Application of ex situ dynamic nuclear polarization in studying small molecules.

Dynamic nuclear polarization (DNP) has become an attractive technique to boost the sensitivity of NMR experiments. In the case of ex situ polarizations two-dimensional (2D) spectra are limited by the short lifetime of the polarization after dissolution and sample transfer to a high field NMR magnet. This limitation can be overcome by various approaches.

Optimizing the polarization matrix for ex situ dynamic nuclear polarization.

Although recent advances in dynamic nuclear polarization techniques have boosted the otherwise low sensitivity of NMR spectroscopy, the efficiency of the hyperpolarization process depends on the composition of the polarization matrix, in particular on the contact between the radical and the target molecule and the capability of the matrix to transfer polarization through spin diffusion. A concept for optimal matrix design is presented, applied to obtain two-dimensional heterocorrelated spectra of small drug-like molecules in 1-2 min after 90 min of hyperpolarization.

Optimizing the signal enhancement in cryogenic ex situ DNP-NMR spectroscopy.

Dynamic nuclear polarization (DNP) is often carried out at low temperatures to utilize the high spin polarization of the radical electrons at these temperatures. We have observed that in the absence of microwave irradiation and radical a transient negative polarization is observed for the methyl signals of acetone and DMSO. We suggest that this polarization arises from rotational tunneling levels in this system.