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One-thousand-fold enhancement of high field liquid nuclear magnetic resonance signals at room temperature

Nature Chemistry volume 9, pages 676–680 (2017)Cite this article

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Abstract

Nuclear magnetic resonance (NMR) is a fundamental spectroscopic technique for the study of biological systems and materials, molecular imaging and the analysis of small molecules. It detects interactions at very low energies and is thus non-invasive and applicable to a variety of targets, including animals and humans. However, one of its most severe limitations is its low sensitivity, which stems from the small interaction energies involved. Here, we report that dynamic nuclear polarization in liquid solution and at room temperature can enhance the NMR signal of 13C nuclei by up to three orders of magnitude at magnetic fields of ∼3 T. The experiment can be repeated within seconds for signal averaging, without interfering with the sample magnetic homogeneity. The method is therefore compatible with the conditions required for high-resolution NMR. Enhancement of 13C signals on various organic compounds opens up new perspectives for dynamic nuclear polarization as a general tool to increase the sensitivity of liquid NMR.

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Figure 1: 13C DNP–NMR on 13CCl4 doped with 15N-TEMPONE at 3.4 T and room temperature (νEPR = 94 GHz, νNMR (13C) = 36 MHz).
Figure 2: Effect of temperature on 13C-DNP enhancement in 13CCl4 and scalar relaxivity.
Figure 3: 13C relaxivity of CCl4 (black triangles) and CHCl3 (blue squares) in solutions with 200 mM TEMPONE.
Figure 4: 13C DNP–NMR (3.4 T) of biologically relevant compounds.

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Acknowledgements

The authors thank R. Rizzato for discussions on the initial 13C-DNP experiments and I. Tkach for technical support with the 94 GHz EPR spectrometer. Financial support was provided by the Max Planck Society. G.L. acknowledges the Alexander von Humboldt Foundation for a fellowship. C.L. and G.P. acknowledge MIUR PRIN 2012SK7ASN, the European Commission, contracts BioMedBridges 284209 and pNMR 317127, and the EU ESFRI Instruct Core Centre CERM.

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  1. Guoquan Liu

    Present address: Present address: State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, 38 Xueyuan Road, Beijing 100191, China,

Authors and Affiliations

  1. Electron-Spin Resonance Spectroscopy, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Göttingen, 37077, Germany

    Guoquan Liu & Marina Bennati

  2. Department of Chemistry, Georg-August-University, Tammannstraβe 4, Göttingen, 37077, Germany

    Marcel Levien, Niels Karschin & Marina Bennati

  3. Magnetic Resonance Center (CERM) and Department of Chemistry, University of Florence, Via Luigi Sacconi 6, Sesto Fiorentino, 50019, Italy

    Giacomo Parigi & Claudio Luchinat

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  1. Guoquan Liu
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  2. Marcel Levien
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  4. Giacomo Parigi
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  6. Marina Bennati
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Contributions

M.B. and G.L. conceived and designed the research. G.L., N.K. and M.L. performed the DNP and EPR experiments. M.L. and N.K. contributed equally to this work. G.P. and C.L. performed and analysed the NMRD experiments. G.L., G.P., C.L. and M.B. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Guoquan Liu or Marina Bennati.

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Liu, G., Levien, M., Karschin, N. et al. One-thousand-fold enhancement of high field liquid nuclear magnetic resonance signals at room temperature. Nature Chem 9, 676–680 (2017). https://doi.org/10.1038/nchem.2723

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