Continuous hyperpolarization with parahydrogen in a membrane reactor

Lehmkuhl, Sören; Wiese, Martin; Schubert, Lukas; Held, Mathias; Küppers, Markus; Weßling, Matthias; Blümich, Bernhard

doi:10.1016/j.jmr.2018.03.012

Cited by 44 publications

(48 citation statements)

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“…Continuous delivery of parahydrogen by diffusion through gas-permeable membranes has been demonstrated at conventional size scales. 34,35 It has been shown that silicone elastomer membranes can be used to deliver parahydrogen directly to a flowing liquid in a microfluidic device. 21 Bordonali et al 22 have recently combined a microfluidic NMR probe system with a gas exchange chip based on a silicone elastomer membrane to implement the SABRE (signal enhancement by reversible exchange) variant of parahydrogen-induced polarisation, but achieved only small signal enhancement factors (3 to 4).…”

Section: Introductionmentioning

confidence: 99%

High-Resolution Nuclear Magnetic Resonance Spectroscopy with Picomole Sensitivity by Hyperpolarization on a Chip

et al. 2019

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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 µL 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 µL 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 1 µM √ s, 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-( 1 H-1 H) and heteronuclear( 1 H-13 C) 2D NMR experiments at natural 13 C abundance.

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Section: Introductionmentioning

confidence: 99%

High-Resolution Nuclear Magnetic Resonance Spectroscopy with Picomole Sensitivity by Hyperpolarization on a Chip

et al. 2019

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“…For instance, Jiménez-Martínez et al designed an on-chip hyperpolarised Xenon NMR system,16 Causier et al presented a 3D-printed polariser to address hyperpolarisation with different gas species using a hand-wound microcoil,17 Bouchard et al exploited NMR to visualize chemical processes in catalytic microreactors 18. Recently, Lehmkuhl et al demonstrated an in-line flow setup for SABRE on a bench-top NMR spectrometer based on a 3D printed membrane reactor19 while Mompeán et al presented a photo-CIDNP NMR probe for limited-volume samples by leveraging the advantages of microcoils 20…”

Section: Introductionmentioning

confidence: 99%

Parahydrogen based NMR hyperpolarisation goes micro: an alveolus for small molecule chemosensing

et al. 2019

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“…We suspect that 1 H− 1 H scalar couplings involving the detected nuclei, which are more significant in the present study, are responsible of this failure of the DSTE approach. Solutions to deal with motions within the sample, other than using a different pulse sequence, would involve a more elaborate experimental setup, such as a membrane reactor outside the spectrometer, or a capillary plunging into the NMR solution, inside the spectrometer, albeit with a lower NMR signal enhancement factor ,…”

Section: Resultsmentioning

confidence: 99%

Single‐Scan Diffusion‐Ordered NMR Spectroscopy of SABRE‐Hyperpolarized Mixtures

et al. 2019

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The analysis of complex mixtures of dissolved molecules is a major challenge, especially for systems that gradually evolve, e. g., in the course of a chemical reaction or in the case of chemical instability. 1D NMR is a fast and non‐invasive method suitable for detailed molecular analysis, though of low sensitivity. Moreover, the spectral resolution of proton, the most commonly used and most sensitive stable isotope in NMR, is also quite limited. Spatially encoded (SPEN) experiments aim at creating in one acquisition a 2D data set by simultaneously performing different 1D sub‐experiments on different slices of the NMR tube, at the price of an extra loss of sensitivity. Choosing translational diffusion coefficients as the additional dimension (the so‐called DOSY approach) helps to recover proton spectra of each molecule in a mixture. The sensitivity limitation of SPEN NMR can, on the other hand, be addressed with hyperpolarization methods. Within hyperpolarization methods, signal amplification by reversible exchange (SABRE), based on parahydrogen, is the cheapest and the easiest one to set up, and allows multi‐shot experiments. Here we show that the spectra of a mixture's components at millimolar concentration are resolved in few seconds by combining the SABRE, SPEN and DOSY concepts.

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Continuous hyperpolarization with parahydrogen in a membrane reactor

Cited by 44 publications

References 50 publications

High-Resolution Nuclear Magnetic Resonance Spectroscopy with Picomole Sensitivity by Hyperpolarization on a Chip

High-Resolution Nuclear Magnetic Resonance Spectroscopy with Picomole Sensitivity by Hyperpolarization on a Chip

Parahydrogen based NMR hyperpolarisation goes micro: an alveolus for small molecule chemosensing

Single‐Scan Diffusion‐Ordered NMR Spectroscopy of SABRE‐Hyperpolarized Mixtures

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