Article
Quantum Science & Technology
Hongyu Pei, Feng Liu, Wenfeng Fan, Shimiao Fan, Xiaoping Li, Jiayi Wei, Wei Quan
Summary: This paper investigates the dynamical properties of the spin-coupling ensemble and proposes a comprehensive dynamics model of the electron-nuclear spin coupling ensemble. The primary magnetic field is found to effectively disentangle the precession frequency of the two spin-coupling species, resulting in a spin-decoupled state. This state enables high sensitive magnetic field measurements and accurate measurements of electron spin Fermi contact interaction and polarization.
ADVANCED QUANTUM TECHNOLOGIES
(2023)
Article
Chemistry, Multidisciplinary
Yue Zhu, Christian Hilty, Igor Savukov
Summary: The study introduces the dissolution dynamic nuclear polarization technique to enhance the sensitivity of nuclear spin optical rotation (NSOR), allowing the observation of NSOR signals of H-1 and F-19 nuclei in a single scan. This technique is suitable for studying electronic transitions from a specific nucleus in large molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Amrit Venkatesh, Gilles Casano, Yu Rao, Federico De Biasi, Frederic A. Perras, Dominik J. Kubicki, Didier Siri, Sebastien Abel, Hakim Karoui, Maxim Yulikov, Olivier Ouari, Lyndon Emsley
Summary: The sensitivity of NMR spectroscopy is enhanced by DNP, where polarization is transferred from unpaired electrons to proton spins in solids. The efficiency of polarization transfer near the unpaired electron spins is unclear. Experimental results and numerical simulations show that strong hyperfine couplings to nearby protons determine high transfer rates, and fewer hydrogen atoms in TEKPol isotopologues lead to longer H-1 DNP build-up times. Based on this understanding, a new biradical, NaphPol, is designed and yields significantly increased NMR sensitivity, making it the best DNP polarizing agent in organic solvents to date.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Physics, Multidisciplinary
Yu Wang, Kazuyuki Takeda
Summary: The study proposes a correction to the nuclear spin diffusion coefficient by extending the Lowe-Gade theory, indicating that nuclear magnetization transportation accelerates when hyperpolarized and approaches unity for low polarization, coinciding with the conventional diffusion coefficient at high temperatures. This proposed scaling of the nuclear spin diffusion coefficient could have observable effects on the buildup of nuclear polarization by dynamic nuclear polarization.
NEW JOURNAL OF PHYSICS
(2021)
Article
Physics, Applied
Adrisha Sarkar, Brian Blankenship, Emanuel Druga, Arjun Pillai, Ruhee Nirodi, Siddharth Singh, Alexander Oddo, Paul Reshetikhin, Ashok Ajoy
Summary: This study reports a strategy to increase the spin injection rate by utilizing high-power optical pumping to rapidly polarize electrons. Experiments conducted in a model system in diamond demonstrate successful enhancement of the spin-injection rates through a spin-ratchet polarization transfer mechanism. The findings elucidate bottlenecks in the dynamic nuclear polarization process and show potential for rapid spin injection using nonthermally generated electron polarization.
PHYSICAL REVIEW APPLIED
(2022)
Article
Biochemical Research Methods
W. Th Wenckebach, A. Capozzi, S. Patel, J. H. Ardenkjaer-Larsen
Summary: The effect of Gadolinium doping on the dynamic polarization (DNP) of C-13 has been studied, revealing that the rate at which polarization builds up is largely independent of the Gadolinium concentration. On the other hand, the electron spin-lattice relaxation rate varies significantly. The analysis indicates that DNP in this case is primarily due to the cross-effect (CE) and the build-up rate is a direct measurement of the triple spin flip rate responsible for the CE.
JOURNAL OF MAGNETIC RESONANCE
(2021)
Article
Physics, Multidisciplinary
Anna Sonnefeld, Geoffrey Bodenhausen, Kirill Sheberstov
Summary: Long-lived states (LLS) involving pairs of magnetically inequivalent but chemically equivalent proton spins in aliphatic chains are excited by weak selective radio frequency fields. The LLS are delocalized throughout the aliphatic chains by mixing of intrapair singlet states and by excitations involving four and six spin operators.
PHYSICAL REVIEW LETTERS
(2022)
Article
Physics, Multidisciplinary
B. S. Hu, J. Padua-Arguelles, S. Leutheusser, T. Miyagi, S. R. Stroberg, J. D. Holt
Summary: This study presents converged ab initio calculations of structure factors for elastic spin-dependent WIMP scattering off various nuclei used in dark matter direct-detection searches, providing insights into WIMP-nucleon interactions and nuclear responses. The results are generally consistent with previous calculations, but significant uncertainties in I-127 underscore the need for further research.
PHYSICAL REVIEW LETTERS
(2022)
Article
Chemistry, Physical
Andrey N. Pravdivtsev, Jan-Bernd Hoevener, Andreas B. Schmidt
Summary: The proposed selectively pulsed generation of sequences effectively transfers the spin order of parahydrogen to heteronuclei in weakly coupled spin systems, showing promise for hyperpolarization of molecules at high magnetic fields. This method is robust and efficient even when precursor molecules are not fully deuterium-labeled, requiring lower radiofrequency power and offering potential applications in hyperpolarization within MRI systems.
Article
Chemistry, Physical
Reiya Yabuki, Koki Nishimura, Tomoyuki Hamachi, Naoto Matsumoto, Nobuhiro Yanai
Summary: By immobilizing dye molecules on a solid surface, high polarization and long spin-lattice relaxation times can be maintained while allowing molecular contact with a liquid. Anionic porphyrins adsorbed on cationic mesoporous silica gel exhibit high polarization and long spin-lattice relaxation times at the solid-liquid interface. Additionally, porphyrin triplets on the solid surface can exchange spin polarization with TEMPO radicals in solution. This simple and versatile method using the solid-liquid interface opens up possibilities for utilizing photoinduced triplet spin polarization in solution, which was previously mainly limited to the solid-state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Multidisciplinary Sciences
Quentin Stern, Samuel Francois Cousin, Frederic Mentink-Vigier, Arthur Cesar Pinon, Stuart James Elliott, Olivier Cala, Sami Jannin
Summary: Dynamic nuclear polarization is a widely used tool for enhancing the sensitivity of nuclear magnetic resonance spectroscopy and imaging, but its practical applicability is limited by the spin diffusion barrier, which hinders efficient polarization transfer between highly polarized nuclei and bulk nuclei.
Article
Multidisciplinary Sciences
Andrey N. Pravdivtsev, Danila A. Barskiy, Jan-Bernd Hoevener, Igor Koptyug
Summary: This study analyzes the constraints imposed by the topological symmetry on the amplitude of transferred polarization in the process of parahydrogen-induced polarization (PHIP). It is found that in asymmetric systems, heteronuclei can be polarized to the highest extent, while the polarization amplitude decreases in systems with different topological structures. Additionally, the effect of the dipole-dipole-induced spin-order distribution in heterogeneous catalysis or nematic liquid crystals is discussed.
Review
Biochemistry & Molecular Biology
Dmitri V. Stass
Summary: Description and analysis of interacting spin systems rely on understanding the spectral properties, but complex algebraic problems hinder analytical solutions. We present a simple geometric approach to understand energy levels and provide insights beyond numerical simulations.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Biochemical Research Methods
W. Tom Wenckebach, Yifan Quan
Summary: The spectrum of electron spin-spin interactions plays a crucial role in determining the mechanism responsible for the growth of nuclear spin polarization in dynamic nuclear polarization. It influences the dominance of various mechanisms such as solid effect, cross effect, and thermal mixing, as well as the rate of spectral diffusion of electron spin polarization.
JOURNAL OF MAGNETIC RESONANCE
(2021)
Article
Chemistry, Inorganic & Nuclear
V. V. Garaeva, K. A. Spiridonov, I. A. Nikovskii, A. S. Peregudov, A. S. Kiryutin, A. Yurkovskaya, A. A. Polezhaev, V. V. Novikov
Summary: A possibility to generate spin polarization of F-19 nuclei in counterions that do not form covalent bonds with the metal center is shown for the first time in newly synthesized iridium complexes through reversible binding with the substrate and parahydrogen.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2022)
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, Multidisciplinary
Md Shahabuddin Alam, Xinlin Li, Drew O. O. Brittin, Saiful Islam, Pravas Deria, Eduard Y. Y. Chekmenev, Boyd M. M. Goodson
Summary: A novel phenomenon is described in which large antiphase o-H-2 signals are observed when using an intact heterogeneous catalyst constructed using a metal-organic framework (MOF), and this effect is qualitatively independent of substrate nature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
James Eills, Dmitry Budker, Silvia Cavagnero, Eduard Y. Chekmenev, Stuart J. Elliott, Sami Jannin, Anne Lesage, Joerg Matysik, Thomas Meersmann, Thomas Prisner, Jeffrey A. Reimer, Hanming Yang, Igor V. Koptyug
Summary: Magnetic resonance techniques, especially medical magnetic resonance imaging, are widely used in various scientific disciplines and practical applications. The development of spin hyperpolarization has greatly boosted both fundamental and applied magnetic resonance. Hyperpolarization techniques significantly enhance the signal intensity of magnetic resonance, overcoming its low sensitivity and opening up new possibilities for applications.
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
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, Multidisciplinary
David O. Guarin, Sameer M. Joshi, Anna Samoilenko, Mohammad S. H. Kabir, Erin E. Hardy, Atsush M. Takahashi, Jan H. Ardenkjaer-Larsen, Eduard Y. Chekmenev, Yi-Fen Yen
Summary: We present the first report of dissolution Dynamic Nuclear Polarization (d-DNP) of [N-15(3)]metronidazole ([N-15(3)]MNZ). Metronidazole, a clinically approved antibiotic, shows potential as a hypoxia-sensing molecular probe using N-15 hyperpolarized (HP) nucleus. The d-DNP process using trityl radical achieves efficient hyperpolarization of [N-15(3)]MNZ with long-lasting signal and high polarization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Mohammad S. H. Kabir, Sameer M. Joshi, Anna Samoilenko, Isaiah Adelabu, Shiraz Nantogma, Juri G. Gelovani, Boyd M. Goodson, Eduard Y. Chekmenev
Summary: Efficient hyperpolarization of [N-15(3)]metronidazole was achieved using the SABRE-SHEATH technique. The functionalization of [N-15(3)]metronidazole with a fluorine-19 moiety was also successful, resulting in efficient hyperpolarization of all three N-15 sites. The spin-relayed polarization transfer between N-15 and F-19 was found to be less efficient.
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
Andreas B. Schmidt, Isaiah Adelabu, Christopher Nelson, Shiraz Nantogma, Valerij G. Kiselev, Maxim Zaitsev, Abubakar Abdurraheem, Henri de Maissin, Matthew S. Rosen, Soren Lehmkuhl, Stephan Appelt, Thomas Theis, Eduard Y. Chekmenev
Summary: Conventional nuclear magnetic resonance (NMR) is used to detect chemical transformations by exciting and detecting the precessing spins of nuclear spin ensembles. In this study, we employ Radiofrequency Amplification by Stimulated Emission of Radiation (RASER) to detect chemical transformations without the need for external radio frequency pulses or background signals. We investigated the hydrolysis of hyperpolarized ethyl-[1-C-13]-acetate using both conventional NMR and C-13 RASER and observed a complete disappearance and delayed reappearance of the RASER signal without destroying the C-13 polarization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Annalise E. Maughan, Gabrielle Koknat, Peter C. Sercel, Manoj K. Jana, Roman Brunecky, David B. Mitzi, Joseph J. Berry, Volker Blum, Matthew C. Beard
Summary: In this study, a series of chiral antimony and bismuth halide materials were investigated, and the impact of chiral symmetry breaking on the inorganic sublattice was studied, leading to a unique spin texture. The chiral spin-splitting of inorganic states was revealed using density functional theory and a multiband effective mass theory. Additionally, broad red photoluminescence was observed in these compounds.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yi Xie, Jack Morgenstein, Benjamin G. G. Bobay, Ruyi Song, Naidel A. M. S. Caturello, Peter C. C. Sercel, Volker Blum, David B. B. Mitzi
Summary: Cation mixing in 2D HOIP structures is an important factor for modifying organic templating effects and tailoring inorganic structures. In this study, a chiral-chiral mixed-cation system is demonstrated, where a small amount of chiral cation S-2-MeBA can be doped into S-BrMBA(2)PbI4 to modulate the structural symmetry. The concentration of S-2-MeBA determines the structural change from higher symmetry state (C2) to the lowest symmetry state (P1). Atomic occupancy analysis suggests that a specific S-BrMBA cation site is preferentially substituted by S-2-MeBA. The chiral cation doping system provides a material design strategy for enhancing emergent properties sensitive to symmetry breaking.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Vikram Gavini, Stefano Baroni, Volker Blum, David R. Bowler, Alexander Buccheri, James R. Chelikowsky, Sambit Das, William Dawson, Pietro Delugas, Mehmet Dogan, Claudia Draxl, Giulia Galli, Luigi Genovese, Paolo Giannozzi, Matteo Giantomassi, Xavier Gonze, Marco Govoni, Francois Gygi, Andris Gulans, John M. Herbert, Sebastian Kokott, Thomas D. Kuehne, Kai-Hsin Liou, Tsuyoshi Miyazaki, Phani Motamarri, Ayako Nakata, John E. Pask, Christian Plessl, Laura E. Ratcliff, Ryan M. Richard, Mariana Rossi, Robert Schade, Matthias Scheffler, Ole Schutt, Phanish Suryanarayana, Marc Torrent, Lionel Truflandier, Theresa L. Windus, Qimen Xu, Victor W-Z Yu, D. Perez
Summary: Electronic structure calculations provide important insights into physical and chemical properties of various systems, and they are crucial in fields like materials science and computational chemistry. As we enter the exascale era, there are new opportunities and challenges in terms of simulation capabilities and efficient use of new architectures. This roadmap discusses the current status, development priorities, and plans of 14 electronic structure codes in tackling these challenges and leveraging the benefits of exascale computing.
MODELLING AND SIMULATION IN MATERIALS SCIENCE AND ENGINEERING
(2023)
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
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.