Methyl-Driven Overhauser Dynamic Nuclear Polarization

Perras, Frédéric A.; Flesariu, Dragos F.; Southern, Scott A.; Nicolaides, Constantinos; Bazak, J. David; Washton, Nancy M.; Trypiniotis, Theodossis; Constantinides, Christos P.; Koutentis, Panayiotis A.

doi:10.1021/acs.jpclett.2c00748

Methyl-Driven Overhauser Dynamic Nuclear Polarization

Journal Article · Thu Apr 28 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00748· OSTI ID:1874485

^[1]; Flesariu, Dragos F. ^[2]; ^[1]; Nicolaides, Constantinos ^[3]; Bazak, J. David ^[4]; ^[4]; Trypiniotis, Theodossis ^[3]; ^[5]; ^[2]

US DOE, Ames Laboratory, Ames, Iowa 50011, United States
Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus
Department of Physics, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus
Physical & Computational Science Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
Department of Natural Sciences, University of Michigan-Dearborn, 4901 Evergreen Road, Dearborn, Michigan 48128-1491, United States

The Overhauser effect is unique among DNP mechanisms in that it requires the modulation of the electron-nuclear hyperfine interactions. While it dominates DNP in liquids and metals, where unpaired electrons are highly mobile, Overhauser DNP is possible in insulating solids if rapid structural modulations are linked to a modulation in hyperfine coupling. In this study, we report that Overhauser DNP can be triggered by the strategic addition of a methyl group, demonstrated here in a Blatter’s radical. The rotation of the methyl group leads to a modulation of the hyperfine coupling to its protons, which in turn facilitates electron-nuclear cross-relaxation. Removal of the methyl protons, through deuteration, quenches the process, as does the reduction of the hyperfine coupling strength. This result suggests the possibility for the design of tailor-made Overhauser DNP polarizing agents for high-field MAS-DNP.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: Ames Laboratory; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-07CH11358; AC05-76RL01830

OSTI ID:: 1874485

Alternate ID(s):: OSTI ID: 1875760

Report Number(s):: IS-J-10,800; PNNL-SA-172525

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 18 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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