Crossover from a Solid Effect to Thermal Mixing ¹H Dynamic Nuclear Polarization with Trityl-OX063

Trityl-OX063 is a narrow-line, water-soluble, and biocompatible polarizing agent, widely used for dynamic nuclear polarization (DNP) amplified NMR of 13C, but not of the abundant 1H nuclear spin, for which the ineffective solid effect (SE) is expected to be operational. Surprisingly, we observed a crossover from SE to thermal mixing (TM) DNP of 1H with increasing Trityl-OX063 concentration at 7 T. We experimentally ascertained diagnostic signatures of TM-DNP that have only been theoretically predicted: (i) an electron paramagnetic resonance (EPR) spectrum that maintains an asymmetrically broadened EPR line from strong e-e couplings and (ii) hyperpolarization, i.e., cooling of select electron-spin populations, manifested in a characteristic pump-probe electron double-resonance spectrum under DNP conditions. Low microwave power requirements, high polarization transfer rates, and efficient DNP at high magnetic fields are the key benefits of TM-DNP.