Parahydrogen-Induced Polarization of 1-C-Acetates and 1-C-Pyruvates Using Sidearm Hydrogenation of Vinyl, Allyl, and Propargyl Esters

Overview

Journal J Phys Chem C Nanomater Interfaces

Publisher American Chemical Society

Date 2019 Aug 1

PMID 31363383

Citations 18

Authors

Oleg G Salnikov

Nikita V Chukanov

Roman V Shchepin

Isaac V Manzanera Esteve

Kirill V Kovtunov

Igor V Koptyug

Eduard Y Chekmenev

Affiliations

Soon will be listed here.

Abstract

C-hyperpolarized carboxylates, such as pyruvate and acetate, are emerging molecular contrast agents for MRI visualization of various diseases, including cancer. Here we present a systematic study of H and C parahydrogen-induced polarization of acetate and pyruvate esters with ethyl, propyl and allyl alcoholic moieties. It was found that allyl pyruvate is the most efficiently hyperpolarized compound from those under study, yielding 21% and 5.4% polarization of H and C nuclei, respectively, in CDOD solutions. Allyl pyruvate and ethyl acetate were also hyperpolarized in aqueous phase using homogeneous hydrogenation with parahydrogen over water-soluble rhodium catalyst. C polarization of 0.82% and 2.1% was obtained for allyl pyruvate and ethyl acetate, respectively. C-hyperpolarized methanolic and aqueous solutions of allyl pyruvate and ethyl acetate were employed for in vitro MRI visualization, demonstrating the prospects for translation of the presented approach to biomedical in vivo studies.

Citing Articles

Design, Synthesis, and Assessment of Tricarboxylic Acid Cycle Probes.

Chen J, Chao D, Tran U, Billingsley K Synthesis (Stuttg). 2025; 56(18):2909-2917.

PMID: 39896865 PMC: 11784938. DOI: 10.1055/a-2335-8736.

Through-bond and through-space radiofrequency amplification by stimulated emission of radiation.

Trofimov I, Salnikov O, Pravdivtsev A, de Maissin H, Yi A, Chekmenev E Commun Chem. 2024; 7(1):235.

PMID: 39414912 PMC: 11484792. DOI: 10.1038/s42004-024-01313-0.

Carbon-13 Radiofrequency Amplification by Stimulated Emission of Radiation of the Hyperpolarized Ketone and Hemiketal Forms of Allyl [1-C]Pyruvate.

Nantogma S, de Maissin H, Adelabu I, Abdurraheem A, Nelson C, Chukanov N ACS Sens. 2024; 9(2):770-780.

PMID: 38198709 PMC: 10922715. DOI: 10.1021/acssensors.3c02075.

Quasi-continuous production of highly hyperpolarized carbon-13 contrast agents every 15 seconds within an MRI system.

Schmidt A, Zimmermann M, Berner S, de Maissin H, Muller C, Ivantaev V Commun Chem. 2023; 5(1):21.

PMID: 36697573 PMC: 9814607. DOI: 10.1038/s42004-022-00634-2.

Through-Space Multinuclear Magnetic Resonance Signal Enhancement Induced by Parahydrogen and Radiofrequency Amplification by Stimulated Emission of Radiation.

Salnikov O, Trofimov I, Pravdivtsev A, Them K, Hovener J, Chekmenev E Anal Chem. 2022; 94(43):15010-15017.

PMID: 36264746 PMC: 10007960. DOI: 10.1021/acs.analchem.2c02929.

References

Cavallari E, Carrera C, Aime S, Reineri F . C MR Hyperpolarization of Lactate by Using ParaHydrogen and Metabolic Transformation in Vitro. Chemistry. 2016; 23(5):1200-1204. DOI: 10.1002/chem.201605329. View

Shchepin R, Barskiy D, Coffey A, Manzanera Esteve I, Chekmenev E . Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond. Angew Chem Int Ed Engl. 2016; 55(20):6071-4. PMC: 4939483. DOI: 10.1002/anie.201600521. View

Bhattacharya P, Chekmenev E, Perman W, Harris K, Lin A, Norton V . Towards hyperpolarized (13)C-succinate imaging of brain cancer. J Magn Reson. 2007; 186(1):150-5. PMC: 2657725. DOI: 10.1016/j.jmr.2007.01.017. View

Lai M, Gruetter R, Lanz B . Progress towards in vivo brain C-MRS in mice: Metabolic flux analysis in small tissue volumes. Anal Biochem. 2017; 529:229-244. DOI: 10.1016/j.ab.2017.01.019. View

Stevanato G, Eills J, Bengs C, Pileio G . A pulse sequence for singlet to heteronuclear magnetization transfer: S2hM. J Magn Reson. 2017; 277:169-178. DOI: 10.1016/j.jmr.2017.03.002. View

Korchak S, Yang S, Mamone S, Gloggler S . Pulsed Magnetic Resonance to Signal-Enhance Metabolites within Seconds by utilizing -Hydrogen. ChemistryOpen. 2018; 7(5):344-348. PMC: 5938614. DOI: 10.1002/open.201800024. View

Kovtunov K, Zhivonitko V, Skovpin I, Barskiy D, Koptyug I . Parahydrogen-induced polarization in heterogeneous catalytic processes. Top Curr Chem. 2012; 338:123-80. DOI: 10.1007/128_2012_371. View

Kovtunov K, Pokochueva E, Salnikov O, Cousin S, Kurzbach D, Vuichoud B . Hyperpolarized NMR Spectroscopy: d-DNP, PHIP, and SABRE Techniques. Chem Asian J. 2018; . PMC: 6251772. DOI: 10.1002/asia.201800551. View

Korchak S, Mamone S, Gloggler S . Over 50 % H and C Polarization for Generating Hyperpolarized Metabolites-A -Hydrogen Approach. ChemistryOpen. 2018; 7(9):672-676. PMC: 6121117. DOI: 10.1002/open.201800086. View

10.

Buljubasich L, Franzoni M, Munnemann K . Parahydrogen Induced polarization by homogeneous catalysis: theory and applications. Top Curr Chem. 2013; 338:33-74. DOI: 10.1007/128_2013_420. View

11.

Bar S, Lange T, Leibfritz D, Hennig J, von Elverfeldt D, Hovener J . On the spin order transfer from parahydrogen to another nucleus. J Magn Reson. 2012; 225:25-35. DOI: 10.1016/j.jmr.2012.08.016. View

12.

Olsson L, Chai C, Axelsson O, Karlsson M, Golman K, Petersson J . MR coronary angiography in pigs with intraarterial injections of a hyperpolarized 13C substance. Magn Reson Med. 2006; 55(4):731-7. DOI: 10.1002/mrm.20847. View

13.

Chukanov N, Salnikov O, Shchepin R, Kovtunov K, Koptyug I, Chekmenev E . Synthesis of Unsaturated Precursors for Parahydrogen-Induced Polarization and Molecular Imaging of 1-C-Acetates and 1-C-Pyruvates via Side Arm Hydrogenation. ACS Omega. 2018; 3(6):6673-6682. PMC: 6026840. DOI: 10.1021/acsomega.8b00983. View

14.

Day S, Kettunen M, Gallagher F, Hu D, Lerche M, Wolber J . Detecting tumor response to treatment using hyperpolarized 13C magnetic resonance imaging and spectroscopy. Nat Med. 2007; 13(11):1382-7. DOI: 10.1038/nm1650. View

15.

Dumez J . Perspectives on hyperpolarised solution-state magnetic resonance in chemistry. Magn Reson Chem. 2016; 55(1):38-46. DOI: 10.1002/mrc.4496. View

16.

Mikkelsen E, Mariager C, Norlinger T, Qi H, Schulte R, Jakobsen S . Hyperpolarized [1-C]-acetate Renal Metabolic Clearance Rate Mapping. Sci Rep. 2017; 7(1):16002. PMC: 5700138. DOI: 10.1038/s41598-017-15929-x. View

17.

Reineri F, Boi T, Aime S . ParaHydrogen Induced Polarization of 13C carboxylate resonance in acetate and pyruvate. Nat Commun. 2015; 6:5858. DOI: 10.1038/ncomms6858. View

18.

Harrison C, Yang C, Jindal A, DeBerardinis R, Hooshyar M, Merritt M . Comparison of kinetic models for analysis of pyruvate-to-lactate exchange by hyperpolarized 13 C NMR. NMR Biomed. 2012; 25(11):1286-94. PMC: 3469722. DOI: 10.1002/nbm.2801. View

19.

Barskiy D, Coffey A, Nikolaou P, Mikhaylov D, Goodson B, Branca R . NMR Hyperpolarization Techniques of Gases. Chemistry. 2016; 23(4):725-751. PMC: 5462469. DOI: 10.1002/chem.201603884. View

20.

Bastiaansen J, Cheng T, Mishkovsky M, Duarte J, Comment A, Gruetter R . In vivo enzymatic activity of acetylCoA synthetase in skeletal muscle revealed by (13)C turnover from hyperpolarized [1-(13)C]acetate to [1-(13)C]acetylcarnitine. Biochim Biophys Acta. 2013; 1830(8):4171-8. DOI: 10.1016/j.bbagen.2013.03.023. View