title: Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR.
abstract: 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.
authors: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors: Albert A
authors: AA
authors: Smith
authors: Björn
authors: B
authors: Corzilius
authors: Olesya
authors: O
authors: Haze
authors: Timothy M
authors: TM
authors: Swager
authors: Robert G
authors: RG
authors: Griffin
mesh_terms: D000465:Algorithms; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D014320:Triphenylmethyl Compounds / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D014320:Triphenylmethyl Compounds