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. Here we show how the use of ¹³C-labelled acetyl tags can help to obtain 2D-HMQC spectra for many small molecules, owing to a nuclear Overhauser enhancement between ¹³C spins originating from the long-lived carbonyl carbon, which extends the lifetimes of other ¹³C spins with shorter longitudinal relaxation times. We also show an alternative approach of using an optimized polarization matrix.