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

dc.contributor.author Perras, Frédéric
dc.contributor.author Sadow, Aaron
dc.contributor.author Pruski, Marek
dc.contributor.author Sadow, Aaron
dc.contributor.department Ames Laboratory
dc.contributor.department Chemistry
dc.date 2019-09-26T23:11:25.000
dc.date.accessioned 2020-06-30T01:17:03Z
dc.date.available 2020-06-30T01:17:03Z
dc.date.copyright Sun Jan 01 00:00:00 UTC 2017
dc.date.issued 2017-08-18
dc.description.abstract <p>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. Generally, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near‐optimal DNP performance. Our 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. Lastly, the calculations showed that the electron <em>T</em>1e value should be near 500 μs 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.</p>
dc.description.comments <p>This is the peer-reviewed version of the following article: Perras, Frédéric A., Aaron Sadow, and Marek Pruski. "In silico design of DNP polarizing agents: can current dinitroxides Be improved?." <em>ChemPhysChem</em> 18, no. 16 (2017): 2279-2287, which has been published in final form at <a href="http://dx.doi.org/10.1002/cphc.201700299" target="_blank">10.1002/cphc.201700299</a>. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/1155/
dc.identifier.articleid 2159
dc.identifier.contextkey 15433758
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/1155
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14462
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/1155/2017_SadowAaron_InSilicoDesign.pdf|||Fri Jan 14 18:52:48 UTC 2022
dc.source.uri 10.1002/cphc.201700299
dc.subject.disciplines Physical Chemistry
dc.subject.keywords dinitroxides
dc.subject.keywords dynamic nuclear polarization
dc.subject.keywords MAS-DNP
dc.subject.keywords simulations
dc.subject.keywords solid-state NMR
dc.title In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication a9d328ff-ec5e-4d1d-8c2f-aed9d5a290ed
relation.isOrgUnitOfPublication 25913818-6714-4be5-89a6-f70c8facdf7e
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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