut des Sciences et Ingénierie Chimiques

G

Gilles Casano

Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire (UMR 7273), Av. Esc. Normandie Niemen, 13013 Marseille, France

Y

Yuxuan Zhang

College of Chemistry

I

Ivanska M. Gierbolini‐Colón

National High Magnetic Field Laboratory Florida State University Tallahassee FL 32301 USA

Y

Yu Rao

Institut des Sciences et Ingénierie Chimiques

S

Shubha S. Gunaga

National High Magnetic Field Laboratory

F

Faith J. Scott

National High Magnetic Field Laboratory

J

Jiaxin Zhou

Tianjin Key Laboratory of Biosensing and Molecular Recognition, Research Center for Analytical Science, Frontiers Science Center for New Organic Matter, College of Chemistry

S

Satyaki Chatterjee

Department of Chemistry, Science Institute, University of Iceland

S

Sanyog Kumari

Department of Chemistry University of Iceland Science Institute Reykjavik 107 Iceland

H

Hakim Karoui

Aix‐Marseille Univ., CNRS Institut de Chimie Radicalaire UMR 7273 Marseille 13013 France

M

Mang Huang

Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics, School of Pharmacy Tianjin Medical University Tianjin 300070 P.R. China

S

Snorri Th. Sigurdsson

Science Institute, University of Iceland, Dunhaga 5, Reykjavik 107, Iceland

G

Gaël De Paëpe

Univ. Grenoble Alpes, CEA, CNRS, IRIG, MEM

Y

Yangping Liu

F

Frederic Mentink‐Vigier

National High Magnetic Field Laboratory Florida State University Tallahassee FL USA

A

Amrit Venkatesh

Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL)

O

Olivier Ouari

Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire (UMR 7273), Av. Esc. Normandie Niemen, 13013 Marseille, France

L

Lyndon Emsley

Laboratory of Magnetic Resonance, Institut des Sciences et Ingénierie Chimiques