Solid-state MAS NMR at ultra low temperature of hydrated alanine doped with DNP radicals

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments at ultra low temperature (ULT) (≪ 100 K) have demonstrated clear benefits for obtaining large signal sensitivity gain and probing spin dynamics phenomena at ULT. ULT NMR is furthermore a highly promising platform for solid-state dynamic nuclear polarization (DNP). However, ULT NMR is not widely used, given limited availability of such instrumentation from commercial sources. In this paper, we present a comprehensive study of hydrated [U-¹³C]alanine, a standard bio-solid sample, from the first commercial 14.1 Tesla NMR spectrometer equipped with a closed-cycle helium ULT-MAS system. The closed-cycle helium MAS system provides precise temperature control from 25 K to 100 K and stable MAS from 1.5 kHz to 12 kHz. The ¹³C CP-MAS NMR of [U-¹³C]alanine showed 400% signal gain at 28 K compared with at 100 K. The large sensitivity gain results from the Boltzmann factor, radio frequency circuitry quality factor improvement, and the suppression of its methyl group rotation at ULT. We further observed that the addition of organic biradicals widely used for solid-state DNP significantly shortens the ¹H T₁ spin lattice relaxation time at ULT, without further broadening the ¹³C spectral linewidth compared to at 90 K. The mechanism of ¹H T₁ shortening is dominated by the two-electron-one-nucleus triple flip transition underlying the Cross Effect mechanism, widely relied upon to drive solid-state DNP. Our experimental observations suggest that the prospects of MAS NMR and DNP under ULT conditions established with a closed-cycle helium MAS system are bright.