Aqueous, Heterogeneous para-Hydrogen-Induced 15N Polarization

Liana B. Bales; Kirill V. Kovtunov; Danila A. Barskiy; Roman V. Shchepin; Aaron M. Coffey; Larisa M. Kovtunova; Andrey V. Bukhtiyarov; Matthew A. Feldman; Valerii I. Bukhtiyarov; Eduard Y. Chekmenev; Igor V. Koptyug; Boyd M. Goodson

doi:10.1021/acs.jpcc.7b05912

Aqueous, Heterogeneous para-Hydrogen-Induced ¹⁵N Polarization

Liana B. Bales, Kirill V. Kovtunov, Danila A. Barskiy, Roman V. Shchepin, Aaron M. Coffey, Larisa M. Kovtunova, Andrey V. Bukhtiyarov, Matthew A. Feldman, Valerii I. Bukhtiyarov, Eduard Y. Chekmenev, Igor V. Koptyug, Boyd M. Goodson

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39 Scopus citations

Abstract

The successful transfer of para-hydrogen-induced polarization to ¹⁵N spins using heterogeneous catalysts in aqueous solutions was demonstrated. Hydrogenation of a synthesized unsaturated ¹⁵N-labeled precursor (neurine) with parahydrogen (p-H₂) over Rh/TiO₂ heterogeneous catalysts yielded a hyperpolarized structural analogue of choline. As a result, ¹⁵N polarization enhancements of over 2 orders of magnitude were achieved for the ¹⁵N-labeled ethyltrimethylammonium ion product in deuterated water at elevated temperatures. Enhanced ¹⁵N NMR spectra were successfully acquired at 9.4 and 0.05 T. Importantly, long hyperpolarization lifetimes were observed at 9.4 T, with a ¹⁵N T₁ of ∼6 min for the product molecules, and the T₁ of the deuterated form exceeded 8 min. Taken together, these results show that this approach for generating hyperpolarized species with extended lifetimes in aqueous, biologically compatible solutions is promising for various biomedical applications.

Original language	English
Pages (from-to)	15304-15309
Number of pages	6
Journal	Journal of Physical Chemistry C
Volume	121
Issue number	28
DOIs	https://doi.org/10.1021/acs.jpcc.7b05912
State	Published - Jul 20 2017
Externally published	Yes

Funding

We thank NSF (CHE-1416432, CHE-1416268, and REU DMR-1461255), NIH (1R21EB018014, 5R00CA134749, 5R00CA134749-02S1, and 1R21EB020323), and DoD (CDMRP BRP W81XWH-12-1-0159/BC112431, PRMRP W81XWH-15-1-0271, and W81XWH-15-1-0272). I.V.K., V.I.B., and K.V.K. thank RFBR (17-54-33037 and 16-03- 00407-a), MK-4498.2016.3, and FASO Russia Project # 0333- 2016-0001 for basic funding. B.M.G. and A.M.C. acknowledge the SIUC MTC and NIH 1F32EB021840. L.M.K. thanks SB RAS Integrated Program of Fundamental Scientific Research No. II.2 (No. 0303-2015-0010) for catalyst preparation. The BIC team thanks RSCF (Grant #14-23- 00146).

Funders	Funder number
SIUC	1F32EB021840
National Science Foundation	1416432, 1416268, REU DMR-1461255, CHE-1416432, CHE-1416268
National Institutes of Health	1R21EB020323, 1R21EB018014, 5R00CA134749
U.S. Department of Defense
Congressionally Directed Medical Research Programs	PRMRP W81XWH-15-1-0271, W81XWH-12-1-0159/BC112431, W81XWH-15-1-0272
Robert Sterling Clark Foundation	14-23- 00146
Russian Foundation for Basic Research	MK-4498.2016.3, 17-54-33037, 16-03- 00407-a
Siberian Branch, Russian Academy of Sciences	0303-2015-0010
Federal Agency for Scientific Organizations	0333- 2016-0001

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Bales, L. B., Kovtunov, K. V., Barskiy, D. A., Shchepin, R. V., Coffey, A. M., Kovtunova, L. M., Bukhtiyarov, A. V., Feldman, M. A., Bukhtiyarov, V. I., Chekmenev, E. Y., Koptyug, I. V., & Goodson, B. M. (2017). Aqueous, Heterogeneous para-Hydrogen-Induced ¹⁵N Polarization. Journal of Physical Chemistry C, 121(28), 15304-15309. https://doi.org/10.1021/acs.jpcc.7b05912

@article{129f2b09006e401796894bc879ff6e5f,

title = "Aqueous, Heterogeneous para-Hydrogen-Induced 15N Polarization",

abstract = "The successful transfer of para-hydrogen-induced polarization to 15N spins using heterogeneous catalysts in aqueous solutions was demonstrated. Hydrogenation of a synthesized unsaturated 15N-labeled precursor (neurine) with parahydrogen (p-H2) over Rh/TiO2 heterogeneous catalysts yielded a hyperpolarized structural analogue of choline. As a result, 15N polarization enhancements of over 2 orders of magnitude were achieved for the 15N-labeled ethyltrimethylammonium ion product in deuterated water at elevated temperatures. Enhanced 15N NMR spectra were successfully acquired at 9.4 and 0.05 T. Importantly, long hyperpolarization lifetimes were observed at 9.4 T, with a 15N T1 of ∼6 min for the product molecules, and the T1 of the deuterated form exceeded 8 min. Taken together, these results show that this approach for generating hyperpolarized species with extended lifetimes in aqueous, biologically compatible solutions is promising for various biomedical applications.",

author = "Bales, {Liana B.} and Kovtunov, {Kirill V.} and Barskiy, {Danila A.} and Shchepin, {Roman V.} and Coffey, {Aaron M.} and Kovtunova, {Larisa M.} and Bukhtiyarov, {Andrey V.} and Feldman, {Matthew A.} and Bukhtiyarov, {Valerii I.} and Chekmenev, {Eduard Y.} and Koptyug, {Igor V.} and Goodson, {Boyd M.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.jpcc.7b05912",

language = "English",

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T1 - Aqueous, Heterogeneous para-Hydrogen-Induced 15N Polarization

AU - Bales, Liana B.

AU - Kovtunov, Kirill V.

AU - Barskiy, Danila A.

AU - Shchepin, Roman V.

AU - Coffey, Aaron M.

AU - Kovtunova, Larisa M.

AU - Bukhtiyarov, Andrey V.

AU - Feldman, Matthew A.

AU - Bukhtiyarov, Valerii I.

AU - Chekmenev, Eduard Y.

AU - Koptyug, Igor V.

AU - Goodson, Boyd M.

PY - 2017/7/20

Y1 - 2017/7/20

N2 - The successful transfer of para-hydrogen-induced polarization to 15N spins using heterogeneous catalysts in aqueous solutions was demonstrated. Hydrogenation of a synthesized unsaturated 15N-labeled precursor (neurine) with parahydrogen (p-H2) over Rh/TiO2 heterogeneous catalysts yielded a hyperpolarized structural analogue of choline. As a result, 15N polarization enhancements of over 2 orders of magnitude were achieved for the 15N-labeled ethyltrimethylammonium ion product in deuterated water at elevated temperatures. Enhanced 15N NMR spectra were successfully acquired at 9.4 and 0.05 T. Importantly, long hyperpolarization lifetimes were observed at 9.4 T, with a 15N T1 of ∼6 min for the product molecules, and the T1 of the deuterated form exceeded 8 min. Taken together, these results show that this approach for generating hyperpolarized species with extended lifetimes in aqueous, biologically compatible solutions is promising for various biomedical applications.

AB - The successful transfer of para-hydrogen-induced polarization to 15N spins using heterogeneous catalysts in aqueous solutions was demonstrated. Hydrogenation of a synthesized unsaturated 15N-labeled precursor (neurine) with parahydrogen (p-H2) over Rh/TiO2 heterogeneous catalysts yielded a hyperpolarized structural analogue of choline. As a result, 15N polarization enhancements of over 2 orders of magnitude were achieved for the 15N-labeled ethyltrimethylammonium ion product in deuterated water at elevated temperatures. Enhanced 15N NMR spectra were successfully acquired at 9.4 and 0.05 T. Importantly, long hyperpolarization lifetimes were observed at 9.4 T, with a 15N T1 of ∼6 min for the product molecules, and the T1 of the deuterated form exceeded 8 min. Taken together, these results show that this approach for generating hyperpolarized species with extended lifetimes in aqueous, biologically compatible solutions is promising for various biomedical applications.

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JO - Journal of Physical Chemistry C

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IS - 28

ER -

Aqueous, Heterogeneous para-Hydrogen-Induced ¹⁵N Polarization

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