Research Article

Hybrid polarizing solids for pure hyperpolarized liquids through dissolution dynamic nuclear polarization

David Gajan, Aurélien Bornet, Basile Vuichoud, Jonas Milani, Roberto Melzi, Henri A. van Kalkeren, Laurent Veyre, Chloé Thieuleux, Matthew P. Conley, Wolfram R. Grüning, Martin Schwarzwälder, Anne Lesage, Christophe Copéret, Geoffrey Bodenhausen, Lyndon Emsley, and Sami Jannin
PNAS October 14, 2014 111 (41) 14693-14697; first published September 29, 2014; https://doi.org/10.1073/pnas.1407730111

  1. Edited* by Timothy M. Swager, Massachusetts Institute of Technology, Cambridge, MA, and approved August 25, 2014 (received for review April 30, 2014)

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Figures

  • Fig. 1.
    Fig. 1.

    Hyperpolarization by D-DNP with HYPSO. (A) HYPSO 1.0 is impregnated with a solution of the analyte to be polarized without addition of any glass-forming agents. The transmission EM image (taken with a Philips CM30 TEM operated at 300 kV) shows the porous structure of the material. The red dots schematically represent the PAs. (B) Proton DNP is performed (Methods) on 20 mg HYPSO 1.0 material (88 µmol/g) impregnated with 36 µL 3 M solution of [1-13C]-pyruvate in D2O. The proton polarization rapidly builds up with a time constant τDNP(1H) = 119 ± 1.5 s, and by applying 1H→13C CP, a polarization of P(13C) > 20% is reached in 17 min. CW, continuous wave. (C) The DNP solution is dissolved and expulsed from HYPSO 1.0 by injecting 5 mL superheated D2O (more details in Methods) and transferring to a 300-MHz spectrometer; a series of 13C NMR spectra of [1-13C]-pyruvate is measured every 5 s. The liquid-state polarization obtained P(13C) = 25.3% corresponds to an enhancement εDNP > 32,000 compared with the Boltzmann equilibrium at 300 K and 7 T, and decays with T1(13C) = 49.4 ± 0.4 s are typical of a pure D2O solution of [1-13C]-pyruvate without any free radicals.

  • Fig. 2.
    Fig. 2.

    Hyperpolarized [1-13C]-acetate, [1-13C]-pyruvate, l-alanine-glycine, and fumarate. Thermal equilibrium and hyperpolarized signals of (A) [1-13C]-acetate, (B) [1-13C]-pyruvate, and (C) l-alanine-glycine and fumarate. Hyperpolarization was performed as described in the text by 1H→13C CP-DNP with HYPSO 1.0 followed by dissolution. The hyperpolarized signals were acquired with single 5° nutation angle pulses, whereas the thermal equilibrium signals, scaled by a factor of 5,000, were measured with 27, 128, and 512 scans for [1-13C]-acetate, [1-13C]-pyruvate, and l-alanine-glycine and fumarate, respectively, using 90° nutation angle pulses applied every 300 s.

  • Fig. 3.
    Fig. 3.

    (A) 1H→13C CP-DNP performed on 20 mg HYPSO 2.0 material (41 µmol/g) impregnated with 36 µL 3 M solution of [1-13C]-pyruvate in D2O. P(13C) > 30% is reached in 32.5 min with 1H→13C CP applied at 7.5-min intervals. (B) Direct 13C DNP performed on 20 mg HYPSO 1.2 material (16 µmol/g) impregnated with 36 µL 3 M solution of [1-13C]-pyruvate in D2O. P(13C) = 15% is achieved after 2 h with a monoexponential buildup time τDNP(13C) = 104.6 ± 2.4 min, potentially toward a maximum P(13C)max = 22.9%. Note that the horizontal scale has been extended by a factor of 10 for B with respect to A. Schematic representations of the radicals in the materials are given in A, Right and B, Right.

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Hybrid solids for pure hyperpolarized liquids
David Gajan, Aurélien Bornet, Basile Vuichoud, Jonas Milani, Roberto Melzi, Henri A. van Kalkeren, Laurent Veyre, Chloé Thieuleux, Matthew P. Conley, Wolfram R. Grüning, Martin Schwarzwälder, Anne Lesage, Christophe Copéret, Geoffrey Bodenhausen, Lyndon Emsley, Sami Jannin
Proceedings of the National Academy of Sciences Oct 2014, 111 (41) 14693-14697; DOI: 10.1073/pnas.1407730111
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Proceedings of the National Academy of Sciences: 111 (41)
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