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Start Over Author "Geoffrey, Bodenhausen" Topic 0104 chemical sciences
153 results on '"Geoffrey, Bodenhausen"'

1. Hyperpolarized Water Enhances Two-Dimensional Proton NMR Correlations: A New Approach for Molecular Interactions

Author

Aude Sadet, Paul R. Vasos, Mihai Radu, Cristina Stavarache, Mihaela Bacalum, Geoffrey Bodenhausen, and Dennis Kurzbach

Subjects
chemistry.chemical_classification, Peptide, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Nuclear magnetic resonance, chemistry, Structural biology, Proton NMR, Hyperpolarization (physics), Spectroscopy, Conformational isomerism, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

Protein and peptide interactions are characterized in the liquid state by multidimensional NMR spectroscopy experiments, which can take hours to record. We show that starting from hyperpolarized HDO, two-dimensional (2D) proton correlation maps of a peptide, either free in solution or interacting with liposomes, can be acquired in less than 60 s. In standard 2D NMR spectroscopy without hyperpolarization, the acquisition time required for similar spectral correlations is on the order of hours. This hyperpolarized experiment enables the identification of amino acids featuring solvent-interacting hydrogens and provides fast spectroscopic analysis of peptide conformers. Sensitivity-enhanced 2D proton correlation spectroscopy is a useful and straightforward tool for biochemistry and structural biology, as it does not recur to nitrogen-15 or carbon-13 isotope enrichment.

Published
2019
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2. Cross-term Splittings Due to the Orientational Inequivalence of Proton Magnetic Shielding Tensors: Do Water Molecules Trapped in Crystals Hop or Tunnel?

Author

Diego Carnevale, Geoffrey Bodenhausen, Philippe Pelupessy, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Materials science, Proton, 02 engineering and technology, Atmospheric temperature range, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, 0104 chemical sciences, Hop (networking), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Electromagnetic shielding, Cross term, Molecule, General Materials Science, Physical and Theoretical Chemistry, 0210 nano-technology, Spinning, Barium chlorate
Abstract

International audience; Water molecules trapped in crystals of barium chlorate monohydrate have been investigated by magic-angle spinning (MAS) proton NMR spectroscopy in the temperature range 110−300 K. At high temperatures, a single spinning sideband pattern is observed. Below 150 K, however, two interleaved spinning sideband manifolds appear, with distinct centerbands that do not coincide with the average isotropic chemical shift seen at high temperatures. This hitherto unknown "cross-term splitting" results from the interplay of the homonuclear dipole−dipole coupling and two anisotropic proton shielding tensors that have identical principal components but nonequivalent orientations. The resulting cross terms cannot be averaged out by rotation about the magic angle. The analysis of the exchange-induced broadening, coalescence, and narrowing of the cross-term splitting in MAS spectra allows one to estimate the rate of exchange of the two protons between 140 and 190 K. The experimental data is compared with 2 H and 1 H NMR studies of the same sample reported in the literature. Density functional theory methods are utilized to estimate the thermal activation energy for a 2-fold hopping process of proton exchange about the H− O−H bisector. The Bell−Limbach model allows one to take into account contributions due to incoherent quantum tunneling in the low-temperature regime.

Published
2019
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3. Early Days of Two-Dimensional Ion Cyclotron Resonance

Author

Geoffrey Bodenhausen, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Gestionnaire, Hal Sorbonne Université, Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
analytical_chemistry, parent ions, [SDV]Life Sciences [q-bio], precursor ions, Pharmaceutical Science, Context (language use), Bibliometrics, 010402 general chemistry, Atmosphere (architecture and spatial design), 01 natural sciences, Analytical Chemistry, QD241-441, Political science, Drug Discovery, Applied research, Physical and Theoretical Chemistry, two-dimensional Fourier-transform (2D FT) spectroscopy, 010401 analytical chemistry, Organic Chemistry, daughter ions, 0104 chemical sciences, Epistemology, [SDV] Life Sciences [q-bio], ion cyclotron resonance (ICR), nuclear magnetic resonance, Chemistry (miscellaneous), Perspective, Molecular Medicine, Theoretical psychology, Ion cyclotron resonance
Abstract

This contribution is an attempt to reconstruct the favorable atmosphere that prevailed in Lau-sanne in 1986-87 and provided the backdrop of our invention of two-dimensional ion cyclotron resonance mass spectroscopy (2D ICR-MS). To avoid a self-centered histoire d’ancien combattant, we shall try to emphasize the context, the contributions of key players within our nascent research group at UNIL and the established group of Tino Gäumann at EPFL, the role of external speakers, and the open atmosphere that was not yet polluted by bibliometrics, obsessive concern with im-pact factors, and top-down management of research. We shall also explain why the idea of 2D ICR-MS has been ignored for many years and still has a limited impact: different scientific cul-tures in the ICR and NMR communities, different concerns with fundamental vs. applied research, different status of theory and numerical simulations, different levels of commitment of instrument manufacturers, not to mention many theoretical problems that appear to be at least as challenging in ICR as in NMR.

Published
2021
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4. Natural abundance oxygen-17 solid-state NMR of metal organic frameworks enhanced by dynamic nuclear polarization

Author

Diego Carnevale, Geoffrey Bodenhausen, Sujing Wang, Daniel Abergel, Christian Serre, Georges Mouchaham, Mathieu Baudin, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Mouchaham, Georges

Subjects
Materials science, Diego, General Physics and Astronomy, Protonation, 010402 general chemistry, 01 natural sciences, Magic Angle Spinning, chemistry.chemical_compound, Carnevale, Wang, Baudin, [CHIM]Chemical Sciences, Carboxylate, Physical and Theoretical Chemistry, Polarization (electrochemistry), Bodenhausen, Metal-Organic Frameworks, Sujing, Oxygen-17, Dynamic Nuclear Polarization, [CHIM.MATE] Chemical Sciences/Material chemistry, Mathieu, 010405 organic chemistry, Christian, Chemical shift, Serre, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, Zirconium-Oxo Clusters, 0104 chemical sciences, Geoffrey, chemistry, Solid-state nuclear magnetic resonance, Chemical physics, Physical chemistry, Oxygen-17 NMR, Metal-organic framework, Density functional theory, Mouchaham, Georges, Solid-State NMR
Abstract

International audience; The 17 O resonances of Zirconium-oxo clusters that can be found in porous Zr carboxylate metal-organic frameworks (MOFs) have been investigated by magic-angle spinning (MAS) NMR spectroscopy enhanced by dynamic nuclear polarization (DNP). High-resolution 17 O spectra at 0.037 % natural abundance could be obtained in 48 hours, thanks to DNP enhancement of the 1 H polarization by factors   = S with /S without = 28, followed by 1 H 17 O cross-polarization, allowing a saving in experimental time by a factor of ca. 800. The distinct 17 O sites from the oxo-clusters can be resolved at 18.8 T. Their assignment is supported by density functional theory (DFT) calculations of chemical shifts and quadrupolar parameters. Protonation of 17 O sites seems to be leading to large characteristic shifts. Markedly, natural abundance 17 O NMR spectra of diamagnetic MOFs can thus be used to probe and characterize the local environment of different 17 O sites on an atomic scale.

Published
2021
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5. Proton Relaxometry of Long-Lived Spin Order

Author

Konstantin L. Ivanov, Alexey S. Kiryutin, Alexandra V. Yurkovskaya, Geoffrey Bodenhausen, and Mikhail S. Panov

Subjects
Relaxometry, Materials science, Proton, Kinetics, Relaxation (NMR), Protonation, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Chemical physics, Deuterated methanol, Singlet state, Physical and Theoretical Chemistry, 0210 nano-technology, Spin-½
Abstract

A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2 O and 240 s in deuterated methanol, which are much longer than the T1 -relaxation times (18 and 30 s, respectively, at a field B 0 =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than T 1 . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years.

Published
2019
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6. Spin Thermometry: a Straightforward Measure of Millikelvin Deuterium Spin Temperatures Achieved by Dynamic Nuclear Polarization

Author

Behdad Aghelnejad, Geoffrey Bodenhausen, Diego Carnevale, Sina Marhabaie, Mathieu Baudin, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Materials science, Zeeman effect, Spins, Isotope, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, Spectral line, 0104 chemical sciences, symbols.namesake, Deuterium, Excited state, symbols, [CHIM]Chemical Sciences, General Materials Science, Physics::Atomic Physics, Physical and Theoretical Chemistry, Atomic physics, 0210 nano-technology, Nuclear Experiment
Abstract

International audience; Dynamic nuclear polarization of samples at low temperatures, typically between 1.2 and 4.2 K, allows one to achieve spin temperatures of as low as 2 mK so that for many nuclear isotopes the high-temperature approximation is violated for the nuclear Zeeman interaction. This leads to characteristic asymmetries in powder spectra. We show that the line shapes due to the quadrupolar couplings of deuterium spins present in virtually all solvents used for such experiments (DNP juice) allow the quick yet accurate determination of the deuterium spin temperature or, equivalently, the deuterium polarization. The observation of quadrupolar echoes excited by small flip-angle pulses allows one to monitor the build-up and decay of the positive or negative deuterium polarization.

Published
2020
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7. Sensitivity-enhanced three-dimensional and carbon-detected two-dimensional NMR of proteins using hyperpolarized water

Author

Geoffrey Bodenhausen, Isabella C. Felli, Roberta Pierattelli, Borja Mateos, Dennis Kurzbach, Fabien Ferrage, Robert Konrat, Pavel Kadeřávek, Gregory L. Olsen, Lucio Frydman, Or Szekely, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Amide proton, 010402 general chemistry, Intrinsically disordered proteins, 01 natural sciences, Biochemistry, Article, Direct 13C detection, Humans, Hyperpolarization (physics), Non-uniform sampling, Spectroscopy, Nuclear Magnetic Resonance, Biomolecular, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 3D NMR, Spectrometer, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Ubiquitin, 010405 organic chemistry, Water, Polarization (waves), 0104 chemical sciences, Amino acid, Intrinsically Disordered Proteins, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Hyperpolarization, chemistry, BEST-HNCO, Chemical physics, Osteopontin, Dissolution-dynamic nuclear polarization (D-DNP), Order of magnitude
Abstract

Signal enhancements of up to two orders of magnitude in protein NMR can be achieved by employing HDO as a vector to introduce hyperpolarization into folded or intrinsically disordered proteins. In this approach, hyperpolarized HDO produced by dissolution-dynamic nuclear polarization (D-DNP) is mixed with a protein solution waiting in a high-field NMR spectrometer, whereupon amide proton exchange and nuclear Overhauser effects (NOE) transfer hyperpolarization to the protein and enable acquisition of a signal-enhanced high-resolution spectrum. To date, the use of this strategy has been limited to 1D and 1H-15N 2D correlation experiments. Here we introduce 2D 13C-detected D-DNP, to reduce exchange-induced broadening and other relaxation penalties that can adversely affect proton-detected D-DNP experiments. We also introduce hyperpolarized 3D spectroscopy, opening the possibility of D-DNP studies of larger proteins and IDPs, where assignment and residue-specific investigation may be impeded by spectral crowding. The signal enhancements obtained depend in particular on the rates of chemical and magnetic exchange of the observed residues, thus resulting in non-uniform ‘hyperpolarization-selective’ signal enhancements. The resulting spectral sparsity, however, makes it possible to resolve and monitor individual amino acids in IDPs of over 200 residues at acquisition times of just over a minute. We apply the proposed experiments to two model systems: the compactly folded protein ubiquitin, and the intrinsically disordered protein (IDP) osteopontin (OPN). Electronic supplementary material The online version of this article (10.1007/s10858-020-00301-5) contains supplementary material, which is available to authorized users.

Published
2020
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8. Rates of Chemical Reactions Embedded in a Metabolic Network by Dissolution Dynamic Nuclear Polarisation NMR

Author

Aditya Jhajharia, Aude Sadet, Daniel Abergel, Dennis Kurzbach, Emeric Miclet, Geoffrey Bodenhausen, Emmanuelle M. M. Weber, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Structure et Dynamique des Biomolécules (LBM-E3), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
0301 basic medicine, Magnetic Resonance Spectroscopy, Metabolic network, 010402 general chemistry, Gluconates, 01 natural sciences, Chemical reaction, Catalysis, Pentose Phosphate Pathway, Reaction rate, 03 medical and health sciences, Hydrolysis, Computational chemistry, [CHIM]Chemical Sciences, Dissolution, Chemistry, Organic Chemistry, Dynamic nuclear polarisation, General Chemistry, 0104 chemical sciences, Kinetics, 030104 developmental biology, Solubility, Scientific method, Isomerization, Metabolic Networks and Pathways
Abstract

International audience; The isomerisation of 6-phosphogluconolactones and their hydrolyses into 6-phosphogluconic acid form a non enzymatic side cycle of the pentose-phosphate pathway (PPP) in cells. We show that dissolution dynamic nuclear polarization can be used for determining the kinetic rates of the involved transformations in real time. It is found that the hydrolysis of both lactones is significantly slower than the isomeration process, thereby shedding new light onto this subtle chemical process.

Published
2018
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9. Characterizing Thermal Mixing Dynamic Nuclear Polarization via Cross-Talk between Spin Reservoirs

Author

Geoffrey Bodenhausen, Dennis Kurzbach, David Guarin, Konstantin L. Ivanov, Alberto Rosso, Daniel Abergel, Sina Marhabaie, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire de Physique Théorique et Modèles Statistiques (LPTMS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), Novosibirsk State University (NSU), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Chemistry, Radical, Physics::Medical Physics, Time evolution, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, Nitroxide radical, 0104 chemical sciences, Magnetic field, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical physics, Thermal, General Materials Science, Hyperpolarization (physics), Physical and Theoretical Chemistry, 0210 nano-technology, Spectroscopy
Abstract

International audience; Dynamic nuclear polarization (DNP) embraces a family of methods to increase signal intensities in nuclear magnetic resonance (NMR) spectroscopy. Despite extensive theoretical work that allows one to distinguish at least five distinct mechanisms, it remains challenging to determine the relative weights of the processes that are responsible for DNP in state-of-the-art experiments operating with stable organic radicals like nitroxides at high magnetic fields and low temperatures. Specifically, determining experimental conditions where DNP involves thermal mixing, which denotes a spontaneous heat exchange between different spin reservoirs, remains challenging. We propose an experimental approach to ascertain the prevalence of the thermal mixing regime by monitoring characteristic signature properties of the time evolution of the hyperpolarization. We find that thermal mixing is the dominant DNP mechanism at high nitroxide radical concentrations, while a mixture of different mechanisms prevails at lower concentrations.

Published
2017
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10. Dynamic Nuclear Polarization of Long-Lived Nuclear Spin States in Methyl Groups

Author

Malcolm H. Levitt, Jean-Nicolas Dumez, Daniele Mammoli, Geoffrey Bodenhausen, Aurélien Bornet, Benno Meier, Gabriele Stevanato, Arthur C. Pinon, Basile Vuichoud, Sami Jannin, Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Centre de Résonance Magnetique Nucleaire (CRMN), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry [Southampton, UK], University of Southampton, Université Pierre et Marie Curie - Paris 6 (UPMC), The research leading to these results has received funding from COST (CA15209), Royal Society CNRS (Grant Code IE140525), EPSRC-UK (Grant Codes EP/N002482/1, EP/P009980/1), the European Research Council under the European Union's Horizon 2020 research and innovation programme (ERC Grant Agreement n 714519/HP4all), the ERC grant 'Dilute para-water', the EPFL, the Swiss National Science Foundation, and Bruker BioSpin SA Switzerland., European Project: 714519,HP4all, European Project: 339754,EC:FP7:ERC,ERC-2013-ADG,DILUTEPARAWATER(2014), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Range (particle radiation), Zeeman effect, Chemistry, Relaxation (NMR), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Solvent, symbols.namesake, Nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Chemical physics, symbols, General Materials Science, Physical and Theoretical Chemistry, 0210 nano-technology, Polarization (electrochemistry), Dissolution, Quantum tunnelling, Protein ligand
Abstract

The authors thank Lyndon Emsley for making means available.; International audience; We have induced hyperpolarized long-lived states in compounds containing C-13-bearing methyl groups by dynamic nuclear polarization (DNP) at cryogenic temperatures, followed by dissolution with a warm solvent. The hyper polarized methyl long-lived states give rise to enhanced antiphase C-13 NMR signals in solution, which often persist for times much longer than the C-13 and H-1 spin-lattice relaxation times under the same conditions. The DNP-induced effects are similar to quantum-rotor-induced polarization (QRIP) but are observed in a wider range of compounds because they do not depend critically on the height of the rotational barrier. We interpret our observations with a model in which nuclear Zeeman and methyl tunnelling reservoirs adopt an approximately uniform temperature, under DNP conditions. The generation of hyperpolarized NMR signals that persist for relatively long times in a range of methyl-bearing substances may be important for applications such as investigations of metabolism, enzymatic reactions, protein ligand binding, drug screening, and molecular imaging.

Published
2017
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11. Full Correlations across Broad NMR Spectra by Two‐Field Total Correlation Spectroscopy

Author

Geoffrey Bodenhausen, Léonard Strouk, Fabien Ferrage, Samuel F. Cousin, Werner Maas, Jean-Max Tyburn, Pierre-Alain Bovier, Pavel Kadeřávek, Cyril Charlier, Thorsten Marquardsen, Frank Engelke, Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Bruker Biospin GmbH, bruker, Bruker BioSpin [Wissembourg], Bruker Biospin AG, Bruker BioSpin GmbH, D-76287 Rheinstetten, Germany, affiliation inconnue, Bruker BioSpin [Billerica, MA], Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Field (physics), 010405 organic chemistry, Chemistry, Chemical shift, Analytical chemistry, Nuclear magnetic resonance spectroscopy, Fluorine-19 NMR, 010402 general chemistry, 01 natural sciences, Atomic and Molecular Physics, and Optics, Spectral line, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, NMR spectra database, Nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Molecule, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Spectroscopy
Abstract

International audience; Total correlation spectroscopy (TOCSY) is a key experiment to assign nuclear magnetic resonance (NMR) spectra of complex molecules. Carbon-13 TOCSY experiments are essential to assign signals of protein side chains. However, the performance of carbon-13 TOCSY deteriorates at high magnetic fields since the necessarily limited radiofrequency irradiation fails to cover the broad range of carbon-13 frequencies. Here, we introduce a new concept to overcome the limitations of TOCSY by using two-field NMR spectroscopy. In two-field TOCSY experiments, chemical shifts are labelled at high field but isotropic mixing is performed at a much lower magnetic field, where the frequency range of the spectrum is drastically reduced. We obtain complete correlations between all carbon-13 nuclei belonging to amino acids across the entire spectrum: aromatic, aliphatic and carboxylic. Two-field TOCSY should be a robust and general approach for the assignment of uniformly carbon-13 labelled molecules in high-field and ultra-high field NMR spectrometers beyond 1000 MHz.

Published
2017
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12. Orientation-Dependent Proton Relaxation of Water Molecules Trapped in Solids: Crystallites with Long-Lived Magnetization

Author

Diego Carnevale, Sina Marhabaie, Geoffrey Bodenhausen, Philippe Pelupessy, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
010304 chemical physics, Proton, Chemistry, Relaxation (NMR), 010402 general chemistry, 01 natural sciences, Molecular physics, Spectral line, 0104 chemical sciences, Magnetic field, Magnetization, 0103 physical sciences, Proton NMR, Crystallite, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Anisotropy
Abstract

International audience; The longitudinal spin–lattice relaxation properties of water molecules trapped in a static powdered polycrystalline sample of barium chlorate monohydrate are investigated by means of solid-state 1H NMR spectroscopy. Different portions of the inhomogeneous Pake pattern that are associated with crystallites at different orientations with respect to the external magnetic field show either a mono- or a biexponential recovery. At high field (9.4 T), the chemical shift anisotropy is the main interaction that is responsible for the inhomogeneity of the relaxation rates. A theoretical description of rapid two-site hopping about the H–O–H bisector in the framework of Liouville space agrees very well with the experimental evidence. Numerical simulations predict a distribution of monoexponential time constants associated with individual single-crystal orientations. Overlapping signals give rise to biexponential recovery. This is confirmed experimentally by 1H NMR spectra of static single crystals.

Published
2019
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13. Long-Lived States in Hyperpolarized Deuterated Methyl Groups Reveal Weak Binding of Small Molecules to Proteins

Author

Thomas Kress, Astrid Walrant, Dennis Kurzbach, Geoffrey Bodenhausen, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and University of Vienna [Vienna]

Subjects
Population, Serum albumin, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Plasma protein binding, 010402 general chemistry, Photochemistry, 01 natural sciences, chemistry.chemical_compound, medicine, Animals, General Materials Science, Dimethyl Sulfoxide, Trypsin, Physical and Theoretical Chemistry, Bovine serum albumin, education, Nuclear Magnetic Resonance, Biomolecular, education.field_of_study, biology, 010405 organic chemistry, Dimethyl sulfoxide, Serum Albumin, Bovine, Deuterium, Small molecule, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, biology.protein, Cattle, Methyl group, medicine.drug, Protein Binding
Abstract

International audience; We introduce a method for the detection of weak interactions of small molecules such as metabolites or medicaments that contain deuterated methyl groups with proteins in solution. The technique relies on long-lived imbalances of spin state populations, which are generated by dissolution dynamic nuclear polarization (D-DNP) and feature lifetimes that depend on the frequency of internal rotation of deuterated methyl groups. We demonstrate the technique for interactions between deuterated dimethyl sulfoxide (DMSO-d6) and bovine serum albumin (BSA) or trypsin, where the methyl group rotation is slowed down upon protein binding, which causes a marked reduction in the lifetime of the population imbalances.

Published
2019
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14. Recovering Invisible Signals by Two-Field NMR Spectroscopy

Author

Pierre-Alain Bovier, Werner Maas, Baptiste Haddou, Philippe Pelupessy, Thorsten Marquardsen, Cyril Charlier, Samuel F. Cousin, Jean-Max Tyburn, Frank Engelke, Fabien Ferrage, Geoffrey Bodenhausen, Pavel Kadeřávek, Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Université Pierre et Marie Curie - Paris 6 (UPMC), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory of Chemical Physics [Bethesda] (LCP), National Institutes of Health, Bruker Biospin GmbH, bruker, Bruker BioSpin [Wissembourg], Bruker Biospin AG, Bruker BioSpin GmbH, D-76287 Rheinstetten, Germany, affiliation inconnue, Bruker BioSpin [Billerica, MA], École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Carbon-13 NMR satellite, Chemistry, 010405 organic chemistry, General Chemistry, Fluorine-19 NMR, Nuclear magnetic resonance spectroscopy, Nuclear magnetic resonance crystallography, General Medicine, Carbon-13 NMR, 010402 general chemistry, Molecular physics, 01 natural sciences, Catalysis, 0104 chemical sciences, Nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Transverse relaxation-optimized spectroscopy, Two-dimensional nuclear magnetic resonance spectroscopy, Earth's field NMR
Abstract

Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two-field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low-field dimension. Two-field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields.

Published
2016
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15. Transport of hyperpolarized samples in dissolution-DNP experiments

Author

Dennis Kurzbach, Alexandra V. Yurkovskaya, Konstantin L. Ivanov, Geoffrey Bodenhausen, Bogdan A. Rodin, Alexey S. Kiryutin, Sami Jannin, David Guarin, Daniel Abergel, Novosibirsk State University (NSU), University of Vienna [Vienna], Centre de RMN à très hauts champs de Lyon (CRMN), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Physics, Field cycling, General Physics and Astronomy, Spin hamiltonian, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, Molecular physics, 0104 chemical sciences, Magnet, Singlet state, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, 0210 nano-technology, Adiabatic process, Multiplet, Dissolution
Abstract

International audience; Dissolution dynamic nuclear polarization (D-DNP) experiments rely on the transfer of a sample between two high-field magnets. During this transfer, samples might experience passage through regions where the stray fields of the magnets are very weak, can approach zero, and even change their sign. This can lead to unexpected spectral features in spin systems that undergo transitions from weak-to strong-coupling regimes and vice versa, much like in field cycling nuclear magnetic resonance experiments. We herein demonstrate that the spectral features observed in D-DNP experiments can be rationalized, provided the time-dependence of the spin Hamiltonian upon field cycling is sufficiently adiabatic. Under such conditions, a passage through a weak static field can lead to the emergence of a long-lived state (LLS) based on an imbalance between the populations of singlet and triplet states in pairs of nuclei that are strongly coupled during the passage through low field. The LLS entails the appearance of anti-phase multiplet components upon transfer to a high-field magnet for observation of NMR signals.

Published
2019
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16. Dipolar couplings in solid polypeptides probed by 14N NMR spectroscopy

Author

Benoit Grosjean, Diego Carnevale, Geoffrey Bodenhausen, Temps, espaces, langages Europe méridionale-Méditerranée (TELEMME), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Gestionnaire, HAL Sorbonne Université 5, Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Proton, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Isotopic labeling, lcsh:Chemistry, chemistry.chemical_compound, Protein structure, Amide, Materials Chemistry, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Environmental Chemistry, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Nuclear Experiment, Isotope, General Chemistry, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, 0104 chemical sciences, NMR spectra database, chemistry, lcsh:QD1-999, Chemical physics, Density functional theory, 0210 nano-technology
Abstract

The acquisition of 14N NMR spectra in solid samples is challenging due to quadrupolar couplings with magnitudes up to several MHz. This nucleus is nonetheless important as it is involved in the formation of essential secondary structures in biological systems. Here we report the structural study of the atomic environment of amide functions in polypeptides using magic-angle spinning NMR spectroscopy of the ubiquitous 14N isotope. The cyclic undecapeptide cyclosporin, in which only four hydrogen atoms are directly bound to nitrogen atoms, is chosen for illustration. Structural details of different environments can be revealed without resorting to isotopic enrichment. The network of inter- and intra-residue dipolar couplings between amide 14N nuclei and nearby protons can be probed and mapped out up to a tunable cutoff distance. Density functional theory calculations of NMR quadrupolar interaction tensors agree well with the experimental evidence and allow the unambiguous assignment of all four non-methylated NH nitrogen sites and neighboring proton nuclei. Solid-state NMR of nitrogen nuclei offers a powerful way to solve protein structures but often requires isotopic labeling. Here through-space interactions between nitrogen-14 and protons allows structural assignment of cyclosporin without the need for isotopic enrichment with nitrogen-15.

Published
2018
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17. Tailored Microstructured Hyperpolarizing Matrices for Optimal Magnetic Resonance Imaging

Author

David Baudouin, Geoffrey Bodenhausen, Laurent Veyre, Sami Jannin, Basile Vuichoud, Christophe Copéret, Aurélien Bornet, Chloé Thieuleux, Matthieu Cavaillès, Xavier Jaurand, Mathieu Baudin, Jean-Nicolas Dumez, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Centre Technologique des Microstructures (CTµ), Université de Lyon-Université de Lyon, ISA - Hyperpolarized Magnetic Resonance, Institut des Sciences Analytiques (ISA), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory of Inorganic Chemistry, This work was supported by the European Research Council under the European Union's Horizon 2020 research and innovation programme (ERC Grant Agreements 339754/Dilute para‐water and 714519/HP4all), Bruker BioSpin, the Commission pour la Technologie et l′Innovation (CTI), the Ecole Polytechnique Fédérale de Lausanne (EPFL), the ETH Zurich, the Fonds National pour la Recherche Scientifique (FNRS), the ENS‐Lyon, the CNRS, and the University of Lyon 1., European Project: 714519,HP4all, European Project: 339754,EC:FP7:ERC,ERC-2013-ADG,DILUTEPARAWATER(2014), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Radical, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, dynamic nuclear polarization, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, medicine, magnetic resonance imaging, Hyperpolarization (physics), Dissolution, ComputingMilieux_MISCELLANEOUS, hyperpolarization, medicine.diagnostic_test, Spectrometer, 010405 organic chemistry, sol-gel processes, Magnetic resonance imaging, General Medicine, General Chemistry, Polarizer, 021001 nanoscience & nanotechnology, Polarization (waves), 0104 chemical sciences, silica, Porous solids, 0210 nano-technology
Abstract

Tailoring the physical features and the porous network architecture of silica-based hyperpolarizing solids containing TEMPO radicals, known as HYPSO (hybrid polarizing solids), enabled unprecedented performance of dissolution dynamic nuclear polarization (d-DNP). High polarization values up to P(1H)=99 % were reached for samples impregnated with a mixture of H2O/D2O and loaded in a 6.7 T polarizer at temperatures around 1.2 K. These HYPSO materials combine the best performance of homogeneous DNP formulations with the advantages of solid polarizing matrices, which provide hyperpolarized solutions free of any—potentially toxic—additives (radicals and glass-forming agents). The hyperpolarized solutions can be expelled from the porous solids, filtered, and rapidly transferred either to a nuclear magnetic resonance (NMR) spectrometer or to a magnetic resonance imaging (MRI) system.

Published
2018
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18. Generating para-water from para-hydrogen: A Gedankenexperiment

Author

Konstantin L. Ivanov and Geoffrey Bodenhausen

Subjects
Physics, Nuclear and High Energy Physics, education.field_of_study, Population, Biophysics, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Spin isomers of hydrogen, 01 natural sciences, Biochemistry, 0104 chemical sciences, Conceptual approach, Chemical physics, Hyperpolarization (physics), 0210 nano-technology, education, Signal amplification
Abstract

A novel conceptual approach is described that is based on the transfer of hyperpolarization from para-hydrogen in view of generating a population imbalance between the two spin isomers of H2O. The approach is analogous to SABRE (Signal Amplification By Reversible Exchange) and makes use of the transfer of spin order from para-hydrogen to H2O in a hypothetical organometallic complex. The spin order transfer is expected to be most efficient at avoided level crossings. The highest achievable enrichment levels of para- and ortho-water are discussed.

Published
2018

19. Reifung von Proben beeinflusst die Effizienz der Kernpolarisation

Author

Dennis Kurzbach, Geoffrey Bodenhausen, Hervé Vezin, Daniel Abergel, Giuseppe Sicoli, Ghislaine Frébourg, Emmanuelle M. M. Weber, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Microscopie Electronique [IBPS] (IBPS-ME), Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), European Project: 339754,EC:FP7:ERC,ERC-2013-ADG,DILUTEPARAWATER(2014), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Phasentrennung, Kernspinresonanz, Nanophasen, 02 engineering and technology, General Medicine, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, Dynamische Kernpolarisation, 0104 chemical sciences
Abstract

International audience; Mischungen von Wasser und Glycerin sind populäre Matrizen für die Tieftemperaturspektroskopie verglaster Proben. Allerdings besitzen solche Mischungen konterintuitive Eigenschaften, wie spontane Nanophasenseparation in Lösungen, die makroskopisch homogen scheinen. Wir zeigen hier, dass solche Phänomene die Effizienz der dynamischen Kernpolarisation stark beeinflussen können, durch Fluktuation der lokalen Konzentration der Polarisationsmittel (Radikale) um bis zu 20 %. Spontane Nanophasenseparationen, die auf Zeitskalen von 30–60 min stattfinden, resultieren in lokalen wasserreichen Einschlüssen mit erhöhter Radikalkonzentration. Solche Phänomene wurden für die drei häufigen Polarisationsmittel TEMPOL, AMUPol und Trityl beobachtet.

Published
2018
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20. Ligand-Protein Affinity Studies Using Long-Lived States of Fluorine-19 Nuclei

Author

Daniele Mammoli, Estel Canet, Geoffrey Bodenhausen, and Roberto Buratto

Subjects
Models, Molecular, Screening techniques, Magnetic Resonance Spectroscopy, Hydrocarbons, Fluorinated, Analytical chemistry, chemistry.chemical_element, 010402 general chemistry, Ligands, 01 natural sciences, Drug Discovery, Molecule, Trypsin, Molecular Structure, 010405 organic chemistry, Drug discovery, Ligand, Nuclear magnetic resonance spectroscopy, Fluorine, 0104 chemical sciences, Dissociation constant, chemistry, Chemical physics, Drug Design, Molecular Medicine, Proton spectra
Abstract

The lifetimes T-LLS of long-lived states or T-LLC of long-lived coherences can be used for the accurate determination of dissociation constants of weak protein ligand complexes. The remarkable contrast between signals derived from LLS or LLC in free and bound ligands can be exploited to search for weak binders with large dissociation constants K-D > 1 mM that are important for fragment-based drug discovery but may escape detection by other screening techniques. Alternatively, the high sensitivity of the proposed method can be exploited to work with large ligand-to-protein ratios, with an evident advantage of reduced consumption of precious proteins. The detection of F-19-F-19 long-lived states in suitably designed fluorinated spy molecules allows one to perform competition binding experiments with high sensitivity while avoiding signal overlap that tends to hamper the interpretation of proton spectra of mixtures.

Published
2016
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21. Cubic three-dimensional hybrid silica solids for nuclear hyperpolarization

Author

Aurélien Bornet, Laurent Veyre, David Baudouin, Christophe Copéret, Matthieu Cavaillès, David Gajan, Lyndon Emsley, Anne Lesage, Geoffrey Bodenhausen, Wei-Chih Liao, Chloé Thieuleux, Basile Vuichoud, Sami Jannin, H. A. van Kalkeren, Martin Schwarzwälder, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), This work was supported by the CNRS, the SATT Lyon (Pulsalys), the European Research Council (ERC) Advanced Grant No. 320860, the Swiss National Science Foundation (SNSF), the Ecole Polytechnique Federale de Lausanne (EPFL), ETH Zurich, and the Swiss Commission for Technology & Innovation (CTI)., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, Radical, technology, industry, and agriculture, General Chemistry, 010402 general chemistry, behavioral disciplines and activities, 01 natural sciences, humanities, Porous network, 0104 chemical sciences, Chemistry, Nuclear magnetic resonance, Chemical engineering, [CHIM]Chemical Sciences, Hyperpolarization (physics), Mesoporous material, Dissolution
Abstract

Hyperpolarization of metabolites by dissolution dynamic nuclear polarization (D-DNP) for MRI applications often requires fast and efficient removal of the radicals (polarizing agents). Ordered mesoporous SBA-15 silica materials containing homogeneously dispersed radicals, referred to as HYperPolarizing SOlids (HYPSOs), enable high polarization – P(1H) = 50% at 1.2 K – and straightforward separation of the polarizing HYPSO material from the hyperpolarized solution by filtration. However, the one-dimensional tubular pores of SBA-15 type materials are not ideal for nuclear spin diffusion, which may limit efficient polarization. Here, we develop a generation of hyperpolarizing solids based on a SBA-16 structure with a network of pores interconnected in three dimensions, which allows a significant increase of polarization, i.e. P(1H) = 63% at 1.2 K. This result illustrates how one can improve materials by combining a control of the incorporation of radicals with a better design of the porous network structures., Chemical Science, 7 (11), ISSN:2041-6520, ISSN:2041-6539

Published
2016
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22. Theory for spiralling ions for 2D FT-ICR and comparison with precessing magnetization vectors in 2D NMR

Author

Geoffrey Bodenhausen, Christian Rolando, Philippe Pelupessy, Akansha Ashvani Sehgal, Jacobs University [Bremen], Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Laboratoire de Chimie Organique et Macromoleculaire (UMR CNRS 8009), Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Université de Lille, Sciences et Technologies, Université Pierre et Marie Curie - Paris 6 (UPMC), École normale supérieure - Paris (ENS-PSL), and Université de Lille, Sciences et Technologies-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)

Subjects
Physics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010401 analytical chemistry, Analytical chemistry, General Physics and Astronomy, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Fourier transform ion cyclotron resonance, 0104 chemical sciences, Ion, Magnetization, Fragmentation (mass spectrometry), Monochromatic color, Physical and Theoretical Chemistry, Atomic physics, Two-dimensional nuclear magnetic resonance spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

Two-dimensional (2D) Fourier transform ion cyclotron resonance (FT-ICR) offers an approach to mass spectrometry (MS) that pursuits similar objectives as MS/MS experiments. While the latter must focus on one ion species at a time, 2D FT ICR can examine all possible correlations due to ion fragmentation in a single experiment: correlations between precursors, charged and neutral fragments. We revisited the original 2D FT-ICR experiment that has hitherto fallen short of stimulating significant analytical applications, probably because it is technically demanding. These shortcomings can now be overcome by improved FT-ICR instrumentation and computer hard- and software. We seek to achieve a better understanding of the intricacies of the behavior of ions during a basic two-dimensional ICR sequence comprising three simple monochromatic pulses. Through simulations based on Lorentzian equations, we have mapped the ion trajectories for different pulse durations and phases.

Published
2016
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23. Sisyphus desperately seeking publisher

Author

Antoinette Molinié and Geoffrey Bodenhausen

Subjects
Hubris, Punishment, 010405 organic chemistry, media_common.quotation_subject, Scientific Misconduct, General Medicine, 010402 general chemistry, 01 natural sciences, General Biochemistry, Genetics and Molecular Biology, 0104 chemical sciences, Scholarly Communication, Power (social and political), Law, Political science, Narcissism, medicine, Humans, medicine.symptom, Journal Impact Factor, Periodicals as Topic, General Agricultural and Biological Sciences, Editorial Policies, media_common
Abstract

As a punishment for his trickery, King Sisyphus was made to endlessly roll a huge boulder up a steep hill. The maddening nature of the punishment was reserved for King Sisyphus due to his hubristic belief that his cleverness surpassed that of Zeus himself. Today’s scientists also pay a heavy price for their hubris and narcissism. They try to trick the editors of a few ‘top’ journals by peppering their papers with glitter and ‘bling-bling’, making overblown promises, and giving minimal credit to their predecessors. The editors wield their Olympian authority by making today’s scientists endlessly push their weighty boulders up steep hills. By bowing to this implacable ritual, we scientists confer undue power to a handful of popular but irresponsible journals.

Published
2018

24. Overhauser effects in non-conducting solids at 1.2 K

Author

Robert G. Griffin, Jonas Milani, Thach V. Can, Basile Vuichoud, Geoffrey Bodenhausen, Sami Jannin, Marc A. Caporini, Aurélien Bornet, Xiao Ji, M. Goldman, Frederic Mentink-Vigier, Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Francis Bitter Magnet Lab, Massachusetts Institute of Technology (MIT), Natl High Magnet Field Lab, Florida State University [Tallahassee] (FSU), ISA - Hyperpolarized Magnetic Resonance, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Amgen Inc, This work was supported by the Swiss National Science Foundation (SNSF), the Ecole Polytechnique Federale de Lausanne (EPFL), the French CNRS, the European Research Council (ERC contract 'Dilute para-water' and ERC Grant Agreement n 714519/HP4all) and by the US National Institute of Biomedical Imaging and Bioengineering (EB-002804 and EB-002026)., European Project: 714519,HP4all, European Project: 339754,EC:FP7:ERC,ERC-2013-ADG,DILUTEPARAWATER(2014), Massachusetts Institute of Technology. Department of Chemistry, Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nuclear and High Energy Physics, Materials science, Biophysics, 02 engineering and technology, Nuclear Overhauser effect, Solid effect, 010402 general chemistry, 01 natural sciences, Biochemistry, Molecular physics, Article, chemistry.chemical_compound, Dynamic nuclear polarization, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Magic angle spinning, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], ComputingMilieux_MISCELLANEOUS, Doping, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Magnetic field, chemistry, Microwave irradiation, Polystyrene, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology, Overhauser effect, Derivative (chemistry)
Abstract

Recently, it was observed that protons in non-conducting solids doped with 1,3-bisdiphenylene-2-phenylallyl (BDPA) or its sulfonated derivative (SA-BDPA) can be polarized through Overhauser effects via resonant microwave irradiation. These effects were present under magic angle spinning conditions in magnetic fields between 5 and 18.8 T and at temperatures near 100 K. This communication reports similar effects in static samples at 6.7 T and, more importantly, at temperatures as low as 1.2 K, in a different dynamic regime than in the previous study. Our results provide new information towards understanding the mechanism of the Overhauser effect in non-conducting solids. We discuss possible origins of the fluctuations that can give rise to an Overhauser effect at such low temperatures., US National Institute of Biomedical Imaging and Bioengineering (grant nos. EB-002804 and EB-002026)

Published
2018
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25. Relaxation of long-lived modes in NMR of deuterated methyl groups

Author

Daniel Abergel, Thomas Kress, Geoffrey Bodenhausen, Dennis Kurzbach, Mathieu Baudin, David Guarin, Konstantin L. Ivanov, Siberian Branch of the Russian Academy of Sciences (SB RAS), Novosibirsk State University (NSU), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Physics, 010304 chemical physics, Spin states, Dynamic nuclear polarisation, General Physics and Astronomy, Symmetry group, 010402 general chemistry, Polarization (waves), 01 natural sciences, Molecular physics, 0104 chemical sciences, Deuterium, Irreducible representation, 0103 physical sciences, Molecule, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Order of magnitude
Abstract

International audience; Long-lived imbalances of spin state populations can circumvent fast quadrupolar relaxation by reducing effective longitudinal relaxation rates by about an order of magnitude. This opens new avenues for the study of dynamic processes in deuterated molecules. Here we present an analysis of the relaxation properties of deuterated methyl groups CD3. The number of coupled equations that describe cross-relaxation between the 27 symmetry-adapted spin states of a D3 system can be reduced to only 2 non-trivial “lumped modes” by (i) taking the sums of the populations of all states that equilibrate rapidly within each irreducible representation of the symmetry group, and (ii) by combining populations that have similar relaxation rates although they belong to different irreducible representations. The quadrupolar relaxation rates of the spin state imbalances in CD3 groups are determined not by the correlation time of overall tumbling of the molecule, but by the frequency of jumps of methyl groups about their three-fold symmetry axis. We access these states via dissolution dynamic nuclear polarization (D-DNP), a method that allows one to populate the desired long-lived states at cryogenic temperatures and their subsequent detection at ambient temperatures after rapid dissolution. Experimental examples of DMSO-d6 and ethanol-d6 demonstrate that long-lived deuterium spin states are indeed accessible and that their lifetimes can be determined. Our analysis of the system via “lumped” modes allows us to visualize different possible spin-state populations of symmetry A, B, or E. Thus, we identify a long-lived spin state involving all three deuterons in a CD3 group as an A/E imbalance that can be populated through DNP at low temperatures.

Published
2018
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26. High-Resolution NMR of Folded Proteins in Hyperpolarized Physiological Solvents

Author

Dennis Kurzbach, Geoffrey Bodenhausen, Pavel Kadeřávek, Fabien Ferrage, Central European Institute of Technology [Brno] (CEITEC MU), Brno University of Technology [Brno] (BUT), Masaryk University [Brno] (MUNI), Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
0301 basic medicine, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Chemistry, Organic Chemistry, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Spectral line, 0104 chemical sciences, Solvent, 03 medical and health sciences, chemistry.chemical_compound, 030104 developmental biology, Amide, Molecule, Target protein, Hyperpolarization (physics), Two-dimensional nuclear magnetic resonance spectroscopy, Dissolution
Abstract

International audience; Hyperpolarized 2D exchange spectroscopy (HYPEX) to obtain high‐resolution nuclear magnetic resonance (NMR) spectra of folded proteins under near‐physiological conditions is reported. The technique is based on hyperpolarized water, which is prepared by dissolution dynamic nuclear polarization and mixed in situ in an NMR spectrometer with a protein in a physiological saline buffer at body temperature. Rapid exchange of labile protons with the hyperpolarized solvent, combined with cross‐relaxation effects (NOEs), leads to boosted signal intensities for many amide 1H–15N correlations in the protein ubiquitin. As the introduction of hyperpolarization to the target protein is mediated via the solvent, the method is applicable to a broad spectrum of target molecules.

Published
2018
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27. Sample Ripening through Nanophase Separation Influences the Performance of Dynamic Nuclear Polarization

Author

Ghislaine Frébourg, Emmanuelle M. M. Weber, Geoffrey Bodenhausen, Daniel Abergel, Dennis Kurzbach, Giuseppe Sicoli, Hervé Vezin, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, CNRS, Laboratoire des biomolécules [LBM UMR 7203], Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516, and Université Pierre et Marie Curie - Paris 6 [UPMC]

Subjects
Materials science, Radical, Vesicle, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dynamic nuclear polarization, nanophases, nuclear magnetic resonance, phase separation, chemistry.chemical_compound, chemistry, Homogeneous, Chemical physics, Phase (matter), Glycerol, 0210 nano-technology, Polarization (electrochemistry), Spectroscopy, Nanoscopic scale
Abstract

International audience; Mixtures of water and glycerol provide popular matrices for low‐temperature spectroscopy of vitrified samples. However, they involve counterintuitive physicochemical properties, such as spontaneous nanoscopic phase separations (NPS) in solutions that appear macroscopically homogeneous. We demonstrate that such phenomena can substantially influence the efficiency of dynamic nuclear polarization (DNP) by factors up to 20 % by causing fluctuations in local concentrations of polarization agents (radicals). Thus, a spontaneous NPS of water/glycerol mixtures that takes place on time scales on the order of 30–60 min results in a confinement of polarization agents in nanoscopic water‐rich vesicles, which in return affects the DNP. Such effects were found for three common polarization agents, TEMPOL, AMUPol and Trityl.

Published
2018
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28. Double cross polarization for the indirect detection of nitrogen-14 nuclei in magic angle spinning NMR spectroscopy

Author

Xiao Ji, Diego Carnevale, Geoffrey Bodenhausen, Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Structure et Dynamique des Biomolécules (LBM-E3), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and HAL-UPMC, Gestionnaire

Subjects
Magic angle, [PHYS.PHYS]Physics [physics]/Physics [physics], Chemistry, Analytical chemistry, General Physics and Astronomy, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, Spectral line, 0104 chemical sciences, Amorphous solid, NMR spectra database, Dipole, 13. Climate action, [CHIM] Chemical Sciences, Magic angle spinning, [CHIM]Chemical Sciences, Crystallite, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Nitrogen-14 NMR spectra at fast magic-angle spinning rates can be acquired indirectly by means of two-dimensional techniques based on double cross polarization transfer 1H → 14N →1H. Experimental evidence is given for polycrystalline samples of glycine, l-histidine, and the dipeptide Ala-Gly. Either one-bond or long-range correlations can be favored by choosing the length of the cross polarization contact pulses. Longer contact pulses allow the detection of unprotonated nitrogen sites. In contrast to earlier methods that exploited second-order quadrupolar/dipolar cross-terms, cross polarization operates in the manner of the method of Hartmann and Hahn, even for 14N quadrupolar couplings up to 4 MHz. Simulations explain why amorphous samples tend to give rise to featureless spectra because the 14N quadrupolar interactions may vary dramatically with the lattice environment. The experiments are straightforward to set up and are shown to be effective for different nitrogen environments and robust with respect to the rf-field strengths and to the 14N carrier frequency during cross polarization. The efficiency of indirect detection of 14N nuclei by double cross polarization is shown to be similar to that of isotopically enriched 13C nuclei.

Published
2017
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29. Drug Screening Boosted by Hyperpolarized Long-Lived States in NMR

Author

Sandrine Gerber-Lemaire, Sami Jannin, Basile Vuichoud, Daniele Mammoli, Solène Passemard, Jonas Milani, Aurélien Laguerre, Maninder Singh, Nicola Salvi, Geoffrey Bodenhausen, Aurélien Bornet, Roberto Buratto, Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des sciences et d'ingénierie chimiques (ISIC), and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Bromides, Magnetic Resonance Spectroscopy, Stereochemistry, Drug Evaluation, Preclinical, Thiophenes, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, dynamic nuclear polarization, chemistry.chemical_compound, NMR spectroscopy, Catalytic Domain, Drug Discovery, General Pharmacology, Toxicology and Pharmaceutics, Pharmacology, Spins, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Drug discovery, Organic Chemistry, Relaxation (NMR), Proteins, Nuclear magnetic resonance spectroscopy, Full Papers, Ligand (biochemistry), 0104 chemical sciences, Crystallography, chemistry, Covalent bond, long-lived states, Excited state, Functional group, Molecular Medicine
Abstract

International audience; : Transverse and longitudinal relaxation times (T1ρ and T1 ) have been widely exploited in NMR to probe the binding of ligands and putative drugs to target proteins. We have shown recently that long-lived states (LLS) can be more sensitive to ligand binding. LLS can be excited if the ligand comprises at least two coupled spins. Herein we broaden the scope of ligand screening by LLS to arbitrary ligands by covalent attachment of a functional group, which comprises a pair of coupled protons that are isolated from neighboring magnetic nuclei. The resulting functionalized ligands have longitudinal relaxation times T1 ((1) H) that are sufficiently long to allow the powerful combination of LLS with dissolution dynamic nuclear polarization (D-DNP). Hyperpolarized weak "spy ligands" can be displaced by high-affinity competitors. Hyperpolarized LLS allow one to decrease both protein and ligand concentrations to micromolar levels and to significantly increase sample throughput.

Published
2014
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30. Microwave frequency modulation to enhance Dissolution Dynamic Nuclear Polarization

Author

Angel J. Perez Linde, Basile Vuichoud, Aurélien Bornet, Geoffrey Bodenhausen, Jonas Milani, Sami Jannin, Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL)-Batochime, Université Pierre et Marie Curie - Paris 6 (UPMC), Swiss National Science Foundation, Ecole Polytechnique Federale de Lausanne ( EPFL), Swiss Commission for Technology and Innovation ( CTI), CNRS, and European Research Council ( ERC)

Subjects
Chemistry, Radical, General Physics and Astronomy, 02 engineering and technology, Microwave frequency, Atmospheric temperature range, Physics and Astronomy(all), 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Paramagnetism, Nuclear magnetic resonance, Critical frequency, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Hyperpolarization (physics), Monochromatic color, Atomic physics, Physical and Theoretical Chemistry, 0210 nano-technology, Dissolution
Abstract

Hyperpolarization by Dissolution Dynamic Nuclear Polarization is usually achieved by monochromatic microwave irradiation of the ESR spectrum of free radicals embedded in glasses at 1.2 K and 3.35 T. Hovav et al. (2014) have recently shown that by using frequency-modulated (rather than monochromatic) microwave irradiation one can improve DNP at 3.35 T in the temperature range 10–50 K. We show in this Letter that this is also true under Dissolution-DNP conditions at 1.2 K and 6.7 T. We demonstrate the many virtues of using frequency-modulated microwave irradiation: higher polarizations, faster buildup rates, lower radical concentrations, less paramagnetic broadening, more efficient cross-polarization, and less critical frequency adjustments. 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

Published
2014
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31. Solid-state NMR measurements and DFT calculations of the magnetic shielding tensors of protons of water trapped in barium chlorate monohydrate

Author

Geoffrey Bodenhausen, Sharon E. Ashbrook, Diego Carnevale, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, GGRC-ISIC-EPFL, Ecole Polytechnique Fédérale de Lausanne (EPFL), School of Chemistry, University of St Andrews [Scotland], and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
General Chemical Engineering, Plane wave, 02 engineering and technology, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, QD Chemistry, 01 natural sciences, Molecular physics, 0104 chemical sciences, Pseudopotential, chemistry.chemical_compound, Condensed Matter::Materials Science, Solid-state nuclear magnetic resonance, chemistry, Computational chemistry, Electromagnetic shielding, [CHIM]Chemical Sciences, QD, Fast motion, 0210 nano-technology, Spinning, Barium chlorate
Abstract

This work was supported by the Swiss National Science Foundation (SNSF), the Ecole Polytechnique Fédérale de Lausanne (EPFL), the Swiss Commission for Technology and Innovation (CTI) and the European Research Council (ERC, contract ‘dilute para-water’). Accepted 15th October 2014. The magnetic shielding tensors of protons of water in barium chlorate monohydrate are investigated at room temperature by means of solid-state NMR spectroscopy, both for static powders and under magic-angle spinning conditions, using one- and two-dimensional techniques. First-principles DFT calculations based on a periodic planewave pseudopotential formalism for a static periodic system provide support for our spectral interpretation and corroborate the experimental findings in the fast motion regime. Publisher PDF

Published
2014
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32. Solid-state proton NMR of paramagnetic metal complexes: DANTE spin echoes for selective excitation in inhomogeneously broadened lines

Author

A. J. Perez Linde, Geoffrey Bodenhausen, Diego Carnevale, Gerald Bauer, Université Pierre et Marie Curie - Paris 6 (UPMC), Institut des Sciences et Ingénierie Chimiques (ISIC), and Ecole Polytechnique Fédérale de Lausanne (EPFL)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nutation, General Physics and Astronomy, 010402 general chemistry, 01 natural sciences, Spectral line, 0104 chemical sciences, Paramagnetism, Nuclear magnetic resonance, Excited state, Proton NMR, Irradiation, Physical and Theoretical Chemistry, Atomic physics, Hyperfine structure, ComputingMilieux_MISCELLANEOUS, Excitation
Abstract

The paramagnetic complex bis(oxazolinylphenyl)amine-Fe(III)Cl-2 is investigated by means of solid-state proton NMR at 18.8 T (800 MHz) using magic-angle spinning at 65 kHz. Spin echoes that are excited and refocused by combs of rotor-synchronized pulses in the manner of 'Delays Alternating with Nutation for Tailored Excitation' (DANTE) allow one to characterize different chemical environments that severely overlap in conventional MAS spectra. Such sequences combine two apparently contradictory features: an overall bandwidth exceeding several MHz, and very selective irradiation of a few kHz within inhomogeneously broadened sidebands. The experimental hyperfine interactions correlate well with DFT calculations. (C) 2013 Elsevier B.V. All rights reserved.

Published
2013
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33. Quantitative one- and two-dimensional 13C spectra of microcrystalline proteins with enhanced intensity

Author

Geoffrey Bodenhausen, Rudra N. Purusottam, Piotr Tekely, and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Carbon Isotopes, 0303 health sciences, Proton, Protein Conformation, Ubiquitin, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Analytical chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Spectral line, 0104 chemical sciences, 03 medical and health sciences, Magnetization, Microcrystalline, Receptors, GABA-B, Solid-state nuclear magnetic resonance, Isotope Labeling, Phase (matter), Spin diffusion, Irradiation, Nuclear Magnetic Resonance, Biomolecular, Spectroscopy, 030304 developmental biology
Abstract

International audience; We recorded quantitative, uniformly enhanced one- and two-dimensional (13)C spectra of labelled microcrystalline proteins. The approach takes advantage of efficient equilibration of magnetization by low-power proton irradiation using Phase Alternated Recoupling Irradiation Schemes and benefits simultaneously from uniform sensitivity enhancement due to efficient spin exchange that can overcome T1((13)C) constraints and the presence of heteronuclear Overhauser effects.

Published
2013
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34. Solid-state NMR enhanced by dynamic nuclear polarization as a novel tool for ribosome structural biology

Author

Geoffrey Bodenhausen, Sean R. Connell, Neha Dhimole, Veronika Vitzthum, Ioannis Gelis, Marc A. Caporini, Diego Carnevale, Paola Fucini, Andreas Schedlbauer, Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Models, Molecular, Ribosome structure, Carbon-13 NMR satellite, Molecular Conformation, Analytical chemistry, Nuclear magnetic resonance spectroscopy of nucleic acids, Fluorine-19 NMR, 010402 general chemistry, Solid-state NMR, 01 natural sciences, Biochemistry, 03 medical and health sciences, Freezing, Transverse relaxation-optimized spectroscopy, Nuclear Magnetic Resonance, Biomolecular, Spectroscopy, 030304 developmental biology, Magic-angle spinning NMR (MAS-NMR), 0303 health sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Nuclear magnetic resonance spectroscopy, Carbon-13 NMR, 0104 chemical sciences, Solid-state nuclear magnetic resonance, Chemical physics, TOTAPOL, Dynamic nuclear polarization (DNP), Ribosomes, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

International audience; The impact of Nuclear Magnetic Resonance (NMR) on studies of large macromolecular complexes hinges on improvements in sensitivity and resolution. Dynamic nuclear polarization (DNP) in the solid state can offer improved sensitivity, provided sample preparation is optimized to preserve spectral resolution. For a few nanomoles of intact ribosomes and an 800 kDa ribosomal complex we demonstrate that the combination of DNP and magic-angle spinning NMR (MAS-NMR) allows one to overcome current sensitivity limitations so that homo- and heteronuclear (13)C and (15)N NMR correlation spectra can be recorded. Ribosome particles, directly pelleted and frozen into an NMR rotor, yield DNP signal enhancements on the order of ~25-fold and spectra that exhibit narrow linewidths, suitable for obtaining site-specific information. We anticipate that the same approach is applicable to other high molecular weight complexes.

Published
2013
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35. Hyperpolarization of nitrogen-15 nuclei by cross polarization and dissolution dynamic nuclear polarization

Author

Sami Jannin, Aurélien Bornet, Geoffrey Bodenhausen, Jonas Milani, Basile Vuichoud, Roberto Melzi, ISA - Hyperpolarized Magnetic Resonance, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Bruker BioSpin, Université Pierre et Marie Curie - Paris 6 (UPMC), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Spins, Radical, Dynamic nuclear polarisation, Analytical chemistry, 02 engineering and technology, Electron, 010402 general chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, 7. Clean energy, 0104 chemical sciences, law.invention, Nuclear magnetic resonance, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Hyperpolarization (physics), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Insensitive nuclei enhanced by polarization transfer, 0210 nano-technology, Electron paramagnetic resonance, Instrumentation
Abstract

International audience; Dynamic Nuclear Polarization (DNP) is often achieved by the direct transfer of polarization from electrons to nuclei such as C-13, induced by microwave saturation of the wings of narrow EPR lines of radicals like trityl. In the indirect approach on the other hand, DNP is used to transfer the polarization from the electrons of radicals such as nitroxides that have broad EPR lines to nuclear spins I = H-1, followed by cross-polarization (CP) from I = H-1 to S = C-13 or other nuclei with low gyromagnetic ratios. This approach is particularly attractive for S = N-15, since direct DNP yields modest polarizations P(N-15) < 4% with build-up times that can be as long as tau DNP(N-15) > 2 h. In this paper, we show that CP from H-1 to N-15 at 1.2 K can yield P(N-15) = 25% with iota CP-DNP(N-15) = 10-15 min. After rapid dissolution and transfer to a solution-state NMR spectrometer, a polarization P(N-15) = 20% was observed at 300 K. The longitudinal relaxation times in solution can be as long as T-1(N-15) > 800 s in favorable cases.

Published
2017
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36. Phenylazide Hybrid-Silica – Polarization Platform for Dynamic Nuclear Polarization at Cryogenic Temperatures

Author

Aurélien Bornet, Laurent Veyre, David Baudouin, David Gajan, Sami Jannin, Jonas Milani, Wolfram R. Grüning, Geoffrey Bodenhausen, Harald Bieringer, Chloé Thieuleux, Christophe Copéret, Anne Lesage, Martin Schwarzwälder, Basile Vuichoud, Laboratory of Inorganic Chemistry, ISA - Centre de RMN à très hauts champs, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), ISA - Hyperpolarized Magnetic Resonance, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences et Ingénierie Chimiques, and Ecole Polytechnique Fédérale de Lausanne (EPFL)-Batochime

Subjects
Sol-Gel, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, Spectral line, Inorganic Chemistry, chemistry.chemical_compound, Phenyl azide, Drug Discovery, Magic angle spinning, [CHIM]Chemical Sciences, Hyperpolarization (physics), Physical and Theoretical Chemistry, Dissolution, Sol-gel, Dynamic Nuclear Polarization, Chemistry, Organic Chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), Hybrid Materials, 0104 chemical sciences, Hyperpolarization, 0210 nano-technology, Hybrid material
Abstract

Hyperpolarization of NMR-active nuclei is key to gather high quality spectra of rare species and insensitive isotopes. We have recently established that silica-based materials containing regularly distributed nitroxyl radicals connected to the silica matrix by flexible linkers can serve as promising polarization matrices for dynamic nuclear polarization (DNP). Here we investigate the influence of the linker on the efficiency of the polarization. The materials were fully characterized and exhibit high surface areas and narrow pore size distributions with a tunable amount of phenyl azide groups over a broad range of concentrations. The phenyl azide groups can be easily functionalized via a two-step procedure with 4-carboxy-2,2,6,6-tetramethyl-1-oxylpiperidine (TEMPO) to give polarizing matrices with controllable radical content. The DNP efficiency was found to be similar as in materials with flexible linkers, both for magic angle spinning at 105 K and dissolution DNP at 4 K.

Published
2017
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37. Exciting Wide NMR Spectra of Static Solid Samples with Weak Radiofrequency Fields

Author

Diego Carnevale, Geoffrey Bodenhausen, Srinivas Chinthalapalli, Neuchâtel Platform of Analytical Chemistry (NPAC), Université de Neuchâtel (UNINE), Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Vikram Sarabhai Space Ctr, Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Analytical chemistry, 02 engineering and technology, dipolar echoes, 010402 general chemistry, 01 natural sciences, Molecular physics, Spectral line, Homonuclear molecule, NMR spectroscopy, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Anisotropy, hydration water, solid echoes, dipolar interactions, quadrupolar interactions, Chemistry, Chemical shift, 021001 nanoscience & nanotechnology, 0104 chemical sciences, NMR spectra database, quadrupolar echoes, solid-state NMR of static samples, Dipole, DANTE, Crystallite, 0210 nano-technology, Excitation
Abstract

Trains of short pulses in the manner of ‘delays alternating with nutations for tailored excitation’ (DANTE) have been applied to the Pake patterns of protons of water molecules trapped in a static powdered sample of barium chlorate monohydrate. The spin dynamics in the course of such experiments have been investigated by means of numerical simulations and compared with the ideal refocusing that can be achieved under magic-angle spinning (MAS). Solid echoes yield essentially undistorted lineshapes, in contrast to direct excitation without refocusing that leads to severe dispersions of the phases because of inhomogeneous interactions such as homonuclear dipolar couplings and anisotropic chemical shifts. The selectivity of DANTE sequences allows one to access ‘slices’ of the Pake pattern that can be related to particular crystallite orientations. Single-crystal spectra can therefore be extracted from powder spectra. A similar behavior is expected for both dipolar and quadrupolar echoes.

Published
2017
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38. Anisotropic longitudinal electronic relaxation affects DNP at cryogenic temperatures

Author

Dennis Kurzbach, Daniel Abergel, Hervé Vezin, Geoffrey Bodenhausen, Emmanuelle M. M. Weber, James G. Kempf, Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL)-Institut de Chimie du CNRS (INC)-Université de Lille, Bruker BioSpin, GmbH, Université de Lille, CNRS, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE], Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL)

Subjects
[PHYS]Physics [physics], Nitroxide mediated radical polymerization, Condensed matter physics, Chemistry, Radical, Relaxation (NMR), General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, 0104 chemical sciences, law.invention, Magnetic field, law, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Diffusion (business), 0210 nano-technology, Electron paramagnetic resonance, Anisotropy
Abstract

International audience; We report the observation of anisotropic longitudinal electronic relaxation in nitroxide radicals under typical dynamic nuclear polarization conditions. This anisotropy affects the efficiency of dynamic nuclear polarization at cryogenic temperatures of 4 K and high magnetic fields of 6.7 T. Under our experimental conditions, the electron paramagnetic resonance spectrum of nitroxides such as TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl) is only partly averaged by electronic spectral diffusion, so that the relaxation times T 1e (o) vary across the spectrum. We demonstrate how the anisotropy of T 1e (o) can be taken into account in simple DNP models.

Published
2017
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39. Collisional cross-section of water molecules in vapour studied by means of 1 H relaxation in NMR

Author

Lothar Helm, Daniele Mammoli, Estel Canet, Pascal Miéville, Geoffrey Bodenhausen, Roberto Buratto, Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Larmor precession, Angular momentum, Multidisciplinary, Materials science, Proton, Field (physics), Relaxation (NMR), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Rotation, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, Magnetization, [CHIM]Chemical Sciences, Atomic physics, 0210 nano-technology, Spin (physics), Astrophysics::Galaxy Astrophysics
Abstract

In gas phase, collisions that affect the rotational angular momentum lead to the return of the magnetization to its equilibrium (relaxation) in Nuclear Magnetic Resonance (NMR). To the best of our knowledge, the longitudinal relaxation rates R1 = 1/T1 of protons in H2O and HDO have never been measured in gas phase. We report R1 in gas phase in a field of 18.8 T, i.e., at a proton Larmor frequency ν0 = 800 MHz, at temperatures between 353 and 373 K and pressures between 9 and 101 kPa. By assuming that spin rotation is the dominant relaxation mechanism, we estimated the effective cross-section σJ for the transfer of angular momentum due to H2O-H2O and HDO-D2O collisions. Our results allow one to test theoretical predictions of the intermolecular potential of water in gas phase.

Published
2016
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40. High-Resolution Two-Field Nuclear Magnetic Resonance Spectroscopy

Author

Thorsten Marquardsen, Simone Ulzega, Cyril Charlier, Frank Engelke, Pierre-Alain Bovier, Werner Maas, Pavel Kadeřávek, Dimitrios Sakellariou, Thomas Speck, Philippe Pelupessy, Geoffrey Bodenhausen, Fabien Ferrage, Dirk Wilhelm, Samuel F. Cousin, Jean-Max Tyburn, Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Bruker BioSpin GmbH, D-76287 Rheinstetten, Germany, affiliation inconnue, Bruker BioSpin [Wissembourg], Bruker Biospin AG, Bruker BioSpin [Billerica, MA], Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-BS07-0031,DYN-IDP,Protéines : cinétique et désordre.(2011), European Project: 279519,EC:FP7:ERC,ERC-2011-StG_20101014,2F4BIODYN(2012), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Condensed matter physics, Chemistry, 530: Physik, General Physics and Astronomy, Magnetic resonance force microscopy, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Magnetostatics, 01 natural sciences, Molecular physics, 0104 chemical sciences, Solid-state nuclear magnetic resonance, Spin echo, Transverse relaxation-optimized spectroscopy, Physical and Theoretical Chemistry, 0210 nano-technology, Two-dimensional nuclear magnetic resonance spectroscopy, Earth's field NMR
Abstract

Nuclear magnetic resonance (NMR) is a ubiquitous branch of spectroscopy that can explore matter at the scale of an atom. Significant improvements in sensitivity and resolution have been driven by a steady increase of static magnetic field strengths. However, some properties of nuclei may be more favourable at low magnetic fields. For example, transverse relaxation due to chemical shift anisotropy increases sharply at higher magnetic fields leading to line-broadening and inefficient coherence transfers. Here, we present a two-field NMR spectrometer that permits the application of rf-pulses and acquisition of NMR signals in two magnetic centres. Our prototype operates at 14.1 T and 0.33 T. The main features of this system are demonstrated by novel NMR experiments, in particular a proof-of-concept correlation between zero-quantum coherences at low magnetic field and single quantum coherences at high magnetic field, so that high resolution can be achieved in both dimensions, despite a ca. 10 ppm inhomogeneity of the low-field centre. Two-field NMR spectroscopy offers the possibility to circumvent the limits of high magnetic fields, while benefiting from their exceptional sensitivity and resolution. This approach opens new avenues for NMR above 1 GHz.

Published
2016
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41. Highly Repeatable Dissolution Dynamic Nuclear Polarization for Heteronuclear NMR Metabolomics

Author

Geoffrey Bodenhausen, Daniel J. Jacob, Jonas Milani, Sami Jannin, Annick Moing, Basile Vuichoud, Mickaël Maucourt, Jean-Nicolas Dumez, Aurélien Bornet, Catherine Deborde, Xiao Ji, Patrick Giraudeau, Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Biologie du fruit et pathologie (BFP), Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA)-Université Sciences et Technologies - Bordeaux 1, 1074 Institut de Biologie Végétale Moléculaire : actions communes, Institut National de la Recherche Agronomique (INRA)-Santé des plantes et environnement (S.P.E.)-Institut de Biologie Végétale Moléculaire : actions communes (IBVM), UMR1332 Fruit Biology and Pathology, Institut National de la Recherche Agronomique (INRA), Platetorme Métabolome Bordeaux, Université Pierre et Marie Curie - Paris 6 (UPMC), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Bruker Biospin AG, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - Faculté des Sciences et des Techniques, Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS), CORSAIRE metabolomics platform (Biogenouest network), Swiss National Science Foundation (SNSF), Ecole Polytechnique Federale de Lausanne (EPFL), Swiss Commission for Technology and Innovation (CTI), CNRS, European Research Council (ERC) [339754], Bruker BioSpin, MetaboHUB [ANR-11-INBS-010], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA)-Université Sciences et Technologies - Bordeaux 1 (UB), Plateforme Bordeaux Metabolome, Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-MetaboHUB-Bordeaux, MetaboHUB-MetaboHUB, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Detection limit, Carbon Isotopes, Chromatography, Chemistry, 010401 analytical chemistry, Analytical chemistry, Reproducibility of Results, Repeatability, Signal-To-Noise Ratio, 010402 general chemistry, Polarization (waves), 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Metabolomics, Solanum lycopersicum, Heteronuclear molecule, Limit of Detection, Fruit, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Hyperpolarization (physics), Nuclear Magnetic Resonance, Biomolecular, Dissolution, Nmr based metabolomics
Abstract

International audience; At natural C-13 abundance, metabolomics based on heteronuclear NMR is limited by sensitivity. We have recently demonstrated how hyperpolarization by dissolution dynamic nuclear polarization (D-DNP) assisted by cross-polarization (CP) provides a reliable way of enhancing the sensitivity of heteronudear NMR in dilute mixtures of metabolites. In this Technical Note, we evaluate the precision of this experimental approach, a critical point for applications to metabolomics. The higher the repeatability, the greater the likelihood that one can detect small biologically relevant differences between samples. The average repeatability of our state-of-the-art D-DNP NMR equipment for samples of metabolomic relevance (20 mg dry weight tomato extracts) is 3.6% for signals above the limit of quantification (LOQ) and 6.4% when all the signals above the limit of detection (LOD) are taken into account. This first report on the repeatability of D-DNP highlights the compatibility of the technique with the requirements of metabolomics and confirms its potential as an analytical tool for such applications.

Published
2016
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42. Fifty years of 'Progress in NMR Spectroscopy' - An editorial from the present Editorial Board

Author

David G. Gadian, David Neuhaus, Gareth A. Morris, Geoffrey Bodenhausen, Beat H. Meier, Medical Research Council Laboratory of Molecular Biology, Université Pierre et Marie Curie - Paris 6 (UPMC), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Physical Chemistry [ETH Zürich], Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich)- Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), and École normale supérieure - Paris (ENS-PSL)

Subjects
Nuclear and High Energy Physics, Engineering, business.industry, Nanotechnology, Nuclear magnetic resonance spectroscopy, Editorial board, 010402 general chemistry, 01 natural sciences, Biochemistry, 030218 nuclear medicine & medical imaging, 0104 chemical sciences, Analytical Chemistry, 03 medical and health sciences, 0302 clinical medicine, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, business, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; no abstract

Published
2016
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43. Kinetic isotope effects for fast deuterium and proton exchange rates

Author

Daniele Mammoli, Philippe Pelupessy, Pavel Kadeřávek, Geoffrey Bodenhausen, Estel Canet, Laboratoire de Résonance Magnétique Biomoléculaire, Ecole Polytechnique Fédérale de Lausanne (EPFL), Université Paris sciences et lettres (PSL), Université Pierre et Marie Curie - Paris 6 (UPMC), Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Proton, Kinetics, Analytical chemistry, General Physics and Astronomy, 010402 general chemistry, Kinetic energy, 01 natural sciences, Magnetization, Isotopes, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, Kinetic isotope effect, Physical and Theoretical Chemistry, Nuclear Experiment, Isotope, 010405 organic chemistry, Chemistry, Radiochemistry, Temperature, Tryptophan, Hydrogen-Ion Concentration, Deuterium, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Protons
Abstract

By monitoring the effect of deuterium decoupling on the decay of transverse 15N magnetization in D–15N spin pairs during multiple-refocusing echo sequences, we have determined fast D–D exchange rates kD and compared them with fast H–H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.

Published
2016
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44. Disentangling Crystallographic Inequivalence and Crystallographic Forms of <scp>l</scp>-Arginine by One- and Two-Dimensional Solid-State NMR Spectroscopy

Author

Henri Colaux, Geoffrey Bodenhausen, José Enrique Herbert-Pucheta, Piotr Tekely, Université Pierre et Marie Curie - Paris 6 (UPMC), Institut des sciences et d'ingénierie chimiques (ISIC), and Ecole Polytechnique Fédérale de Lausanne (EPFL)

Subjects
Carbon Isotopes, Quantitative Biology::Biomolecules, Magnetic Resonance Spectroscopy, Nitrogen Isotopes, Proton, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Spin–lattice relaxation, Arginine, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, NMR spectra database, Dipole, Crystallography, Solid-state nuclear magnetic resonance, Materials Chemistry, Molecule, Protons, Physical and Theoretical Chemistry, Spectroscopy
Abstract

International audience; Overlapping (13)C or (15)N solid-state NMR spectra from crystallographically different forms of L-arginine hydrochloride can be separated by exploiting differential proton T(1) relaxation in conjunction with cross-polarization. Dipolar (13)C-(13)C and (15)N-(15)N two-dimensional correlation experiments reveal resonances belonging to crystallographically and magnetically inequivalent molecules.

Published
2011
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45. A spinning thermometer to monitor microwave heating and glass transitions in dynamic nuclear polarization

Author

Sandrine Gerber-Lemaire, Geoffrey Bodenhausen, Marc A. Caporini, Veronika Vitzthum, Pascal Miéville, and Sami Jannin

Subjects
Chemistry, Analytical chemistry, General Chemistry, 010402 general chemistry, Polarization (waves), 01 natural sciences, 0104 chemical sciences, Thin disk, Thermometer, 0103 physical sciences, Magic angle spinning, General Materials Science, Irradiation, 010306 general physics, Glass transition, Spinning, Microwave
Abstract

As previously demonstrated by Thurber and Tycko, the peak position of (79)Br in potassium bromide (KBr) allows one to determine the temperature of a spinning sample. We propose to adapt the original design by using a compact KBr tablet placed at the bottom of the magic angle spinning rotor, separated from the sample under investigation by a thin disk made of polytetrafluoroethylene (or 'Teflon'®). This design allows spinning the sample up to at least 16 kHz. The KBr tablet can remain in the rotor when changing the sample under investigation. Calibration in the range of 98 < T < 320 K has been carried out in a static rotor by inserting a platinum thermometer. The accuracy is better than ± 0.9 K, even in the presence of microwave irradiation. Irradiation with 5 W microwaves at 263 GHz leads to a small temperature increase of 3.6 ± 1.4 K in either static or spinning samples. The dynamic nuclear polarization enhancement decreases with increasing temperature, in particular when a frozen glassy sample undergoes a glass transition.

Published
2011
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46. Broadband excitation and indirect detection of nitrogen-14 in rotating solids using Delays Alternating with Nutation (DANTE)

Author

Veronika Vitzthum, Simone Ulzega, Marc A. Caporini, Geoffrey Bodenhausen, Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire de Résonance Magnétique Biomoléculaire, Université Pierre et Marie Curie - Paris 6 (UPMC), and Institut des sciences et d'ingénierie chimiques (ISIC)

Subjects
Nuclear and High Energy Physics, Magnetic Resonance Spectroscopy, Magic angle, Nitrogen, Nuclear-Magnetic-Resonance, Overtone, Nmr-Spectroscopy, Glycine, Biophysics, 02 engineering and technology, 010402 general chemistry, Delays Alternating with Nutations for Tailored Excitation (DANTE), Solid-state NMR, 01 natural sciences, Biochemistry, law.invention, law, Nitrogen-14 NMR, Magic angle spinning (MAS), Histidine, Broadband excitation, State Nmr, Nitrogen Isotopes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Rotor (electric), Chemistry, Nutation, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Dipole, Amplitude, Calibration, Dipolar Heteronuclear Multiple-Quantum Correlation (D-HMQC), Quadrupole, Quadrupolar nuclei, Selective Excitation, Atomic physics, Crystallization, 0210 nano-technology, Excitation
Abstract

A train of short rotor-synchronized pulses in the manner of Delays Alternating with Nutations for Tailored Excitation (DANTE) applied to nitrogen-14 nuclei (I = 1) in samples spinning at the magic angle at high frequencies (typically nu(rot) = 62.5 kHz so that tau(rot) = 16 mu s) allows one to achieve uniform excitation of a great number of spinning sidebands that arise from large first-order quadrupole interactions, as occur for aromatic nitrogen-14 nuclei in histidine. With routine rf amplitudes omega(1)(N-14)/(2 pi) = 60 kHz and very short pulses of a typical duration 0.5 < tau(p) < 2 mu s, efficient excitation can be achieved with 13 rotor-synchronized pulses in 13 tau(rot) = 208 mu s. Alternatively, with 'overtone' DANTE sequences using 2, 4, or 8 pulses per rotor period one can achieve efficient broadband excitation in fewer rotor periods, typically 2-4 tau(rot). These principles can be combined with the indirect detection of N-14 nuclei via spy nuclei with S = 1/2 such as H-1 or C-13 in the manner of Dipolar Heteronuclear Multiple-Quantum Correlation (D-HMQC). (C) 2011 Elsevier Inc. All rights reserved.

Published
2011
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47. Transverse Relaxation of Scalar-Coupled Protons

Author

Geoffrey Bodenhausen, Bikash Baishya, Takuya F. Segawa, Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
transverse relaxation, Magnetic Resonance Spectroscopy, Proton, 010402 general chemistry, 01 natural sciences, multiple refocusing, Homonuclear molecule, Spin–spin relaxation, Magnetization, NMR spectroscopy, scalar couplings, Physical and Theoretical Chemistry, Carbon Isotopes, spin echoes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nuclear magnetic resonance spectroscopy, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Dipole, Cyclosporine, Spin echo, Protons, Atomic physics, Peptides, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

International audience; In a preliminary communication (B. Baishya, T. F. Segawa, G. Bodenhausen, J. Am. Chem. Soc. 2009, 131, 17538-17539), we recently demonstrated that it is possible to obtain clean echo decays of protons in biomolecules despite the presence of homonuclear scalar couplings. These unmodulated decays allow one to determine apparent transverse relaxation rates R(2) (app) of individual protons. Herein, we report the observation of R(2) (app) for three methyl protons, four amide H(N) protons, and all 11 backbone H(α) protons in cyclosporin A. If the proton resonances overlap, their R(2) (app) rates can be measured by transferring their magnetization to neighboring (13)C nuclei, which are less prone to overlap. The R(2) (app) rates of protons attached to (13)C are faster than those attached to (12)C because of (13)C-(1)H dipolar interactions. The differences of these rates allow the determination of local correlation functions. Backbone H(N) and H(α) protons that have fast decay rates R(2) (app) also feature fast longitudinal relaxation rates R(1) and intense NOESY cross peaks that are typical of crowded environments. Variations of R(2) (app) rates of backbone H(α) protons in similar amino acids reflect differences in local environments.

Published
2010
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48. Microwave-gated dynamic nuclear polarization

Author

Jan Henrik Ardenkjær-Larsen, Aurélien Bornet, Geoffrey Bodenhausen, Aditya Jhajharia, Lyndon Emsley, Xiao Ji, Mathieu Baudin, Arthur C. Pinon, Sami Jannin, Ecole Polytechnique Fédérale de Lausanne (EPFL), Université Pierre et Marie Curie - Paris 6 (UPMC), Université Paris sciences et lettres (PSL), DTU Electrical Engineering [Lyngby], Technical University of Denmark [Lyngby] (DTU), GE Healthcare, ISA - Hyperpolarized Magnetic Resonance, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Bruker BioSpin, Danmarks Tekniske Universitet = Technical University of Denmark (DTU), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Millisecond, 010405 organic chemistry, Chemistry, Sodium, Time constant, Analytical chemistry, General Physics and Astronomy, chemistry.chemical_element, Gating, 010402 general chemistry, Polarization (waves), 01 natural sciences, 7. Clean energy, 0104 chemical sciences, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Microwave irradiation, Physical and Theoretical Chemistry, Dissolution, Microwave
Abstract

International audience; Dissolution dynamic nuclear polarization (D-DNP) has become a method of choice to enhance signals in nuclear magnetic resonance (NMR). Recently, we have proposed to combine cross-polarization (CP) with D-DNP to provide high polarization P(13C) in short build-up times. In this paper, we show that switching microwave irradiation off for a few hundreds of milliseconds prior to CP can significantly boost the efficiency. By implementing microwave gating, 13C polarizations on sodium [1-13C]acetate as high as 64% could be achieved with a polarization build-up time constant as short as 160 s. A polarization of P(13C) = 78% could even be reached for [13C]urea.

Published
2016
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49. Homonuclear decoupling for spectral simplification of carbon-13 enriched molecules in solution-state NMR enhanced by dissolution DNP

Author

Geoffrey Bodenhausen, Srinivas Chinthalapalli, Diego Carnevale, Aurélien Bornet, Sami Jannin, GGRC-ISIC-EPFL, Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des sciences et d'ingénierie chimiques (ISIC), Institut de Chimie, Université de Neuchâtel, Université de Neuchâtel (UNINE), Bruker Biospin AG, Université Pierre et Marie Curie - Paris 6 (UPMC), and Université Paris sciences et lettres (PSL)

Subjects
Spins, 010405 organic chemistry, Solution state, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Carbon-13, Analytical chemistry, General Physics and Astronomy, 010402 general chemistry, 01 natural sciences, Molecular physics, Homonuclear molecule, 0104 chemical sciences, Molecule, Hyperpolarization (physics), Irradiation, Physical and Theoretical Chemistry, Dissolution, ComputingMilieux_MISCELLANEOUS
Abstract

Complex overlapping multiplets due to scalar couplings (n)J(C-13, C-13) in fully C-13-enriched molecules can be simplified by polychromatic irradiation of selected spins. The signal intensities of the remaining non-irradiated signals are proportional to the concentrations, as shown in this work for the anomeric C-13 signals of the alpha- and beta-conformers of glucose. Homonuclear decoupling can therefore be useful for quantitative NMR studies. The resulting decoupled lineshapes show residual fine structures that have been investigated by means of numerical simulations. Simulations also show that homonuclear decoupling schemes remain effective despite inhomogeneous static fields that tend to hamper in cellulo and in vivo studies. Homonuclear decoupling schemes can be combined with dissolution DNP to obtain signal enhancements of more than four orders of magnitude. Polychromatic irradiation of selected spins does not cause significant losses of hyperpolarization of the remaining non-irradiated spins.

Published
2016
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50. Boosting Dissolution Dynamic Nuclear Polarization by Cross Polarization

Author

Aurélien Bornet, Patrick Hautle, Roberto Melzi, Angel J. Perez Linde, Geoffrey Bodenhausen, Sami Jannin, Ben van den Brandt, Institut des sciences et d'ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Université Pierre et Marie Curie - Paris 6 (UPMC), Swiss National Science Foundation, Ecole Polytechnique Federale de Lausanne (EPFL), Swiss Commission for Technology and Innovation (CTI), Bruker BioSpin Switzerland AG, and French CNRS

Subjects
Materials science, 010405 organic chemistry, Cross polarization, Nanotechnology, 010402 general chemistry, Polarization (waves), 01 natural sciences, Molecular physics, 0104 chemical sciences, General Materials Science, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Hyperpolarization (physics), Physical and Theoretical Chemistry, Dissolution
Abstract

International audience; The efficiency of dissolution dynamic nuclear polarization can be boosted by Hartmann-Hahn cross polarization at temperatures near 1.2 K. This enables high throughput of hyperpolarized solutions with substantial gains in buildup times and polarization levels. During dissolution and transport, the C-13 nuclear spin polarization P(C-13) merely decreases from 45 to 40%.

Published
2015
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