High-resolution Overhauser dynamic nuclear polarization enhanced proton NMR spectroscopy at low magnetic fields

Abstract

Dynamic nuclear polarization (DNP) has gained large interest due to its ability to increase signal intensities in nuclear magnetic resonance (NMR) experiments by several orders of magnitude. Currently, DNP is typically used to enhance high-field, solid-state NMR experiments. However, the method is also capable of dramatically increasing the observed signal intensities in solution-state NMR spectroscopy. In this work, we demonstrate the application of Overhauser dynamic nuclear polarization (ODNP) spectroscopy at an NMR frequency of 14.5 MHz (0.35 T) to observe DNP-enhanced high-resolution NMR spectra of small molecules in solutions. Using a compact hybrid magnet with integrated shim coils to improve the magnetic field homogeneity we are able to routinely obtain proton linewidths of less than 4 Hz and enhancement factors >30. The excellent field resolution allows us to perform chemical-shift resolved ODNP experiments on ethyl crotonate to observe proton J-coupling. Furthermore, recording high-resolution ODNP-enhanced NMR spectra of ethylene glycol allows us to characterize the microwave induced sample heating in-situ, by measuring the separation of the OH and CH2 proton peaks.