Redrouthu, Venkata SubbaRao, and Guinevere Mathies. “Efficient Pulsed Dynamic Nuclear Polarization with the X-Inverse-X Sequence.” Journal of the American Chemical Society, January 25, 2022.
https://doi.org/10.1021/jacs.1c09900.
Pulsed dynamic nuclear polarization (DNP) is a promising new approach to enhancing the sensitivity of high-resolution magic-angle spinning (MAS) NMR. In pulsed DNP, the transfer of polarization from unpaired electrons to nuclei (usually 1H) is induced by a sequence of microwave pulses. Enhancement factors of the thermal 1H polarization are expected to be independent of the magnetic field, and sample heating by absorption of microwave irradiation will be strongly reduced. The development of DNP pulse sequences is still in its infancy. Of the two basic sequences in existence, NOVEL and TOP DNP, the former is, due to an extremely high power requirement, incompatible with high-resolution MAS NMR, while the latter displays a relatively slow transfer of polarization from electrons to 1H. We introduce here a new pulse sequence for DNP of solids, termed X-inverse-X (XiX) DNP. In experiments at 1.2 T, XiX DNP produces, compared to TOP DNP, a 2-fold higher gain in sensitivity. Our data suggest that a faster transfer of polarization from electrons to 1H is behind the superior performance of XiX DNP. Numerical simulations and experiments indicate that microwave pulse lengths can be chosen across a broad range, without loss of efficiency. These findings are a substantial step toward the implementation of pulsed DNP at high magnetic fields.