A Spectrometer for Dynamic Nuclear Polarization and Electron Paramagnetic Resonance at High Frequencies

Abstract

A high-frequency dynamic nuclear polarization (DNP)/electron paramagnetic resonance spectrometer operating at 211 MHz for1H and 140 GHz forg= 2 paramagnetic centers (5 T static field) is described. The salient feature of the instrument is a cyclotron-resonance maser (gyrotron) which generates high-frequency, high-power microwave radiation. This gyrotron, which under conventional operation produces millisecond pulses at kilowatt powers, has been adapted to operate at ∼100 W for 1 to 20 s pulses and in the continuous wave mode at the 10 W power level. Experiments combining DNP with magic-angle spinning (MAS) nuclear magnetic resonance were performed on samples consisting of 2% by weight of the free radical BDPA doped into polystyrene. Room-temperature DNP enhancement factors of 10 for1H and 40 for13C were obtained in the NMR-MAS spectra. Static DNP NMR has also been performed on samples containing nitroxides dissolved in water:glycerol solvent mixtures. Enhancements of approximately 200 have been obtained for low-temperature (14 K)1H NMR. A pulsed/CW EPR spectrometer operating at 140 GHz has been developed in conjunction with the DNP spectrometer. Microwave sources include Gunn-diode oscillators which provide low-power (20 mW) radiation, and the gyrotron, which has been used to deliver higher power levels in pulsed experiments. Results using this spectrometer are presented for continuous-wave and echo-detected EPR, electron spin-echo-envelope modulation (ESEEM), and Fourier-transform EPR.