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Weak nuclear spin singlet relaxation mechanisms revealed by experiment and computation’

Weak nuclear spin singlet relaxation mechanisms revealed by experiment and computation’
Weak nuclear spin singlet relaxation mechanisms revealed by experiment and computation’
Nuclear spin singlet states are often found to allow long-lived storage of nuclear magnetization, which can form the basis of novel applications in spectroscopy, imaging, and in studies of dynamic processes. Precisely how long such polarization remains intact, and which factors affect its lifetime is often difficult to determine and predict. We present a combined experimental/computational study to demonstrate that molecular dynamics simulations and ab initio calculations can be used to fully account for the experimentally observed proton singlet lifetimes in ethyl-d5-propyl-d7-maleate in deuterated chloroform as solvent. The correspondence between experiment and simulations is achieved without adjustable parameters. These studies highlight the importance of considering unusual and difficult-to-control mechanisms, such as dipolar couplings to low-gamma solvent nuclei, and to residual paramagnetic species, which often can represent lifetime limiting factors. These results also point to the power of molecular dynamics simulations to provide insights into little-known NMR relaxation mechanisms.
1463-9076
7531-7538
Kharkov, Boris
1361c219-1d43-4aec-a3fd-065aca444099
Duan, Xueyou
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Rantaharju, Jyrki JS
3e150a26-27de-460f-bb8d-56053a080618
Sabba, Mohamed
bef5e5e8-18b2-43d9-8969-4a9b25bb8691
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Canary, James W.
af79af1b-a7c6-4947-9129-3648ab822c1a
Jerschow, Alexej
4809ea26-1ad9-4f59-a7e4-e66ea2ed6692
Kharkov, Boris
1361c219-1d43-4aec-a3fd-065aca444099
Duan, Xueyou
9c1b0cf0-e0a0-4f48-8287-2cd3477fe16f
Rantaharju, Jyrki JS
3e150a26-27de-460f-bb8d-56053a080618
Sabba, Mohamed
bef5e5e8-18b2-43d9-8969-4a9b25bb8691
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Canary, James W.
af79af1b-a7c6-4947-9129-3648ab822c1a
Jerschow, Alexej
4809ea26-1ad9-4f59-a7e4-e66ea2ed6692

Kharkov, Boris, Duan, Xueyou, Rantaharju, Jyrki JS, Sabba, Mohamed, Levitt, Malcolm H., Canary, James W. and Jerschow, Alexej (2022) Weak nuclear spin singlet relaxation mechanisms revealed by experiment and computation’. Physical Chemistry Chemical Physics, 24 (12), 7531-7538. (doi:10.1039/D1CP05537B).

Record type: Article

Abstract

Nuclear spin singlet states are often found to allow long-lived storage of nuclear magnetization, which can form the basis of novel applications in spectroscopy, imaging, and in studies of dynamic processes. Precisely how long such polarization remains intact, and which factors affect its lifetime is often difficult to determine and predict. We present a combined experimental/computational study to demonstrate that molecular dynamics simulations and ab initio calculations can be used to fully account for the experimentally observed proton singlet lifetimes in ethyl-d5-propyl-d7-maleate in deuterated chloroform as solvent. The correspondence between experiment and simulations is achieved without adjustable parameters. These studies highlight the importance of considering unusual and difficult-to-control mechanisms, such as dipolar couplings to low-gamma solvent nuclei, and to residual paramagnetic species, which often can represent lifetime limiting factors. These results also point to the power of molecular dynamics simulations to provide insights into little-known NMR relaxation mechanisms.

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Kharkov-2022-accepted - Accepted Manuscript
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More information

Accepted/In Press date: 25 February 2022
e-pub ahead of print date: 28 February 2022
Published date: 23 March 2022
Additional Information: AJ acknowledges funding through an award of the U.S. National Science Foundation, award no. CHE 2108205, an award by the Heising-Simons Foundation. AJ acknowledges the receipt of a Diamond Jubilee Visiting Fellowship to the University of Southampton. This work was supported in part through the NYU IT High Performance Computing resources, services, and staff expertise (in particular by Dr Shenglong Wang). During manuscript preparation, B.B. Kharkov was supported by grant 72777155 from St. Petersburg State University awarded to the Laboratory of Biomolecular NMR at SPbSU. This research was further supported by EPSRC-UK (grant numbers EP/P009980/1, EP/T004320/1 and EP/P030491/1), and the European Unions Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 891400, and the European Research Council (grant 786707-FunMagResBeacons). We thank Harry Harbor Collins for pointing us to a typo in eqn (10), which we were able to correct at proof stage. We acknowledge extensive discussions with Dr Christian Bengs with regard to nuclear spin singlet relaxation mechanisms.

Identifiers

Local EPrints ID: 456764
URI: http://eprints.soton.ac.uk/id/eprint/456764
ISSN: 1463-9076
PURE UUID: 12940a00-ba35-4e4d-b21f-33cef1e4e517
ORCID for Mohamed Sabba: ORCID iD orcid.org/0000-0003-2707-1821
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180

Catalogue record

Date deposited: 10 May 2022 17:08
Last modified: 06 Jun 2024 04:03

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Contributors

Author: Boris Kharkov
Author: Xueyou Duan
Author: Mohamed Sabba ORCID iD
Author: James W. Canary
Author: Alexej Jerschow

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