U.S. Department of EnergyOffice of Scientific and Technical Information
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:
-
[1];
[2];
[2]
- Ames Lab., Ames, IA (United States)
- Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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:
- Journal Article: 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. https://doi.org/10.1002/cphc.201700299
Perras, Frédéric A., Sadow, Aaron, and Pruski, Marek. 2017.
"In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1371891},
journal = {ChemPhysChem},
issn = {1439-4235},
number = 16,
volume = 18,
place = {United States},
year = {Fri Jun 09 00:00:00 EDT 2017},
month = {Fri Jun 09 00:00:00 EDT 2017}
}
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