31P nuclear spin singlet lifetimes in a system with switchable magnetic inequivalence: experiment and simulation: experiment and simulation
31P nuclear spin singlet lifetimes in a system with switchable magnetic inequivalence: experiment and simulation: experiment and simulation
31P NMR spectroscopy and the study of nuclear spin singlet relaxation phenomena are of interest in particular due to the importance of phosphorus-containing compounds in physiology. We report the generation and measurement of relaxation of 31P singlet order in a chemically equivalent but magnetically inequivalent case. Nuclear magnetic resonance singlet state lifetimes of 31P pairs have heretofore not been reported. Couplings between 1H and 31P nuclei lead to magnetic inequivalence and serve as a mechanism of singlet state population conversion within this molecule. We show that in this molecule singlet relaxation occurs at a rate significantly faster than spin–lattice relaxation, and that anticorrelated chemical shift anisotropy can account for this observation. Calculations of this mechanism, with the help of molecular dynamics simulations and ab initio calculations, provide excellent agreement with the experimental findings. This study could provide guidance for the study of 31P singlets within other compounds, including biomolecules.
19465-19471
Korenchan, David E.
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Lu, Jiaqi
995cde48-0e10-41ea-9e45-aee786371859
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Jerschow, Alexej
4809ea26-1ad9-4f59-a7e4-e66ea2ed6692
17 August 2021
Korenchan, David E.
9aa08b6b-8a5f-4131-894c-539bc9e838eb
Lu, Jiaqi
995cde48-0e10-41ea-9e45-aee786371859
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Jerschow, Alexej
4809ea26-1ad9-4f59-a7e4-e66ea2ed6692
Korenchan, David E., Lu, Jiaqi, Levitt, Malcolm H. and Jerschow, Alexej
(2021)
31P nuclear spin singlet lifetimes in a system with switchable magnetic inequivalence: experiment and simulation: experiment and simulation.
Physical Chemistry Chemical Physics, 23 (35), .
(doi:10.1039/D1CP03085J).
Abstract
31P NMR spectroscopy and the study of nuclear spin singlet relaxation phenomena are of interest in particular due to the importance of phosphorus-containing compounds in physiology. We report the generation and measurement of relaxation of 31P singlet order in a chemically equivalent but magnetically inequivalent case. Nuclear magnetic resonance singlet state lifetimes of 31P pairs have heretofore not been reported. Couplings between 1H and 31P nuclei lead to magnetic inequivalence and serve as a mechanism of singlet state population conversion within this molecule. We show that in this molecule singlet relaxation occurs at a rate significantly faster than spin–lattice relaxation, and that anticorrelated chemical shift anisotropy can account for this observation. Calculations of this mechanism, with the help of molecular dynamics simulations and ab initio calculations, provide excellent agreement with the experimental findings. This study could provide guidance for the study of 31P singlets within other compounds, including biomolecules.
Text
D1CP03085J
- Accepted Manuscript
More information
Accepted/In Press date: 17 August 2021
Published date: 17 August 2021
Additional Information:
Funding Information:
We acknowledge funding though an award of the U.S. National Science Foundation, award no. CHE 2108205, and an award by the Heising-Simons Foundation. AJ acknowledges the receipt of a Diamond Jubilee Visiting Fellowship to the University of Southampton. We thank Dr Christian Bengs for extensive discussions on singlet relaxation mechanisms and critical reading of the manuscript. We further thank Dr Mohamed Sabba for helpful and stimulating discussions of phosphorus relaxation mechanisms. This work was supported in part through the NYU IT High Performance Computing resources, services, and staff expertise (especially Dr. Shenglong Wang).
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Local EPrints ID: 451680
URI: http://eprints.soton.ac.uk/id/eprint/451680
ISSN: 1463-9076
PURE UUID: 4c9316d0-bb9b-421d-8bfb-5a4a464412f6
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Date deposited: 19 Oct 2021 16:32
Last modified: 06 Jun 2024 04:06
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Author:
David E. Korenchan
Author:
Jiaqi Lu
Author:
Alexej Jerschow
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