Assaf, Charbel D., Gui, Xin, Auer, Alexander A. et al. (3 more authors) (2024) J Coupling Constants of <1 Hz Enable 13C Hyperpolarization of Pyruvate via Reversible Exchange of Parahydrogen. JOURNAL OF PHYSICAL CHEMISTRY LETTERS. pp. 1195-1203. ISSN 1948-7185
Abstract
Observing pyruvate metabolism in vivo has become a focal point of molecular magnetic resonance imaging. Signal amplification by reversible exchange (SABRE) has recently emerged as a versatile hyperpolarization technique. Tuning of the spin order transfer (SOT) in SABRE is challenging as the small 1H-13C J couplings, in the 13C-pyruvate case, result in SOT being not readily discernible. We demonstrate an experimental method using frequency-selective excitation of parahydrogen-derived polarization SOT sequence (SEPP-SPINEPT); its application led to up to 5700-fold 13C signal gain. In this way, we estimated the lifetime of two Ir-pyruvate SABRE complexes alongside the individual probing of eight small 1H-13C J couplings that connect the hydride protons in these complexes to 1- and 2-13C pyruvate spins, affording values between 0 and 2.69 Hz. Using electronic structure calculations, we define the low-energy structure of the corresponding complexes. Hence, this study demonstrates a novel approach to analyzing the spin topology of short-lived organometallic complexes.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Funding Information: The authors acknowledge funding from the German Federal Ministry of Education and Research (BMBF) within the framework of the e: Med research and funding concept (01ZX1915C), DFG (PR 1868/3-1, HO-4602/2-2, HO-4602/3, GRK2154-2019, EXC2167, FOR5042, and TRR287). MOIN CC was founded by a grant from the European Regional Development Fund (ERDF) and the Zukunftsprogramm Wirtschaft of Schleswig-Holstein (Project 122-09-053). A.A.A. and X.G. acknowledge funding by the Max-Planck-Society and the MPI für Kohlenforschung. Publisher Copyright: © 2024 The Authors. Published by American Chemical Society. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 26 Feb 2024 16:20 |
Last Modified: | 08 Feb 2025 00:53 |
Published Version: | https://doi.org/10.1021/acs.jpclett.3c02980 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpclett.3c02980 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:209651 |
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Description: assaf-et-al-2024-j-coupling-constants-of-1-hz-enable-13c-hyperpolarization-of-pyruvate-via-reversible-exchange-of
Licence: CC-BY 2.5