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J -Driven dynamic nuclear polarization for sensitizing high field solution state NMR

J -Driven dynamic nuclear polarization for sensitizing high field solution state NMR
J -Driven dynamic nuclear polarization for sensitizing high field solution state NMR

Dynamic nuclear polarization (DNP) is widely used to enhance solid state nuclear magnetic resonance (NMR) sensitivity. Its efficiency as a generic signal-enhancing approach for liquid state NMR, however, decays rapidly with magnetic field B 0, unless mediated by scalar interactions arising only in exceptional cases. This has prevented a more widespread use of DNP in structural and dynamical solution NMR analyses. This study introduces a potential solution to this problem, relying on biradicals with exchange couplings J ex of the order of the electron Larmor frequency ω E. Numerical and analytical calculations show that in such J ex ≈ ± ω E cases a phenomenon akin to that occurring in chemically induced DNP (CIDNP) happens, leading to different relaxation rates for the biradical singlet and triplet states which are hyperfine-coupled to the nuclear α or β states. Microwave irradiation can then generate a transient nuclear polarization build-up with high efficiency, at all magnetic fields that are relevant in contemporary NMR, and for all rotational diffusion correlation times that occur in small- and medium-sized molecules in conventional solvents.

1463-9076
2118-2125
Concilio, Maria Grazia
a28efff1-e031-475b-afbc-10129875c879
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Frydman, Lucio
4f00a1a4-d3a4-47fc-b9c9-50813cb39110
Concilio, Maria Grazia
a28efff1-e031-475b-afbc-10129875c879
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Frydman, Lucio
4f00a1a4-d3a4-47fc-b9c9-50813cb39110

Concilio, Maria Grazia, Kuprov, Ilya and Frydman, Lucio (2022) J -Driven dynamic nuclear polarization for sensitizing high field solution state NMR. Physical Chemistry Chemical Physics, 24 (4), 2118-2125. (doi:10.1039/d1cp04186j).

Record type: Article

Abstract

Dynamic nuclear polarization (DNP) is widely used to enhance solid state nuclear magnetic resonance (NMR) sensitivity. Its efficiency as a generic signal-enhancing approach for liquid state NMR, however, decays rapidly with magnetic field B 0, unless mediated by scalar interactions arising only in exceptional cases. This has prevented a more widespread use of DNP in structural and dynamical solution NMR analyses. This study introduces a potential solution to this problem, relying on biradicals with exchange couplings J ex of the order of the electron Larmor frequency ω E. Numerical and analytical calculations show that in such J ex ≈ ± ω E cases a phenomenon akin to that occurring in chemically induced DNP (CIDNP) happens, leading to different relaxation rates for the biradical singlet and triplet states which are hyperfine-coupled to the nuclear α or β states. Microwave irradiation can then generate a transient nuclear polarization build-up with high efficiency, at all magnetic fields that are relevant in contemporary NMR, and for all rotational diffusion correlation times that occur in small- and medium-sized molecules in conventional solvents.

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Accepted/In Press date: 5 January 2022
Published date: 26 January 2022
Additional Information: Funding Information: This project was funded by the Weizmann-UK Joint Research Programme, the Israel Science Foundation (ISF 965/18), the Perlman Family Foundation, and the US National Science Foundation (grants numbers CHE-1808660, DMR-1644779). MGC acknowledges Weizmann’s Faculty of Chemistry for a Dean Fellowship. LF holds the Bertha and Isadore Gudelsky Professorial Chair and Heads the Clore Institute for High-Field Magnetic Resonance Imaging and Spectroscopy, whose support is acknowledged. Publisher Copyright: © the Owner Societies. Copyright: Copyright 2022 Elsevier B.V., All rights reserved.

Identifiers

Local EPrints ID: 455169
URI: http://eprints.soton.ac.uk/id/eprint/455169
ISSN: 1463-9076
PURE UUID: ef620a48-d06e-45a2-a2f0-f642b206fbb1
ORCID for Ilya Kuprov: ORCID iD orcid.org/0000-0003-0430-2682

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Date deposited: 11 Mar 2022 17:30
Last modified: 28 Apr 2022 02:07

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Contributors

Author: Maria Grazia Concilio
Author: Ilya Kuprov ORCID iD
Author: Lucio Frydman

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