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Title: In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

Abstract

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Ames Lab., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1371891
Alternate Identifier(s):
OSTI ID: 1375526
Report Number(s):
IS-J-9360
Journal ID: ISSN 1439-4235
Grant/Contract Number:  
AC02-07CH11358; FY2015-MPRU-0812
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 18; Journal Issue: 16; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dynamic nuclear polarization; solid-state NMR; MAS-DN; dinitroxides; simulations

Citation Formats

Perras, Frédéric A., Sadow, Aaron, and Pruski, Marek. In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?. United States: N. p., 2017. Web. doi:10.1002/cphc.201700299.
Perras, Frédéric A., Sadow, Aaron, & Pruski, Marek. In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?. United States. doi:10.1002/cphc.201700299.
Perras, Frédéric A., Sadow, Aaron, and Pruski, Marek. Fri . "In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?". United States. doi:10.1002/cphc.201700299. https://www.osti.gov/servlets/purl/1371891.
@article{osti_1371891,
title = {In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?},
author = {Perras, Frédéric A. and Sadow, Aaron and Pruski, Marek},
abstractNote = {Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.},
doi = {10.1002/cphc.201700299},
journal = {ChemPhysChem},
number = 16,
volume = 18,
place = {United States},
year = {2017},
month = {6}
}

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