Improved waveguide coupling for 1.3 mm MAS DNP probes at 263 GHz.

We consider the geometry of a radially irradiated microwave beam in MAS DNP NMR probes and its impact on DNP enhancement. Two related characteristic features are found to be relevant: (i) the focus of the microwave beam on the DNP MAS sample and (ii) the microwave magnetic field magnitude in the sample. We present a waveguide coupler setup that enables us to significantly improve beam focus and field magnitude in 1.3 mm MAS DNP probes at a microwave frequency of 263 GHz, which results in an increase of the DNP enhancement by a factor of 2 compared to previous standard hardware setups. We discuss the implications of improved coupling and its potential to enable cutting-edge applications, such as pulsed high-field DNP and the use of low-power solid-state microwave sources.

High-Field Liquid-State Dynamic Nuclear Polarization in Microliter Samples.

Nuclear hyperpolarization in the liquid state by dynamic nuclear polarization (DNP) has been of great interest because of its potential use in NMR spectroscopy of small samples of biological and chemical compounds in aqueous media. Liquid state DNP generally requires microwave resonators in order to generate an alternating magnetic field strong enough to saturate electron spins in the solution. As a consequence, the sample size is limited to dimensions of the order of the wavelength, and this restricts the sample volume to less than 100 nL for DNP at 9 T (∼260 GHz). We show here a new approach that overcomes this sample size limitation. Large saturation of electron spins was obtained with a high-power (∼150 W) gyrotron without microwave resonators. Since high power microwaves can cause serious dielectric heating in polar solutions, we designed a planar probe which effectively alleviates dielectric heating. A thin liquid sample of 100 µm of thickness is placed on a block of high thermal conductivity aluminum nitride, with a gold coating that serves both as a ground plane and as a heat sink. A meander or a coil were used for NMR. We performed 1H DNP at 9.2 T (∼260 GHz) and at room temperature with 10 µL of water, a volume that is more than 100× larger than reported so far. The 1H NMR signal is enhanced by a factor of about -10 with 70 W of microwave power. We also demonstrated the liquid state of 31P DNP in fluorobenzene containing triphenylphosphine and obtained an enhancement of ∼200.