Article
Chemistry, Inorganic & Nuclear
Ralph W. Adams, Richard O. John, Damir Blazina, Beatriz Eguillor, Martin C. R. Cockett, John P. Dunne, Joaquin Lopez-Serrano, Simon B. Duckett
Summary: This article describes the thermal and photochemical reactions of Ru metal complexes with H-2 and diphenylacetylene. The reactions were monitored and validated using various techniques including NMR spectroscopy. The results show that the reaction mechanisms and products vary with different complexes and reaction conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Nikita V. Chukanov, Oleg G. Salnikov, Ivan A. Trofimov, Mohammad S. H. Kabir, Kirill V. Kovtunov, Igor V. Koptyug, Eduard Y. Chekmenev
Summary: Signal Amplification by Reversible Exchange (SABRE) technique allows for nuclear spin hyperpolarization of various compounds using parahydrogen, with potential applications in drug synthesis and scientific research. Experimental results demonstrate that the 7-hour-long activation of SABRE pre-catalyst in the presence of [N-15]dalfampridine can be resolved by the use of a pyridine co-ligand, maintaining the compound's N-15 polarization levels. Further investigations were conducted on the effects of experimental conditions on the N-15 polarization levels of [N-15]dalfampridine.
Review
Chemistry, Multidisciplinary
Nikita V. Chukanov, Roman V. Shchepin, Sameer M. Joshi, Mohammad S. H. Kabir, Oleg G. Salnikov, Alexandra Svyatova, Igor V. Koptyug, Juri G. Gelovani, Eduard Y. Chekmenev
Summary: NMR hyperpolarization techniques greatly increase nuclear spin polarization, leading to significant sensitivity gains for applications in high-resolution NMR spectroscopy and real-time metabolic imaging. Various hyperpolarization techniques exist, with a focus on targeting C-13 and N-15 sites in biocompatible agents. Long T-1 values of these sites allow hyperpolarized states to be retained for extended periods, with SABRE being a versatile low-cost technique for hyperpolarization of N-15 nuclei.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Ben J. Tickner, S. Karl-Mikael Svensson, Juha Vaara, Simon B. Duckett
Summary: The SABRE-Relay method enhances the H-1 and (13)C NMR signals of lactate esters, making them more detectable. This method is predicted to be beneficial for the detection and quantification of low concentrations of lactate esters and can serve as a precursor for hyperpolarized lactate.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Ben J. Tickner, S. Karl-Mikael Svensson, Juha Vaara, Simon B. Duckett
Summary: The SABRE-Relay hyperpolarization method significantly enhances the NMR signals of lactate esters, making them easier to detect in various applications. By indirectly transferring magnetization from para-hydrogen to OH-containing lactate esters, the method achieves a high sensitivity boost in H-1 and C-13 NMR signal enhancements. This technique has important implications for the detection and quantification of low concentrations of lactate esters and could be used as a precursor for the production of hyperpolarized lactate.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Baptiste Joalland, Thomas Theis, Stephan Appelt, Eduard Y. Chekmenev
Summary: This study demonstrates the utility of Radiofrequency Amplification by Stimulated Emission Radiation (RASER) for background-free proton detection of hyperpolarized biomolecules in a clinically relevant magnetic field. The results show that RASER detection without radio-frequency excitation could pave the way to new applications in high-resolution NMR spectroscopy and in vivo spectroscopy and imaging.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kailai Lin, Patrick TomHon, Soren Lehmkuhl, Raul Laasner, Thomas Theis, Volker Blum
Summary: This study provides an in-depth theoretical analysis of key chemical equilibria in Signal Amplification by Reversible Exchange (SABRE) using density functional theory calculations and harmonic transition state theory. The research shows that under typical experimental conditions, the Gibbs free energies of the two key states involved in pyridine-hydrogen exchange are essentially the same, indicating optimality for SABRE. Additionally, a methanol-containing intermediate is proposed as a plausible transient species in the process.
Article
Chemistry, Multidisciplinary
Oleg G. Salnikov, Nikita V. Chukanov, Alexandra Svyatova, Ivan A. Trofimov, Mohammad S. H. Kabir, Juri G. Gelovani, Kirill V. Kovtunov, Igor V. Koptyug, Eduard Y. Chekmenev
Summary: Nimorazole, an imidazole-based antibiotic, is being tested in Phase 3 clinical trials in Europe for its potential use as a hypoxia radiosensitizer for head and neck cancers. Researchers have successfully created a long-lasting hyperpolarized state for three N-15 sites of [N-15(3)]nimorazole, showing promise for its application in next-generation MRI-LINAC systems. The study also demonstrates the potential for efficient hyperpolarization of a wide range of imidazole-based antibiotics and chemotherapeutics using a spin-relayed technique.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Peter J. Rayner, Michael J. Burns, Elizabeth J. Fear, Simon B. Duckett
Summary: The utility of the pyridazine motif in pharmaceutical and agrochemical applications is increasing, with signal amplification by reversible exchange (SABRE) offering a route to improve magnetic resonance sensitivity. The study found that sensitivity is significantly improved when steric bulk is added to the 3- and 6-positions of the pyridazine ring.
MAGNETIC RESONANCE IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Andreas B. Schmidt, Henri de Maissin, Isaiah Adelabu, Shiraz Nantogma, Jessica Ettedgui, Patrick TomHon, Boyd M. Goodson, Thomas Theis, Eduard Y. Chekmenev
Summary: Despite successes in oncology, patient outcomes are often disappointing. Diagnostic imaging is shifting towards functional imaging of pathology for better understanding of individual disease biology and personalized therapies. This study presents a fast and low-cost hyperpolarization method using chemical exchange with parahydrogen, allowing for the cost-effective production of hyperpolarized [1-13C]pyruvate biosensors with great potential for in vivo applications.
Article
Chemistry, Multidisciplinary
Henri de Maissin, Philipp R. Gross, Obaid Mohiuddin, Moritz Weigt, Luca Nagel, Marvin Herzog, Zirun Wang, Robert Willing, Wilfried Reichardt, Martin Pichotka, Lisa Hess, Thomas Reinheckel, Henning J. Jessen, Robert Zeiser, Michael Bock, Dominik von Elverfeldt, Maxim Zaitsev, Sergey Korchak, Stefan Gloeggler, Jan-Bernd Hoevener, Eduard Y. Chekmenev, Franz Schilling, Stephan Knecht, Andreas B. Schmidt
Summary: Metabolic magnetic resonance imaging (MRI) using hyperpolarized (HP) pyruvate is a non-invasive technique for diagnosing, staging, and monitoring response to treatment in various diseases. The Signal Amplification By Reversible Exchange (SABRE) method provides a fast and low-cost way to produce HP pyruvate. In this study, a novel routine to produce aqueous HP [1-C-13]pyruvate-d(3) for injection in 6 minutes was demonstrated, making HP pyruvate MRI available to a wide biomedical community for fast metabolic imaging of living organisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ewoud Vaneeckhaute, Jean-Max Tyburn, James G. Kempf, Johan A. Martens, Eric Breynaert
Summary: Amino acids and ammonia are essential metabolic markers for nitrogen metabolism and cellular regulation. This study demonstrates a high-field approach using NMR to investigate these metabolic pathways, providing a valuable alternative to existing techniques. By designing a specialized catalyst, spin order can be transferred from p-H-2 to N-15, allowing for reversible hyperpolarization of alanine and ammonia under ambient conditions. The stereochemistry and kinetics of these catalyst complexes are determined using isotopological fingerprinting and 2D-ZQ-NMR.
Article
Chemistry, Analytical
Piotr Put, Szymon Pustelny, Dmitry Budker, Emanuel Druga, Tobias F. Sjolander, Alexander Pines, Danila A. Barskiy
Summary: Researchers constructed a portable zero-field NMR spectrometer, successfully acquiring spectra of several small representative biomolecules and investigating an approach relying on the presence of a transverse magnetic field for relaxometry purposes.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Christopher Nelson, Andreas B. Schmidt, Isaiah Adelabu, Shiraz Nantogma, Valerij G. Kiselev, Abubakar Abdurraheem, Henri de Maissin, Soeren Lehmkuhl, Stephan Appelt, Thomas Theis, Eduard Y. Chekmenev
Summary: The feasibility of Carbon-13 Radiofrequency (RF) Amplification by Stimulated Emission of Radiation (C-13 RASER) is demonstrated on a bolus of liquid hyperpolarized ethyl [1-C-13]acetate. The study successfully observed C-13 RASER signals and demonstrated its potential application on biomolecular carriers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
O. Bondar, E. Cavallari, C. Carrera, S. Aime, F. Reineri
Summary: ParaHydrogen Induced Polarization-Side Arm Hydrogenation (PHIP-SAH) is an inexpensive tool for obtaining hyperpolarized pyruvate for in vivo diagnostics. The solvent used in the hydrogenation process can affect efficiency and hyperpolarization level. Coordinating solvents can significantly increase efficiency or hyperpolarization level, but may not be compatible with metabolic applications. The extraction of hyperpolarized product in an aqueous solution can improve biocompatibility by removing traces of organic solvents.
Article
Quantum Science & Technology
Vladimir Schkolnik, Dmitry Budker, Oliver Fartmann, Victor Flambaum, Leo Hollberg, Tigran Kalaydzhyan, Shimon Kolkowitz, Markus Krutzik, Andrew Ludlow, Nathan Newbury, Christoph Pyrlik, Laura Sinclair, Yevgeny Stadnik, Ingmari Tietje, Jun Ye, Jason Williams
Summary: This is a concept for a high-precision optical atomic clock operating on an Earth-orbiting space station, aiming to search for potential dark matter candidates near Earth's surface by comparing with terrestrial atomic clocks. It opens up the exploration of new physics models that are inaccessible to ground-based experiments.
QUANTUM SCIENCE AND TECHNOLOGY
(2023)
Article
Chemistry, Analytical
Roman Picazo-Frutos, Quentin Stern, John W. Blanchard, Olivier Cala, Morgan Ceillier, Samuel F. Cousin, James Eills, Stuart J. Elliott, Sami Jannin, Dmitry Budker
Summary: Zero- to ultralow-field nuclear magnetic resonance is a magnetic resonance experiment that does not require strong superconducting magnets. It allows high-resolution detection of nuclear magnetism through metal and within heterogeneous media. By using dissolution dynamic nuclear polarization, signals in zero-field nuclear magnetic resonance experiments can be enhanced on sample mixtures, and this technique can be applied to a wide range of molecules. The signal enhancements can reach up to 11,000 compared to thermal prepolarization in a 2 T permanent magnet. The relaxation effects of the TEMPOL radicals used in the hyperpolarization process at zero- and ultralow-fields are also investigated to further increase the signal in future experiments.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Christopher Nelson, Andreas B. Schmidt, Isaiah Adelabu, Shiraz Nantogma, Valerij G. Kiselev, Abubakar Abdurraheem, Henri de Maissin, Soeren Lehmkuhl, Stephan Appelt, Thomas Theis, Eduard Y. Chekmenev
Summary: The feasibility of Carbon-13 Radiofrequency (RF) Amplification by Stimulated Emission of Radiation (C-13 RASER) is demonstrated on a bolus of liquid hyperpolarized ethyl [1-C-13]acetate. The study successfully observed C-13 RASER signals and demonstrated its potential application on biomolecular carriers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Anton Duchowny, Johannes Denninger, Lars Lohmann, Thomas Theis, Soeren Lehmkuhl, Alina Adams
Summary: This work demonstrates p-H-2-based SABRE hyperpolarization at pressures up to 200 bar, which is much higher than previously reported. The study shows that increasing pressure enhances signal intensities until reaching a plateau. It is also found that H-2 solubility increases linearly with pressure, indicating that p-H-2 availability is not the limiting factor beyond a certain pressure. Additionally, the use of liquefied ethane and compressed CO2 as removable solvents for hyperpolarization is demonstrated.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Isaiah Adelabu, Md Raduanul H. Chowdhury, Shiraz Nantogma, Clementinah Oladun, Firoz Ahmed, Lukas Stilgenbauer, Marianna Sadagurski, Thomas Theis, Boyd M. Goodson, Eduard Y. Chekmenev
Summary: Efficient C-13 hyperpolarization of ketoisocaproate was achieved using SABRE-SHEATH. By undergoing simultaneous chemical exchange with an Ir-IMes-based complex, parahydrogen atoms transferred their polarization to the C-13 nucleus of ketoisocaproate, resulting in high polarization values. The polarization build-up was possible due to favorable relaxation dynamics. Evaluation: 8 points.
Article
Chemistry, Analytical
Keilian MacCulloch, Austin Browning, Patrick TomHon, Soeren Lehmkuhl, Eduard Y. Chekmenev, Thomas Theis
Summary: Hyperpolarization modalities, particularly SABRE, are employed to enhance 15N polarization of nitrile-containing anticancer drugs. Optimal parameters, including temperature, magnetic field, and field profile, are fine-tuned for different substrates. Over 10% hyperpolarization and 280,000-fold signal enhancement are achieved for letrozole and anastrozole. Prolonged polarization storage and signal detection are enabled by the nitrile 15N sites.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Jakob M. Steiner, Yifan Quan, Tim R. Eichhorn, Anna J. Parker, Mohammad Usman Qureshi, Jochen Scheuer, Christoph Mueller, John W. Blanchard, Ilai Schwartz, Patrick Hautle
Summary: This paper addresses a fundamental issue in the use of dynamic nuclear polarization (DNP) regarding the short lifetime of hyperpolarization due to the polarizing agent (PA) used. The authors demonstrate that naphthalene single crystals can serve as a long-lived reservoir of proton polarization, which can be utilized to enhance NMR signals of target molecules in solution at a remote site by several thousand fold. The polarization of naphthalene protons is achieved using short-lived optically excited triplet states, providing a solution to the restricted storage and transport of hyperpolarized samples.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Ridvan Ince, Abdelatif Doudouh, Nicolas Claiser, Eric Furet, Thierry Guizouarn, Laurent Le Polle, Gwendal Kervern
Summary: Exploring magnetic properties at the molecular level is a challenge that has been met by developing many experimental and theoretical solutions. In order to complement the possibilities offered by these methods, a new tool combining simulation and fitting for high-resolution solid-state NMR spectra of lanthanide-based paramagnetic species is proposed. This method relies on a rigorous acquisition of high-resolution solid-state NMR isotropic and anisotropic data on a powdered magnetic material and an efficient modeling of this data based on a parametrization of the local magnetism and the crystal structure provided by diffraction methods.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Andrey N. Pravdivtsev, Kai Buckenmaier, Nicolas Kempf, Gabriele Stevanato, Klaus Scheffler, Joern Engelmann, Markus Plaumann, Rainer Koerber, Jan-Bernd Hoevener, Thomas Theis
Summary: Nuclear spin hyperpolarization allows for real-time observation of metabolism and intermolecular interactions in vivo. The use of 1-13C-pyruvate as a hyperpolarized tracer is being evaluated in clinical trials and shows promise as a molecular imaging agent. However, the search for a simple, fast, and efficient hyperpolarization technique is ongoing.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Anna J. Parker, Arnab Dey, Mohammad Usman Qureshi, Jakob M. Steiner, John W. Blanchard, Jochen Scheuer, Nikolas Tomek, Stephan Knecht, Felix Josten, Christoph Mueller, Patrick Hautle, Ilai Schwartz, Patrick Giraudeau, Tim R. Eichhorn, Jean-Nicolas Dumez
Summary: The HYPNOESYS method, relying on the dissolution of optically polarized crystals, enhances the sensitivity of NMR spectroscopy in the solution state. This study demonstrates the acquisition of 2D NMR spectra from HYPNOESYS-polarized samples using single-scan methods, paving the way for a sensitive, information-rich, and affordable analytical technique.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Optics
Lars Lohmann, Soeren Lehmkuhl, Simon Fleischer, Matthew S. Rosen, Eduard Y. Chekmenev, Thomas Theis, Alina Adams, Stephan Appelt
Summary: A nuclear-spin-based RASER is used to explore nonlinear interaction phenomena of nuclear spins coupled via virtual photons to a resonator. The experiment shows various nonlinear phenomena in the parahydrogen-pumped two-compartment proton RASER, including mode oscillations, frequency shifts, frequency combs, period doublings, and chaos. The mode separation in the RASER is precisely controlled by a magnetic field gradient to select the observed nonlinear phenomena.
Article
Chemistry, Physical
Austin Browning, Keilian Macculloch, Patrick TomHon, Iuliia Mandzhieva, Eduard Y. Chekmenev, Boyd M. Goodson, Soeren Lehmkuhl, Thomas Theis
Summary: Hyperpolarization of C-13-pyruvate via Signal Amplification By Reversible Exchange (SABRE) is an important recent discovery due to the simplicity of hyperpolarization and the relevance of pyruvate as a biomolecular probe. This study analyzes the [1,2-C-13(2)]pyruvate-SABRE spin system theoretically and experimentally, providing insights into spin state mixing, dynamics, and resulting spectra. The results are compared to systematic experiments, enhancing our understanding of the [1,2-C-13(2)]pyruvate-SABRE system.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Physics, Multidisciplinary
John W. Blanchard, Dmitry Budker, David DeMille, Mikhail G. Kozlov, Leonid V. Skripnikov
Summary: CeNTREX is developing an experiment using a TlF molecular beam to search for hadronic interactions that violate both time-reversal (T) and parity (P) invariance. They also propose to use the same beam to look for a T-invariance conserving but P-nonconserving (PNC) effect induced by the anapole moment of the Tl nucleus. To measure the nuclear anapole moment, they replace the dc electric and magnetic fields in CeNTREX with rf fields resonant with a nuclear spin-flip transition. They use the relativistic coupled-cluster method in combination with relativistic density functional theory to calculate the molecular PNC spin-spin vector coupling constant that links the experimental signal with the anapole moment. The calculated value of the P-conserving spin-spin coupling constant is in good agreement with available experimental data.
PHYSICAL REVIEW RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Iuliia Mandzhieva, Isaiah Adelabu, Shiraz Nantogma, Eduard Y. Chekmenev, Thomas Theis
Summary: This study presents a new pulse sequence approach that allows the use of hyperpolarized MRI for molecular imaging of metabolic diseases on clinical MRI scanners. The approach transfers C-13 hyperpolarization to methyl protons for detection and is robust to magnetic field inhomogeneities.
Article
Physics, Multidisciplinary
Julian Walter, Hendrik Bekker, John Blanchard, Dmitry Budker, Nataniel L. Figueroa, Arne Wickenbrock, Yuzhe Zhang, Pengyu Zhou
Summary: This article presents a method based on Bayesian optimization for automated tuning of magnetic field coil currents to optimize magnetic field homogeneity for improved sensitivity in magnetic resonance searches for axion-like dark matter. Experimental results demonstrate that this method converges to the desired sub-10 parts-per-million field homogeneity in a few iterations.
ANNALEN DER PHYSIK
(2023)
