Creating a hyperpolarised pseudo singlet state through polarisation transfer from parahydrogen under SABRE

Olaru, Alexandra M.; Roy, Soumya Singha; Lloyd, Lyrelle S.; Coombes, Steven R.; Green, Gary; Duckett, Simon B.

doi:10.1039/c6cc02020h

Cited by 24 publications

(19 citation statements)

References 32 publications

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“…[44] TheS ABRE technique can hyperpolarize such states,a sw as exemplified for the strongly coupled 1 H-pair in 2-aminothiazole [45] in which the singlet state was accessed in 90 %efficiency by r.f. In this context, singlet states are non-magnetic spin isomers of ac oupled spin-1/2 pair, which are immune to external dipolar coupling.I ti st herefore possible to identify other molecules in which two almost identical protons exist in as inglet state.…”

Section: Sabre-derived 1 H-singlet Statesmentioning

confidence: 99%

“…In this context, singlet states are non-magnetic spin isomers of ac oupled spin-1/2 pair, which are immune to external dipolar coupling.I ti st herefore possible to identify other molecules in which two almost identical protons exist in as inglet state. [44] TheS ABRE technique can hyperpolarize such states,a sw as exemplified for the strongly coupled 1 H-pair in 2-aminothiazole [45] in which the singlet state was accessed in 90 %efficiency by r.f. methods and using aspin-lock as pioneered by Levitt.…”

Section: Sabre-derived 1 H-singlet Statesmentioning

confidence: 99%

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Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

2018

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Signal amplification by reversible exchange (SABRE) turns typically weak magnetic resonance responses into strong signals making previously impractical measurements possible. This technique has gained significant popularity because of its speed and simplicity. This Minireview tracks the development of SABRE from the initial hyperpolarization of pyridine in 2009 to the point in which 50 % H polarization levels have been achieved in a di-deuterio-nicotinate, a key step in the pathway to potential clinical use. Simple routes to highly efficient N hyperpolarization and the creation of hyperpolarized long-lived magnetic states are illustrated. To conclude, we describe how the recently reported SABRE-RELAY approach offers a route for parahydrogen to hyperpolarize a much wider array of molecular scaffolds, such as amides, alcohols, carboxylic acids, and phosphates, than was previously thought possible. We predict that collectively these developments ensure that SABRE will significantly impact on both chemical analysis and the diagnosis of disease in the future.

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Section: Sabre-derived 1 H-singlet Statesmentioning

confidence: 99%

Section: Sabre-derived 1 H-singlet Statesmentioning

confidence: 99%

Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

2018

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“…28 These hyperpolarized nuclear spin singlet states of 15 N 2 diazirines display relaxation time constants of above 20 minutes. Similarly, SABRE was used to hyperpolarize long-lived singlet states on 1 H 2 -pairs, 29–30 where polarization decay time constants of above 4 min were observed. 31 Such long hyperpolarization lifetime promises biomolecular tracking and imaging of low concentration analytes on significantly extended timescales.…”

mentioning

confidence: 99%

Long-Lived ¹³C₂ Nuclear Spin States Hyperpolarized by Parahydrogen in Reversible Exchange at Microtesla Fields

Zhou

Colell

et al. 2017

J. Phys. Chem. Lett.

147

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Parahydrogen is an inexpensive and readily available source of hyperpolarization used to enhance magnetic resonance signals by up to 4 orders of magnitude above thermal signals obtained at ~10 T. A significant challenge for applications is fast signal decay after hyperpolarization. Here, we use parahydrogen based polarization transfer catalysis at micro-Tesla fields (first introduced as SABRE-SHEATH) to hyperpolarize 13C2 spin pairs and find decay time constants of 12 s for magnetization at 0.3 mT, which are extended to 2 minutes at that same field, when long-lived singlet states are hyperpolarized instead. Enhancements over thermal at 8.5 T are between 30 and 170 fold (0.02% to 0.12% polarization). We control the spin dynamics of polarization transfer by choice of μT field allowing for deliberate hyperpolarization of either magnetization or long-lived singlet states. Density functional theory (DFT) calculations and experimental evidence identify two energetically close mechanisms for polarization transfer: First, a model that involves direct binding of the 13C2 pair to the polarization transfer catalyst (PTC), and second, a model transferring polarization through auxiliary protons in substrates.

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“…demonstrated that long‐lived 15 N magnetization can be created and integrated into the chemically benign SABRE approach . A parallel approach of using SABRE to prepare hyperpolarized LLS in weakly coupled 1 H spin pairs have also been reported but the magnetization lasted under 90 s …”

Section: Methodsmentioning

confidence: 99%

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,inmany cases the applicability of NMR and MRI are limited by inherently poor sensitivity and insufficient nuclear spin lifetime.H ere we demonstrate acost-efficient and fast techniquethat tackles both issues simultaneously.W eu se the signal amplification by reversible exchange (SABRE) technique to hyperpolarizet he target 1 Hnuclei and store this polarization in long-lived singlet (LLS) form after suitable radiofrequency (rf) pulses.C ompared to the normal scenario,weachieve three orders of signal enhancement and one order of lifetime extension, leading to 1 HNMR 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.Nuclear spin hyperpolarization has evolved as one of most important developments in NMR and MRI in recent years as it starts finding applications in human metabolomics, [1][2][3][4] where their detection holds great potential to create tools for the diagnose of diseases.A mong the various hyperpolarization techniques, [5] dynamic nuclear polarization (DNP) [6] and para-hydrogen-induced hyperpolarization (PHIP) [7] are two of the most popular techniques.I n2 009, an important variant to the PHIP technique [8,9] termed SABRE [10] was described that no longer required am olecular change to use para-hydrogen (p-H 2 )d erived hyperpolarization. Instead, in SABRE am etal catalyst reversibly binds p-H 2 and the hyperpolarization target. Thed ormant magnetism of p-H 2 transfers into the target through the scalar-coupling framework of these catalysts as illustrated in Scheme 1. Since its inception, this method has stimulated many developments which include the hyperpolarization of al arge class of molecules comprising of 1 H, 13 C, 15 N, and 31 Pn uclei. [11][12][13][14] When compared to dissolution DNP,S ABRE provides alow cost alternative that takes just seconds to hyperpolarize the agent in acontinuous process that, while being inherently simple in concept, can be augmented by rf excitation. [15] In order to advance the future integration of SABRE with molecular imaging,i ti sh ighly desirable to create hyperpolarized targets,t he magnetism of which survives transfer into ad iagnostically relevant region of the body.T his requirement is based on observations with DNP and PHIP, techniques that have been used to successfully prepare and detect 13 C-based magnetization in vivo [3,4] and also show potential for 15 N-based agents. [16] These reported low-gamma nuclei-based in vivo studies employ relatively slowly relaxing Zeeman-derived magnetization in order to overcome the rate of signal loss,b ut these approaches inherently measure aw eaker response than would be provided by 1 Hd etection, whilst requiring al arger gradient ...

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Creating a hyperpolarised pseudo singlet state through polarisation transfer from parahydrogen under SABRE

Abstract: SABRE is harnessed to create a hyperpolarised long-lived state in 2-aminothiazole with >90% efficiency and 27 seconds lifetime.

Cited by 24 publications

References 32 publications

Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

Long-Lived ¹³C₂ Nuclear Spin States Hyperpolarized by Parahydrogen in Reversible Exchange at Microtesla Fields

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

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Creating a hyperpolarised pseudo singlet state through polarisation transfer from parahydrogen under SABRE

Abstract: SABRE is harnessed to create a hyperpolarised long-lived state in 2-aminothiazole with >90% efficiency and 27 seconds lifetime.

Cited by 24 publications

References 32 publications

Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

Signal Amplification by Reversible Exchange (SABRE): From Discovery to Diagnosis

Long-Lived 13C2 Nuclear Spin States Hyperpolarized by Parahydrogen in Reversible Exchange at Microtesla Fields

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

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Long-Lived ¹³C₂ Nuclear Spin States Hyperpolarized by Parahydrogen in Reversible Exchange at Microtesla Fields

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