Hyperpolarized Hadamard spectroscopy using flow NMR

Anal Chem. 2013 Aug 6;85(15):7385-90. doi: 10.1021/ac401293n. Epub 2013 Jul 8.

Abstract

The emergence of the dissolution dynamic nuclear polarization (D-DNP) technique provides an important breakthrough to overcome inherent sensitivity limitations in nuclear magnetic resonance (NMR) experiments. In dissolution DNP, only a small amount of frozen sample is polarized, dissolved, and injected into an NMR spectrometer. Although substantially enhanced NMR signals can be obtained, the single scan nature of this technique a priori impedes the use of correlation experiments, which represent some of the most powerful applications of NMR spectroscopy. Here, an alternative method for multiscan spectroscopy from D-DNP samples utilizing a flow NMR probe is described. Multiple hyperpolarized segments of sample are sequentially injected using a purpose designed device. Hadamard spectroscopy can then be applied for obtaining chemical shift correlation information even from a small number of scans. This capability is demonstrated with a four-scan data set for obtaining the [(13)C,(1)H] correlations in the test molecule 1-butanol. Because of the effects of spin-lattice relaxation and concentration gradients in the D-DNP experiment, the subtractive process for Hadamard reconstruction requires an additional step of intensity scaling. For this purpose, a reconstruction procedure was developed that uses entropy maximization and is robust with respect to noise and signal overlap. In a broader sense, the multiscan NMR as described here is amenable to various correlation NMR experiments, and increases the versatility of D-DNP in small-molecule characterization.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Magnetic Resonance Spectroscopy / methods*
  • Organic Chemicals / chemistry

Substances

  • Organic Chemicals