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High-resolution nuclear magnetic resonance spectroscopy with picomole sensitivity by hyperpolarisation on a chip

High-resolution nuclear magnetic resonance spectroscopy with picomole sensitivity by hyperpolarisation on a chip
High-resolution nuclear magnetic resonance spectroscopy with picomole sensitivity by hyperpolarisation on a chip
We show that high-resolution NMR can reach picomole sensitivity for micromolar concentrations of analyte by combining parahydrogen induced hyperpolarisation (PHIP) with a high-sensitivity transmission line micro-detector. The para-enriched hydrogen gas is introduced into solution by diffusion through a membrane integrated into a microfluidic chip. NMR microdetectors, operating with sample volumes of a few mL or less, benefit from a favourable scaling of mass sensitivity. However, the small volumes make it very difficult to detect species present at less than millimolar concentrations in microfluidic NMR systems. In view of overcoming this limitation, we implement parahydrogen-induced polarisation (PHIP) on a microfluidic device with 2.5 mL detection volume. Integrating the hydrogenation reaction into the chip minimises polarisation losses to spin-lattice relaxation, allowing the detection of picomoles of substance. This corresponds to a concentration limit of detection of better than 1mMps, unprecedented at this sample volume. The stability and sensitivity of the system allows quantitative characterisation of the signal dependence on flow rates and other reaction parameters and permits homo- (1H-1H) and heteronuclear (1H-13C) 2D NMR experiments at natural 13C abundance.
0002-7863
9955-9963
Eills, James
23130b21-68fa-4c8b-9399-e55f2e71ef36
Hale, William, George
08ed5dd7-febd-4a58-920a-e5cd4babe792
Sharma, Manvendra
e249236d-221d-4e59-8440-011f6863f891
Rossetto, Matheus
35a91b2e-002b-4924-b20e-e517fb72c17e
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Utz, Marcel
c84ed64c-9e89-4051-af39-d401e423891b
Eills, James
23130b21-68fa-4c8b-9399-e55f2e71ef36
Hale, William, George
08ed5dd7-febd-4a58-920a-e5cd4babe792
Sharma, Manvendra
e249236d-221d-4e59-8440-011f6863f891
Rossetto, Matheus
35a91b2e-002b-4924-b20e-e517fb72c17e
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Utz, Marcel
c84ed64c-9e89-4051-af39-d401e423891b

Eills, James, Hale, William, George, Sharma, Manvendra, Rossetto, Matheus, Levitt, Malcolm H. and Utz, Marcel (2019) High-resolution nuclear magnetic resonance spectroscopy with picomole sensitivity by hyperpolarisation on a chip. Journal of the American Chemical Society, 141 (25), 9955-9963. (doi:10.1021/jacs.9b03507).

Record type: Article

Abstract

We show that high-resolution NMR can reach picomole sensitivity for micromolar concentrations of analyte by combining parahydrogen induced hyperpolarisation (PHIP) with a high-sensitivity transmission line micro-detector. The para-enriched hydrogen gas is introduced into solution by diffusion through a membrane integrated into a microfluidic chip. NMR microdetectors, operating with sample volumes of a few mL or less, benefit from a favourable scaling of mass sensitivity. However, the small volumes make it very difficult to detect species present at less than millimolar concentrations in microfluidic NMR systems. In view of overcoming this limitation, we implement parahydrogen-induced polarisation (PHIP) on a microfluidic device with 2.5 mL detection volume. Integrating the hydrogenation reaction into the chip minimises polarisation losses to spin-lattice relaxation, allowing the detection of picomoles of substance. This corresponds to a concentration limit of detection of better than 1mMps, unprecedented at this sample volume. The stability and sensitivity of the system allows quantitative characterisation of the signal dependence on flow rates and other reaction parameters and permits homo- (1H-1H) and heteronuclear (1H-13C) 2D NMR experiments at natural 13C abundance.

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phip@chip-1 - Accepted Manuscript
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Accepted/In Press date: 30 May 2019
e-pub ahead of print date: 30 May 2019
Published date: 26 June 2019

Identifiers

Local EPrints ID: 431567
URI: http://eprints.soton.ac.uk/id/eprint/431567
ISSN: 0002-7863
PURE UUID: d8de1297-2508-4cd6-b7fc-5a75e651dec2
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180
ORCID for Marcel Utz: ORCID iD orcid.org/0000-0003-2274-9672

Catalogue record

Date deposited: 07 Jun 2019 16:30
Last modified: 18 Feb 2021 17:20

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Contributors

Author: James Eills
Author: William, George Hale
Author: Manvendra Sharma
Author: Matheus Rossetto
Author: Marcel Utz ORCID iD

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