Application of Parahydrogen-Induced Polarization to Unprotected Dehydroamino Carboxylic Acids

Trantzschel, Thomas; Plaumann, Markus; Bernarding, Johannes; Lego, Denise; Ratajczyk, Tomasz; Dillenberger, Sonja; Buntkowsky, Gerd; Bargon, Joachim; Bommerich, Ute

doi:10.1007/s00723-012-0391-0

Cited by 27 publications

(34 citation statements)

References 44 publications

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“…A prerequisite for the application of PHIP is the presence of an unsaturated moiety that can be efficiently hydrogenated towards the hyperpolarized species. In the case of peptides or proteins, such species can be generated at unsaturated carbon–carbon bonds introduced at the side chains of amino acids both upon post‐translational modifications of natural proteins and synthetically ,–. The obvious advantage of the synthetic route is its versatility.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Single‐Scan 2D NMR Spectroscopic Detection of a PHIP‐Hyperpolarized Protease Inhibitor

Kiryutin

Sauer

Tietze

et al. 2019

Chemistry A European J

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Two‐dimensional NMR spectroscopy is one of the most important spectroscopic tools for the investigation of biological macromolecules. However, due to the low sensitivity of NMR spectroscopy, it takes usually from several minutes to many hours to record such spectra. Here, the possibility of detecting a bioactive derivative of the sunflower trypsin inhibitor‐1 (SFTI‐1), a tetradecapeptide, by combining parahydrogen‐induced polarization (PHIP) and ultrafast 2D NMR spectroscopy is shown. The PHIP activity of the inhibitor was achieved by labeling with O‐propargyl‐l‐tyrosine. In 1D PHIP experiments a signal enhancement of a factor of approximately 1200 compared to standard NMR was found. This enhancement permits measurement of 2D NMR correlation spectra of low‐concentrated SFTI‐1 in less than 10 seconds, employing ultrafast single‐scan 2D NMR detection. As experimental examples PHIP‐assisted ultrafast single‐scan TOCSY spectra of SFTI‐1 are shown.

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Section: Methodsmentioning

confidence: 99%

Ultrafast Single‐Scan 2D NMR Spectroscopic Detection of a PHIP‐Hyperpolarized Protease Inhibitor

Kiryutin

Sauer

Tietze

et al. 2019

Chemistry A European J

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“…19−23 Some of these results have employed polarization transfer to longer-lived 13 C nuclei by means of r.f. sequence application.…”

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confidence: 99%

Toward Biocompatible Nuclear Hyperpolarization Using Signal Amplification by Reversible Exchange: Quantitative in Situ Spectroscopy and High-Field Imaging

et al. 2014

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Signal amplification by reversible exchange (SABRE) of a substrate and parahydrogen at a catalytic center promises to overcome the inherent insensitivity of magnetic resonance. In order to apply the new approach to biomedical applications, there is a need to develop experimental equipment, in situ quantification methods, and a biocompatible solvent. We present results detailing a low-field SABRE polarizer which provides well-controlled experimental conditions, defined spins manipulations, and which allows in situ detection of thermally polarized and hyperpolarized samples. We introduce a method for absolute quantification of hyperpolarization yield in situ by means of a thermally polarized reference. A maximum signal-to-noise ratio of ∼103 for 148 μmol of substance, a signal enhancement of 106 with respect to polarization transfer field of SABRE, or an absolute 1H-polarization level of ≈10–2 is achieved. In an important step toward biomedical application, we demonstrate 1H in situ NMR as well as 1H and 13C high-field MRI using hyperpolarized pyridine (d3) and 13C nicotinamide in pure and 11% ethanol in aqueous solution. Further increase of hyperpolarization yield, implications of in situ detection, and in vivo application are discussed.

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“…Since this approach creates hyperpolarization at the H α ‐ and H β ‐position of the amino acid, it can be transferred to the carbonyl 13 C of the amino acid, which offers comparatively long polarization storage (tens of seconds) . Alternatively, α‐amino acids can be derivatized to add polarizable groups, or propargylglycine, a noncanonical α‐amino acid with an unsaturated side chain, can be used . For the general use of PHIP hyperpolarized α‐amino acids and peptides in biochemical and biomedical studies, further steps towards biocompatibility of the hyperpolarization strategies would be desirable.…”

Section: Methodsmentioning

confidence: 99%

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

Kaltschnee

Jagtap

McCormick

et al. 2019

Chemistry A European J

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NMR offers many possibilitiesi nc hemical analysis, structurali nvestigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity.H yperpolarization techniques enhanceN MR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the parahydrogen's singlet state to create enhanced signals is of particular interests ince it allows to producem olecular imagingagentswithin seconds. Herein,wepresent astrategy for signal enhancement of the carbonyl 13 Ci na mino acids by using parahydrogen,a sd emonstratedf or glycine and alanine. Importantly,t he hyperpolarizations tep is carried out in water and chemically unmodifiedc anonical amino acids are obtained. Our approach thus offers ah igh degree of biocompatibility,w hich is crucial for furthera pplication. The rapid sample hyperpolarization (withins econds) may enable the continuous productiono fb iologically useful probes, such as metabolic contrast agents or probes for structuralbiology.[e] Prof. Dr.M.U tz SchoolofC hemistry,University of Southampton SouthamptonS O171BJ (UK)Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Application of Parahydrogen-Induced Polarization to Unprotected Dehydroamino Carboxylic Acids

Cited by 27 publications

References 44 publications

Ultrafast Single‐Scan 2D NMR Spectroscopic Detection of a PHIP‐Hyperpolarized Protease Inhibitor

Ultrafast Single‐Scan 2D NMR Spectroscopic Detection of a PHIP‐Hyperpolarized Protease Inhibitor

Toward Biocompatible Nuclear Hyperpolarization Using Signal Amplification by Reversible Exchange: Quantitative in Situ Spectroscopy and High-Field Imaging

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

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