LC - ¹³C NMR utilizing dynamic nuclear polarization (DNP) for signal enhancement

Abstract

The primary difficulty for successful LC - ¹³C NMR (whether ¹H or ¹³C) is overcoming the relatively low sensitivity of NHR as a chromatographic detector. For the ¹H nuclide this is much less of a problem; the sensitivity ;s approximately 6000 times more sensitive than that of ¹³C nuclei. For this reason, much of the literature focuses on LC - ¹H NMR. To ever successfully realize LC - ¹³C NMR, it is mandatory that an augmentation of ¹³C signal intensity must be effectuated to overcome this sensitivity deficit (~ three orders of magnitude). To satisfy this requirement, our laboratory has utilized dynamic nuclear polarization (DNP) to ameliorate these otherwise weak or non-existent signals. For favorable molecules, sensitivity recoveries of up to two orders of magnitude have been developed. This improvement (relative to 'H) narrows the sensitivity gap between 'H and ¹³C NMR detection of chromatographically separated analytes. Despite the fact that relatively large injection volumes were required in most LC experiments, the wealth of structural information inherent to ¹³C NMR justifies any attempt to successfully couple nuclear magnetic resonance to liquid chromatography.

In addition, DNP was utilized in a series of SLIT and LLIT experiments where a test mixture was recycled through a NMR spectrometer. Results indicate that ¹³C spectra were obtained with a significantly higher signal-to-noise ratio in a shorter amount of analysis time relative to experiments where DNP was not employed for signal enhancement.