19F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy

Jasmine Viger-Gravel; Claudia E. Avalos; Dominik J. Kubicki; David Gajan; Moreno Lelli; Olivier Ouari; Anne Lesage; Lyndon Emsley

doi:10.1002/anie.201814416

¹⁹F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy

Jasmine Viger-Gravel, Claudia E. Avalos, Dominik J. Kubicki, David Gajan, Moreno Lelli, Olivier Ouari, Anne Lesage, Lyndon Emsley

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The introduction of high-frequency, high-power microwave sources, tailored biradicals, and low-temperature magic angle spinning (MAS) probes has led to a rapid development of hyperpolarization strategies for solids and frozen solutions, leading to large gains in NMR sensitivity. Here, we introduce a protocol for efficient hyperpolarization of ¹⁹F nuclei in MAS DNP enhanced NMR spectroscopy. We identified trifluoroethanol-d₃ as a versatile glassy matrix and show that 12 mm AMUPol (with microcrystalline KBr) provides direct ¹⁹F DNP enhancements of over 100 at 9.4 T. We applied this protocol to obtain DNP-enhanced ¹⁹F and ¹⁹F–¹³C cross-polarization (CP) spectra for an active pharmaceutical ingredient and a fluorinated mesostructured hybrid material, using incipient wetness impregnation, with enhancements of approximately 25 and 10 in the bulk solid, respectively. This strategy is a general and straightforward method for obtaining enhanced ¹⁹F MAS spectra from fluorinated materials.

Original language	English (US)
Pages (from-to)	7249-7253
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	22
DOIs	https://doi.org/10.1002/anie.201814416
State	Published - May 27 2019

Keywords

active pharmaceutical ingredients
dynamic nuclear polarization
magic angle spinning
NMR spectroscopy

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201814416

Cite this

@article{6e7753cf13d74387bae25a2a77d7f30b,

title = "19F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy",

abstract = "The introduction of high-frequency, high-power microwave sources, tailored biradicals, and low-temperature magic angle spinning (MAS) probes has led to a rapid development of hyperpolarization strategies for solids and frozen solutions, leading to large gains in NMR sensitivity. Here, we introduce a protocol for efficient hyperpolarization of 19F nuclei in MAS DNP enhanced NMR spectroscopy. We identified trifluoroethanol-d3 as a versatile glassy matrix and show that 12 mm AMUPol (with microcrystalline KBr) provides direct 19F DNP enhancements of over 100 at 9.4 T. We applied this protocol to obtain DNP-enhanced 19F and 19F–13C cross-polarization (CP) spectra for an active pharmaceutical ingredient and a fluorinated mesostructured hybrid material, using incipient wetness impregnation, with enhancements of approximately 25 and 10 in the bulk solid, respectively. This strategy is a general and straightforward method for obtaining enhanced 19F MAS spectra from fluorinated materials.",

keywords = "active pharmaceutical ingredients, dynamic nuclear polarization, magic angle spinning, NMR spectroscopy",

author = "Jasmine Viger-Gravel and Avalos, {Claudia E.} and Kubicki, {Dominik J.} and David Gajan and Moreno Lelli and Olivier Ouari and Anne Lesage and Lyndon Emsley",

note = "Funding Information: This work was supported by ERC AdG No. 320860 and ANR-15-CE29-0022-01. We thank Dr. C. Reiter and Dr. F. Engelke (Bruker Biospin) for their support modifying the LTMAS probe to tune to F-19. We are indebted to A. D{\"a}pp for providing technical assistance. We thank F. M. Parruzo for his assistance with calculations. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = may,

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AU - Avalos, Claudia E.

AU - Kubicki, Dominik J.

AU - Gajan, David

AU - Lelli, Moreno

AU - Ouari, Olivier

AU - Lesage, Anne

AU - Emsley, Lyndon

N1 - Funding Information: This work was supported by ERC AdG No. 320860 and ANR-15-CE29-0022-01. We thank Dr. C. Reiter and Dr. F. Engelke (Bruker Biospin) for their support modifying the LTMAS probe to tune to F-19. We are indebted to A. Däpp for providing technical assistance. We thank F. M. Parruzo for his assistance with calculations. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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N2 - The introduction of high-frequency, high-power microwave sources, tailored biradicals, and low-temperature magic angle spinning (MAS) probes has led to a rapid development of hyperpolarization strategies for solids and frozen solutions, leading to large gains in NMR sensitivity. Here, we introduce a protocol for efficient hyperpolarization of 19F nuclei in MAS DNP enhanced NMR spectroscopy. We identified trifluoroethanol-d3 as a versatile glassy matrix and show that 12 mm AMUPol (with microcrystalline KBr) provides direct 19F DNP enhancements of over 100 at 9.4 T. We applied this protocol to obtain DNP-enhanced 19F and 19F–13C cross-polarization (CP) spectra for an active pharmaceutical ingredient and a fluorinated mesostructured hybrid material, using incipient wetness impregnation, with enhancements of approximately 25 and 10 in the bulk solid, respectively. This strategy is a general and straightforward method for obtaining enhanced 19F MAS spectra from fluorinated materials.

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