Article
Chemistry, Multidisciplinary
Rania Harrabi, Thomas Halbritter, Fabien Aussenac, Ons Dakhlaoui, Johan van Tol, Krishna K. Damodaran, Daniel Lee, Subhradip Paul, Sabine Hediger, Frederic Mentink-Vigier, Snorri Th Sigurdsson, Gael De Paepe
Summary: Efficiently polarizing proton-dense molecular solids through dynamic nuclear polarization (DNP) solid-state NMR has been a great challenge. In this study, we introduce a new polarizing agent, cAsymPol-POK, which shows outstanding performance in polarizing biomolecular assemblies and organic microcrystals at high magnetic fields and fast magic angle spinning frequencies. Simulation and experimental results demonstrate the compatibility of cAsymPol-POK with challenging biomolecular applications and its ability to rapidly acquire crucial structural data of pharmaceutical drugs at natural isotopic abundance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Yifan Quan, Yifu Ouyang, Michael Mardini, Ravi Shankar Palani, Daniel Banks, James Kempf, W. Tom Wenckebach, Robert G. G. Griffin
Summary: We propose a new mechanism for dynamic nuclear polarization called Resonant Mixing (RM). It arises from the evolution of the density matrix for a simple electron-nucleus coupled spin pair subject to weak microwave irradiation, similar to the solid effect. However, unlike the solid effect, RM is optimal when the microwave field is on-resonance and involves the mixing of states by the microwave field together with the electron-nuclear coupling. We argue that this mechanism is responsible for the observed dispersive-shaped DNP field profile for trityl samples near the electron paramagnetic resonance center.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
David Guarin, Diego Carnevale, Mathieu Baudin, Philippe Pelupessy, Daniel Abergel, Geoffrey Bodenhausen
Summary: In this study, the buildup of proton polarization due to dynamic nuclear polarization (DNP) was monitored by observing echoes instead of FIDs. It was found that under DNP conditions, the proton coherence lifetime was extended, leading to transient surges in spin echo amplitudes.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Biochemical Research Methods
Subhradip Paul, Eric Bouleau, Quentin Reynard-Feytis, Jean-Pierre Arnaud, Florian Bancel, Bertrand Rollet, Pierre Dalban-Moreynas, Christian Reiter, Armin Purea, Frank Engelke, Sabine Hediger, Gael De Paepe
Summary: We report instrumental developments for sustainable and cost-effective cryogenic Helium sample spinning in order to conduct dynamic nuclear polarisation (DNP) and solid-state NMR (ssNMR) at ultra-low temperatures. The system integrates a powerful heat exchanger, a cryocooler, and a helium compressor, along with a triple-channel NMR probe that minimizes thermal losses and maintains RF performance and spinning stability. The system allows for significant sensitivity gain at low temperatures and includes an innovative cryogenic sample exchange system.
JOURNAL OF MAGNETIC RESONANCE
(2023)
Article
Chemistry, Physical
Adam N. Smith, Rania Harrabi, Thomas Halbritter, Daniel Lee, Fabien Aussenac, Patrick C. A. van der Wel, Sabine Hediger, Snorri Th. Sigurdsson, Gael De Paepe
Summary: We demonstrate a technique for acquiring multidimensional solid-state NMR 13C-13C correlation spectra of biomolecular assemblies and microcrystalline organic molecules at natural isotopic abundance using only milligram quantities of sample. This technique combines fast Magic Angle Spinning, low-power dipolar recoupling, and dynamic nuclear polarization with AsymPol biradicals as polarizing agents. These experiments are crucial for structural characterization as they provide information on short-and long-range distances. We showcase the effectiveness of this approach on various sample types, including polyglutamine fibrils involved in Huntington's disease and microcrystalline ampicillin, a small antibiotic molecule.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2023)
Article
Chemistry, Physical
Nathan A. Prisco, Arthur C. Pinon, Lyndon Emsley, Bradley F. Chmelka
Summary: By analogy to heat and mass transfer film theory, a general approach is introduced for determining hyperpolarization transfer rates between dilute electron spins and a surrounding nuclear ensemble. The empirical DNP polarization-transfer coefficient measured as a function of the bulk matrix H-1 spin density indicates the presence of two distinct kinetic regimes. The quantitative analyses closely agree with experimental measurements for the accumulation, propagation, and dissipation of hyperpolarization in solids, providing evidence for kinetically-limited transfer associated with a spin-diffusion barrier.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Saiya Fujiwara, Naoto Matsumoto, Koki Nishimura, Nobuo Kimizuka, Kenichiro Tateishi, Tomohiro Uesaka, Nobuhiro Yanai
Summary: Utilizing the induced-fit-type structural transformation of a metal-organic framework (MOF), we demonstrate DNP of guest molecules at around room temperature, resulting in enhanced NMR signal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Mika Takamuku, Tomoaki Sugishita, Hajime Tamaki, Lingyingzi Dong, Masatomo So, Toshimichi Fujiwara, Yoh Matsuki
Summary: Protein fibrillation and human neurodegenerative diseases are closely connected and understanding the molecular mechanisms behind this connection is crucial for understanding the causes and effects of diseases. Through investigating the liquid-liquid phase separation of α-synuclein, it was found that the conformation evolved from a monomeric state to a β-rich ensemble, eventually leading to the formation of amyloid fibrils.
NEUROCHEMISTRY INTERNATIONAL
(2022)
Article
Chemistry, Analytical
Estelle Morvan, Nada Taib-Maamar, Axelle Grelard, Antoine Loquet, Erick J. Dufourc
Summary: Understanding the membrane dynamics of complex systems is crucial to understanding their function. This study explores NMR methods to filter highly mobile molecular parts from more restricted environments. The researchers developed a quantitative MAS C-13 NMR approach coupled with CP and/or INEPT techniques to study rigid and fluid model membranes. They found that INEPT can detect only very mobile lipid headgroups in gel phases, while CP is required to detect the rigid parts. The study also reveals the potential of C-13 NMR chemical shift to monitor order-disorder phase transitions and provide information about membrane dynamics without isotopic labeling.
ANALYTICAL CHEMISTRY
(2023)
Editorial Material
Multidisciplinary Sciences
Jason Detwiler
Summary: This article discusses the use of a cubic metre of tellurium held at cryogenic temperatures over many years to search for matter created in a rare nuclear process. The achievement paves the way for stabilizing other complex systems at low temperatures.
Article
Chemistry, Multidisciplinary
David Beriashvili, Ru Yao, Francesca D'Amico, Michaela Krafcikova, Andrei Gurinov, Adil Safeer, Xinyi Cai, Monique P. C. Mulder, Yangping Liu, Gert E. Folkers, Marc Baldus
Summary: We demonstrate that the polarizing agent SNAPol-1 can enter human cells and enable DNP solid-state NMR measurements at 800 MHz, resulting in remarkable sensitivity and resolution. This allows for the identification of structural heterogeneity of ubiquitin at the atomic scale and with sub-cellular specificity. The use of SNAPol-1 also enables faster measurement times and provides a unique structural view of the nuclear ubiquitin pool.
Article
Nanoscience & Nanotechnology
Min Lin, Vincent Breukels, Tom W. J. Scheenen, Jos M. J. Paulusse
Summary: This study investigated the potential of alpha-SiC and beta-SiC phases for dynamic nuclear polarization (DNP), with alpha-SiC showing promising results in hyperpolarizing Si-29 and C-13 nuclei. The long T1 relaxation times in alpha-SiC particles make them suitable for magnetic resonance imaging applications.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Mark Hoefler, Waranya Limprasart, Lorenz Roesler, Max Fleckenstein, Martin Brodrecht, Kevin Herr, Jan-Lukas Schaefer, Markus Biesalski, Hergen Breitzke, Torsten Gutmann
Summary: An efficient method using 4-dimethylamino-pyridine and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as coupling reagents is presented for the functionalization of cotton linter paper substrates with the 19F spin label N-boc-cis-4-fluoro-L-proline. The intactness of the spin label is confirmed during the functionalization process, as demonstrated by 1H-19F heterocorrelation experiments. Through combination with dynamic nuclear polarization, the N-boc-cis-4-fluoro-L-proline spin label allows for the analysis of molecular loadings as low as 1 mu mol/g on paper substrates, providing a highly sensitive local probe for nanoscale biofunctionalization analysis in the future.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Hideka Ando, Katsuaki Suzuki, Hironori Kaji, Takashi Kambe, Yuta Nishina, Chiyu Nakano, Kazuma Gotoh
Summary: Dynamic nuclear polarizing (DNP) technique in nuclear magnetic resonance (NMR) is a powerful tool for microanalysis, but its application to carbon materials like graphene oxide (GO) and amorphous carbon has been limited by their electroconductivity and microwave absorption. In this study, DNP-NMR was successfully applied to analyze surface functional groups on GO and sucrose-derived carbon, revealing enhanced peaks of 13C and the presence of previously undetectable functional groups. The dominant enhancement mechanism was found to be the cross effect, except for the CH3 groups on GO, which were mainly enhanced through Overhauser effect or solid effect.
Article
Multidisciplinary Sciences
Hsueh-Ying Chen, C. Blake Wilson, Robert Tycko
Summary: The spatial resolution of MRI is limited by signal detection sensitivity, but can be improved by performing measurements at low temperature and using dynamic nuclear polarization (DNP) technique. This allows for higher resolution and shorter data acquisition times, offering a promising direction for high-resolution MRI studies.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Engineering, Electrical & Electronic
J. Genoud, J. F. Picard, S. C. Schaub, S. K. Jawla, M. A. Shapiro, R. J. Temkin
Summary: The effect of reflection on a high-power 110-GHz gyrotron operating in different modes is studied, showing that excessive reflection can lead to mode switching. Additionally, as the reflection is increased, the output power gradually decreases.
JOURNAL OF INFRARED MILLIMETER AND TERAHERTZ WAVES
(2021)
Correction
Engineering, Electrical & Electronic
J. Genoud, J. F. Picard, S. C. Schaub, S. K. Jawla, M. A. Shapiro, R. J. Temkin
JOURNAL OF INFRARED MILLIMETER AND TERAHERTZ WAVES
(2021)
Article
Chemistry, Multidisciplinary
Kushagra Gahlot, Sytze de Graaf, Herman Duim, Georgian Nedelcu, Razieh M. Koushki, Majid Ahmadi, Dnyaneshwar Gavhane, Alessia Lasorsa, Oreste De Luca, Petra Rudolf, Patrick C. A. van der Wel, Maria A. Loi, Bart J. Kooi, Giuseppe Portale, Joaquin Calbo, Loredana Protesescu
Summary: Lead halide perovskite nanocrystals are easily synthesized and offer great compositional and morphological tunability; however, the replacement of lead by tin is hindered by the unstable nature of the Sn2+ oxidation state. An optimized synthetic route has been demonstrated to obtain stable CsSnI3 nanocrystals.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Applied
Mustapha El Hariri El Nokab, Alessia Lasorsa, Khaled O. Sebakhy, Francesco Picchioni, Patrick C. A. van der Wel
Summary: Alginate hydrogels are versatile materials with diverse applications in biomedicine and food industry. The formation of hydrogel involves cross-linking with calcium ions and hydration of alginate groups. Solid-state NMR spectroscopy is used to detect and study water molecules in re-hydrated alginate hydrogels, revealing the different water phases and the effects of calcium cross-linking on water-filled macropores.
FOOD HYDROCOLLOIDS
(2022)
Article
Physics, Nuclear
Julian Picard, Ivan Mastovsky, Michael A. Shapiro, Richard J. Temkin, Xueying Lu, Manoel Conde, D. Scott Doran, Gwanghui Ha, John G. Power, Jiahang Shao, Eric E. Wisniewski, Chunguang Jing
Summary: The study reported the generation of high-power pulses from a metamaterial structure at the Argonne Wakefield Accelerator, which can be used to accelerate main bunches. Testing showed that the metamaterial structure did not exhibit breakdown at peak power levels and produced output power levels in excellent agreement with simulations.
PHYSICAL REVIEW ACCELERATORS AND BEAMS
(2022)
Article
Physics, Applied
J. Genoud, E. L. Claveau, S. K. Jawla, G. Li, J. F. Picard, M. A. Shapiro, R. J. Temkin
Summary: A 250 GHz quasi-optical ring resonator with an input coupler and three mirrors has been designed and tested. It utilizes a low-loss silicon wafer for output coupling when irradiated by a pulse from a 532 nm laser. The resonator generates high-power pulses and has a wide range of applications, including spectroscopy at low power and testing of accelerator structures and materials at high power.
APPLIED PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
Zahra Asgar Pour, Romar Koelewijn, Mustapha El Hariri El Nokab, Patrick C. A. van der Wel, Khaled O. Sebakhy, Paolo P. Pescarmona
Summary: Three zeolites were synthesized in the form of binder-free macroscopic beads using hydrothermal method with anion-exchange resin beads as hard template. The beads consisted of interconnected crystalline zeolite domains, forming a hierarchical porous network. H-Beta beads showed the best catalytic performance in the Friedel-Crafts acylation reaction and could be reused in multiple runs without loss of activity. In continuous-flow tests, H-Beta beads exhibited higher average activity but deactivated more rapidly than the extrudates.
Article
Chemistry, Physical
Adam N. Smith, Rania Harrabi, Thomas Halbritter, Daniel Lee, Fabien Aussenac, Patrick C. A. van der Wel, Sabine Hediger, Snorri Th. Sigurdsson, Gael De Paepe
Summary: We demonstrate a technique for acquiring multidimensional solid-state NMR 13C-13C correlation spectra of biomolecular assemblies and microcrystalline organic molecules at natural isotopic abundance using only milligram quantities of sample. This technique combines fast Magic Angle Spinning, low-power dipolar recoupling, and dynamic nuclear polarization with AsymPol biradicals as polarizing agents. These experiments are crucial for structural characterization as they provide information on short-and long-range distances. We showcase the effectiveness of this approach on various sample types, including polyglutamine fibrils involved in Huntington's disease and microcrystalline ampicillin, a small antibiotic molecule.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2023)
Article
Engineering, Electrical & Electronic
Carter M. Armstrong, Emma C. Snively, Muhammad Shumail, Christopher Nantista, Zenghai Li, Sami Tantawi, Bill W. Loo, Richard J. Temkin, Robert G. Griffin, Jinjun Feng, Roberto Dionisio, Felix Mentgen, Natanael Ayllon, Mark A. Henderson, Timothy P. Goodman
Summary: The application of radio frequency vacuum electronics has been continuously advancing since the invention of the first vacuum tubes in the 1920s, contributing to the improvement of human conditions. Today, microwave vacuum devices play crucial roles in various fields such as health treatment, material and biological science, wireless communication, Earth environment remote sensing, and the promise of reliable energy.
IEEE TRANSACTIONS ON ELECTRON DEVICES
(2023)
Article
Multidisciplinary Sciences
Hamoon Hemmatpour, Oreste De Luca, Dominic Crestani, Marc C. A. Stuart, Alessia Lasorsa, Patrick C. A. van der Wel, Katja Loos, Theodosis Giousis, Vahid Haddadi-Asl, Petra Rudolf
Summary: Polydopamine formation on halloysite nanotubes was systematically investigated. The oxidative coupling reaction of dopaminechrome molecules was found to be the main reaction pathway, leading to the formation of polycatecholamine oligomers as intermediates, followed by the post cyclization of linear oligomers. Furthermore, TRIS molecules were incorporated into the initially formed oligomers.
NATURE COMMUNICATIONS
(2023)
Article
Engineering, Biomedical
Devlina Ghosh, Damla Keskin, Abigail M. Forson, Colin W. K. Rosman, Reinier Bron, Clio M. Siebenmorgen, Guangyue Zu, Alessia Lasorsa, Patrick C. A. Van Der Wel, Theo G. Van Kooten, Max J. H. Witjes, Jelmer Sjollema, Henny C. Van Der Mei, Patrick Van Rijn
Summary: Coatings are crucial for biomedical applications, and nanogel (nGel)-based coatings are particularly interesting. However, specific coating strategies need to be developed for different biomaterials, leading to complexity. A universal nGel-based coating approach is proposed, utilizing oxygen plasma-activated surfaces and positively charged nGels, to achieve the same coating on a wide range of implant materials. The coating is stable and functional under in vitro physiological conditions and shows biocompatibility in vivo, making it a highly impactful approach for future clinical developments.
ADVANCED NANOBIOMED RESEARCH
(2023)
Article
Chemistry, Applied
Pushpa Rampratap, Alessia Lasorsa, Barbara Perrone, Patrick C. A. van der Wel, Marthe T. C. Walvoort
Summary: Hyaluronic acid (HA), a polysaccharide in the extracellular matrix (ECM) of vertebrate cells, is being widely studied for its applications in hydrogels due to its high viscoelasticity and biocompatibility. However, there are limited techniques available to understand the structural and functional properties of HA-containing hydrogels. In this study, a convenient method to obtain enriched high molecular weight (HMW)-HA labeled with 13C and 15N is presented, which allows for advanced NMR techniques to study the structure and dynamics of HMW-HA-based hydrogels and their interactions with proteins and other ECM components.
CARBOHYDRATE POLYMERS
(2023)
Meeting Abstract
Clinical Neurology
Irina Matlahov, Jennifer C. Boatz, Patrick C. A. van der Wel
JOURNAL OF NEUROLOGY NEUROSURGERY AND PSYCHIATRY
(2022)
Article
Biochemistry & Molecular Biology
Irina Matlahov, Jennifer C. Boatz, Patrick C. A. van der Wel
Summary: This study utilizes magic angle spinning solid-state NMR experiments to probe semi-rigid residues near the fibril core of amyloid-forming proteins and examines the impact of solvent dynamics on the dynamics of fibril segments. Dynamic spectral editing based on a combination of cross-polarization ssNMR with selective dipolar dephasing allows for the observation of weak signals of solvent-mobilized residues while suppressing the strong background signals from the rigid core. This approach provides valuable insights into the structure and properties of protein fibrils.
JOURNAL OF STRUCTURAL BIOLOGY-X
(2022)
Correction
Engineering, Electrical & Electronic
Guy Rosenzweig, Sudheer K. Jawla, Julian F. Picard, Michael A. Shapiro, Richard J. Temkin
JOURNAL OF INFRARED MILLIMETER AND TERAHERTZ WAVES
(2022)
