ABSTRACT
(1)H dynamic nuclear polarization (DNP) has been measured in supercritical ethylene in the pressure range 60-300 bar in an external field of 1.4 T. A single-cell sapphire tube was used as a high-pressure cell, and powdered 1,3-bisdiphenylene-2-phenyl allyl (BDPA) free radicals were added and distributed at the wall of the cell. At all pressures the dominant DNP mechanism was a positive Overhauser enhancement, caused by proton-electron contact interactions at the fluid/solid radical interface. The observed enhancements varied from 12 at 60 bar to 17 at 300 bar. Besides the Overhauser enhancement, small solid state and thermal mixing enhancements also were observed, indicating that part of the ethylene was adsorbed at the radical surface for a prolonged time. The impacts of the experimental conditions on the Overhauser enhancement factors are discussed, and enhancements of at least 40-60 are estimated when the EPR saturation factor and the leakage factor become maximal. These data indicate that DNP-enhanced NMR has the potential of extending the impact of NMR in research areas involving supercritical fluids.
Subject(s)
Ethylenes/chemistry , Magnetic Resonance Spectroscopy/methodsABSTRACT
A 15N dynamic nuclear polarization (DNP) experiment is reported in which a 15N DNP enhancement factor of approximately 2.6 x 10(2) is obtained on free radical doped samples of 99% 15N labeled benzamide. The free radicals BDPA (1:1 complex of alpha, gamma-bisdiphenylene-beta-phenylallyl with benzene) and DPPH (2,2-Di(4-tert-octylphenyl)-1-picrylhydrazyl) are used as dopants and the spin relaxation effects of adding these dopants are studied by means of changes in proton and nitrogen T1 values of the samples. The combination in solids of a very low natural abundance, 0.37%, a small gyromagnetic ratio, and a long spin-lattice relaxation time for 15N nuclei create severe sensitivity problems that, in large part, are ameliorated by the signal enhancement observed in the 15N DNP experiment on samples containing free electrons.
