Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization
The synthesis and characterization of oxidized bis-thioketal-trispiro dinitroxide biradicals that orient the nitroxides in a rigid, approximately orthogonal geometry are reported. The biradicals show better performance as polarizing agents in dynamic nuclear polarization (DNP) NMR experiments as com...
| Main Authors: | , , , , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society
2013
|
| Online Access: | http://hdl.handle.net/1721.1/78309 https://orcid.org/0000-0003-1589-832X |
| _version_ | 1826213914477592576 |
|---|---|
| author | Dane, Eric L. Corzilius, Bjorn Rizzato, Egon Stocker, Pierre Maly, Thorsten Smith, Albert A. Griffin, Robert Guy Ouari, Olivier Tordo, Paul Swager, Timothy M |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Dane, Eric L. Corzilius, Bjorn Rizzato, Egon Stocker, Pierre Maly, Thorsten Smith, Albert A. Griffin, Robert Guy Ouari, Olivier Tordo, Paul Swager, Timothy M |
| author_sort | Dane, Eric L. |
| collection | MIT |
| description | The synthesis and characterization of oxidized bis-thioketal-trispiro dinitroxide biradicals that orient the nitroxides in a rigid, approximately orthogonal geometry are reported. The biradicals show better performance as polarizing agents in dynamic nuclear polarization (DNP) NMR experiments as compared to biradicals lacking the constrained geometry. In addition, the biradicals display improved solubility in aqueous media due to the presence of polar sulfoxides. The results suggest that the orientation of the radicals is not dramatically affected by the oxidation state of the sulfur atoms in the biradical, and we conclude that a biradical polarizing agent containing a mixture of oxidation states can be used for improved solubility without a loss in performance. |
| first_indexed | 2024-09-23T15:56:52Z |
| format | Article |
| id | mit-1721.1/78309 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:56:52Z |
| publishDate | 2013 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/783092022-10-02T05:16:03Z Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization Dane, Eric L. Corzilius, Bjorn Rizzato, Egon Stocker, Pierre Maly, Thorsten Smith, Albert A. Griffin, Robert Guy Ouari, Olivier Tordo, Paul Swager, Timothy M Massachusetts Institute of Technology. Department of Chemistry Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) Swager, Timothy Manning Swager, Timothy Manning Dane, Eric L. Corzilius, Bjorn Maly, Thorsten Smith, Albert A. Griffin, Robert Guy The synthesis and characterization of oxidized bis-thioketal-trispiro dinitroxide biradicals that orient the nitroxides in a rigid, approximately orthogonal geometry are reported. The biradicals show better performance as polarizing agents in dynamic nuclear polarization (DNP) NMR experiments as compared to biradicals lacking the constrained geometry. In addition, the biradicals display improved solubility in aqueous media due to the presence of polar sulfoxides. The results suggest that the orientation of the radicals is not dramatically affected by the oxidation state of the sulfur atoms in the biradical, and we conclude that a biradical polarizing agent containing a mixture of oxidation states can be used for improved solubility without a loss in performance. National Institutes of Health (U.S.) (grant EB002804) National Institutes of Health (U.S.) (grant EB002026) National Institutes of Health (U.S.) (grant GM095843) European Commission (Design Study project Bio-DNP) Deutsche Forschungsgemeinschaft (postdoctoral fellowship) 2013-04-09T20:43:02Z 2013-04-09T20:43:02Z 2012-02 2011-11 Article http://purl.org/eprint/type/JournalArticle 0022-3263 1520-6904 http://hdl.handle.net/1721.1/78309 Dane, Eric L. et al. “Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization.” The Journal of Organic Chemistry 77.4 (2012): 1789–1797. CrossRef. Web. https://orcid.org/0000-0003-1589-832X en_US http://dx.doi.org/10.1021/jo202349j Journal of Organic Chemistry Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Prof. Swager via Erja Kajosalo |
| spellingShingle | Dane, Eric L. Corzilius, Bjorn Rizzato, Egon Stocker, Pierre Maly, Thorsten Smith, Albert A. Griffin, Robert Guy Ouari, Olivier Tordo, Paul Swager, Timothy M Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title | Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title_full | Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title_fullStr | Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title_full_unstemmed | Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title_short | Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization |
| title_sort | rigid orthogonal bis tempo biradicals with improved solubility for dynamic nuclear polarization |
| url | http://hdl.handle.net/1721.1/78309 https://orcid.org/0000-0003-1589-832X |
| work_keys_str_mv | AT daneericl rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT corziliusbjorn rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT rizzatoegon rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT stockerpierre rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT malythorsten rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT smithalberta rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT griffinrobertguy rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT ouariolivier rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT tordopaul rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization AT swagertimothym rigidorthogonalbistempobiradicalswithimprovedsolubilityfordynamicnuclearpolarization |