Dynamic nuclear polarization mechanisms using TEMPOL and trityl OX063 radicals at 1 T and 77 K

Abstract

A sensitivity increase of two orders of magnitude in proton (1H) and carbon (13C) spins via dynamic nuclear polarization (DNP) has been accomplished recently using a compact benchtop DNP polarizer operating at 1 T and 77 K. However, the DNP mechanisms at play at such a low magnetic field and high operating temperature are still not fully elucidated. A deeper understanding of the dominant polarization transfer mechanisms between electrons and 1H and 13C spins under these benchtop conditions is, therefore, required if one wants to devise strategies to boost sensitivity further. In this study, we found that DNP is generally dominated by solid effect (two-spin and three-spin) for narrow electron paramagnetic resonance (EPR) line radicals (15 mM trityl OX063) and cross effect for broad EPR line radicals (50 mM TEMPOL). For both radicals, the dominant DNP mechanisms were investigated varying the microwave frequency and measuring the 1H and 13C DNP enhancement factors to obtain 1H and 13C DNP spectra. The impact of varying the microwave power on the 1H DNP buildup times and the 1H nuclear spin relaxation times were important as well to distinguish between solid effect and cross effect DNP. Finally, time-resolved electron saturation simulations under continuous microwave irradiation could replicate the experimental 1H and 13C DNP spectra at 1 T and 77 K for both radicals considering their electron relaxation properties. Only for trityl OX063, the 13C DNP spectra showed additional DNP maxima compared to the simulations. This has been attributed to methyl rotor induced 1H–13C heteronuclear cross relaxation in [1–13C] acetate present at 1 T and 77 K.