Reversible Interactions with para-Hydrogen Enhance NMR Sensitivity by Polarization Transfer

Adams, Ralph W.; Aguilar, J. A.; Atkinson, Kevin D.; Cowley, Michael J.; Elliott, Paul I. P.; Duckett, Simon B.; Green, Gary; Khazal, Iman G.; López‐Serrano, Joaquín; Williamson, D.S.

doi:10.1126/science.1168877

Cited by 864 publications

(1,326 citation statements)

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“…NH-PHIP works on a wide and still growing range of analytes. 4,37,38 The presented analysis suggests that all NH-PHIP substrates are polarizable and detectable under identical zero-field conditions. In the future, we expect the combination of sensitive optical magnetometers with general hyperpolarization techniques such as NH-PHIP to enable chemical analysis in locations not accessible by traditional bulky and expensive NMR technology, thereby making NMR more widely accessible.…”

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confidence: 82%

Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

et al. 2012

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ABSTRACT:We have recently demonstrated that sensitive and chemically specific NMR spectra can be recorded in the absence of a magnetic field using hydrogenative parahydrogen induced polarization (PHIP) 1−3 and detection with an optical atomic magnetometer. Here, we show that non-hydrogenative parahydrogen-induced polarization 4−6 (NH-PHIP) can also dramatically enhance the sensitivity of zero-field NMR. We demonstrate the detection of pyridine, at concentrations as low as 6 mM in a sample volume of 250 μL, with sufficient sensitivity to resolve all identifying spectral features, as supported by numerical simulations. Because the NH-PHIP mechanism is nonreactive, operates in situ, and eliminates the need for a prepolarizing magnet, its combination with optical atomic magnetometry will greatly broaden the analytical capabilities of zero-field and low-field NMR.T he past decade has witnessed increasing interest in the development of low-cost portable NMR spectrometers. 7 Such spectrometers promise to enable chemical analysis at greatly reduced cost in environments not accessible to standard high-field NMR technology. Detection of analytes at low concentrations primarily requires sensitive detectors and sufficient nuclear polarization. The weak thermal polarization of nuclear spins has given NMR the reputation of being an inherently insensitive method. For example, even in magnetic fields of superconducting magnets, the polarization obtained does not exceed 10 −4 .A variety of available hyperpolarization techniques such as dynamic nuclear polarization (DNP), 8,9 chemically induced DNP (CIDNP), 1 0 spin-exchange optical pumping (SEOP) 11−13 of noble gases, and parahydrogen induced polarization (PHIP) [1][2][3]14,15 suggest that sensitivity limitations given by the Boltzmann thermal polarization can be overcome for a large range of analytes. All these hyperpolarization techniques, DNP, 16−19 CIDNP, 20−22 SEOP 23 and PHIP, 24,25 have been shown to greatly enhance sensitivity of low-field NMR experiments where thermal polarization is even lower.Of equal importance, sensitive low-field NMR detectors of nuclear magnetization have been developed. These include systems based on inductive detectors, 7,26,27 superconducting quantum-interference devices (SQUIDs), 19,28−30 and optical magnetometers. 24,31−34 These technologies, in varying stages of maturity, permit the sensitive detection of low-frequency NMR signals, including NMR spectra in Earth's magnetic field.Combinations of hyperpolarization and novel detection schemes are thus particularly attractive in unconventional or portable NMR applications. For example, we have recently demonstrated that high-resolution and high SNR spectra can be recorded at zero field using PHIP from standard hydrogenative processes and an atomic magnetometer. 24 In the present contribution, we describe the first NMR experiments in zero field employing non-hydrogenative parahydrogen induced polarization (NH-PHIP) producing signal amplification by reversible exchange (SABRE). 4−6 Following the...

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Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

et al. 2012

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“…The transformation of total spin magnetization into singlet order, and back again, is an important manipulation in the NMR of long-lived states [13,14,15,16,17,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44] and in parahydrogen-enhanced NMR [18,19,20,21,22,45,46,47,48,49].…”

Section: Magnetization To Singlet Ordermentioning

confidence: 99%

“…I examine closely the spin dynamical manipulations of four-spin systems, involving long-lived spin states [13,14,15,16,17] and SABRE (Signal Amplification by Reversible Exchange) experiments [18,19,20,21,22]. Such experiments sometimes involve four-spin-1/2 systems of the type A 2 X 2 (two magnetically equivalent pairs) or AA XX (two chemically equivalent but magnetically inequivalent pairs).…”

Section: Introductionmentioning

confidence: 99%

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Symmetry constraints on spin dynamics: Application to hyperpolarized NMR

Levitt

2016

Journal of Magnetic Resonance

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Spin dynamical evolution is constrained by the symmetries of the spin Hamiltonians that generate the quantum dynamics. The consequences of symmetry-induced constraints are examined for some common hyperpolarized NMR experiments, including the excitation of singlet order in spin-pair systems, and the transfer of parahydrogen-induced hyperpolarized singlet order to magnetization in systems displaying chemical and magnetic equivalence.

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“…Among the various hyperpolarization techniques,5 dynamic nuclear polarization (DNP)6 and para‐hydrogen‐induced hyperpolarization (PHIP)7 are two of the most popular techniques. In 2009, an important variant to the PHIP technique8, 9 termed SABRE10 was described that no longer required a molecular change to use para‐hydrogen ( p ‐H 2 ) derived hyperpolarization. Instead, in SABRE a metal catalyst reversibly binds p ‐H 2 and the hyperpolarization target.…”

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A Hyperpolarizable ¹H Magnetic Resonance Probe for Signal Detection 15 Minutes after Spin Polarization Storage

et al. 2016

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Nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) are two extremely important techniques with applications ranging from molecular structure determination to human imaging. However, in many cases the applicability of NMR and MRI are limited by inherently poor sensitivity and insufficient nuclear spin lifetime. Here we demonstrate a cost‐efficient and fast technique that tackles both issues simultaneously. We use the signal amplification by reversible exchange (SABRE) technique to hyperpolarize the target 1H nuclei and store this polarization in long‐lived singlet (LLS) form after suitable radiofrequency (rf) pulses. Compared to the normal scenario, we achieve three orders of signal enhancement and one order of lifetime extension, leading to 1H NMR signal detection 15 minutes after the creation of the detected states. The creation of such hyperpolarized long‐lived polarization reflects an important step forward in the pipeline to see such agents used as clinical probes of disease.

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Reversible Interactions with para-Hydrogen Enhance NMR Sensitivity by Polarization Transfer

Cited by 864 publications

References 19 publications

Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

Symmetry constraints on spin dynamics: Application to hyperpolarized NMR

A Hyperpolarizable ¹H Magnetic Resonance Probe for Signal Detection 15 Minutes after Spin Polarization Storage

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Reversible Interactions with para-Hydrogen Enhance NMR Sensitivity by Polarization Transfer

Cited by 864 publications

References 19 publications

Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

Zero-Field NMR Enhanced by Parahydrogen in Reversible Exchange

Symmetry constraints on spin dynamics: Application to hyperpolarized NMR

A Hyperpolarizable 1H Magnetic Resonance Probe for Signal Detection 15 Minutes after Spin Polarization Storage

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A Hyperpolarizable ¹H Magnetic Resonance Probe for Signal Detection 15 Minutes after Spin Polarization Storage