Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR
We present electron paramagnetic resonance experiments for which solid effect dynamic nuclear polarization transitions were observed indirectly via polarization loss on the electron. This use of indirect observation allows characterization of the dynamic nuclear polarization (DNP) process close to t...
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American Institute of Physics (AIP)
2015
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Online Access: | http://hdl.handle.net/1721.1/95738 https://orcid.org/0000-0003-1589-832X |
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author | Smith, Albert A. Haze, Olesya Corzilius, Bjorn Griffin, Robert Guy Swager, Timothy M |
author2 | Massachusetts Institute of Technology. Department of Chemistry |
author_facet | Massachusetts Institute of Technology. Department of Chemistry Smith, Albert A. Haze, Olesya Corzilius, Bjorn Griffin, Robert Guy Swager, Timothy M |
author_sort | Smith, Albert A. |
collection | MIT |
description | We present electron paramagnetic resonance experiments for which solid effect dynamic nuclear polarization transitions were observed indirectly via polarization loss on the electron. This use of indirect observation allows characterization of the dynamic nuclear polarization (DNP) process close to the electron. Frequency profiles of the electron-detected solid effect obtained using trityl radical showed intense saturation of the electron at the usual solid effect condition, which involves a single electron and nucleus. However, higher order solid effect transitions involving two, three, or four nuclei were also observed with surprising intensity, although these transitions did not lead to bulk nuclear polarization—suggesting that higher order transitions are important primarily in the transfer of polarization to nuclei nearby the electron. Similar results were obtained for the SA-BDPA radical where strong electron-nuclear couplings produced splittings in the spectrum of the indirectly observed solid effect conditions. Observation of high order solid effect transitions supports recent studies of the solid effect, and suggests that a multi-spin solid effect mechanism may play a major role in polarization transfer via DNP. |
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institution | Massachusetts Institute of Technology |
language | en_US |
last_indexed | 2024-09-23T17:10:02Z |
publishDate | 2015 |
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spelling | mit-1721.1/957382022-10-03T10:51:11Z Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR Smith, Albert A. Haze, Olesya Corzilius, Bjorn Griffin, Robert Guy Swager, Timothy M Massachusetts Institute of Technology. Department of Chemistry Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) Smith, Albert A. Corzilius, Bjorn Haze, Olesya Swager, Timothy Manning Griffin, Robert Guy We present electron paramagnetic resonance experiments for which solid effect dynamic nuclear polarization transitions were observed indirectly via polarization loss on the electron. This use of indirect observation allows characterization of the dynamic nuclear polarization (DNP) process close to the electron. Frequency profiles of the electron-detected solid effect obtained using trityl radical showed intense saturation of the electron at the usual solid effect condition, which involves a single electron and nucleus. However, higher order solid effect transitions involving two, three, or four nuclei were also observed with surprising intensity, although these transitions did not lead to bulk nuclear polarization—suggesting that higher order transitions are important primarily in the transfer of polarization to nuclei nearby the electron. Similar results were obtained for the SA-BDPA radical where strong electron-nuclear couplings produced splittings in the spectrum of the indirectly observed solid effect conditions. Observation of high order solid effect transitions supports recent studies of the solid effect, and suggests that a multi-spin solid effect mechanism may play a major role in polarization transfer via DNP. National Institutes of Health (U.S.) (Grant EB002804) National Institutes of Health (U.S.) (Grant EB002026) National Institutes of Health (U.S.) (Grant GM095843) Deutsche Forschungsgemeinschaft (Research Fellowship CO 802/1-1) 2015-02-27T17:08:30Z 2015-02-27T17:08:30Z 2013-12 2013-09 Article http://purl.org/eprint/type/JournalArticle 00219606 1089-7690 http://hdl.handle.net/1721.1/95738 Smith, Albert A., Bjorn Corzilius, Olesya Haze, Timothy M. Swager, and Robert G. Griffin. “Observation of Strongly Forbidden Solid Effect Dynamic Nuclear Polarization Transitions via Electron-Electron Double Resonance Detected NMR.” The Journal of Chemical Physics 139, no. 21 (2013): 214201. https://orcid.org/0000-0003-1589-832X en_US http://dx.doi.org/10.1063/1.4832323 The Journal of Chemical Physics 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 Institute of Physics (AIP) PMC |
spellingShingle | Smith, Albert A. Haze, Olesya Corzilius, Bjorn Griffin, Robert Guy Swager, Timothy M Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title | Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title_full | Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title_fullStr | Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title_full_unstemmed | Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title_short | Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR |
title_sort | observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron electron double resonance detected nmr |
url | http://hdl.handle.net/1721.1/95738 https://orcid.org/0000-0003-1589-832X |
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