Solid-state nitrogen-14 nuclear magnetic resonance enhanced by dynamic nuclear polarization using a gyrotron

摘要

By combining indirect detection of ~(14)N with dynamic nuclear polarization (DNP) using a gyrotron, the signal-to-noise ratio can be dramatically improved and the recovery delay between subsequent experiments can be shortened. Spectra of glassy samples of the amino acid proline doped with the stable bi-radical TOTAPOL rotating at 15.625 kHz at 110 K were obtained in a 400 MHz solid-state NMR spectrometer equipped with a gyrotron for microwave irradiation at 263 GHz. DNP enhancement factors on the order of ～ 40 were achieved. The recovery delays can be reduced from 60 s without radicals at 300 K to 6 s with radicals at 110 K. In the absence of radicals at room temperature, the proton relaxation in proline is inefficient due to the absence of rotating methyl groups and other heat sinks, thus making long recovery delays mandatory. DNP allows one to reduce the acquisition times of ~(13)C-detected ~(14)N spectra from several days to a few hours.