NMR SLIC sensing of hydrogenation reactions using parahydrogen in low magnetic fields

Danila A. Barskiy, Oleg G. Salnikov, Roman V. Shchepin, Matthew A. Feldman, Aaron M. Coffey, Kirill V. Kovtunov, Igor V. Koptyug, Eduard Y. Chekmenev

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Parahydrogen-induced polarization (PHIP) is an NMR hyperpolarization technique that increases nuclear spin polarization by orders of magnitude, and it is particularly well-suited to study hydrogenation reactions. However, the use of high-field NMR spectroscopy is not always possible, especially in the context of potential industrial-scale reactor applications. On the other hand, the direct low-field NMR detection of reaction products with enhanced nuclear spin polarization is challenging due to near complete signal cancellation from nascent parahydrogen protons. We show that hydrogenation products prepared by PHIP can be irradiated with weak (on the order of spin-spin couplings of a few hertz) alternating magnetic field (called Spin-Lock Induced Crossing or SLIC) and consequently efficiently detected at low magnetic field (e.g., 0.05 T used here) using examples of several types of organic molecules containing a vinyl moiety. The detected hyperpolarized signals from several reaction products at tens of millimolar concentrations were enhanced by 10000-fold, producing NMR signals an order of magnitude greater than the background signal from protonated solvents. (Figure Presented).

Original languageEnglish
Pages (from-to)29098-29106
Number of pages9
JournalJournal of Physical Chemistry C
Volume120
Issue number51
DOIs
StatePublished - Oct 26 2016
Externally publishedYes

Funding

This work was supported by NIH 1R21EB018014, 1R21EB020323, and 1F32EB021840, NSF CHE-1416268, and CHE-1416432, DOD CDMRP W81XWH-12-1-0159/BC112431 and W81XWH-15-1-0271, ExxonMobil Research and Engineering Company. The Russian team thanks the Russian Science Foundation (Grant 14-35-00020) for support of the hydrogenation experiments. K.V.K. thanks President's of Russian Federation Funding (Grant # MK-4498.2016.3) for catalysts testing.

FundersFunder number
DOD CDMRPW81XWH-12-1-0159/BC112431, W81XWH-15-1-0271
Russian Federation FundingMK-4498.2016.3
National Science FoundationCHE-1416432, CHE-1416268
National Institutes of Health1F32EB021840, 1R21EB020323, 1R21EB018014
ExxonMobil Research and Engineering Company
Russian Science Foundation14-35-00020

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