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28 results on '"Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP)"'

1. Identification and Quantification of Glycans in Whole Cells: Architecture of Microalgal Polysaccharides Described by Solid-State Nuclear Magnetic Resonance

Author: Tuo Wang, Artur Muszyński, Alexandre A. Arnold, Malitha C. Dickwella Widanage, Parastoo Azadi, Dror E. Warschawski, Isabelle Marcotte, Alexandre Poulhazan, Université du Québec à Montréal = University of Québec in Montréal (UQAM), Louisiana State University (LSU), University of Georgia [USA], 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), EADS Innovation Works [Toulouse], EADS - European Aeronautic Defense and Space, Département de Chimie [Montréal], 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), and Gestionnaire, HAL Sorbonne Université 5
Subjects: [CHIM.POLY] Chemical Sciences/Polymers, Glycan, glycolipids, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, carbohydrates, Chlorella, 010402 general chemistry, Polysaccharide, 01 natural sciences, Biochemistry, Catalysis, Article, Cell wall, 03 medical and health sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Polysaccharides, Bioproducts, Carbohydrate Conformation, Microalgae, [CHIM]Chemical Sciences, Glycosyl, [SDV.MP] Life Sciences [q-bio]/Microbiology and Parasitology, Nuclear Magnetic Resonance, Biomolecular, 030304 developmental biology, mass spectrometry, chemistry.chemical_classification, 0303 health sciences, biology, Chemistry, starch, General Chemistry, biology.organism_classification, Xylan, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, Solid-state nuclear magnetic resonance, biology.protein, solid-state NMR, cell wall
Abstract: International audience; Microalgae are photosynthetic organisms widely distributed in nature and serve as a sustainable source of bioproducts. Their carbohydrate components are also promising candidates for bioenergy production and bioremediation, but the structural characterization of these heterogeneous polymers in cells remains a formidable problem. Here we present a widely applicable protocol for identifying and quantifying the glycan content using magic-angle-spinning (MAS) solid-state NMR (ssNMR) spectroscopy, with validation from glycosyl linkage and composition analysis deduced from mass-spectrometry (MS). Two-dimensional 13 C− 13 C correlation ssNMR spectra of a uniformly 13 C-labeled green microalga Parachlorella beijerinckii reveal that starch is the most abundant polysaccharide in a naturally cellulose-deficient strain, and this polymer adopts a well-organized and highly rigid structure in the cell. Some xyloses are present in both the mobile and rigid domains of the cell wall, with their chemical shifts partially aligned with the flat-ribbon 2-fold xylan identified in plants. Surprisingly, most other carbohydrates are largely mobile, regardless of their distribution in glycolipids or cell walls. These structural insights correlate with the high digestibility of this cellulose-deficient strain, and the in-cell ssNMR methods will facilitate the investigations of other economically important algae species.
Published: 2021

2. Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Author: Antonella Iadecola, Matthieu Saubanère, Marie-Liesse Doublet, Jean-Marie Tarascon, Jordi Cabana, Haifeng Li, Quentin Jacquet, Gwenaëlle Rousse, Erik J. Berg, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), University of Illinois System, Paul Scherrer Institute (PSI), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Band gap, Chemistry, Cationic polymerization, Salt (chemistry), Charge (physics), General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, Cathode, 0104 chemical sciences, law.invention, Ion, Hysteresis, Colloid and Surface Chemistry, law, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], ComputingMilieux_MISCELLANEOUS
Abstract: Disordered rock salt cathodes showing both anionic and cationic redox are being extensively studied for their very high energy storage capacity. Mn-based disordered rock salt compounds show much higher energy efficiency compared to the Ni-based materials as a result of the different voltage hysteresis, 0.5 and 2 V, respectively. To understand the origin of this difference, we herein report the design of two model compounds, Li
Published: 2019

3. Detection of Metabolite–Protein Interactions in Complex Biological Samples by High-Resolution Relaxometry: Toward Interactomics by NMR

Author: Jean-Max Tyburn, Simone Pisano, Ziqing Wang, Veronica Ghini, Philippe Pelupessy, Morgan Kazmierczak, Giacomo Parigi, Thorsten Marquardsen, Fabien Ferrage, Guillaume Bouvignies, Claudio Luchinat, Pavel Kadeřávek, Milan Zachrdla, 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), Consorzio Interuniversitario Risonanze Magnetiche di Metallo Proteine (CIRMMP), Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence (UniFI)-University of Bologna/Università di Bologna-Partenaires INRAE, Structure et Dynamique des Biomolécules (LBM-E3), 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)-Chimie Moléculaire de Paris Centre (FR 2769), Ecole Polytechnique Fédérale de Lausanne (EPFL), Bruker BioSpin MRI GmbH [Ettlingen, Germany], Università degli Studi di Firenze = University of Florence (UniFI), Gestionnaire, HAL Sorbonne Université 5, 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), 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), Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)-University of Bologna-Partenaires INRAE, 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 Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)
Subjects: Relaxometry, Human blood, Chemistry, Metabolite, High resolution, General Chemistry, Computational biology, 010402 general chemistry, 01 natural sciences, Biochemistry, Small molecule, Catalysis, NMR, 0104 chemical sciences, Protein–protein interaction, chemistry.chemical_compound, Colloid and Surface Chemistry, Metabolomics, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Interactomics, Macromolecule
Abstract: International audience; Metabolomics, the systematic investigation of metabolites in biological fluids, cells or tissues, reveals essential information about metabolism and diseases. Metabolites have functional roles in myriads of biological processes, as substrates and products of enzymatic reactions, but also as cofactors and regulators of large numbers of biochemical mechanisms. These functions involve interactions of metabolites with macromolecules. Yet, methods to systematically investigate these interactions are hitherto still scarce. In particular, there is a need for techniques suited to identify and characterize weak metabolite-macromolecule interactions directly in complex media such as biological fluids. Here, we introduce a method to investigate weak interactions between metabolites and macromolecules in biological fluids. Our approach is based on high-resolution NMR relaxometry and does not require any invasive procedure or separation step. We show that we can detect interactions between small and large molecules in human blood serum and quantify the size of the complex. Our work opens the way for investigations of metabolite-(or other small molecules) protein interactions in biological fluids for interactomics or pharmaceutical applications.
Published: 2021
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4. Electrolyte Reactivity in the Double Layer in Mg Batteries: An Interface Potential-Dependent DFT Study

Author: Jean-Sébastien Filhol, T. Rejec, Robert Dominko, Marie-Liesse Doublet, Jan Bitenc, Anja Kopač Lautar, Laboratory for Materials Electrochemistry, National Institute of Chemistry, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Ljubljana, Jozef Stefan Institute [Ljubljana] (IJS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Double layer (biology), Battery (electricity), Chemical substance, General Chemistry, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, Catalysis, Dimethoxyethane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Chemical engineering, [CHIM]Chemical Sciences, Chemical stability, [CHIM.OTHE]Chemical Sciences/Other, Ethylene carbonate, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The electrochemical degradation of two solvent-based electrolytes for Mg-metal batteries is investigated through a Grand canonical DFT approach. Both electrolytes are highly reactive in the double layer region where the solvated species have no direct contact with the Mg-surface, hence emphasising that surface reactions are not the only phenomena responsible for electrolyte degradation. Applied to dimethoxyethane (DME) and ethylene carbonate (EC), the present methodology shows that both solvents should thermodynamically decompose in the double layer prior to the Mg 2+ /Mg 0 reduction, leading to electrochemically inactive reaction products. Based on thermodynamic considerations, Mg 0 deposition should not be possible, which is not in agreement with experiments, at least for DME-based electrolytes. This apparent contradiction is here addressed through the rationalization of the electrochemical mechanism underlying solvent electro-activation. An extended operation potential window (OPW) is defined, in which the Mg 2+ /Mg 0 reduction can compete with electrolyte decomposition, thus enabling battery operation beyond the solvated species thermodynamic stability. The chemical study of the degradation products is in excellent agreement with experiments and it offer rationale for the Mg-battery failure in EC electrolyte and 2 capacity fade in DME electrolyte. Potential-dependent approach proposed herein is thus able to successfully tackle the challenging problem of interface electrochemistry. Being fully transferable to any other electrochemical systems, this methodology should provide rational guidelines for the development of viable electrolytes for multivalent batteries, and more generally, energy conversion and storage devices.
Published: 2020
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5. Time-Resolved Protein Side-Chain Motions Unraveled by High-Resolution Relaxometry and Molecular Dynamics Simulations

Author: Lei Bruschweiler-Li, Yina Gu, Rafael Brüschweiler, Jean-Max Tyburn, Thorsten Marquardsen, Nicolas Bolik-Coulon, Cyril Charlier, Pavel Kadeřávek, Samuel F. Cousin, Ludovic Carlier, Fabien Ferrage, 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, 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 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)-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), Bruker Biospin GmbH, bruker, Bruker BioSpin [Wissembourg], Department of Chemistry and Biochemistry, and National High Magnetic Field Laboratory, Florida State University [Tallahassee] (FSU), Cousin, Samuel, 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)-Chimie Moléculaire de Paris Centre (FR 2769), 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 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 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: 0301 basic medicine, Relaxometry, 010405 organic chemistry, Chemistry, General Chemistry, Conformational entropy, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Protein–protein interaction, 03 medical and health sciences, Molecular dynamics, 030104 developmental biology, Colloid and Surface Chemistry, Solid-state nuclear magnetic resonance, Chemical physics, [CHIM] Chemical Sciences, Side chain, [CHIM]Chemical Sciences, Molecule, Conformational isomerism, ComputingMilieux_MISCELLANEOUS
Abstract: Motions of proteins are essential for the performance of their functions. Aliphatic protein side chains and their motions play critical roles in protein interactions: for recognition and binding of partner molecules at the surface or serving as an entropy reservoir within the hydrophobic core. Here, we present a new NMR method based on high-resolution relaxometry and high-field relaxation to determine quantitatively both motional amplitudes and time scales of methyl-bearing side chains in the picosecond-to-nanosecond range. We detect a wide variety of motions in isoleucine side chains in the protein ubiquitin. We unambiguously identify slow motions in the low nanosecond range, which, in conjunction with molecular dynamics computer simulations, could be assigned to transitions between rotamers. Our approach provides unmatched detailed insight into the motions of aliphatic side chains in proteins and provides a better understanding of the nature and functional role of protein side-chain motions.
Published: 2018

6. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

Author: Marie-Liesse Doublet, Moulay Tahar Sougrati, Artem M. Abakumov, Matthieu Courty, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Meiling Sun, Jean-Marie Tarascon, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Pierre et Marie Curie - Paris 6 (UPMC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), RS2E, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Electrode material, Chemistry, Inorganic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Octahedron, Phase (matter), Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract: International audience; High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion–deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.
Published: 2014

7. Elucidation of the Na2/3FePO4 and Li2/3FePO4 Intermediate Superstructure Revealing a Pseudouniform Ordering in 2D

Author: Philippe Moreau, Dominique Guyomard, Marine Cuisinier, Florent Boucher, Joël Gaubicher, Institut des Matériaux Jean Rouxel (IMN), 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)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), university hospital, University Hospital, Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Chemistry, Intercalation (chemistry), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Metastability, Vacancy defect, Mössbauer spectroscopy, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Supercell (crystal), 0210 nano-technology, Superstructure (condensed matter), ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system, Electrochemical potential
Abstract: Based on TEM, synchrotron X-ray diffraction, DFT calculations, and Mossbauer spectroscopy, a unified understanding of the Na and Li intercalation process in FePO4 is proposed. The key to this lies in solving the highly sought-after intermediate A(2/3)FePO4 (A = Na, Li) superstructures that are characterized by alkali ions as well as Fe(II)/Fe(III) charge orderings in a monoclinic three-fold supercell. Formation energies and electrochemical potential calculations confirm that Na(2/3)FePO4 and Li(2/3)FePO4 are stable and metastable, respectively, and that they yield insertion potentials in fair agreement with experimental values. The 2/3 Na(Li) and 1/3 vacancy sublattice of the intermediate phases forms a dense (101)(Pnma) plane in which the atom/vacancy ordering is very similar to that predicted for the most uniform distribution of 1/3 of vacancies in a 2D square lattice. Structural analysis strongly suggests that the key role of this dense plane is to constrain the intercalation in the diffusion channels to operate by cooperative filling of (bc)(Pnma). From a practical point of view, this generalized mechanism highlights the fact that an interesting strategy for obtaining high-rate FePO4 materials would consist in designing grains with an enhanced (101) surface area, thereby offering potential for substantial improvements with respect to the performance of rechargeable Li and Na batteries.
Published: 2014

8. 87Sr Solid-State NMR as a Structurally Sensitive Tool for the Investigation of Materials: Antiosteoporotic Pharmaceuticals and Bioactive Glasses

Author: Mark E. Smith, Jincheng Du, Ye Xiang, Frédérique Pourpoint, Edouard Jallot, Christian Bonhomme, Jonathan Lao, Nicolas Folliet, Dinu Iuga, Danielle Laurencin, Jean-Marie Nedelec, John V. Hanna, Cristina Coelho Diogo, Christel Gervais, Joséphine Lacroix, Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), Institut des matériaux de Paris-Centre (IMPC), 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)-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), Laboratoire de Physique Corpusculaire - Clermont-Ferrand (LPC), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Physics, University of Warwick [Coventry], Solid State NMR Group, University of Warwick, Department of Materials Science and Engineering (Dallas, USA), University of Texas at Dallas [Richardson] (UT Dallas), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), US NSF DMR Biomaterials program award no. 0907593. Montpellier-Warwick partnership grant (JP090313, Institut de Chimie du CNRS (INC)-SIGMA Clermont (SIGMA Clermont)-Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, inorganic chemicals, Magnetic Resonance Spectroscopy, chemistry.chemical_element, Biocompatible Materials, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Strontium Isotopes, Colloid and Surface Chemistry, Tissue engineering, Organic chemistry, Bone growth, Strontium, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Malonates, 0104 chemical sciences, Pharmaceutical Preparations, Solid-state nuclear magnetic resonance, Local environment, Glass, 0210 nano-technology, Strontium malonate
Abstract: International audience; Strontium is an element of fundamental importance in biomedical science. Indeed, it has been demonstrated that Sr(2+) ions can promote bone growth and inhibit bone resorption. Thus, the oral administration of Sr-containing medications has been used clinically to prevent osteoporosis, and Sr-containing biomaterials have been developed for implant and tissue engineering applications. The bioavailability of strontium metal cations in the body and their kinetics of release from materials will depend on their local environment. It is thus crucial to be able to characterize, in detail, strontium environments in disordered phases such as bioactive glasses, to understand their structure and rationalize their properties. In this paper, we demonstrate that (87)Sr NMR spectroscopy can serve as a valuable tool of investigation. First, the implementation of high-sensitivity (87)Sr solid-state NMR experiments is presented using (87)Sr-labeled strontium malonate (with DFS (double field sweep), QCPMG (quadrupolar Carr-Purcell-Meiboom-Gill), and WURST (wideband, uniform rate, and smooth truncation) excitation). Then, it is shown that GIPAW DFT (gauge including projector augmented wave density functional theory) calculations can accurately compute (87)Sr NMR parameters. Last and most importantly, (87)Sr NMR is used for the study of a (Ca,Sr)-silicate bioactive glass of limited Sr content (only 9 wt %). The spectrum is interpreted using structural models of the glass, which are generated through molecular dynamics (MD) simulations and relaxed by DFT, before performing GIPAW calculations of (87)Sr NMR parameters. Finally, changes in the (87)Sr NMR spectrum after immersion of the glass in simulated body fluid (SBF) are reported and discussed.
Published: 2012

9. α-Na3M2(PO4)3 (M = Ti, Fe): Absolute Cationic Ordering in NASICON-Type Phases

Author: Marie Colmont, Houria Kabbour, Christian Masquelier, Daniel Coillot, Olivier Mentré, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Diffusion, Cationic polymerization, Crystallographic data, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, Type (model theory), 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Zigzag, Homogeneous, Vacancy defect, [CHIM.CRIS]Chemical Sciences/Cristallography, Fast ion conductor, 0210 nano-technology
Abstract: International audience; The structure of the fully ordered R-Na3Ti2(PO4)3 NASICON compound was elucidated using highquality single-crystal data. The cation/vacancy distribution forms a homogeneous 3D arrangement and could represent the absolute cationic ordering available in the full Na3M2(PO4)3 series, as verified for M = Fe. For M = Ti, the reversible Rfγ transition was observed at 85 C, leading to the standard disordered R3c γ model. Through JPDF analysis, the most probable Na+ zigzag M(2) M(1) diffusion scheme was directly deduced using our accurate crystallographic data.
Published: 2011

10. Controlling Electron Trap Depth To Enhance Optical Properties of Persistent Luminescence Nanoparticles for In Vivo Imaging

Author: Michel Bessodes, Daniel Scherman, Thomas Maldiney, Aurélie Lecointre, Bruno Viana, Aurélie Bessière, Didier Gourier, Cyrille Richard, Laboratoire Charles Friedel, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), Laboratoire de Chimie de la Matière Condensée de Paris (site ENSCP) (LCMCP (site ENSCP)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Unité de pharmacologie chimique et génétique et d'imagerie (UPCGI - UMR 8151 / UMR_S 1022 ), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie Appliquée de l'État Solide (LCAES), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Unité de Pharmacologie Chimique et Génétique (UPCG - UMR_S 640/UMR 8151), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut des sciences du Médicament -Toxicologie - Chimie - Environnement (IFR71), Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Université Paris Descartes - Paris 5 (UPD5)-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)-Université Paris Descartes - Paris 5 (UPD5)-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 Recherche pour le Développement (IRD)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Institut des sciences du Médicament -Toxicologie - Chimie - Environnement (IFR71), and Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, Luminescence, Optical Phenomena, Analytical chemistry, Nanoparticle, Electrons, 02 engineering and technology, 010402 general chemistry, Lanthanoid Series Elements, 01 natural sciences, Biochemistry, Catalysis, Mice, Colloid and Surface Chemistry, Persistent luminescence, Animals, [CHIM]Chemical Sciences, Irradiation, ComputingMilieux_MISCELLANEOUS, Chemistry, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Penning trap, Molecular Imaging, 0104 chemical sciences, Afterglow, Nanoparticles, 0210 nano-technology
Abstract: Focusing on the use of nanophosphors for in vivo imaging and diagnosis applications, we used thermally stimulated luminescence (TSL) measurements to study the influence of trivalent lanthanide Ln(3+) (Ln = Dy, Pr, Ce, Nd) electron traps on the optical properties of Mn(2+)-doped diopside-based persistent luminescence nanoparticles. This work reveals that Pr(3+) is the most suitable Ln(3+) electron trap in the diopside lattice, providing optimal trap depth for room temperature afterglow and resulting in the most intense luminescence decay curve after X-ray irradiation. This luminescence dependency toward the electron trap is maintained through additional doping with Eu(2+), allowing UV-light excitation, critical for bioimaging applications in living animals. We finally identify a novel composition (CaMgSi(2)O(6):Eu(2+),Mn(2+),Pr(3+)) for in vivo imaging, displaying a strong near-infrared afterglow centered on 685 nm, and present evidence that intravenous injection of such persistent luminescence nanoparticles in mice allows not only improved but highly sensitive detection through living tissues.
Published: 2011

11. Designing Multifunctional Expanded Pyridiniums: Properties of Branched and Fused Head-to-Tail Bipyridiniums

Author: Philippe P. Lainé, Jérôme Fortage, Francesco Nastasi, Fausto Puntoriero, Sebastiano Campagna, Cyril Peltier, Ilaria Ciofini, Sophie Griveau, Fabien Tuyèras, Fethi Bedioui, Carlo Adamo, PSL Research University (PSL), Unité de pharmacologie chimique et génétique et d'imagerie (UPCGI - UMR 8151 / UMR_S 1022 ), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP), Department of Chemical Sciences, messina, Université Paris sciences et lettres (PSL), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), and Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP)
Subjects: Biphenyl, 010405 organic chemistry, Chemistry, Stereochemistry, Aryl, General Chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Pyridinium, ComputingMilieux_MISCELLANEOUS
Abstract: The multifaceted potentialities of expanded pyridiniums (EPs), based on one pyridinium core bearing a 4-pyridyl or 4-pyridylium as the N-pyridinio group, are established at both experimental and theoretical levels. Two classes of head-to-tail (htt) EPs were designed, and their first representative elements were synthesized and fully characterized. The branched (B) family is made up of 2,6-diphenyl-4-aryl-1,4'-bipyridin-1-ium (or 1,1'-diium) species, denoted 1B and 2B for monocationic EPs (with aryl = phenyl and biphenyl, respectively) and 1B(Me) and 2B(Me) for related quaternarized dicationic species. The series of fused (F) analogues comprises 9-aryl-benzo[c]benzo[1,2]quinolizino[3,4,5,6-ija][1,6]naphthyridin-15-ium species, denoted 1F and 2F, and their 2,15-diium derivatives referred to as 1F(Me) and 2F(Me). Electrochemistry (in MeCN vs SCE) reveals that branched EPs undergo a single reversible bielectronic reduction at ca. -0.92 V for 1B/2B and -0.59 V for 1B(Me)/2B(Me), whereas pericondensed species show two reversible monoelectronic reductions at ca. -0.83 and -1.59 V for 1F/2F and ca. -0.42 and -1.07 V for 1F(Me)/2F(Me). Regarding electronic absorption features, all htt-EP chromophores show absorptivity in the range of ca. 1-4 × 10(4) M(-1) cm(-1), with red-edge absorptions extending toward 450 and 500 nm (in MeCN) for 2B(Me) and 2F(Me), respectively. These lowest-energy pi-pi* transitions are ascribed to intramolecular charge transfer between the electron-releasing biphenyl group and the htt-bipyridinium electron-withdrawing subsystems. EPs display room-temperature photoemission quantum yields ranging from 10% to 50%, with the exception of 1B, and branched luminophores are characterized by larger Stokes shifts (8000-10 000 cm(-1)) than fused ones. Lastly, a method to predict the efficiency of photobiscyclization of branched EPs into fused ones, based on the analysis of computed difference maps in total electron density for singlet excited states, is proposed.
Published: 2010

12. Both Water- and Organo-Soluble Supramolecular Polymer Stabilized by Hydrogen-Bonding and Hydrophobic Interactions

Author: Catherine Lehen-Ferrenbach, Mathilde Bellot, Florence Andrioletti, François Boué, Edouard Obert, Laurent Bouteiller, Chimie des polymères (LCP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Parisien de Chimie Moléculaire (IPCM), 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)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Division of Cognis, LLB - Matière molle et biophysique (MMB), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), 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)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay
Subjects: Calorimetry, Neutron scattering, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Hydrophobic effect, chemistry.chemical_compound, Colloid and Surface Chemistry, [CHIM]Chemical Sciences, Physics::Chemical Physics, chemistry.chemical_classification, Physics::Biological Physics, Quantitative Biology::Biomolecules, 010405 organic chemistry, Hydrogen bond, General Chemistry, Toluene, 0104 chemical sciences, Condensed Matter::Soft Condensed Matter, Supramolecular polymers, Solvent, Crystallography, Monomer, chemistry, Chemical engineering
Abstract: International audience; A new bis-urea based supramolecular polymer is reported and shown by viscosimetry, neutron scattering (SANS) and calorimetry (ITC) to self-assemble in a wide range of solvents, encompassing the polarity scale from water to toluene. The presence of both hydrogen bonding and hydrophobic groups ensures that self-assembly occurs in water, aprotic polar solvents or non-polar solvents. Both the driving force for the assembly and the exact structure of the filaments is solvent dependent, but whatever the solvent, long rigid filaments are formed in dynamic equilibrium with the monomer
Published: 2007

13. Unraveling the Capacitive Charge Storage Mechanism of Nitrogen-Doped Porous Carbons by EQCM and ssNMR

Author: En Zhang, Yih-Chyng Wu, Hui Shao, Vytautas Klimavicius, Hanyue Zhang, Pierre-Louis Taberna, Julia Grothe, Gerd Buntkowsky, Fei Xu, Patrice Simon, Stefan Kaskel, Publica, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Vilnius University [Vilnius], Technische Universität Darmstadt - Technical University of Darmstadt (TU Darmstadt), Fraunhofer Institute Material and Beam Technology [Dresden] (Fraunhofer IWS), Fraunhofer (Fraunhofer-Gesellschaft), and German Science Foundation (Deutsche Forschungsgemeinschaft, grants no. KA 1698/27-1)
Subjects: Ions, X-ray photoelectron spectroscopy, Magnetic Resonance Spectroscopy, Nitrogen, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Lithium, Biochemistry, Catalysis, Carbon, Colloid and Surface Chemistry, Cations, Electrical properties, Quartz Crystal Microbalance Techniques, [CHIM.OTHE]Chemical Sciences/Other, Electrodes, Porosity, Nuclear magnetic resonance spectroscopy
Abstract: International audience; Fundamental understanding of ion electroadsorption processes in porous electrodes on a molecular level provides important guidelines for next-generation energy storage devices like electric double layer capacitors (EDLCs). Porous carbons functionalized by heteroatoms show enhanced capacitive performance, but the underlying mechanism is still elusive, due to the lack of reliable tools to precisely identify multiple N species and establish clear structure property relations. Here, we use advanced analytical techniques such as lowtemperature solid-state NMR (ssNMR) and electrochemical quartz crystal microbalance (EQCM) to relate the complex nitrogen functionalities to the charging mechanisms and capacitive performance. For the first time, it is demonstrated at a molecular level that N-doping strongly influences the electroadsorption mechanism in EDLCs. Without N-doping, anion (SO 4 2−) adsorption−desorption dominates the charging mechanism, whereas after doping, Li + electroadsorption plays a key role. With the help of EQCM, it is demonstrated that SO 4 2− is strongly immobilized on the Ndoped surface, leaving Li + as the main charge carrier. The smaller size and higher concentration of Li + compared to SO 4 2− benefit a higher capacitance. Amine/amide N is responsible for high capacitance, but surprisingly the pyridinic, pyrrolic, and graphitic N groups have no significant influence. 2D 1 H-15 N NMR spectroscopy indicates that the conversion from pyridinium to pyrrolic N gives rise to a slightly decreased capacitance. This work not only demonstrates ssNMR as a powerful tool for surface chemistry characterization of electrode materials but also uncovers the related charging mechanism by EQCM, paving the way toward a comprehensive picture of EDLC chemistry.
Published: 2022

14. Structure of the human telomere in K+ solution: a stable basket-type G-quadruplex with only two G-tetrad layers

Author: Lim, Kah Wai, Amrane, Samir, Bouaziz, Serge, Xu, Weixin, Mu, Yuguang, Patel, Dinshaw, Luu, Kim Ngoc, Phan, Anh Tuan, Phan, Anh Tuân, School of Physical and Mathematical Sciences, Nanyang Technological University [Singapour], Régulations Naturelles et Artificielles (ARNA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Bordeaux Ségalen [Bordeaux 2], Unité de Pharmacologie Chimique et Génétique (UPCG - UMR_S 640/UMR 8151), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Descartes - Paris 5 (UPD5)-Institut des sciences du Médicament -Toxicologie - Chimie - Environnement (IFR71), Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC), Department of Atmospheric Science [Fort Collins], Colorado State University [Fort Collins] (CSU), School of Biological sciences, Modélisation, Intelligence, Processus et Système (MIPS), Ecole Nationale Supérieure d'Ingénieur Sud Alsace-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-IUT de Colmar-IUT de Mulhouse, Bouaziz, Serge, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut des sciences du Médicament -Toxicologie - Chimie - Environnement (IFR71), Institut de Recherche pour le Développement (IRD)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))
Subjects: Models, Molecular, Guanine, Magnetic Resonance Spectroscopy, [SDV.BBM.BS] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Stereochemistry, Molecular Conformation, 010402 general chemistry, Antiparallel (biochemistry), G-quadruplex, 01 natural sciences, Biochemistry, Catalysis, Article, MESH: Circular Dichroism, 03 medical and health sciences, Colloid and Surface Chemistry, MESH: Spectrophotometry, Ultraviolet, Humans, Tetrad, 030304 developmental biology, chemistry.chemical_classification, MESH: Guanine, 0303 health sciences, MESH: Molecular Conformation, MESH: Humans, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], MESH: Magnetic Resonance Spectroscopy, Circular Dichroism, MESH: DNA, Temperature, Glycosidic bond, General Chemistry, DNA, Telomere, MESH: Temperature, 0104 chemical sciences, G-Quadruplexes, MESH: Nucleic Acid Conformation, chemistry, Telomeric dna, Intramolecular force, MESH: Potassium, Potassium, Nucleic Acid Conformation, Spectrophotometry, Ultraviolet, MESH: Telomere, MESH: Models, Molecular, MESH: G-Quadruplexes
Abstract: International audience; Previously, it has been reported that human telomeric DNA sequences could adopt in different experimental conditions four different intramolecular G-quadruplexes each involving three G-tetrad layers, namely, Na(+) solution antiparallel-stranded basket form, K(+) crystal parallel-stranded propeller form, K(+) solution (3 + 1) Form 1, and K(+) solution (3 + 1) Form 2. Here we present a new intramolecular G-quadruplex adopted by a four-repeat human telomeric sequence in K(+) solution (Form 3). This structure is a basket-type G-quadruplex with only two G-tetrad layers: loops are successively edgewise, diagonal, and edgewise; glycosidic conformations of guanines are syn x syn x anti x anti around each tetrad. Each strand of the core has both a parallel and an antiparallel adjacent strands; there are one narrow, one wide, and two medium grooves. Despite the presence of only two G-tetrads in the core, this structure is more stable than the three-G-tetrad intramolecular G-quadruplexes previously observed for human telomeric sequences in K(+) solution. Detailed structural elucidation of Form 3 revealed extensive base pairing and stacking in the loops capping both ends of the G-tetrad core, which might explain the high stability of the structure. This novel structure highlights the conformational heterogeneity of human telomeric DNA. It establishes a new folding principle for G-quadruplexes and suggests new loop sequences and structures for targeting in human telomeric DNA.
Published: 2009

15. Transient Catenation in a Zirconium-Based Metal–Organic Framework and Its Effect on Mechanical Stability and Sorption Properties

Author: Omar K. Farha, Xingjie Wang, Xinyi Gong, Austin M. Evans, Nathan C. Gianneschi, Florencia A. Son, Megan C. Wasson, Karam B. Idrees, François-Xavier Coudert, Timur Islamoglu, Massimiliano Delferro, Zhijie Chen, William R. Dichtel, Louis R. Redfern, Lee Robison, Zoha H. Syed, Northwestern University [Evanston], Argonne National Laboratory [Lemont] (ANL), Institut de Recherche de Chimie Paris (IRCP), 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 Paris sciences et lettres (PSL)-Ministère de la Culture (MC)
Subjects: Diffraction, Zirconium, chemistry.chemical_element, Sorption, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Porosimetry, mechanical properties, Nanoindentation, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, catenation, 0104 chemical sciences, Catenation, Colloid and Surface Chemistry, chemistry, Chemical engineering, transmission electron microscopy, Metal-organic framework, Density functional theory, metal-organic frameworks
Abstract: International audience; Interpenetration of two or more sublattices is common among many metal–organic frameworks (MOFs). Herein, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.
Published: 2021

16. Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

Author: O. Ulas Kudu, Wolfgang G. Zeier, Olaf J. Borkiewicz, Emmanuelle Suard, M. Saiful Islam, Christian Masquelier, Steffen P. Emge, Pieremanuele Canepa, Houssny Bouyanfif, James A. Dawson, Mohamed Zbiri, Theodosios Famprikis, François Fauth, Clare P. Grey, Damien Dambournet, Jean-Noël Chotard, Sorina Cretu, University of Cambridge [UK] (CAM), Physikalisch-Chemisches Institut, Justus-Liebig-Universität Gießen = Justus Liebig University (JLU), University of Bath [Bath], Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Delft University of Technology (TU Delft), National University of Singapore (NUS), CELLS ALBA, Barcelona 08290, Spain, Institut Laue-Langevin (ILL), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), X-ray Science Division (XSD), Laboratoire de Physique de la Matière Condensée - UR UPJV 2081 (LPMC), and Université de Picardie Jules Verne (UPJV)
Subjects: Materials science, Chemistry(all), Ab initio, Thermodynamics, Electrolyte, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Ion, Tetragonal crystal system, symbols.namesake, Colloid and Surface Chemistry, Fast ion conductor, Ionic conductivity, Ceramic, Chemistry, Pair distribution function, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 0104 chemical sciences, Dielectric spectroscopy, visual_art, visual_art.visual_art_medium, symbols, Raman spectroscopy
Abstract: Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and ab-initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations about the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ~30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ~10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain and activation volume.
Published: 2020

17. Emergence of Homochiral Benzene-1,3,5-tricarboxamide Helical Assemblies and Catalysts upon Addition of an Achiral Monomer

Author: Laurent Bouteiller, Yan Li, Ahmad Hammoud, Matthieu Raynal, Département d'Informatique [Bruxelles] (ULB), Faculté des Sciences [Bruxelles] (ULB), Université libre de Bruxelles (ULB)-Université libre de Bruxelles (ULB), Institut Parisien de Chimie Moléculaire (IPCM), 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)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Génie des Procédés Catalytiques (LGPC), École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Thomson-CSF Laboratoire Central de Recherches (THOMSON-CSF LCR), Thomson, Chimie des polymères (LCP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Parisien de Chimie Moléculaire (IPCM), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: inorganic chemicals, Chemistry, Comonomer, Supramolecular chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, Enantiopure drug, Helix, [CHIM]Chemical Sciences, Racemic mixture, Homochirality, Enantiomeric excess, Chirality (chemistry)
Abstract: International audience; Chirality amplification refers to the ability of a small chiral bias to fully control the main chain helicity of polymers and assemblies. Further implementation of functional chirally-amplified helices as switchable asymmetric catalysts, chiral sensors and circularly-polarized light emitters will require a greater control of the energetics governing these chirality amplification effects. In this work, we report on the counterintuitive ability of an achiral molecule to suppress conformational defects in supramolecular helices thus leading to the emergence of homochirality in a system containing a very small chiral bias. We focus our investigation on supramolecular helices composed of an achiral benzene-1,3,5-tri-carboxamide (BTA) ligand, coordinated to copper, and an enanti-opure BTA co-monomer. Amplification of chirality as probed by varying the amount (sergeants-and-soldiers effect) or the optical purity (diluted majority-rules effect) of the enantiopure co-mono-mer, are modest in this initial system. However, both effects are hugely enhanced upon addition of a second achiral BTA monomer leading to a perfect control of the helicity either by means of a remarkably low amount of sergeants (0.5%) or a small bias from a racemic mixture of enantiopure co-monomers (10% e.e.). Such an enhancement in the amplification of chirality is only achieved by mixing the three components, i.e. the two achiral and the enanti-opure co-monomers, highlighting a synergistic effect upon co-assembly of the three monomers. Investigation of the role of the achiral additive by multifarious analytical techniques supports its ability to stabilize the helical co-assemblies and suppress helix reversals i.e. conformational defects. Implementation of these heli-cal copper precatalysts in the hydrosilylation of 1-(4-nitro-phenyl)ethanone confirms that the effect of the achiral BTA additive is also operative under the conditions of the catalytic experiment. A highly enantioenriched product (90% e.e.) is produced by a supramolecular catalyst operating with ppm levels of chiral species .
Published: 2020

18. Electron Storage System Based on a Two-Way Inversion of Redox Potentials

Author: Ilaria Ciofini, Fabien Tuyèras, Magdaléna Hromadová, Štěpánka Nováková Lachmanová, Philippe P. Lainé, Christian Perruchot, Henri-Pierre Jacquot de Rouville, Philippe Ochsenbein, Grégory Dupeyre, Lubomír Pospíšil, Alexis Gosset, Hyacinthe Randriamahazaka, Romana Sokolová, Liam Wilbraham, Université de Paris, Laboratoire ITODYS, CNRS, F-75006 Paris, Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), J. Heyrovský Institute of Physical Chemistry of the ASCR, Czech Academy of Sciences [Prague] (CAS), Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sanofi-Aventis R&D, SANOFI Recherche, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Electronique et intelligence artificielle (UR ELAN), and Centre national du machinisme agricole, du génie rural, des eaux et forêts (CEMAGREF)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, General Chemistry, Electron, 010402 general chemistry, 01 natural sciences, Biochemistry, Inversion (discrete mathematics), Redox, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Solar energy harvesting, Electron storage, Colloid and Surface Chemistry, Chemical bond, Chemical physics, ComputerApplications_MISCELLANEOUS, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of "structronics" (a neologism derived from "structure" and "electronics"). Through this concept, we establish, synthesize, and thoroughly study two multicomponent "super-electrophores": 1,8-dipyridyliumnaphtha-lene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this "super-LUMO" serves as an empty reservoir, which can be filled by a two-electron reduction, giving rise to an elongated C−C bond or "super-HOMO". Because of its weakened nature, this bond can undergo an electrochemically driven cleavage at a significantly more anodicyet accessiblepotential, thereby restoring the availability of the electron pair (reservoir emptying). In the representative case study of 2, an inversion of potential in both of the two-electron processes of bond formation and bond-cleavage is demonstrated. Overall, the structronic function is characterized by an electrochemical hysteresis and a chemical reversibility. This structronic superelectrophore can be viewed as the three-dimensional counterpart of benchmark methyl viologen (MV).
Published: 2020

19. Photodecaging of a Mitochondria-Localized Iridium(III) Endoperoxide Complex for Two-Photon Photoactivated Therapy under Hypoxia

Author: Kuang, Shi, Wei, Fangmian, Karges, Johannes, Ke, Libing, Xiong, Kai, Liao, Xinxing, Gas- Ser, Gilles, Ji, Liangnian, Chao, Hui, Gasser, Gilles, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), ERC, and European Project: 681679, H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),681679,PhotoMedMet(2017)
Subjects: Photosensitizing Agents, Singlet Oxygen, Medicinal Inorganic Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, Iridium, Biochemistry, Catalysis, Mitochondria, Photoactivated Chemotherapy, Mice, Colloid and Surface Chemistry, Photochemotherapy, Cell Line, Tumor, Neoplasms, Photodynamic Therapy, Animals, Prodrugs, Hypoxia, Bioinorganic Chemistry
Abstract: International audience; Despite the clinical success of photodynamic therapy (PDT), the application of this medical technique is intrinsically limited by the low oxygen concentrations found in cancer tumors which are hampering the production of the therapeutically necessary singlet oxygen (1 O2). To overcome this limitation, we report on a novel mitochondria-localized iridium(III) endoperoxide prodrug (2-O-IrAn), which, upon two-photon irradiation in the NIR, synergistically releases a highly cytotoxic iridium(III) complex (2-IrAn), singlet oxygen and an alkoxy radical. 2-O-IrAn was found to be highly (photo-)toxic in hypoxic tumor cells and multicellular tumor spheroids in the nanomolar range. To provide cancer selectivity and improve the pharmacological properties of 2-O-IrAn, it was encapsulated with a biotin functionalized polymer. The generated nanoparticles were found to nearly fully eradicate the tumor inside a mouse model within a single treatment. This study presents, to the best of our knowledge, the first example of an iridium(III)-based endoperoxide prodrug for synergistic photodynamic therapy/photoactivated chemotherapy, opening up new avenues for the treatment of hypoxic tumors.
Published: 2022

20. Arene-Bridged Dithorium Complexes: Inverse Sandwiches Supported by a δ Bonding Interaction

Author: Paula L. Diaconescu, Guillaume Lefèvre, Chao Yu, Chong Deng, Wenliang Huang, Thibault Cantat, Jiefeng Liang, Beijing National Laboratory for Molecular Sciences (BNLMS), Beihang University (BUAA), Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), 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), Department of Chemistry and Biochemistry [Los Angeles], University of California [Los Angeles] (UCLA), University of California (UC)-University of California (UC), NSF Grant CHE-1809116, Beijing National Laboratory for Molecular Sciences Postdoctoral Fellowship, 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-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and University of California-University of California
Subjects: Biphenyl, Anthracene, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Toluene, Catalysis, 0104 chemical sciences, Cyclooctatetraene, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, chemistry, Azobenzene, Covalent bond, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Density functional theory, Benzene
Abstract: International audience; A series of arene-bridged dithorium complexes was synthesized via the reduction by potassium graphite of a Th(IV) precursor in the presence of arenes. All these compounds adopt an inverse-sandwich structure, with the arene bridging two thorium centers in a μ-η6,η6-mode. Structural and spectroscopic data support the assignment of two Th(IV) ions and an arene tetraanion, which is an aromatic structure according to Hückel’s rule. Arene exchange reactions revealed that the stability of the corresponding compounds follows the series naphthalene ≪ toluene < benzene ≈ biphenyl. Reactivity studies showed that they function as four-electron reductants capable to reduce anthracene, cyclooctatetraene, alkynes, and azobenzene, while a mononuclear thorium anthracene complex could reduce benzene. Density functional theory calculations unveiled that the bonding interactions consist of δ bonds between thorium 6d and 5f orbitals and arene π* orbitals, showing a significant covalent character, able to stabilize highly reduced arene ligands.
Published: 2020

21. Structure and Dynamics of an Intrinsically Disordered Protein Region That Partially Folds upon Binding by Chemical-Exchange NMR

Author: Aneel K. Aggarwal, Nicolas Bolik-Coulon, Fabien Ferrage, Ludovic Carlier, Philippe Pelupessy, Guillaume Bouvignies, Cyril Charlier, Sandrine Sagan, Rodrigue Marquant, Mikhail Kozlov, Astrid Walrant, Pablo De Ioannes, Patricia Cortes, 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), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), 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, 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)-Chimie Moléculaire de Paris Centre (FR 2769), 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), Peptides, glycoconjugués et métaux en biologie (LBM-E1), Icahn School of Medicine at Mount Sinai [New York] (MSSM), 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), and HAL-UPMC, Gestionnaire
Subjects: 0301 basic medicine, Protein Folding, Protein Conformation, [SDV.BBM.BS] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Plasma protein binding, Crystallography, X-Ray, 010402 general chemistry, Intrinsically disordered proteins, 01 natural sciences, Biochemistry, Catalysis, DNA Ligase ATP, 03 medical and health sciences, Colloid and Surface Chemistry, Protein structure, Bound state, Nuclear Magnetic Resonance, Biomolecular, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Chemistry, Chemical shift, Relaxation (NMR), General Chemistry, 0104 chemical sciences, Intrinsically Disordered Proteins, Molecular Docking Simulation, Folding (chemistry), Crystallography, 030104 developmental biology, Protein folding, Protein Binding
Abstract: International audience; Many intrinsically disordered proteins (IDPs) and protein regions (IDRs) engage in transient, yet specific, interactions with a variety of protein partners. Often, if not always, interactions with a protein partner lead to partial folding of the IDR. Characterizing the conformational space of such complexes is challenging: in solution-‐state NMR, signals of the IDR in the interacting region become broad, weak and often invisible; while X-‐ray crystallography only provides information on fully ordered regions. There is thus a need for a simple method to characterize both fully and partially ordered regions in the bound state of IDPs. Here, we introduce an approach based on monitoring chemical ex-‐ change by NMR to investigate the state of an IDR that folds upon binding through the observation of the free state of the protein. Structural constraints for the bound state are obtained from chemical shifts and site-‐specific dynamics of the bound state are characterized by relaxation rates. The conformation of the interacting part of the IDR was determined and subsequently docked onto the structure of the folded partner. We apply the method to investigate the interaction between the disordered C-‐terminal region of Artemis and the DNA binding domain of Ligase IV. We show that we can accurately reproduce the structure of the core of the complex determined by X-‐ray crystallography and identify a broader interface. The method is widely applicable to the biophysical investigation of complexes of disordered proteins and folded proteins.
Published: 2017

22. Insulator-to-Proton-Conductor Transition in a Dense Metal–Organic Framework

Author: Anthony K. Cheetham, François-Xavier Coudert, Satoshi Tominaka, Thang Duy Dao, Tadaaki Nagao, University of Cambridge [UK] (CAM), International Center for Materials Nanoarchitectonics, National Institute for Materials Science (NIMS), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and 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)-Ministère de la Culture (MC)
Subjects: Phase transition, Chemistry, Pair distribution function, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Activation energy, Crystal structure, Conductivity, Biochemistry, Catalysis, Crystallography, Colloid and Surface Chemistry, Molecule, Metal-organic framework, Proton conductor
Abstract: International audience; Metal–organic frameworks (MOFs) are prone to exhibit phase transitions under stimuli such as changes in pressure, temperature, or gas sorption because of their flexible and responsive structures. Here we report that a dense MOF, ((CH3)2NH2)2[Li2Zr(C2O4)4], exhibits an abrupt increase in proton conductivity from < 10^{–9} to 3.9 × 10^{–5} S/cm at 17 °C (activation energy, 0.64 eV) upon exposure to humidity. The conductivities were determined using single crystals, and the structures were analyzed by X-ray diffraction and X-ray pair distribution function analysis. The initial anhydrous structure transforms to another dense structure via topotactic hydration (H2O / Zr = 0.5), wherein one-fourth of the Li ions are irreversibly rearranged and coordinated by water molecules. This structure further transforms into a third crystalline structure by water uptake (H2O / Zr = 4.0). The abrupt increase in conductivity is reversible and is associated with the latter reversible structure transformation. The H2O molecules coordinated to Li ions, which are formed in the first step of the transformation, are considered to be the proton source, and the absorbed water molecules, which are formed in the second step, are considered to be proton carriers.
Published: 2015

23. Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization

Author: Aron Walsh, Davide Tiana, Christopher H. Hendon, Laurence Rozes, Marc Fontecave, Loïc D'Arras, Clément Sanchez, Caroline Mellot-Draznieks, Capucine Sassoye, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chaire Chimie des processus biologiques, Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chaire Chimie des matériaux hybrides, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), Royal Society University Research Fellowship, ERC Starting Grant, EPSRC [EP/F067496], Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Collège de France - Chaire Chimie des processus biologiques
Subjects: Models, Molecular, Optical Phenomena, Chemistry, Multidisciplinary, Molecular Conformation, Band-gaps, 02 engineering and technology, Ligands, 01 natural sciences, Biochemistry, Engineering, Colloid and Surface Chemistry, General chemistry, Titanium, Chemistry, Photocatalyst, SUBSTITUTION, Optical Processes, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, CO2 capture, Physical Sciences, SEPARATION, Metal-organic framework, 03 Chemical Sciences, 0210 nano-technology, Amino, BAND-GAPS, Stereochemistry, Band gap, PHOTOCATALYST, Phthalic Acids, Electronic structure, 010402 general chemistry, MOFS, Catalysis, Separation, AMINO, Organometallic Compounds, CO2 CAPTURE, Reduction, Group 2 organometallic chemistry, TUNABILITY, Science & Technology, Ligand, Tunability, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, REDUCTION, Surface modification, Substitution, Linker
Abstract: International audience; Herein we discuss band gap modification of MIL-125, a TiO2/1,4-benzenedicarboxylate (bdc) metal-organic framework (MOF). Through a combination of synthesis and computation, we elucidated the electronic structure of MIL-125 with aminated linkers. The band gap decrease observed when the monoaminated bdc-NH2 linker was used arises from donation of the N 2p electrons to the aromatic linking unit, resulting in a red-shifted band above the valence-band edge of MIL-125. We further explored in silico MIL-125 with the diaminated linker bdc(NH2)(2) and other functional groups (-OH, -CH3, -Cl) as alternative substitutions to control the optical response. The bdc-(NH2)2 linking unit was predicted to lower the band gap of MIL-125 to 1.28 eV, and this was confirmed through the targeted synthesis of the bdc-(NH2)(2)-based MIL,-125. This study illustrates the possibility of tuning the optical response of MOFs through rational functionalization of the linking unit, and the strength of combined synthetic/computational approaches for targeting functionalized hybrid materials.
Published: 2013

24. Microscopic Mechanism of Chiral Induction in a Metal-Organic Framework

Author: Jack D. Evans, François-Xavier Coudert, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and 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)-Ministère de la Culture (MC)
Subjects: 010405 organic chemistry, Chemistry, Enantioselective synthesis, Molecular simulation, Nanotechnology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid and Surface Chemistry, Adsorption, Mechanism (philosophy), Chemical physics, Molecule, [CHIM]Chemical Sciences, Chirality (chemistry), Chiral induction
Abstract: International audience; The recently reported process of chiral induction in a metal–organic framework (MOF) by nonchiral guest adsorption, demonstrated on the prototypical MOF-5, may revolutionize the production of MOFs for enantioselective separation and catalysis. Herein, we describe an investigation employing multiscale molecular simulation to discover the microscopic mechanism of chiral induction and investigate the stability of the resulting framework. Our results explain how the molecular size and chemical nature of N-methyl-2-pyrrolidone (NMP) give rise to the chiral transformation in MOF-5, whereas it cannot occur for other guest molecules, such as N,N-dimethylformamide (DMF). Moreover, we show that the guest-free CMOF-5 structure is energetically unstable, with either the achiral conventional structure or a closed pore structure preferred, demonstrating that chirality will not be retained upon activation of CMOF-5. While this limits the usability of chiral induction in MOFs, our study opens new avenues for the use of other guest molecules and provides microscopic insight into this unexpected outcome of guest–framework interactions in a soft porous crystal.
Published: 2016

25. Regioselective Activation of Oxo Ligands in Functionalized Dawson Polyoxotungstates

Author: René Thouvenot, Serge Thorimbert, Kévin Micoine, Bernold Hasenknopf, Emmanuel Lacôte, Max Malacria, Etienne Derat, Cecile Boglio, Institut Parisien de Chimie Moléculaire (IPCM), 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)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Organic molecules, Acylation, Colloid and Surface Chemistry, Organometallic Compounds, Side chain, Moiety, Organic chemistry, Computer Simulation, ComputingMilieux_MISCELLANEOUS, Molecular Structure, 010405 organic chemistry, Chemistry, Ligand, Regioselectivity, Stereoisomerism, General Chemistry, Tungsten Compounds, Combinatorial chemistry, 0104 chemical sciences, Models, Chemical, Tin, Electrophile, lipids (amino acids, peptides, and proteins)
Abstract: The organic side chain of tin-substituted Dawson polyoxotungstates alpha1- and alpha2-[P2W17O61{SnCH2CH2COOH}]7- can be used to direct regioselective acylations of oxo ligands in the inorganic backbone, which was examined both experimentally and computationally. Acylation of the oxo ligand gave exalted electrophilicity to the acyl moiety, and the compounds that were obtained led to direct ligation of POMs to complex organic molecules.
Published: 2008

26. Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

Author: Anne Boutin, Caroline Mellot-Draznieks, Alain H. Fuchs, François-Xavier Coudert, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Centre National de la Recherche Scientifique (CNRS), University College of London [London] (UCL), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), 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), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: General method, Chromatography, Chemistry, Nanoporous, Binary number, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid and Surface Chemistry, Adsorption, Chemical physics, Metal-organic framework, Gas separation, 0210 nano-technology, Selectivity, AND gate
Abstract: International audience; Among the numerous applications of metal−organic frameworks (MOFs), a topical class of nanoporous materials, adsorptive separation is gaining considerable attention. Some of the most exciting candidates for gas separation processes exhibit structural transitions, such as breathing and gate opening. While predictive analytical methods are crucial in separation science and have been widely used for rigid nanoporous solids, a lack exists for materials that exhibit flexibility. We propose here a general method predicting, for the first time, the evolution of structural transitions and selectivity upon adsorption of gas mixtures in flexible nanoporous solids.
Published: 2009

27. Reactivity of titanium oxo ethoxo cluster [Ti16O16(OEt)32]. Versatile precursor of nanobuilding block-based hybrid materials

Author: Stéphanie Le Calvé, Marie Noelle Rager, Kamal Boubekeur, Dominique Massiot, Giulia Fornasieri, Clément Sanchez, Laurence Rozes, Michel Evain, Bruno Alonso, Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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), Centre de recherches sur les matériaux à haute température (CRMHT), Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), and Université de Nantes (UN)-Université de Nantes (UN)
Subjects: chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Nanomaterials, Colloid and Surface Chemistry, Polymer chemistry, Cluster (physics), Organic chemistry, Reactivity (chemistry), Alkyl, chemistry.chemical_classification, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Carbon-13 NMR, 021001 nanoscience & nanotechnology, Hybrid, NMR, 0104 chemical sciences, chemistry, Alkoxy group, 0210 nano-technology, Hybrid material, Titanium
Abstract: Oxo alcoxo metallic clusters can be employed as inorganic nanobuilding blocks to obtain well-defined organic-inorganic hybrid materials. A better understanding of the surface reactivity of the clusters should allow optimization of the elaboration of hybrid materials through a better control of the hybrid interface. The oxo alcoxo cluster Ti(16)O(16)(OEt)32 presents a shell of labile ethoxy groups that can be selectively transalcoholyzed with preservation of the titanium oxo core, leading to new oxo alcoxo clusters Ti(16)O(16)(OEt)32-x(OR)x (R: alkyl, phenyl, styrenic, etc. groups). The reactivity of the Ti(16)O(16)(OEt)32 cluster toward aliphatic and aromatic alcohols is investigated to determine both the kinetics and the number of substituted titanium atoms, which are strongly dependent on the nature of the alcohol. Characterization of the organic modification of the cluster is performed in situ by liquid (13)C NMR measurements, using the molecular structures of two new clusters, Ti(16)O(16)(OEt)28(OnPr)4 and Ti(16)O(16)(OEt)(24)(OnPr)(8) (OnPr = propoxy groups), as references. The structures of these clusters have been established using single-crystal X-ray diffraction. Moreover, a complete spectroscopic assignment of each ethoxy group is proposed after combining crystallographic data, (13)C NMR T(1) relaxation measurements, and (1)H-(1)H, (1)H-(13)C 2D NMR experiments. Finally, the cluster is functionalized with polymerizable ligands via transalcoholysis and transesterification reactions using hydroxystyrene and acetoxystyrene.
Published: 2005

28. Controlled Formation of Highly Organized Mesoporous Titania Thin Films: From Mesostructured Hybrids to Mesoporous Nanoanatase TiO2

Author: Florence Cagnol, François Ribot, Galo J. A. A. Soler-Illia, Eduardo L. Crepaldi, David Grosso, Clément Sanchez, Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Novel Advanced Nano-Objects (LCMCP-NANO), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and 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)
Subjects: Oxide, Mineralogy, 02 engineering and technology, Thermal treatment, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, law.invention, chemistry.chemical_compound, Colloid and Surface Chemistry, law, Crystallization, Thin film, ComputingMilieux_MISCELLANEOUS, Extended X-ray absorption fine structure, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, XANES, 0104 chemical sciences, Characterization (materials science), Chemical engineering, 0210 nano-technology, Mesoporous material
Abstract: In this paper, we report the complete synthesis and characterization procedures to generate highly organized and oriented mesoporous titania thin films, using poly(ethylene oxide) (PEO)-based templates. Controlled conditions in the deposition, postsynthesis, and thermal treatment steps allow one to tailor the final mesostructure (2D hexagonal, p6m, or 3D cubic, Im3m). Various techniques were used to determine the time evolution of the mesostructure. Spectroscopic techniques (UV/vis, (17)O NMR) and EXAFS/XANES have been used to follow the chemical changes in the Ti(IV) environment. Crossing these techniques spanning all ranges permits a complete description of the chemistry all the way from solution to the mesostructured metal oxide. A critical discussion on all important chemical and processing parameters is provided; the understanding of these features is essential for a rational design and the reproducible construction of mesoporous materials.
Published: 2003

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28 results on '"Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP)"'

1. Identification and Quantification of Glycans in Whole Cells: Architecture of Microalgal Polysaccharides Described by Solid-State Nuclear Magnetic Resonance

2. Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

3. Detection of Metabolite–Protein Interactions in Complex Biological Samples by High-Resolution Relaxometry: Toward Interactomics by NMR

4. Electrolyte Reactivity in the Double Layer in Mg Batteries: An Interface Potential-Dependent DFT Study

5. Time-Resolved Protein Side-Chain Motions Unraveled by High-Resolution Relaxometry and Molecular Dynamics Simulations

6. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

7. Elucidation of the Na2/3FePO4 and Li2/3FePO4 Intermediate Superstructure Revealing a Pseudouniform Ordering in 2D

8. 87Sr Solid-State NMR as a Structurally Sensitive Tool for the Investigation of Materials: Antiosteoporotic Pharmaceuticals and Bioactive Glasses

9. α-Na3M2(PO4)3 (M = Ti, Fe): Absolute Cationic Ordering in NASICON-Type Phases

10. Controlling Electron Trap Depth To Enhance Optical Properties of Persistent Luminescence Nanoparticles for In Vivo Imaging

11. Designing Multifunctional Expanded Pyridiniums: Properties of Branched and Fused Head-to-Tail Bipyridiniums

12. Both Water- and Organo-Soluble Supramolecular Polymer Stabilized by Hydrogen-Bonding and Hydrophobic Interactions

13. Unraveling the Capacitive Charge Storage Mechanism of Nitrogen-Doped Porous Carbons by EQCM and ssNMR

14. Structure of the human telomere in K+ solution: a stable basket-type G-quadruplex with only two G-tetrad layers

15. Transient Catenation in a Zirconium-Based Metal–Organic Framework and Its Effect on Mechanical Stability and Sorption Properties

16. Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

17. Emergence of Homochiral Benzene-1,3,5-tricarboxamide Helical Assemblies and Catalysts upon Addition of an Achiral Monomer

18. Electron Storage System Based on a Two-Way Inversion of Redox Potentials

19. Photodecaging of a Mitochondria-Localized Iridium(III) Endoperoxide Complex for Two-Photon Photoactivated Therapy under Hypoxia

20. Arene-Bridged Dithorium Complexes: Inverse Sandwiches Supported by a δ Bonding Interaction

21. Structure and Dynamics of an Intrinsically Disordered Protein Region That Partially Folds upon Binding by Chemical-Exchange NMR

22. Insulator-to-Proton-Conductor Transition in a Dense Metal–Organic Framework

23. Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization

24. Microscopic Mechanism of Chiral Induction in a Metal-Organic Framework

25. Regioselective Activation of Oxo Ligands in Functionalized Dawson Polyoxotungstates

26. Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

27. Reactivity of titanium oxo ethoxo cluster [Ti16O16(OEt)32]. Versatile precursor of nanobuilding block-based hybrid materials

28. Controlled Formation of Highly Organized Mesoporous Titania Thin Films: From Mesostructured Hybrids to Mesoporous Nanoanatase TiO2

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28 results on '"Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP)"'

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