Efficient Dynamic Nuclear Polarization at 800 MHz/527 GHz with Trityl-Nitroxide Biradicals

Guinevere Mathies; Marc A Caporini; Vladimir K Michaelis; Yangping Liu; Kan-Nian Hu; Deni Mance; Jay L Zweier; Melanie Rosay; Marc Baldus; Robert G Griffin

doi:10.1002/anie.201504292

Efficient Dynamic Nuclear Polarization at 800 MHz/527 GHz with Trityl-Nitroxide Biradicals

Angew Chem Int Ed Engl. 2015 Sep 28;54(40):11770-4. doi: 10.1002/anie.201504292. Epub 2015 Aug 12.

Authors

Guinevere Mathies¹, Marc A Caporini^{2

3}, Vladimir K Michaelis⁴, Yangping Liu^{5

6}, Kan-Nian Hu^{4

7}, Deni Mance⁸, Jay L Zweier⁹, Melanie Rosay², Marc Baldus⁸, Robert G Griffin¹⁰

Affiliations

¹ Francis Bitter Magnet Laboratory, Department of Chemistry, Massachusetts Institute of Technology, 170 Albany Street, Cambridge, MA 02139 (USA). mathies@mit.edu.
² Bruker BioSpin Corporation, 15 Fortune Drive, Billerica, MA 01821 (USA).
³ Current address: Amgen Inc., 360 Binney Street, Cambridge, MA 02142 (USA).
⁴ Francis Bitter Magnet Laboratory, Department of Chemistry, Massachusetts Institute of Technology, 170 Albany Street, Cambridge, MA 02139 (USA).
⁵ Tianjin Key Laboratory on Technologies Enabling, Development of Clinical Therapeutics and Diagnostics, School of Pharmacy, Tianjin Medical University, Tianjin 300070 (China). liuyangping@tmu.edu.cn.
⁶ Center for Biomedical EPR Spectroscopy and Imaging, Davis Heart and Lung Research Institute and Division of Cardiovascular Medicine, Department of Internal Medicine, The Ohio State University, Columbus, OH 43210 (USA). liuyangping@tmu.edu.cn.
⁷ Current address: Vertex Pharmaceuticals Incorporated, 50 Northern Avenue, Boston, MA 02210 (USA).
⁸ NMR Spectroscopy, Department of Chemistry, Faculty of Science, Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht (The Netherlands).
⁹ Center for Biomedical EPR Spectroscopy and Imaging, Davis Heart and Lung Research Institute and Division of Cardiovascular Medicine, Department of Internal Medicine, The Ohio State University, Columbus, OH 43210 (USA).
¹⁰ Francis Bitter Magnet Laboratory, Department of Chemistry, Massachusetts Institute of Technology, 170 Albany Street, Cambridge, MA 02139 (USA). rgg@mit.edu.

Abstract

Cross-effect (CE) dynamic nuclear polarization (DNP) is a rapidly developing technique that enhances the signal intensities in magic-angle spinning (MAS) NMR spectra. We report CE DNP experiments at 211, 600, and 800 MHz using a new series of biradical polarizing agents referred to as TEMTriPols, in which a nitroxide (TEMPO) and a trityl radical are chemically tethered. The TEMTriPol molecule with the optimal performance yields a record (1) H NMR signal enhancement of 65 at 800 MHz at a concentration of 10 mM in a glycerol/water solvent matrix. The CE DNP enhancement for the TEMTriPol biradicals does not decrease as the magnetic field is increased in the manner usually observed for bis-nitroxides. Instead, the relatively strong exchange interaction between the trityl and nitroxide moieties determines the magnetic field at which the optimum enhancement is observed.

Keywords: biradicals; cross-effect; dynamic nuclear polarization; polarizing agents; solid-state NMR spectroscopy.

Abstract

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