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