Order-Unity 13 C Nuclear Polarization of [1- 13 C]Pyruvate in Seconds and the Interplay of Water and SABRE Enhancement.

Autor: Adelabu I; Integrative Biosciences, Department of Chemistry Karmanos Cancer Institute, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA., TomHon P; Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695-8204, USA., Kabir MSH; Integrative Biosciences, Department of Chemistry Karmanos Cancer Institute, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA., Nantogma S; Integrative Biosciences, Department of Chemistry Karmanos Cancer Institute, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA., Abdulmojeed M; Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695-8204, USA., Mandzhieva I; Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695-8204, USA., Ettedgui J; Chemistry and Synthesis Center, National Heart, Lung, and Blood Institute, 9800 Medical Center Drive, Building B, Room #2034, Bethesda, Maryland, 20850, USA., Swenson RE; Chemistry and Synthesis Center, National Heart, Lung, and Blood Institute, 9800 Medical Center Drive, Building B, Room #2034, Bethesda, Maryland, 20850, USA., Krishna MC; Center for Cancer Research, National Cancer Institute, Bethesda, 31 Center Drive, Maryland, 20814, USA., Theis T; Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695-8204, USA., Goodson BM; School of Chemical and Biomolecular Sciences Materials Technology Center, Southern Illinois University, 1245 Lincoln Dr., Carbondale, IL, 62901, USA., Chekmenev EY; Integrative Biosciences, Department of Chemistry Karmanos Cancer Institute, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA.; Russian Academy of Sciences, Leninskiy Prospect, 14, 119991, Moscow, Russia.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2022 Jan 19; Vol. 23 (2), pp. e202100839. Date of Electronic Publication: 2021 Dec 09.
DOI: 10.1002/cphc.202100839
Abstrakt: Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of 13 C 1 spins of [1- 13 C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H 2 O. Order-unity 13 C (>50 %) polarization of catalyst-bound [1- 13 C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1- 13 C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build-up in situ. The highest measured polarization of a 30-mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD 3 OD. Efficient 13 C polarization is also enabled by favorable relaxation dynamics in sub-microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T 1 spin-relaxation rates (e. g., ∼0.2 s -1 versus ∼0.1 s -1 , respectively, for a 6 mM catalyst-[1- 13 C]pyruvate sample). Finally, the catalyst-bound hyperpolarized [1- 13 C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1- 13 C]pyruvate produced via comparatively fast and simple SABRE-SHEATH-based approaches.
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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