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143 results on '"Université d'Orléans (UO)"'

1. 55/52Mn2+ Complexes with a Bispidine-Phosphonate Ligand: High Kinetic Inertness for Imaging Applications

Author: Maryame Sy, Daouda Ndiaye, Isidro da Silva, Sara Lacerda, Loïc J. Charbonnière, Éva Tóth, Aline M. Nonat, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and HEP, INSPIRE
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract: International audience; Bispidine (3,7-diazabicyclo[3.3.1]nonane) provides a rigid and preorganized scaffold that is particularly interesting for the stable and inert complexation of metal ions, especially for their application in medical imaging. In this study, we present the synthesis of two bispidine ligands with N-methanephosphonate (H4L1) and N-methanecarboxylate (H3L2) substituents as well as the physico-chemical properties of the corresponding Mn2+ and Zn2+ complexes. The two complexes [Mn(L-1)](2- )and [Mn(L-2)](-) have relatively moderate thermodynamic stability constants according to potentiometric titration data. However, they both display an exceptional kinetic inertness, as assessed by transmetallation experiments in the presence of 50 equiv excess of Zn2+, showing only similar to 40 and 20% of dissociation for [Mn(L-1)](2- ) and [Mn(L-2)](-), respectively, after 150 days at pH 6 and 37°C. Proton relaxivities amount to r(1 )= 4.31 mM(-1 )s(-1 )([Mn(L-1)](2-)) and 3.64 mM(-1) s(-1 )([Mn(L-2)](-)) at 20 MHz, 25°C, and are remarkable for Mn2+ complexes with one inner-sphere water molecule (q = 1); they are comparable to that of the commercial contrast agent [Gd(DOTA)(H2O)](-). The presence of one inner-sphere water molecule and an associative water exchange mechanism was confirmed by temperature-dependent transverse O-17 relaxation rate measurements, which yielded k(ex)(298) = 0.12 x 10(7) and 5.5 x 10(7) s(-1 )for the water exchange rate of the phosphonate and the carboxylate complex, respectively. In addition, radiolabeling experiments with Mn-52 were also performed with H-2(L-1)(2-) showing excellent radiolabeling properties and quantitative complexation at pH 7 in 15 min at room temperature as well as excellent stability of the complex in various biological media over 24 h.
Published: 2022

2. Are Operando Measurements of Rechargeable Batteries Always Reliable? An Example of Beam Effect with a Mg Battery

Author: Lucie Blondeau, Suzy Surblé, Eddy Foy, Hicham Khodja, Stéphanie Belin, Magali Gauthier, Laboratoire d'Etudes des Eléments Légers (LEEL - UMR 3685), 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), Laboratoire Archéomatériaux et Prévision de l'Altération (LAPA - UMR 3685), IRAMAT - Laboratoire Archéomatériaux et Prévision de l'Altération (IRAMAT-LAPA), Institut de Recherche sur les Archéomatériaux (IRAMAT), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE05-0004,MAGICIEN,MAGnésium-Ion: batteries haute Capacité Innovantes à base d'Electrodes négatives Nanostructurées(2016)
Subjects: [CHIM.MATE]Chemical Sciences/Material chemistry, Analytical Chemistry
Abstract: International audience; Operando and in situ techniques are becoming mandatory to study Li-ion, post Li-ion, and solid-state batteries. They are essential for monitoring the (electro)chemical and dynamic processes in the battery environment and for providing understanding at different spatial and temporal scales. While operando measurements are becoming more and more routine, scientists have to keep in mind that such experiments are not always harmless for the battery operation, especially when using synchrotron techniques. This is the case in the example described herein with Mg batteries. We show that the electrode reactivity in a InSb/organohaluminate electrolyte/Mg cell is strongly retarded during operando synchrotron X-ray absorption acquisition. Through comparison of ex situ, operando, and in situ data, we demonstrate that this effect occurred only on the samples’ volumes exposed to the X-ray radiation. This study illustrates how incorrect conclusions might be drawn from operando measurements, especially when looking at new battery chemistries, and calls for extreme caution when designing and interpreting operando data.
Published: 2022

3. Emergence of A-Site Cation Order in the Small Rare-Earth Melilites SrREGa3O7 (RE = Dy–Lu, Y)

Author: Cécile Genevois, Michael J. Pitcher, Yannick Ledemi, Sandra Ory, Younes Messaddeq, Marina Boyer, Mathieu Allix, Haytem Bazzaoui, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), and Université Laval [Québec] (ULaval)
Subjects: 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, metastability, Inorganic Chemistry, Tetragonal crystal system, law, luminescence, Ceramic, Physical and Theoretical Chemistry, Crystallization, STEM-HAADF, Chemistry, Melilite, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Gallate melilite, 0104 chemical sciences, Crystallography, visual_art, visual_art.visual_art_medium, engineering, Orthorhombic crystal system, Crystallite, 0210 nano-technology, Luminescence, Superstructure (condensed matter), cation ordering
Abstract: International audience; SrREGa3O7 melilite ceramics with large rare-earth elements (RE = La to Y) are famous materials especially known for their luminescence properties. Using an innovative approach, the full and congruent crystallization from glass process, SrREGa3O7 transparent polycrystalline ceramics with small rare earth elements (RE = Dy-Lu and Y) have been successfully synthesized and characterized. Interestingly, compared to the classic tetragonal (P-421m) melilite structure composed of mixed Sr/RE cationic sites, these compositions can crystallize in a 3 x 1 x 1 orthorhombic (P21212) superstructure. A detailed study of the superstructure, investigated by different techniques (synchrotron and neutron powder diffraction, STEM-HAADF imaging and EDS mapping), highlights the existence of a Sr/RE cation ordering favored by a large Sr/RE size mismatch and a sufficiently small RE cation. An appropriate control of the synthesis conditions through glass crystallization enables the formation of the desired polymorphs, either ordered or disordered. The influence of this tailored cationic ordering/disordering on the RE luminescent spectroscopic properties have been investigated. A stronger structuration of the RE emission band is observed in the ordered ceramic compared to the disordered ceramic and the glass, whose band shapes are very similar, indicating that the RE environment in the glass and disordered ceramic are close.
Published: 2021

4. Photochromism and Persistent Luminescence in Ni-Doped ZnGa2O4 Transparent Glass-Ceramics: Toward Optical Memory Applications

Author: Didier Gourier, Luidgi Giordano, Bruno Viana, Mathieu Allix, Cyrille Richard, Victor Castaing, 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), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Institut de Chimie du CNRS (INC)-Université de Paris (UP)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), 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)-Ministère de la Culture (MC), 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 Cité (UPCité), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ORANGE, Colette
Subjects: MECHANISM, LONG-PERSISTENT, Materials science, Infrared, EUROPIUM, chemistry.chemical_element, Phosphor, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Photochromism, Persistent luminescence, NANOPARTICLES, Ceramic, Physical and Theoretical Chemistry, TRAP DEPTH, [CHIM.MATE] Chemical Sciences/Material chemistry, SPECTROSCOPY, business.industry, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, General Energy, chemistry, visual_art, visual_art.visual_art_medium, 2-PHOTON EXCITATION, Optoelectronics, VISIBLE-LIGHT, 0210 nano-technology, business, Europium, PEROVSKITE PHOSPHOR, STORAGE, Visible spectrum
Abstract: International audience; Persistent luminescence and photochromism are two fascinating optical properties that involve charge trapping via defects and their release due to an external stimulation. In both processes, it is possible to define 1 (or on) and 0 (or off) optical states. Consequently, materials with one of these phenomena find major interest in view of designing smart, anticounterfeiting, and optical information storage devices. Combining both processes within a single material can lead to a new generation of information storage phosphors, in which it may be possible to obtain three different optical states by playing on the external stimulations applied on the material. For that purpose, the elaboration of nickel-doped ZnGa2O4 spinet transparent nano-glassceramics is presented in this work. The short-wave infrared (SWIR) emission, a broad band located at ca. 1275 nm, arises from Ni2+ cations located in gallium octahedral sites. SWIR persistent luminescence, arising from the same doping ion transition, can also be monitored after UV charging. Interestingly, UV irradiation not only leads to persistent luminescence charging but also to a reversible photochromism effect. By means of a complete optical characterization study combined with electron paramagnetic resonance measurements, the origins of both the persistent luminescence emission and the photochromism are explored. Finally, a discussion on the advantages of such a material combining both persistent luminescence and photochromism properties, leading to three possible optical states of the material, is dressed in view of possible optical memory systems.
Published: 2021

5. Quartz Stressing and Fracturing by Pore Pressure Dropping Down to Negative Pressure

Author: Lionel Mercury, Aurélien Canizares, Claudie Hulin, Kirill I. Shmulovich, Hugues Raimbourg, Isabelle Bergonzi, Emmanuel de Bilbao, Patrick Simon, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Milieux Poreux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Geophysical Center of Russian Academy of Sciences (GC), Russian Academy of Sciences [Moscow] (RAS), ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), ANR-11-EQPX-0036,PLANEX,Planète Expérimentation: simulation et analyse in-situ en conditions extrêmes(2011), and ANR-10-BLAN-0610,ConGé,Confinement géochimique de solutions aqueuses et transitions de phase dans les milieux finement poreux(2010)
Subjects: Raman scattering, Atmospheric Science, Materials science, 010504 meteorology & atmospheric sciences, Deformation (mechanics), Capillary action, Micromechanics, Metrics & More Article Recommendations tensile strength, pore rock damage, quartz weakening, 010502 geochemistry & geophysics, 01 natural sciences, storage safety, Stress field, Stress (mechanics), Pore water pressure, fluid inclusions, [SDU]Sciences of the Universe [physics], Space and Planetary Science, Geochemistry and Petrology, Tension (geology), Fracture (geology), Composite material, 0105 earth and related environmental sciences
Abstract: International audience; In water-bearing porous rocks, pore pressure variations play a major role in deformation, through dissolution−precipitation and fracturing processes. An often-overlooked variation where pressure falls to negative pressure or tension can operate whenever aquifer formations dry out, for instance, in deep storage (nuclear or industrial wastes, long-term CO 2 mitigation, short-term energetic resources, etc.). This can generate capillary tension within the aquifers. This study investigates the mechanical effect of such in-pore tension in the surrounding crystal field, through laboratory experiments at the one-pore scale. Microthermometric procedures were carried out on synthetic fluid inclusions to generate large tensile stress and were combined with Raman microspectrometry to visualize the resulting stress fields in the host quartz. For comparison, we numerically modeled the stress field by linear elasticity theory. The experiments demonstrate that significant damage is produced in crystalline materials by the pore tension. Despite the induced stress measured by micro-Raman spectrometry to remain moderate, it is able to fracture the quartz. The volume of the cavity is a prominent controlling parameter for the stress amplitude. The crystalline heterogeneities of the solid are another major parameter for localizing the mean weak stress and accumulating overstress. Our results call for bringing pore-scale micromechanics into the safety assessment of the geological storage of various wastes inside depleted aquifers. They also show the magnifying effect of heterogeneities on propagating stress and localizing it along certain directions, promoting the final failure of water-bearing minerals, rocks, or pore networks.
Published: 2021

6. Evidence for Strong HONO Emission from Fertilized Agricultural Fields and its Remarkable Impact on Regional O3 Pollution in the Summer North China Plain

Author: Chaoyang Xue, Rongrong Gu, Abdelwahid Mellouki, Junling An, Can Ye, Xiaoxi Zhao, Maofa Ge, Pengfei Liu, Chenglong Zhang, W. Zhang, Likun Xue, Yangang Ren, Jingwei Zhang, Shengrui Tong, Yujing Mu, Zhuobiao Ma, Gisèle Krysztofiak, Valéry Catoire, Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National d’Études Spatiales [Paris] (CNES), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), PIVOTS project provided by the Région Centre − Val de Loire (ARD 2020 program and CPER 2015−2020), and ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010)
Subjects: Pollution, Atmospheric Science, Daytime, 010504 meteorology & atmospheric sciences, Emission flux, media_common.quotation_subject, North china, O3, emission flux, 010501 environmental sciences, Atmospheric sciences, 01 natural sciences, Human fertilization, Geochemistry and Petrology, [CHIM]Chemical Sciences, Air quality index, 0105 earth and related environmental sciences, media_common, HONO, business.industry, Diurnal temperature variation, nitrogen fertilization, 13. Climate action, Space and Planetary Science, Agriculture, Environmental science, agricultural fields, business
Abstract: International audience; Summertime HONO concentrations were synchronously measured at two (agricultural and nonagricultural) sites in the North China Plain (NCP). Daytime HONO (1.4 ± 0.6 ppbv) and HONO/NO2 ((12 ± 8)%) over the agricultural field after fertilization were found to be remarkably higher than those before fertilization, implying strong HONO emission from the fertilized fields. Synchronous enhancements of HONO and O3 after fertilization at both sites suggested that the emitted HONO accelerated the local and the regional O3 pollution. HONO budget analysis further revealed that its emission was significantly enhanced after fertilization. Soil HONO emission flux and its uncertainty were estimated and discussed. The estimated emission flux exhibited a distinct diurnal variation with a noontime maximum. The net OH production rate from HONO photolysis greatly exceeded that from O3 photolysis over the agricultural field, and their maximum ratio of 4.7 was obtained after fertilization. We provide field evidence that fertilized fields in the NCP act as a strong HONO source, which accelerates daytime photochemistry, leading to an increase of regional photo-oxidants such as O3. Considering the severe O3 pollution in the summer NCP and that the large area of the agricultural field is regularly treated with high fertilization amount in this region, HONO emission should be taken into account in the regional air quality deterioration.
Published: 2021

7. Gold(I)-Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Alkynes: Access to Original Heterospirocycles

Author: Sylvain Routier, Kossi Efouako Soklou, Karen Plé, Mathieu Marchivie, Jean-Philippe Bouillon, Hamid Marzag, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank the Région Centre Val de Loire (Ph.D. funding SKE), the Labex programs SYNORG (ANR-11-LABX-0029) and IRON (ANR-11-LABX-0018-01), the Ligue contre le Cancer du Grand Ouest (comités des Deux Sèvres, du Finistère, de l’Ile et Villaine, du Loir et Cher, de Loire Atlantique, du Loiret, de la Vienne), and the Canceropole Grand Ouest for their financial support., ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), PLE, Karen, Synthèse Organique : des molécules au vivant - - SYNORG2011 - ANR-11-LABX-0029 - LABX - VALID, and Radiopharmaceutiques Innovants en Oncologie et Neurologie - - IRON2011 - ANR-11-LABX-0018 - LABX - VALID
Subjects: Annulation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, education, Organic Chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, humanities, 0104 chemical sciences, Catalysis, Cascade reaction, Intramolecular force, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Hydroamination, Physical and Theoretical Chemistry, Tertiary alcohols, Hydroalkoxylation
Abstract: International audience; We report here a simple and robust gold-catalyzed annulation reaction, giving N- and O-spirocycles in good to excellent yields. We have prepared a library of protected amines and tertiary alcohols that give, upon cyclization with alkynes, a representative set of heterospirocycles and illustrate reaction compatibility with diverse functional groups. A change in catalytic activity is possible by modifying the solvent, and two original tricyclic spirocycles were synthesized in a tandem reaction.
Published: 2020

8. First-Principles Determination of Transference Numbers in Cryolitic Melts

Author: Mathieu Salanne, Kelly Machado, Catherine Bessada, Patrice Chartrand, Aĩmen Ernest Gheribi, Didier Zanghi, Polytechnique Montreal, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Université d'Orléans (UO)
Subjects: Materials science, General Chemical Engineering, Ionic bonding, Charge (physics), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, Electron transport chain, Industrial and Manufacturing Engineering, 020401 chemical engineering, Chemical physics, 0204 chemical engineering, 0210 nano-technology
Abstract: International audience; The charge and electron transport properties of molten ionic systems are among the most relevant properties to consider in the control of several electrochemical processes. First-principles-based equilibrium molecular dynamics (EMD) can provide reliable predictions of both the total and partial charge transport properties. In this work we calculate the charge transport properties of the electrolytic bath (Na 3 AlF 6-AlF 3-Al 2 O 3) of the Hall-Héroult electrolysis cells. We predict both the individual and collective charge transport properties (total, partial conductivity and self diffusion coefficients) for 11 different compositions typical of industrial conditions via a series of EMD simulations. The predicted total and partial ionic conductivities and their composition dependence are compared to available experimental data. A good agreement is obtained for all studied compositions. From a more fundamental point of view, the microscopic aspect of the charge transport properties of cryolitic melts is discussed through its correlation to the local structure of different melts. Deviations between the calculated partial conductivities and those derived via the Nernst-Einstein approximation can be explained by the presence of strong short-range ordering within the melts.
Published: 2020

9. Impact of Oil-Prone Sedimentary Organic Matter Quality and Hydrocarbon Generation on Source Rock Porosity: Artificial Thermal Maturation Approach

Author: Amélie Cavelan, Claude Le Milbeau, Mohammed Boussafir, Fatima Laggoun-Défarge, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Laboratoire Interdisciplinaire des Environnements Continentaux (LIEC), Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Terre et Environnement de Lorraine (OTELo), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and Region Centre-Val de Loire, France.
Subjects: 020209 energy, General Chemical Engineering, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, 02 engineering and technology, 010502 geochemistry & geophysics, 01 natural sciences, Article, Methane, chemistry.chemical_compound, 0202 electrical engineering, electronic engineering, information engineering, Sedimentary organic matter, Porosity, QD1-999, 0105 earth and related environmental sciences, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Thermal conductivity detector, General Chemistry, Chemistry, Hydrocarbon, Kimmeridge Clay, Volume (thermodynamics), Source rock, chemistry, Chemical engineering, 13. Climate action
Abstract: International audience; This work investigates the relation between the molecular composition of the organic matter (OM), hydrocarbon generation, and porosity of artificially matured mudstones from the Kimmeridge Clay formation. Anhydrous thermal maturations, geochemical characterization (gas chromatography−mass spec-trometry, gas chromatography with a thermal conductivity detector), scanning electron microscopy observations, and nitrogen adsorption measurements were carried out. The results were compared to the calculated OM porosity after maturation. Our results reveal that samples richer in phytoplanktonic OM generated more abundant oils enriched in alkanes and lighter aromatic hydrocarbons (i.e., biphenyls and naphthalenes) that are more able to fill the adjacent pores of the mineral matrix during maturation. Both the calculated and the observed OM porosity increases during maturation, but the measured rock pore volume shows a non-linear evolution related to the amount of gas generated and the ensuing ability of the rock to preserve the pores. The secondary cracking of highly oil-prone samples generated larger amounts of C 1 −C 5 gases but lower pore volumes, less well preserved. OM composition and its ability to generate oil and gas seem therefore to affect the pore volume. These variations are nevertheless small compared to the effect of thermal maturity, which remains the major process controlling the evolution of porosity. During gas generation, high C 2 −C 5 concentrations are generated compared to methane. The short thermal maturation duration of our experiments may have delayed the conversion of C 2 −C 5 hydrocarbons to methane. In addition, slight differences in the concentrations of saturated and aromatic components and markedly different pore volumes and pore size distributions exist between artificially and naturally matured rocks. The conditions of artificial maturations may thus impact the thermal transformations of OM, emphasizing the necessity to investigate the role of the artificial maturation kinetics on OM and porosity.
Published: 2020

10. First Example of Protonation of Ruddlesden–Popper Sr2IrO4: A Route to Enhanced Water Oxidation Catalysts

Author: Alexis Grimaud, Paul E. Pearce, Daniel Alves Dalla Corte, Domitille Giaume, Ronghuang Zhang, Gwenaëlle Rousse, Heifang Li, Artem M. Abakumov, Michaël Deschamps, Vanessa Pimenta, Jordi Cabana, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Chimie du solide et de l'énergie (CSE), and Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemical transformation, Materials science, Hydrogen, Electrolysis of water, business.industry, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, Protonation, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Catalysis, Renewable energy, chemistry, Value (economics), Materials Chemistry, 0210 nano-technology, business
Abstract: International audience; Water electrolysis is considered as a promising way to store and convert excess renewable energies into hydrogen, which is of high value for many chemical transformation processes such as the Haber-Bosch process. However, to allow for the widespread of the polymer electrolyte membrane water electrolysis (PEMWE) technology, the main challenge lies in the design of robust catalysts for oxygen evolution reaction (OER) under acidic conditions since most of transition metal-based oxides undergo structural degradation under these harsh acidic conditions. To broaden the variety of candidate materials as OER catalysts, a cation-exchange synthetic route was recently explored to reach crystalline pronated iridates with unique structural properties and stability. In this work, a new protonated phase H 3.6 IrO 4 •3.7H 2 O, prepared via Sr 2+ /H + cation exchange at room temperature starting from the parent Ruddlesden-Popper Sr 2 IrO 4 phase, is described. This is the first discovery of crystalline protonated iridate forming from a perovskite-like phase, adopting a layered structure with apex-linked IrO 6 octahedra. Furthermore, H 3.6 IrO 4 •3.7H 2 O is found to possess not only an enhanced specific catalytic activity, superior to that of other perovskite-based iridates, but also a mass activity comparable to that of nanosized IrO x particles, while showing an improved catalytic stability owing to its ability to reversibly exchange protons in acid.
Published: 2020

11. Early Diagenesis of Lacustrine Carbonates in Volcanic Settings: The Role of Magmatic CO2 (Lake Dziani Dzaha, Mayotte, Indian Ocean)

Author: Aurélien Virgone, Gérard Sarazin, François Guyot, Vincent Milesi, Mathieu Debure, Virgile Rouchon, Edouard Bard, Nicolas C.M. Marty, Manuela Capano, Magali Ader, Carl I. Steefel, Patrick Albéric, Eric C. Gaucher, Didier Jézéquel, Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), IFP Energies nouvelles (IFPEN), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), TOTAL-Scientific and Technical Center Jean Féger (CSTJF), TOTAL FINA ELF, CNRS-INSU : INTERRIVECNRS-INSU : ARTEMIS, ANR-13-BS06-0001,Dziani,Ecalairages sur les océans précambriens par l'étude biogéochimique et microbiologique d'un analogue actuel: le lac Dziani Dzaha, Mayotte.(2013), Centre National de la Recherche Scientifique (CNRS)-Université de La Réunion (UR)-Université Paris Diderot - Paris 7 (UPD7)-IPG PARIS-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Chaire Evolution du climat et de l'océan, Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Physique du Globe de Paris (IPGP (UMR_7154)), Institut national des sciences de l'Univers (INSU - CNRS)-Université de La Réunion (UR)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Collège de France - Chaire Evolution du climat et de l'océan, Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Centre scientifique et Technique Jean Feger (CSTJF)
Subjects: saponite, Atmospheric Science, 010504 meteorology & atmospheric sciences, volcanic crater lake, Geochemistry, engineering.material, 010502 geochemistry & geophysics, 01 natural sciences, chemistry.chemical_compound, Geochemistry and Petrology, Crater lake, Dissolved organic carbon, magmatic CO2, Dziani Dzaha, 14. Life underwater, Hydromagnesite, rift settings, 0105 earth and related environmental sciences, magnesium phyllosilicates, geography, geography.geographical_feature_category, Mg silicates saponite rift settings pre-salt reactive transport modeling magmatic CO2 volcanic crater lake South-Atlantic early Cretaceous lacustrine carbonates paleoenvironment, Aragonite, Sediment, reactive transport modeling, Diagenesis, isotopy, Volcano, chemistry, kinetics, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, engineering, Carbonate, Geology, [SDU.STU.MI]Sciences of the Universe [physics]/Earth Sciences/Mineralogy
Abstract: International audience; Lacustrine carbonates formed in rift settings are increasingly studied not only as archives of Earth chemical and climatic history but also as potential hydrocarbon source rocks and/or reservoirs. The role of magmatic gases in their formation and diagenetic evolution, hence in their reservoir properties, remains unclear. We studied the first meter of carbonate sediment of the Dziani Dzaha volcanic crater lake (Mayotte Island) and developed a reactive-transport model with CrunchFlow software that allows the quantification of diagenetic reactions by considering depth-dependent burial rates and sediment compaction. The model is constrained by the previously documented solid-phase compositions of the lake sediment and new data consisting of 14C dating of plant macroremains to characterize the sediment age model, chemical composition of sediment pore waters, and chemical and isotopic composition of gases dissolved and bubbling through the lake. These new data reveal a massive magmatic CO2 contribution to the dissolved inorganic carbon of the lake, which fuels the primary productivity and carbonate formation. A pH value of 9 in the surface sediment pore waters induces supersaturation relative to aragonite, hydromagnesite, and saponite. At 1 m depth in the sediment, our model predicts that magmatic CO2 inflows and organic matter degradation account for 22 and 2 mol % dissolved inorganic carbon, respectively. The magmatic CO2 inflows result in a pH decrease at depth, leading to the destabilization of hydromagnesite, while saponite and aragonite remain stable. These results demonstrate the role of magmatic CO2 in fueling carbonate production and controlling the diagenetic evolution of sediment mineralogy.
Published: 2020

12. Atmospheric Photosensitization: A New Pathway for Sulfate Formation

Author: Xinke Wang, Nathalie Hayeck, Liwu Zhang, Caihong Xu, Sébastien Perrier, Hui Chen, Zhe Wang, Nicolas Charbonnel, Christian George, R. Gemayel, Abdelwahid Mellouki, Lin Wang, Sergey A. Nizkorodov, Xinming Wang, Chao Zhu, Matthieu Riva, Tao Wang, Jianmin Chen, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Catalytic and Atmospheric Reactivity for the Environment (CARE), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Fudan University [Shanghai], Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), JSTI, Nanyang Technological University [Singapour], The Hong Kong Polytechnic University [Hong Kong] (POLYU), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Ministry of Science and Technology, China 2016YFC0202700, National Natural Science Foundation of China, 91843301, 91743202, National research program, DQGG0103, DQGG0102, ANR-16-CE01-0013,SEA-M,Impact des échanges air-mer sur la qualité de l'air dans les mégalopoles du littoral(2016), European Project: 690958,H2020,H2020-MSCA-RISE-2015,MARSU(2016), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS)
Subjects: MECHANISM, China, Asia, Ozone, Haze, [SDE.MCG]Environmental Sciences/Global Changes, 010501 environmental sciences, OXIDATION, Hydrogen atom abstraction, Photochemistry, 01 natural sciences, chemistry.chemical_compound, Electron transfer, Humans, PHOTOOXIDANTS, WATER, [CHIM]Chemical Sciences, Environmental Chemistry, Nitrogen dioxide, Photosensitivity Disorders, Sulfate, Hydrogen peroxide, KINETICS, HAZE, 0105 earth and related environmental sciences, Aerosols, DITHIONITE, Air Pollutants, Sulfates, PHOTOCHEMISTRY, General Chemistry, Aerosol, chemistry, 13. Climate action, Particulate Matter
Abstract: International audience; Northern China is regularly subjected to intense wintertime "haze events", with high levels of fine particles that threaten millions of inhabitants. While sulfate is a known major component of these fine haze particles, its formation mechanism remains unclear especially under highly polluted conditions, with state-of-the-art air quality models unable to reproduce or predict field observations. These haze conditions are generally characterized by simultaneous high emissions of SO2 and photosensitizing materials. In this study, we find that the excited triplet states of photosensitizers could induce a direct photosensitized oxidation of hydrated SO2 and bisulfite into sulfate S(VI) through energy transfer, electron transfer, or hydrogen atom abstraction. This photosensitized pathway appears to be a new and ubiquitous chemical route for atmospheric sulfate production. Compared to other aqueous-phase sulfate formation pathways with ozone, hydrogen peroxide, nitrogen dioxide, or transition-metal ions, the results also show that this photosensitized oxidation of S(IV) could make an important contribution to aerosol sulfate formation in Asian countries, particularly in China.
Published: 2020

13. Aza-BODIPY Platform: Toward an Efficient Water-Soluble Bimodal Imaging Probe for MRI and Near-Infrared Fluorescence

Author: Pierre-Simon Bellaye, Olivier Maury, Célia S. Bonnet, Jacques Pliquett, Océane Florès, Bertrand Collin, Franck Denat, Sandra Même, Ewen Bodio, Laura Abad Galán, Robin Lescure, Christine Goze, Agnès Pallier, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER, Même, Sandra, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Aqueous solution, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, 010405 organic chemistry, Singlet oxygen, Quantum yield, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Wavelength, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Surface modification, Physical and Theoretical Chemistry, Absorption (chemistry), Boron, Excitation
Abstract: In this study, an original aza-BODIPY system comprising two Gd3+ complexes has been designed and synthesized for magnetic resonance imaging/optical imaging application, by functionalization of the boron center. This strategy enabled to obtain a positively-charged bimodal probe, which displays an increased water-solubility, optimized photophysical properties in the near-infrared region, and very promising relaxometric properties. The absorption and emission wavelengths are 705 and 741 nm respectively, with a quantum yield of around 10 % in aqueous media. Moreover, the system does not produce singlet oxygen upon excitation, which would be toxic for tissues. The relaxivity obtained is high at intermediate fields (16.1 mM-1.s-1 at 20 MHz and 310 K) and competes with that of bigger or more rigid systems. A full relaxometric and 17O NMR study and fitting of the data using the Lipari-Szabo approach showed that this high relaxivity can be explained by the size of the system and the presence of some small aggregates. These optimized photophysical and relaxometric properties highlight the potential use of such systems for future bimodal imaging studies.
Published: 2020

14. Residence Time Prediction of Type 1 and 2 Kinase Inhibitors from Unbinding Simulations

Author: Samia Aci-Sèche, Pascal Bonnet, A. Braka, Norbert Garnier, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-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 d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM)
Subjects: General Chemical Engineering, Kinetics, Molecular Dynamics Simulation, Library and Information Sciences, Ligands, 01 natural sciences, Molecular dynamics, In vivo, 0103 physical sciences, Binding site, Protein Kinase Inhibitors, Residence time (statistics), 010304 chemical physics, Drug discovery, Chemistry, Ligand, General Chemistry, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation, [SDV.BIBS]Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], 0104 chemical sciences, Computer Science Applications, 010404 medicinal & biomolecular chemistry, Thermodynamics, Probability distribution, Biological system, [CHIM.CHEM]Chemical Sciences/Cheminformatics, Protein Binding
Abstract: International audience; In the early stage of a drug discovery process, the selection and optimization of a ligand is mainly based on equilibrium thermodynamic constants such as KD or IC50 values, which are representatives of the affinity of the compound for its target. However, these criteria are not able to correctly evaluate the efficacy of compounds in vivo and result in many failures of compound development during phase II of clinical trials. Residence time (RT) is an important parameter associated to an in vivo drug’s safety and efficacy. The determination or modulation of kinetic rates correlated to RT may be performed to identify the best drug candidates in the early stages of a drug design project. For this purpose, a number of experimental methodologies were developed but remain costly in both time and money. Herein, we developed a novel protocol based on biased molecular dynamics simulations and transition-state theory in order to predict relative ligand kinetic rates and relative RTs of a series of compounds. First, we have repeatedly simulated the unbinding process of the ligand from its binding site to the outside of the target. Next, we sample the conformational space along the determined unbinding paths to allow relevant statistical distributions of the system. The free energy profiles associated to these distributions are then computed and used to predict the kinetics parameters. The studied set was composed of eight ligands with fast, intermediate, and slow dissociation rates and binding to the active and inactive states of p38α protein kinase. The proposed method provides an excellent correlation between the predicted values and the experimentally measured kinetic rates, in addition to a detailed characterization of the kinetic paths at the atomic level.
Published: 2019

15. Ba8CoNb6–xTaxO24 Eight-Layer Shifted Hexagonal Perovskite Ceramics with Spontaneous Ta5+ Ordering and Near-Zero τf

Author: Cécile Genevois, Xiaoyan Yang, Tashtanbekova Kyzzhibek, Xiaojun Kuang, Weiwei Cao, Florence Porcher, Mathieu Allix, College of materials science and engineering, Guilin University of Technology, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: Permittivity, 010405 organic chemistry, Chemistry, Analytical chemistry, Energy-dispersive X-ray spectroscopy, Ionic bonding, [CHIM.MATE]Chemical Sciences/Material chemistry, Dielectric, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Polarizability, visual_art, visual_art.visual_art_medium, Ceramic, Physical and Theoretical Chemistry, Temperature coefficient, ComputingMilieux_MISCELLANEOUS, Perovskite (structure)
Abstract: Highly positive temperature coefficients of the resonant frequency (τf) of eight-layer hexagonal perovskites are hardly tunable, hindering their application as microwave dielectric resonators. Here, we show that a near-zero τf (∼0.48 ppm °C-1) can be achieved on eight-layer shifted hexagonal perovskite Ba8CoNb4Ta2O24, along with a permittivity er of ∼30.6 and a Qf of ∼36400 GHz, through substitution of Ta for Nb, satisfying the resonator application requirement. The decrease in the τf of Ba8CoNb6-xTaxO24 takes place mainly through the decrease in the er or temperature coefficient of permittivity, owing to the less covalent bonding and lower polarizability of Ta5+ compared to those of Nb5+. Synchrotron and neutron powder diffraction data, scanning transmission electron microscopy-high-angle annular dark field imaging, and atomic-scale X-ray energy dispersive spectroscopy elemental mapping reveal that Ta5+ cations in Ba8CoNb4Ta2O24 are naturally distributed in a partially ordered manner, showing a strong site preference on the Nb layers close to the central Co layer over the most out-of-center distorted Nb layers next to empty octahedral layers. This spontaneous Ta ordering in the niobate host is driven by different covalent bonding nature and second-order Jahn-Teller distortion extents of Ta5+ and Nb5+. The results demonstrate an effective way of substituting more ionic Ta5+ for Nb5+, which decreases the τf to near-zero values for eight-layer hexagonal perovskite niobate dielectrics.
Published: 2019

16. Synthesis and Characterization of Double Solid Solution (Zr,Ti)2(Al,Sn)C MAX Phase Ceramics

Author: Konstantina Lambrinou, Dominique Thiaudière, Louis Hennet, Joke Hadermann, Bensu Tunca, Daniel R. Neuville, Jozef Vleugels, Thomas Lapauw, Rémi Delville, Thierry Ouisse, Physics, University of Antwerp (UA), Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire des matériaux et du génie physique (LMGP ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de La Réunion (UR)-Université Paris Diderot - Paris 7 (UPD7)-IPG PARIS-Institut national des sciences de l'Univers (INSU - CNRS), Laboratoire des matériaux et du génie physique (LMGP), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique de Grenoble (INPG), Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National Polytechnique de Grenoble (INPG)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Electron Microscopy for Materials Research, University of Huddersfield, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)
Subjects: XRD, Analytical chemistry, Crystal structure, 010402 general chemistry, Hot pressing, 01 natural sciences, Thermal expansion, Inorganic Chemistry, MAX Phases, Phase (matter), Chemistry, Inorganic & Nuclear, CRYSTAL-STRUCTURE, Physical and Theoretical Chemistry, POWDER, ComputingMilieux_MISCELLANEOUS, TI2SNC, Science & Technology, 010405 organic chemistry, Chemistry, Rietveld refinement, Lattice Distortions, MECHANICAL-PROPERTIES, [CHIM.MATE]Chemical Sciences/Material chemistry, Microstructure, CTE, 0104 chemical sciences, Double Solid Solutions, TI3ALC2, OXIDATION RESISTANCE, Physical Sciences, MAX phases, THERMAL-EXPANSION, TI, M2SNC M, BEHAVIOR, Solid solution
Abstract: Quasi phase-pure (>98 wt %) MAX phase solid solution ceramics with the (Zr,Ti)2(Al0.5,Sn0.5)C stoichiometry and variable Zr/Ti ratios were synthesized by both reactive hot pressing and pressureless sintering of ZrH2, TiH2, Al, Sn, and C powder mixtures. The influence of the different processing parameters, such as applied pressure and sintering atmosphere, on phase purity and microstructure of the produced ceramics was investigated. The addition of Sn to the (Zr,Ti)2AlC system was the key to achieve phase purity. Its effect on the crystal structure of a 211-type MAX phase was assessed by calculating the distortions of the octahedral M6C and trigonal M6A prisms due to steric effects. The M6A prismatic distortion values were found to be smaller in Sn-containing double solid solutions than in the (Zr,Ti)2AlC MAX phases. The coefficients of thermal expansion along the ⟨ a⟩ and ⟨ c⟩ directions were measured by means of Rietveld refinement of high-temperature synchrotron X-ray diffraction data of (Zr1- x,Ti x)2(Al0.5,Sn0.5)C MAX phase solid solutions with x = 0, 0.3, 0.7, and 1. The thermal expansion coefficient data of the Ti2(Al0.5,Sn0.5)C solid solution were compared with those of the Ti2AlC and Ti2SnC ternary compounds. The thermal expansion anisotropy increased in the (Zr,Ti)2(Al0.5,Sn0.5)C double solid solution MAX phases as compared to the Zr2(Al0.5,Sn0.5)C and Ti2(Al0.5,Sn0.5)C end-members. ispartof: INORGANIC CHEMISTRY vol:58 issue:10 pages:6669-6683 ispartof: location:United States status: published
Published: 2019

17. Diverted Natural Lossen-type Rearrangement for Bioconjugation through in Situ Myrosinase-Triggered Isothiocyanate Synthesis

Author: Reine Nehmé, Cyrille Sabot, Arnaud Tatibouët, Hélène Castel, Marie Hubert-Roux, Giuliano Cutolo, Pierre-Yves Renard, Benjamin Poret, Marie Schuler, Jean Wilfried Fredy, Pierrick Gandolfo, Différenciation et communication neuronale et neuroendocrine (DC2N), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-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 Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)
Subjects: Glycoside Hydrolases, Biomedical Engineering, Pharmaceutical Science, Bioengineering, 02 engineering and technology, 01 natural sciences, chemistry.chemical_compound, [CHIM]Chemical Sciences, Humans, Fluorescein isothiocyanate, Fluorescent Dyes, Pharmacology, chemistry.chemical_classification, Bioconjugation, 010405 organic chemistry, Myrosinase, Biomolecule, Organic Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Fluorescence, 0104 chemical sciences, HEK293 Cells, Solubility, chemistry, Thiourea, Glucosinolate, Isothiocyanate, 0210 nano-technology, Fluorescein-5-isothiocyanate, Biotechnology
Abstract: International audience; Fluorescein isothiocyanate (FITC) is one of the most extensively used fluorescent probes for the labeling of biomolecules. The isothiocyanate function reacts with lysine residues of proteins to provide a chemically stable thiourea linkage without releasing any byproduct. However, diversification of isothiocyanate-based reagents is still hampered by the lack of mild conditions to generate isothiocyanate chemical functions, as well as by their poor stability and limited solutions available to increase water solubility, restricting the use of isothiocyanate labeling to highly water-soluble fluorophores. Inspired by plant biological processes, we report a safe and biocompatible myrosinase-assisted in situ formation of isothiocyanate conjugates from a highly water-soluble and stable glucosinolate precursor. This method was applied for the fluorescence labeling of a plasmatic protein and fluorescence imaging of living cells.
Published: 2019

18. Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform

Author: Clément Berthonneau, Jean-François Brière, Franck Suzenet, Floris Buttard, Marie-Aude Hiebel, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ROUX-MERLIN, Madeleine, Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Domino, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Michael reaction, Bifunctional, Conjugate
Abstract: International audience; An unprecedented catalytic aza-Michael addition to substituted 3-vinyl-1,2,4-triazines, as original bifunctional platforms for the domino conjugate addition inverse-electron-demand hetero-Diels–Alder/retro-Diels–Alder (ihDA/rDA) reaction, was achieved using the highly acidic triflimide as an organocatalyst. Based on the use of alkoxyamine nucleophiles, this sequence not only highlights a rare example of the catalytic aza-Michael reaction to alkenylazaarenes but also proves to be useful for the elaboration of an array of biorelevant tetrahydro-[1,6]-naphthyridines.
Published: 2019

19. In Situ Electron Paramagnetic Resonance Correlated Spectroscopy and Imaging: A Tool for Lithium-Ion Batteries to Investigate Metallic Lithium Sub-Micrometric Structures Created by Plating and Stripping

Author: Mingxue Tang, Jean-Marie Tarascon, Gourier Didier, Elodie Salager, Hervé Vezin, Charles Emmanuel Dutoit, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), 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 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), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), 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), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), LABEX STORE-EX (ANR-10-LABX-76), CNRS, ANR-15-CE05-0015,OSIRIS,Spectroscopie et imagerie operando de batteries par résonance magnétique in situ(2015), Université d'Orléans (UO)-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 ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), 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)-Ministère de la Culture (MC), Collège de France - Chaire Chimie du solide et énergie, and Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: In situ, Materials science, Nucleation, Analytical chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, law.invention, Electrochemical cell, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, law, Electrode, [CHIM]Chemical Sciences, Spectroscopy, Polarization (electrochemistry), Electron paramagnetic resonance
Abstract: Monitoring the formation of dendrites or filaments of lithium is of paramount importancefor Li-based battery technologies, hence the intense activities in designing in situ techniquesto visualize their growth. Herein we report the benefit of correlating in situ electron para4 magnetic resonance (EPR) spectroscopy and EPR imaging to analyze the morphology andlocation of metallic lithium in a symmetric Li/LiPF6/Li electrochemical cell during polariza6 tion. We exploit the variations in shape, resonance field and amplitude of the EPR spectrato follow, operando, the nucleation of sub-micrometric Li particles (narrow and symmetricalsignal) that conjointly occurs with the fragmentation of bulk Li on the opposite electrode(asymmetrical signal). Moreover, in situ EPR correlated spectroscopy and imaging (spectral10 spatial EPR imaging) allows the identification (spectral) and localization (spatial) of the sub11 micrometric Li particles created by plating (deposition) or stripping (altered bulk Li surface).We finally demonstrate the possibility to visualize, via in situ EPR imaging, dendrites formedthrough the separator in the whole cell. Such a technique could be of great help in masteringthe Li-electrolyte interface issues that plague the development of solid-state batteries.
Published: 2020

20. A Porphyrin Dimer–GdDOTA Conjugate as a Theranostic Agent for One- and Two-Photon Photodynamic Therapy and MRI

Author: Sébastien Jenni, Barbara Ventura, Célia S. Bonnet, Éva Tóth, Angélique Sour, Frédéric Bolze, Valérie Heitz, Agnès Pallier, Julie Schmitt, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Conception et application de molécules bioactives (CAMB), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Université de Strasbourg (UNISTRA), ISOF-CNR, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Université d'Orléans (UO)-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 LEGOUPIL, Laëtitia
Subjects: Porphyrins, [SDV]Life Sciences [q-bio], medicine.medical_treatment, MRI contrast agent, Dimer, Biomedical Engineering, Pharmaceutical Science, Bioengineering, Photodynamic therapy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Theranostic Nanomedicine, HeLa, chemistry.chemical_compound, Nuclear magnetic resonance, Two-photon excitation microscopy, Heterocyclic Compounds, Theranostic agent, Neoplasms, Organometallic Compounds, medicine, Humans, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, Pharmacology, Photons, Photosensitizing Agents, Singlet Oxygen, biology, Singlet oxygen, Organic Chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Magnetic Resonance Imaging, Porphyrin, 0104 chemical sciences, 3. Good health, [SDV] Life Sciences [q-bio], Photochemotherapy, chemistry, Porphyrin dimer, 0210 nano-technology, Dimerization, MRI, HeLa Cells, Biotechnology, Conjugate
Abstract: International audience; A molecular theranostic agent designed for photodynamic therapy (PDT) treatment in the near-infrared and for imaging tissue tumors with magnetic resonance imaging (MRI) is reported. It consists of a linear pi-conjugated Zn(II) porphyrin dimer linked at each extremity to a GdDOTA-type complex. This agent has shown very promising potential for PDT applications with good singlet oxygen generation in DMSO and high linear absorption in the near- infrared (lambda(max) = 746 nm, epsilon approximate to 10(5) M-1 cm(-1)). Moreover, this molecule has a propensity for two-photon excited PDT with high two-photon cross sections (similar to 8000 GM in 880-930 nm range), which should allow for deeper tumor treatments and higher spatial precision as compared to conventional one-photon PDT. Regarding the MRI contrast agent properties, the molecule has shown superior relaxivity (14.4 mM(-1) s(-1) at 40 MHz, 298 K) in comparison to clinical contrast agents and the ability to be internalized in cells, thanks to its amphiphilic character. Irradiation of HeLa cells using either one-photon (740 nm) or two-photon excitation (910 nm) has led in both cases to important cell death.
Published: 2018

21. Palladium-Catalyzed Domino Allenamide Carbopalladation/Direct C–H Allylation of Heteroarenes: Synthesis of Primprinine and Papaverine Analogues

Author: Jonathan Hédouin, Cédric Schneider, Isabelle Gillaizeau, Christophe Hoarau, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-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: 010405 organic chemistry, Chemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Domino, 0104 chemical sciences, Catalysis, Intramolecular force, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Palladium
Abstract: International audience; Palladium-catalyzed intramolecular carbopalladation onto allenamides completed by direct C–H allylation of heterocycles is studied. The domino construction/heteroarylation of isoquinolone process is first achieved. A general three-step one-pot strategy, involving in situ generation of allenamide, π-allyl-Pd complex generation, and interception with heteroarenes, has been subsequently set up. This methodology has been extended to the construction/heteroarylation of indoles, dihydroquinolines, isoquinolin(on)es, and medium-sized nitrogen heterocycles, which are known to be key challenging structural motifs with pharmaceutical significance.
Published: 2018

22. Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries

Author: Jean-Marie Tarascon, Antonella Iadecola, Olaf J. Borkiewicz, Elodie Salager, Kamila M. Wiaderek, Minhua Shao, Guohua Chen, Damien Dambournet, Leiting Zhang, Dmitry Batuk, The Hong Kong Polytechnic University [Hong Kong] (POLYU), 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), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Advanced Photon Source [ANL] (APS), Argonne National Laboratory [Lemont] (ANL)-University of Chicago-US Department of Energy, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Hong Kong University of Science and Technology (HKUST), Sorbonne Université (SU), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, 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: Battery (electricity), Phase transition, Materials science, General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, Electrolyte, Manganese, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, law.invention, law, Materials Chemistry, ComputingMilieux_MISCELLANEOUS, Physics, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, Chemistry, Chemical engineering, chemistry, Electrode, 0210 nano-technology, Solid solution
Abstract: In the quest for high energy density rechargeable batteries, conversion-type cathode materials stand out with their appealing multielectron transfer properties. However, they undergo a series of complex phase transitions upon initial cycling as opposed to conventional intercalation-type materials. Within this category, iron-based mixed-anion solid solutions (FeOxF2-x) have captured the most attention of the battery community, owing to their high theoretical capacity and moderate cyclability. In the meantime, it was recently demonstrated, via a series of electrochemical cycling experiments, the in situ preparation of manganese-based mixed-anion cathode materials based on decomposition of electrolyte salt LiPF6 in the presence of MnO. To take a step forward, we herein report a routine protocol to prepare 220 mAh g(-1)-class composite cathodes. In addition, we provide a comprehensive understanding of the in situ fluorination and locally reversible phase transitions using complementary analytical techniques. The charged phase, with an average Mn oxidation state of ca. +2.8, consists of a highly disordered O-rich cubic-spinel-like core and an F-rich amorphous shell. Upon discharge, lithiation induces further phase transition, forming LiF, MnO, and a lithiated rocksalt-like phase. This work, which we also extended to the iron-based system, offers insights into modification of chemical and electronic properties of electrode materials by in situ fluorination.
Published: 2018

23. Mechanistic Understanding of Uranyl Ion Complexation on Montmorillonite Edges: A Combined First-Principles Molecular Dynamics–Surface Complexation Modeling Approach

Author: Ruth M. Tinnacher, Xiandong Liu, Chi Zhang, Christophe Tournassat, State Key Laboratory for Mineral Deposits Research, Nanjing University (NJU), Department of Chemistry & Biochemistry, California State University [East Bay] (CSUEB), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Milieux Poreux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), and Lawrence Berkeley National Laboratory [Berkeley] (LBNL)
Subjects: Ions, Denticity, General Chemistry, Molecular Dynamics Simulation, 010501 environmental sciences, 010502 geochemistry & geophysics, Uranyl, 01 natural sciences, Atomic units, Ion, chemistry.chemical_compound, Molecular dynamics, Adsorption, Montmorillonite, chemistry, [SDU]Sciences of the Universe [physics], Bentonite, Uranium, Environmental Chemistry, Physical chemistry, 0105 earth and related environmental sciences
Abstract: International audience; Systematic first-principles molecular dynamics (FPMD) simulations were carried out to study the structures, free energies, and acidity constants of UO22+ surface complexes on montmorillonite in order to elucidate the surface complexation mechanisms of the uranyl ion (UO22+) on clay mineral edges at the atomic scale. Four representative complexing sites were investigated, that is, Al(OH)(2) and AlOHSiO on the (010) surface and AlOHOa and SiOOa on the (110) surface. The results show that uranyl ions form bidentate complexes on these sites. All calculated binding free energies for these complexes are very similar. These bidentate complexes can be hydrolyzed, and their corresponding derived pK a values (around 5.0 and 9.0 for pK(a1), and pK(a2), respectively) indicate that UO2(OH)(+) and UO2(OH)(2) surface groups are the dominant surface species in the environmental pH range. The OH groups of UO2(OH)(2) surface complexes can act as complexing sites for subsequent metals. Additional simulations showed that such multinuclear adsorption is feasible and can be important at high pH. Furthermore, FPMD simulation results served as input parameters for an electrostatic thermodynamic surface complexation model (SCM) that adequately reproduced adsorption data from the literature. Overall, this study provides an improved understanding of UO(2)(2+ )complexation on clay mineral edge surfaces.
Published: 2018

24. A Pitzer Parametrization To Predict Solution Properties and Salt Solubility in the H–Na–K–Ca–Mg–NO3–H2O System at 298.15 K

Author: Arnault Lassin, Laurent André, Christomir Christov, Sylvain Guignot, Pierre Henocq, Adeline Lach, Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Milieux Poreux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), konstantin Preslavsky University, and Agence Nationale pour la Gestion des Déchets Radioactifs (ANDRA)
Subjects: Activity coefficient, Chemistry, General Chemical Engineering, Binary number, Thermodynamics, 02 engineering and technology, General Chemistry, Electrolyte, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, 020401 chemical engineering, [SDU]Sciences of the Universe [physics], Osmotic coefficient, 0204 chemical engineering, Solubility, Ternary operation, Phase diagram
Abstract: International audience; A new set of Pitzer interaction parameters is proposed to describe the excess properties of the H–Na–K–Ca–Mg–NO3–H2O system at 298.15 K. From these parameters we reproduce the osmotic coefficient, mean activity coefficients, and density for the binary systems, and also salt solubility in the ternary subsystems. The binary interaction parameters are either selected from the literature or redetermined in this study. In the case of KNO3–H2O and HNO3–H2O binary systems, partial electrolyte dissociation has to be taken into account to represent accurately all the experimental data up to very high concentrations. Then solubility data of salts in the corresponding ternary systems are used to determine the ternary interaction parameters and the solubility products of the double salts. As KNO3 and HNO3 are partially dissociated, we have determined new interaction parameters involving neutral species (for instance ηKNO3/Na+/H+ or μHNO3/KNO3/Na+) to draw the phase diagram of quaternary systems Na–K–H–NO3. To complement the study, we also propose a set of volumetric Pitzer interaction parameters for all the binary systems and for the H–K–NO3 ternary system, so solution density can be computed at 298.15 K.
Published: 2018

25. Local Disorder and Tunable Luminescence in Sr1–x/2Al2–xSixO4 (0.2 ≤ x ≤ 0.5) Transparent Ceramics

Author: Florence Porcher, Wolfgang Wisniewski, Kholoud Al Saghir, Ana I. Becerro, Mathieu Allix, Emmanuel Véron, Guy Matzen, Alberto J. Fernández-Carrión, Franck Fayon, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia de Materiales de Sevilla (ICMSE), Universidad de Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Otto-Schott-Institut für Glaschemie, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], ANR-11-EQPX-0036,PLANEX,Planète Expérimentation: simulation et analyse in-situ en conditions extrêmes(2011), ANR-14-CE07-0002,FOCAL,Fibres Optiques Céramiques pour Applications Lasers(2014), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Universidad de Sevilla / University of Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Junta de Andalucía, Agence Nationale de la Recherche (France), Ministerio de Economía y Competitividad (España), and Department of Energy (US)
Subjects: Transparent ceramics, Chemistry, Doping, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Aerodynamic levitation, law.invention, Inorganic Chemistry, Crystallography, law, Light emission, Physical and Theoretical Chemistry, Crystallization, 0210 nano-technology, Europium, Luminescence, Superstructure (condensed matter)
Abstract: Eu-doped SrAlSiO (x = 0.2, 0.4, and 0.5) transparent ceramics have been synthesized by full and congruent crystallization from glasses prepared by aerodynamic levitation and laser-heating method. Structural refinements from synchrotron and neutron powder diffraction data show that the ceramics adopt a 1 × 1 × 2 superstructure compared to the SrAlO hexagonal polymorph. While the observed superstructure reflections indicate a long-range ordering of the Sr vacancies in the structure, Si and Al solid-state NMR measurements associated with DFT computations reveal a significant degree of disorder in the fully polymerized tetrahedral network. This is evidenced through the presence of Si-O-Si bonds, as well as Si(OAl) units at remote distances of the Sr vacancies and Al(OAl) units in the close vicinity of Sr vacancies departing from local charge compensation in the network. The transparent ceramics can be doped by europium to induce light emission arising from the volume under UV excitation. Luminescence measurements then reveal the coexistence of Eu and Eu in the samples, thereby allowing tuning the emission color depending on the excitation wavelength and suggesting possible applications such as solid state lighting., The authors also thank the French ANR for its financial support to the FOCAL ANR-14-CE07-0002 and Equipex Planex ANR-11-EQPX-36 projects, the CNRS and CSIC for the PICS n° 07490 and PIC2016FR1 projects, as well as the Spanish Ministry of Economy and Competitiveness for the grant MAT2014 54852-R. A. J. F.-C. gratefully acknowledges an F. P. D. I. grant from Junta de Andalucía. Financial support from the TGIR RMN THC FR3050 for conducting the research is gratefully acknowledged. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Published: 2017

26. Solid Fluoride Electrolytes and Their Composite with Carbon: Issues and Challenges for Rechargeable Solid State Fluoride-Ion Batteries

Author: Monique Body, Antonin Grenier, Christophe Legein, Ana Gabriela Porras-Gutierrez, Mickaël Dollé, Damien Dambournet, Fabien Chrétien, Henri Groult, Encarnacion Raymundo-Piñero, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), Université de Montréal [Montréal], Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-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), Université de Montréal (UdeM), 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), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)
Subjects: Anions, Materials science, Composite number, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Electrochemical cells, chemistry.chemical_compound, Ionic conductivity, Redox reactions, Physical and Theoretical Chemistry, Electrodes, Composites, [PHYS]Physics [physics], 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, 13. Climate action, Electrode, Lithium, 0210 nano-technology, Fluoride, Carbon
Abstract: International audience; Solid-state batteries relying on fluoride-ion shuttle are still at their early stage of development. Assessing the fluoride solid electrolyte’s electrochemical stability and its conduction properties in a mixture with carbon, as well as the possible interaction of fluoride-ion with carbon both during the electrode preparation and upon electrochemical reactions, are mandatory to enable future practical applications. Here, we discuss these points using LaF3 doped with BaF2 (La0.95Ba0.05F2.95, LBF) as a benchmark solid fluoride electrolyte. We establish that lithium may be used as a pseudo-reference electrode to assess the electrochemical stability window of LBF and support the experiment with thermodynamic calculations. We demonstrate the chemical compatibility of LBF with carbon upon ball-milling, and investigate the electrical conductivity of the formed LBF-C composite. We use a LBF|LBF-C|LBF cell (in this configuration, LBF serves as electronically blocking electrode) to assess the ionic conductivity of the LBF-C composite. The results confirm that both electronic and ionic percolations are insured within the LBF-C composite despite a noticeable decrease of the ionic conductivity. Finally, we use a Li|LBF|LBF-C cell to evaluate the electrochemical fluorination of the carbon in the LBF-C composite. Our results suggest an electrochemical activity of carbon with fluoride ions. The possible interactions of carbon with fluorides to form insulating carbon fluoride (CFx) must be considered when determining the operating voltage of FIBs.
Published: 2017

27. Domino Aza-Michael-ih-Diels–Alder Reaction to Various 3-Vinyl-1,2,4-triazines: Access to Polysubstituted Tetrahydro-1,6-naphthyridines

Author: Jabrane Jouha, Gérald Guillaumet, Clément Berthonneau, Floris Buttard, Franck Suzenet, Jean-François Brière, Marie-Aude Hiebel, Mostafa Khouili, Magali Lorion, Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM]Chemical Sciences, Organic chemistry, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Domino, 0104 chemical sciences, 3. Good health, Diels–Alder reaction
Abstract: International audience; A straightforward domino aza-Michael-inverse-electron-demand-hetero-Diels–Alder/retro-Diels–Alder reaction between primary and secondary propargylamine derivatives and 3-vinyl-1,2,4-triazines is developed highlighting not only the uniqueness of this dual-heterocyclic platform but also a novel and unprecedented path to polysubstituted tetrahydro-1,6-naphthyridine scaffolds.
Published: 2017

28. Structural, Optical, and Thermophysical Properties of Mesoporous Silicon Layers: Influence of Substrate Characteristics

Author: Domingos De Sousa Meneses, Thomas Defforge, Nadjib Semmar, Amer Melhem, Gaël Gautier, C. Andreazza-Vignolle, Audrey Sauldubois, Groupe de recherches sur l'énergétique des milieux ionisés (GREMI), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), GREMAN (matériaux, microélectronique, acoustique et nanotechnologies) (GREMAN - UMR 7347), Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS), Centre Commun de Caractérisation des Matériaux des Antilles et de la Guyane (C3MAG), Université des Antilles (UA), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Silicon, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, 01 natural sciences, photo thermal, [SPI]Engineering Sciences [physics], Thermal conductivity, Volumetric heat capacity, transmission electron microscopy, 0103 physical sciences, themophysics, [CHIM]Chemical Sciences, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Wafer, Physical and Theoretical Chemistry, Composite material, Porosity, [PHYS]Physics [physics], 010302 applied physics, Thermal contact conductance, silicon, Thermal contact, 021001 nanoscience & nanotechnology, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, FTIR spectroscopy, General Energy, chemistry, mesoporous, 0210 nano-technology, Mesoporous material
Abstract: In this paper, the structural, optical and thermal properties of n-type (100), p-type (100) and (111) mesoporous silicon (MePSi) are reported. The mesoporous silicon was prepared by an electrochemical process from bulk silicon wafer. Depending on the etching depth, analyses show that the porosity of p-type (111) increased by 32 to 40% compared to p (100) which, in turn, increased by 22 to 48% compared to n-type (100). The structure morphology and the abundance of Si-Ox and Si-Hy also depended heavily on the type and crystal orientation of MePSi. The thermal properties of the MePSi layers such as thermal conductivity (κ), volumetric heat capacity (ρCp) and thermal contact resistance (Rth) were determined using the pulsed photothermal method. The thermal conductivity of bulk silicon dropped sharply after etching, decreasing by more than twenty-fold in the case of n-type (100) and by over forty-five fold for p-type (100) and (111). According to the percolation model depending on both porosity and phonon confinement, the drop in thermal conductivity was mainly due to the nanostructure formation after etching. Thermal investigations showed that the volumetric heat capacity (ρCp) followed the barycentric model which depends mainly on the porosity. The thermal contact resistances of MePSi layers were estimated to be in the range of 1x10-8 to 1x10-7 K⋅m2⋅W-1.
Published: 2017

29. Use of Primary and Secondary Polyvinylamines for Efficient Gene Transfection

Author: Jutta Rieger, Christine Jérôme, Philippe Guégan, Antoine Debuigne, Patrick Midoux, Christine Gonçalves, Mathilde Dréan, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Center for Education and Research on Macromolecules, Université de Liège, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), HAL-UPMC, Gestionnaire, Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Polymers and Plastics, Polymers, Radical polymerization, Dispersity, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Polymerization, Biomaterials, [CHIM] Chemical Sciences, Materials Chemistry, Humans, [CHIM]Chemical Sciences, Organic chemistry, Cell Proliferation, chemistry.chemical_classification, Drug Carriers, Molar mass, Cationic polymerization, Genetic Therapy, Polymer, Transfection, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, chemistry, Molar mass distribution, Polyvinyls, Amine gas treating, 0210 nano-technology, HeLa Cells, Plasmids
Abstract: International audience; Gene transfection with polymeric carrier remains a challenge, particularly high transfection levels combined with low toxicity are hard to achieve. We herein revisit polyvinylamines, an old and neglected family of cationic polymers. They can be readily obtained by controlled hydrolysis of polyvinylamides prepared through (controlled) radical polymerization. A series of tailor-made and well-defined polyvinylamines bearing primary amino groups, and poly(N-methylvinylamine) bearing secondary amines, were evaluated for the transfection of cells with pDNA as a function of their molar mass, molar mass distribution and degree of deacetylation. Unexpected high transfection levels, in combination with low cytotoxicity were recorded for both series. Surprisingly, a great impact of the molar mass was observed for the primary amine polyvinylamine series, whereas the results were mostly independent on molar mass or dispersity for the polymer bearing secondary amine. It was further established that a certain percentage of acetamide groups increased the transfection level, while maintaining low cytotoxicity. These results highlight for the first time the real potential of polyvinylamines as gene carriers, and make these polymers very attractive for further development in gene therapy.
Published: 2017

30. 2D-Layered Lithium Carboxylate Based on Biphenyl Core as Negative Electrode for Organic Lithium-Ion Batteries

Author: Frédéric Sauvage, Elodie Salager, Lionel Fédèle, Matthieu Becuwe, Jean-Noël Chotard, Carine Davoisne, Sébastien Gottis, 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), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), 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 de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Biphenyl, Materials science, General Chemical Engineering, chemistry.chemical_element, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Ion, chemistry.chemical_compound, chemistry, Chemical engineering, Transmission electron microscopy, Electrode, Materials Chemistry, Lithium, Carboxylate, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: A 2D-layered conjugated organic lithium carboxylate based on 4,4′-biphenyl core has been synthesized and characterized by combining powder X-ray diffraction, two-dimensional solid-state 13C NMR, and high-resolution transmission electron microscopy. The combination of these complementary technics identifies both molecular packing and structural organization within the solid. The electrochemical performances of this new organic negative electrode have been evaluated. The specific 2D-layer offered by the 4,4′-biphenyl framework confers to the material an unprecedented rate capability, maintaining as high as 180 mAh g–1 over 25 cycles at 2e–/hour rate without any means of electrode formulation. Such electrochemical performances are ascribed at once to the enhancement of lithium conduction inside the mesoscopic crystal structure, promoted by the greater distance between the inorganic LiO4 layers and to the greater structural robustness upon cycling sustaining no structural amorphization during lithium insertio...
Published: 2017

31. Screening Method for Fuels in Homogeneous Charge Compression Ignition Engines: Application to Valeric Biofuels

Author: Christine Mounaïm-Rousselle, Philippe Dagaut, Fabien Halter, Fabrice Foucher, Jean-Baptiste Masurier, Francesco Contino, Guillaume Dayma, Applied Mechanics, Fluid Mechanics and Thermodynamics research group, Combustion and Robust optimization, Vrije Universiteit Brussel (VUB), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Laboratoire pluridisciplinaire de recherche en ingénierie des systèmes, mécanique et énergétique (PRISME), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), European Project: 291049,EC:FP7:ERC,ERC-2011-ADG_20110209,2G-CSAFE(2011), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS)
Subjects: Computer science, business.industry, 020209 energy, General Chemical Engineering, Homogeneous charge compression ignition, Energy Engineering and Power Technology, Biomass, 02 engineering and technology, Diesel engine, Combustion, Key features, 7. Clean energy, Fuel Technology, 13. Climate action, Biofuel, Chemical Engineering(all), 0202 electrical engineering, electronic engineering, information engineering, Screening method, [CHIM]Chemical Sciences, Process engineering, business, Cetane number, Screening Method, Homogeneous Charge Compression Ignition Engines, HCCI, Valeric Biofuels, valerates, combustion
Abstract: International audience; The successful implementation of innovative fuels relies on many factors and requires a precise description of thecombustion characteristics. In practice, traditional indicators, such as octane or cetane numbers, are used. Obtaining thesenumbers however requires a specific setup. Moreover, they are not sufficient to predict the combustion timing for innovativeconcepts, such as homogeneous charge compression ignition (HCCI). Evaluating and reporting the characteristics of new fuels istherefore challenging. Using a regular diesel engine converted to HCCI operation, we developed a screening methodology toeasily characterize and present key features of new fuels. This paper describes the methodology and then applies it to new fuelsproduced from biomass: valeric biofuels. The methodology presented in this study intends to bridge the work on fundamentalchemical kinetics with conventional engine experiments.
Published: 2016

32. Chasing Aqueous Biphasic Systems from simple salts by exploring the LiTFSI/LiCl/H2O phase diagram

Author: Benjamin Rotenberg, Nicolas Dubouis, Joachim Dzubiella, Soufiane Abdelghani-Idrissi, Chanbum Park, Michaël Deschamps, Annie Colin, Mathieu Salanne, Alexis Grimaud, Matej Kanduč, 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), 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), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB), Humboldt-Universität zu Berlin, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL), Jozef Stefan Institute [Ljubljana] (IJS), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Albert-Ludwigs-Universität Freiburg, 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), Humboldt University Of Berlin, Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE05-0008,MIDWAY,Contrôle des Interfaces Electrochimiques pour de meilleurs electrocatalyseurs pour l'oxydation de l'eau(2017)
Subjects: chemistry.chemical_classification, Battery (electricity), Materials science, Aqueous solution, 010405 organic chemistry, General Chemical Engineering, chemistry.chemical_element, General Chemistry, Polymer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, chemistry.chemical_compound, chemistry, Chemical engineering, Ionic liquid, Lithium, Electrochemical energy storage, Imide, QD1-999, Phase diagram
Abstract: Aqueous Biphasic Systems (ABS), in which two aqueous phases with different compositions coexist as separate liquids, have first been reported over a century ago with polymer solutions. Recent observations of ABS forming from concentrated mixtures of inorganic salts and ionic liquids raise the fundamental question of how "different" the components of such mixtures should be for a liquid-liquid phase separation to occur. Here we show that even two monovalent salts sharing a common cation (lithium) but with different anions, namely LiCl and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), may result in the formation of ABSs over a wide range of compositions at room temperature. Using a combination of experimental techniques and molecular simulations, we analyze the coexistence diagram and the mechanism driving the phase separation, arising from the different anion sizes. The understanding and control of ABS may provide new avenues for aqueous-based battery systems.
Published: 2018

33. Experimental and Detailed Kinetic Modeling Study of Cyclopentanone Oxidation in a Jet-Stirred Reactor at 1 and 10 atm

Author: Casimir Togbé, Philippe Dagaut, Zeynep Serinyel, Sébastien Thion, Guillaume Dayma, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS), European Project: 291049,EC:FP7:ERC,ERC-2011-ADG_20110209,2G-CSAFE(2011), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS)
Subjects: Cyclopentenone, Kinetic modeling, General Chemical Engineering, Radical, Energy Engineering and Power Technology, Reaction intermediate, 010402 general chemistry, Cyclopentanone, Hydrogen atom abstraction, Photochemistry, 01 natural sciences, 7. Clean energy, chemistry.chemical_compound, Reaction rate constant, 0103 physical sciences, ComputingMilieux_MISCELLANEOUS, 010304 chemical physics, Chemistry, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, Oxidation -mechanism, cyclopentanone, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Jet-Stirred reactor, Fuel Technology, Physical chemistry, Gas chromatography, Stoichiometry
Abstract: Cyclopentanone oxidation was studied in a jet-stirred reactor at 1 and 10 atm and over the temperature range of 730–1280 K for fuel-lean (φ = 0.5), stoichiometric, and fuel-rich (φ = 2) mixtures. A total of 16 reaction intermediates and products were identified and quantified using online Fourier transform infrared spectrometry and offline gas chromatography. A kinetic submodel was developed, supported by theoretical calculations for the rate constants of hydrogen abstraction reactions by H atoms and OH and CH3 radicals at the MP2/aug-cc-pVDZ level of theory. The resulting model consisting of 343 species involved in 2065 reactions was used to simulate the present experiments and showed good agreement with the data. The main oxygenated intermediates are aldehydes, and cyclopentenone was also found to be an important species for cyclopentanone oxidation. The rate of production analyses showed that cyclopentanone is mainly consumed by a sequence of reactions producing CO and the but-1-en-4-yl radical. Unimol...
Published: 2016

34. Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers

Author: Jorge Gascon, Pierre Fertey, Hala Assi, Charlotte Martineau, Laura C. Pardo Pérez, Maxim A. Nasalevich, Nathalie Guillou, Thomas Devic, Freek Kapteijn, Hubert Chevreau, Georges Mouchaham, Christian Serre, Erik Elkaim, Florence Ragon, Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Delft Univ. of Technology (TUDelft), Delft University of Technology (TU Delft), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)
Subjects: chemistry.chemical_classification, Inorganic chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Hydrothermal circulation, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Octahedron, Photocatalysis, Reactivity (chemistry), Carboxylate, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Titanium, Visible spectrum
Abstract: The reactivity of 2,5-dihydroxyterephthalic acid (H4DOBDC) with titanium(IV) precursors was thoroughly investigated for the synthesis of metal-organic frameworks under solvothermal conditions. Four crystalline phases were isolated whose structures were studied by a combination of single-crystal or powder X-ray diffraction and solid-state NMR. The strong coordination ability of the phenolate moieties was found to favor the formation of isolated TiO6 octahedra bearing solely organic ligands in the resulting structures, unless hydrothermal conditions and precondensed inorganic precursors are used. It is worth noting that these solids strongly absorb visible light, as a consequence of the ligand-to-metal charge transfer (LMCT) arising from Ti-phenolate bonds. Preliminary photocatalytic tests suggest that one compound, namely, MIL-167, presents a higher activity for hydrogen evolution than the titanium carboxylate MIL-125-NH2 but that such an effect cannot be directly correlated with its improved light absorption feature.
Published: 2016

35. Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins

Author: Alain Defontaine, Daniel R. Talham, Franck Fayon, Charles Tellier, Florian Forato, Amina Fateh, Hao Liu, Cathy Charlier, Bruno Bujoli, Roland Benoit, Clémence Queffélec, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), 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), University of Florida [Gainesville] (UF), Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de fonctionnalité et ingénierie de protéines (UFIP), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Phosphopeptides, Surface Properties, Archaeal Proteins, Inorganic chemistry, Organophosphonates, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Monolayer, Electrochemistry, Zirconyl chloride, General Materials Science, ComputingMilieux_MISCELLANEOUS, Spectroscopy, Zirconium, Sulfolobus acidocaldarius, Phosphopeptide, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, Phosphoproteins, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Phosphonate, 0104 chemical sciences, DNA-Binding Proteins, chemistry, Zirconium phosphate, Hydroxide, Amine gas treating, 0210 nano-technology
Abstract: Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.
Published: 2016

36. Mn-Containing N-Doped Monolithic Carbon Aerogels with Enhanced Macroporosity as Electrodes for Capacitive Deionization

Author: ANIA, Conchi, Macías, Carlos, Rasines, Gloria, Lavela, Pedro, Zafra, María, Tirado, José, O. Ania, Conchi, Ministerio de Economía y Competitividad (España), Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diatomite, Resorcinol, Materials science, Capacitive deionization, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Colloid, Carbon black, Environmental Chemistry, ComputingMilieux_MISCELLANEOUS, [SDE.IE]Environmental Sciences/Environmental Engineering, Desalination, Renewable Energy, Sustainability and the Environment, Manganes, Aerogel, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Nitrogen doping, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Polymerization, Electrode, 0210 nano-technology, Carbon
Abstract: We propose the use of siliceous diatomite as an antishrinkage additive for the synthesis of monolithic carbon aerogel electrodes with enhanced electrochemical response for capacitive deionization of NaCl solutions. Hybrid N- and Mn-doped carbon aerogels with improved electrical conductivity and wettability in the aqueous electrolyte are prepared by introducing modifications in the synthesis (carbon black and/or diatomite loading before the polymerization sol–gel polycondensation of the monomers, followed by manganese infiltration). The textural and morphological characterizations of the materials reveal that the presence of the additives does not impede the cross-linking of the monomers to form branched clusters and colloidal aggregates leading to a highly porous structure. Furthermore, the aerogel materials display an open macroporous network inherited by the diatomite, even after its lixiviation. As a result, the monolithic carbon aerogel electrodes present good electrochemical performance in terms of low polarization resistance, high capacitance, and fast electroadsorption., The authors are indebted to the MINECO (Contract IPT-2011-1450-310000 (ADECAR) and FEDER cofunding, and CTM2014-56770-R) for the financial support. We also thank the fruitful collaboration of Isolux Ingeniería, S.A., Fundación Imdea Energía and Proingesa.University of Cordoba thanks to SCAI and IUIQFN for technical support and Junta de Andalucía (FQM-288) for financial support.
Published: 2016

37. Adsorption of Small Molecules in the Porous Zirconium-Based Metal Organic Framework MIL-140A (Zr): A Joint Computational-Experimental Approach

Author: Charlotte Martineau, Farid Nouar, Naseem A. Ramsahye, Daiane Damasceno Borges, Christian Serre, Alexandre A. Leitão, Philip L. Llewellyn, Andrew D. Wiersum, Guillaume Maurin, C. Vieira Soares, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Instituto Nacional de Recursos Biológicos, I.P./L-IPIMAR, Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Isothermal microcalorimetry, Materials science, Monte Carlo method, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Adsorption, Computational chemistry, Molecule, Physics::Chemical Physics, Physical and Theoretical Chemistry, Porosity, Zirconium, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, Chemical engineering, Metal-organic framework, Density functional theory, 0210 nano-technology
Abstract: International audience; The adsorption of small molecules (CO2, CO, H-2, CH4, and N-2) in a small pore zirconium terephthalate MOF was explored by combining quantum and force-field-based molecular simulations and experiments. The Density Functional Theory strategy was first validated by a very good agreement between the predicted and the experimental spectroscopic (infrared, NMR) and structural features of the selected MOF. These quantum calculations further predicted the preferential adsorption sites and the strength of the host/guest interactions for all confined molecules. These conclusions were favorably compared to force field-based Monte Carlo simulations and microcalorimetry measurements. The water stability of this hybrid porous solid was equally explored as well as the interaction between the MOF and a well-known gas pollutant, that is, H2S.
Published: 2016

38. Hybrid Methodology for Retrieving Thermal Radiative Properties of Semi-Transparent Ceramics

Author: Benjamin Bouvry, Patrick Echegut, Olivier Rozenbaum, Leire del Campo, Domingos De Sousa Meneses, Romain Echegut, Michel Gaubil, David Lechevalier, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Saint Gobain CREE, Saint Gobain, Institut des Sciences de la Terre d'Orléans (ISTO), Université de Tours-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Saint-Gobain NRDC, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Work (thermodynamics), Materials science, Mechanical engineering, Infrared spectroscopy, 02 engineering and technology, Semi transparent, 01 natural sciences, 010309 optics, Optics, 0103 physical sciences, Thermal, Radiative transfer, Thermal emittance, Ceramic, Physical and Theoretical Chemistry, business.industry, Experimental data, 021001 nanoscience & nanotechnology, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, [SDU]Sciences of the Universe [physics], visual_art, visual_art.visual_art_medium, 0210 nano-technology, business
Abstract: International audience; Semitransparent materials, like silica or alumina, are highly used by high-temperature industries as refractory materials in blast or glass-making furnaces, first for their good mechanical properties. The knowledge of their radiative properties is also essential to improve thermal transfers. However, characterizing experimentally the high temperature dependence of radiative properties of semitransparent ceramic materials remains nowadays a difficult task. This paper reports a hybrid methodology to address this problem. The approach relies on two or more experimental emittance measurements, performed by infrared spectroscopy on samples of increasing thicknesses, and application of emittance models. The efficiency of the method is illustrated by using experimental data obtained on Jargal M samples, an industrial electrofused ceramic, and a virtual media built from X-ray computed tomography images. Two emittance models, a model from the literature and a new model proposed in this work, are selected to be a part of the hybrid methodology, since they allow retrieving complementary information on the optical and scattering properties of the materials. Both models show a good efficiency to reproduce emittance behavior of the industrial and virtual samples. Parameters are extracted from these models to improve our knowledge of the characteristic thickness of radiative transfer into semitransparent materials and the emittance value of semi-infinite media.
Published: 2016

39. Synthesis of RNA nucleotides in plausible prebiotic conditions from ab initio computer simulations

Author: Jean-François Lambert, Andrea Pérez-Villa, Fabio Pietrucci, François Guyot, Thomas Georgelin, Marie-Christine Maurel, A. Marco Saitta, Institut de Systématique, Evolution, Biodiversité (ISYEB ), Muséum national d'Histoire naturelle (MNHN)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université des Antilles (UA), Gestionnaire, Hal Sorbonne Université, Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-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 d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Muséum national d'Histoire naturelle (MNHN)-École Pratique des Hautes Études (EPHE)
Subjects: Purine, Anomer, Pyrimidine, [SDV]Life Sciences [q-bio], Ab initio, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Nucleobase, chemistry.chemical_compound, Computational chemistry, General Materials Science, Nucleotide, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Physical and Theoretical Chemistry, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, RNA, Ribonucleotides, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Prebiotics, chemistry, Nucleic Acid Conformation, Quantum Theory, Chirality (chemistry)
Abstract: International audience; Understanding the mechanism of spontaneous formation of ribonucleotides under realistic prebiotic conditions is a key open issue of origins-of-life research. In cells, de novo and salvage nucleotide enzymatic synthesis combines 5-phospho-α-d-ribose-1-diphosphate (α-PRPP) and nucleobases. Interestingly, these reactants are also known as prebiotically plausible compounds. Combining ab initio molecular dynamics simulations with recently developed reaction exploration and enhanced sampling methods, we show that nucleobases and α-PRPP should spontaneously combine, under mild hydrothermal conditions, with an exothermic reaction and a facile mechanism, forming both purine and pyrimidine ribonucleotides. Surprisingly, this mechanism is very similar to the biological one and yields ribonucleotides with the same anomeric carbon chirality as in biological systems. Mass spectrometry experiments performed on solutions of adenine and PRPP in similar conditions support the formation of AMP. These results suggest that natural selection might have optimized, through enzymes, a pre-existing ribonucleotide formation mechanism, carrying it forward to modern life forms.
Published: 2018

40. Atmospheric Chemistry of Oxygenated Volatile Organic Compounds: Impacts on Air Quality and Climate

Author: Timothy J. Wallington, Abdelwahid Mellouki, Jianmin Chen, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Systems Analytics and Environmental Sciences Department, Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), National Natural Science Foundation of China (No. 21190053)Taishan Scholar Grant (ts20120552), ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), Laboratoire de combustion et systèmes reactifs (LCSR), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), Ford Motor Company, and Shandong University
Subjects: General Chemistry, 7. Clean energy, Chemical reaction, Atmosphere, chemistry.chemical_compound, chemistry, [SDU.STU.CL]Sciences of the Universe [physics]/Earth Sciences/Climatology, 13. Climate action, Atmospheric chemistry, Environmental chemistry, [SDE]Environmental Sciences, [CHIM]Chemical Sciences, Tropospheric ozone, [CHIM.OTHE]Chemical Sciences/Other, Air quality index, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; It is hard to overstate the importance of oxygenated organiccompounds in atmospheric chemistry. Oxygenated organiccompounds are emitted into the atmosphere from natural andman-made sources, and they are formed in the atmosphere asoxidation products of all hydrocarbons present in theatmosphere. Oxygenated volatile organic compounds(OVOCs) are generally more reactive than the alkanes fromwhich they are derived. OVOCs play an active role in thesequence of chemical reactions responsible for troposphericozone formation in both polluted and remote environments.
Published: 2015

41. Subcritical Hydrothermal Liquefaction of Microalgae Residues as a Green Route to Alternative Road Binders

Author: Maria Paraschiv, Mohand Tazerout, Julie Hémez, Franck Fayon, Isabelle Louvet, Olivier Lépine, Jack Legrand, Clémence Queffélec, Bruno Bujoli, Mariane Audo, Emmanuel Chailleux, Matériaux pour Infrastructure de Transport (IFSTTAR/MAST/MIT), Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-PRES Université Nantes Angers Le Mans (UNAM), Laboratoire de génie des procédés - environnement - agroalimentaire (GEPEA), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Centre National de la Recherche Scientifique (CNRS)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut Universitaire de Technologie - Nantes (IUT Nantes), Université de Nantes (UN)-Institut Universitaire de Technologie Saint-Nazaire (IUT Saint-Nazaire), Université de Nantes (UN)-Institut Universitaire de Technologie - La Roche-sur-Yon (IUT La Roche-sur-Yon), Université de Nantes (UN)-Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Université Bretagne Loire (UBL), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Alpha Biotech, Bioprocédés Appliqués aux Microalgues (GEPEA-BAM), Université de Nantes (UN)-Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Université Bretagne Loire (UBL)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Mines Nantes (Mines Nantes), Mines Nantes (Mines Nantes)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PRES Université Nantes Angers Le Mans (UNAM), Université de Nantes - Faculté des Sciences et des Techniques, Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Centre National de la Recherche Scientifique (CNRS)-Université Bretagne Loire (UBL)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)
Subjects: biology, Renewable Energy, Sustainability and the Environment, Chemistry, 020209 energy, General Chemical Engineering, Biomass, Fraction (chemistry), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, 7. Clean energy, [SPI]Engineering Sciences [physics], Hydrothermal liquefaction, Rheology, Chemical engineering, Asphalt, Yield (chemistry), 0202 electrical engineering, electronic engineering, information engineering, Environmental Chemistry, 0210 nano-technology, Chemical composition, ComputingMilieux_MISCELLANEOUS, Scenedesmus
Abstract: International audience; The valorization of Scenedesmus sp. microalgae byproducts was investigated, as a potential route for the production of road binders from renewable sources. Under hydrothermal liquefaction conditions, a water-insoluble viscous material was obtained in a ca. 55% yield, which consists of an oily fatty acid-based fraction mixed with organic and inorganic solid residues (up to 22%). Although the chemical composition of the obtained materials completely differs from that of petroleum-based bitumen, similar viscoelastic properties were observed in some cases, depending on the hydrothermal liquefaction experimental conditions. A rheological simple material could thus be obtained, which compared well with a bitumen reference.
Published: 2015

42. Pressure Dependence of Butyl Nitrate Formation in the Reaction of Butylperoxy Radicals with Nitrogen Oxide

Author: Marie-Thérèse Rayez, Alexandre Kukui, G. Le Bras, N. I. Butkovskaya, Jean-Claude Rayez, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), and ANR-12-BS06-0017,ONCEM,Chimie des nitrates organiques : sources, puits et impact sur le transport longue distance de l'azote réactif(2012)
Subjects: [PHYS]Physics [physics], chemistry.chemical_classification, Chemical ionization, 010304 chemical physics, Radical, Butyl nitrate, Inorganic chemistry, Analytical chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, 13. Climate action, Torr, Yield (chemistry), 0103 physical sciences, Potential energy surface, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Quadrupole mass analyzer, Alkyl
Abstract: International audience; The yield of 1- and 2-butyl nitrates in the gas-phase reactions of NO with n-C4H9O2 and sec-C4H9O2, obtained from the reaction of F atoms with n-butane in the presence of O2, was determined over the pressure range of 100–600 Torr at 298 K using a high-pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. The yield of butyl nitrates was found to increase linearly with pressure from about 3% at 100 Torr to about 8% at 600 Torr. The results obtained are compared with the available data concerning nitrate formation from NO reaction with other small alkylperoxy radicals. These results are also discussed through the topology of the lowest potential energy surface mainly obtained from DFT(B3LYP/aug-cc-pVDZ) calculations of the RO2 + NO reaction paths. The formation of alkyl nitrates, due essentially to collision processes, is analyzed through a model that points out the pertinent physical parameters of this system.
Published: 2014

43. Enzyme-Coupled Nanoparticles-Assisted Laser Desorption Ionization Mass Spectrometry for Searching for Low-Mass Inhibitors of Enzymes in Complex Mixtures

Author: Raphaël Delépée, Benoît Maunit, Aleksander Salwiński, David Da Silva, Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-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: Immobilized enzyme, Analytical chemistry, Mass spectrometry, 01 natural sciences, Ion, Matrix (chemical analysis), 03 medical and health sciences, Adsorption, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Structural Biology, Ionization, Molecule, Enzyme Inhibitors, ComputingMilieux_MISCELLANEOUS, Spectroscopy, 030304 developmental biology, 0303 health sciences, Plant Extracts, Chemistry, 010401 analytical chemistry, Enzymes, Immobilized, Combinatorial chemistry, Small molecule, 0104 chemical sciences, Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization, Nanoparticles
Abstract: In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: 'ion fading' (IF-ENALDI), based on superficial adsorption of inhibitors and 'ion hunting' (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme-inhibitor pairs: tyrosinase-glabridin and trypsin-leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin-leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.
Published: 2014

44. Mineral Oxides Change the Atmospheric Reactivity of Soot: NO2 Uptake under Dark and UV Irradiation Conditions

Author: Roya Shahla, Manolis N. Romanias, Yuri Bedjanian, Philippe Dagaut, Auréa Andrade-Eiroa, Aggelos Philippidis, Aristotelis M. Zaras, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), European Project: 291049,EC:FP7:ERC,ERC-2011-ADG_20110209,2G-CSAFE(2011), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS)
Subjects: Soot oxidation, 010504 meteorology & atmospheric sciences, Surface Properties, Ultraviolet Rays, Nitrogen Dioxide, Inorganic chemistry, NO2, 010402 general chemistry, medicine.disease_cause, complex mixtures, 01 natural sciences, Redox, Reaction rate, Soot, Aluminum Oxide, medicine, Reactivity (chemistry), Irradiation, uptake coefficient, Physical and Theoretical Chemistry, Quadrupole mass analyzer, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Atmosphere, Chemistry, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, Photodissociation, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, photolysis, kinetics, 13. Climate action, Atmospheric chemistry
Abstract: The heterogeneous reactions between trace gases and aerosol surfaces have been widely studied over the past decades, revealing the crucial role of these reactions in atmospheric chemistry. However, existing knowledge on the reactivity of mixed aerosols is limited, even though they have been observed in field measurements. In the current study, the heterogeneous interaction of NO2 with solid surfaces of Al2O3 covered with kerosene soot was investigated under dark conditions and in the presence of UV light. Experiments were performed at 293 K using a low-pressure flow-tube reactor coupled with a quadrupole mass spectrometer. The steady-state uptake coefficient, γ(ss), and the distribution of the gas-phase products were determined as functions of the Al2O3 mass; soot mass; NO2 concentration, varied in the range of (0.2-10) × 10(12) molecules cm(-3); photon flux; and relative humidity, ranging from 0.0032% to 32%. On Al2O3/soot surfaces, the reaction rate was substantially increased, and the formation of HONO was favored compared with that on individual pure soot and pure Al2O3 surfaces. Uptake of NO2 was enhanced in the presence of H2O under both dark and UV irradiation conditions, and the following empirical expressions were obtained: γ(ss,BET,dark) = (7.3 ± 0.9) × 10(-7) + (3.2 ± 0.5) × 10(-8) × RH and γ(ss,BET,UV) = (1.4 ± 0.2) × 10(-6) + (4.0 ± 0.9) × 10(-8) × RH. Specific experiments, with solid sample preheating and doping with polycyclic aromatic hydrocarbons (PAHs), showed that UV-absorbing organic compounds significantly affect the chemical reactivity of the mixed mineral/soot surfaces. A mechanistic scheme is proposed, in which Al2O3 can either collect electrons, initiating a sequence of redox reactions, or prevent the charge-recombination process, extending the lifetime of the excited state and enhancing the reactivity of the organics. Finally, the atmospheric implications of the observed results are briefly discussed.
Published: 2013

45. Water Radiolysis in Exchanged-Montmorillonites: The H2 Production Mechanisms

Author: Chloé Fourdrin, S. Le Caër, F. Bergaya, C. Latrille, H. Aarrachi, S. Esnouf, Laboratoire des Solides Irradiés (LSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Laboratoire de Radiolyse (LCF) (LRad), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mesures et Modélisation de la Migration des Radionucléides (L3MR), Service d'Etudes du Comportement des Radionucléides (SECR), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Enthalpy, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Ionizing radiation, law.invention, chemistry.chemical_compound, law, Electron beam processing, [CHIM]Chemical Sciences, Environmental Chemistry, Relative humidity, Irradiation, Electron paramagnetic resonance, [PHYS]Physics [physics], Sodium, Water, Humidity, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Montmorillonite, chemistry, 13. Climate action, Radiolysis, Bentonite, 0210 nano-technology, Hydrogen
Abstract: International audience; The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H2 production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H2 production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H2 precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H2 production.
Published: 2013

46. Insights on the Molecular Mechanisms of Hydrogen Adsorption in Zeolites

Author: José B. Parra, Kathryn S. Deeg, Juan José Gutiérrez-Sevillano, Manuel Doblaré, Rocio Bueno-Perez, Sofia Calero, Conchi O. Ania, Instituto Nacional del Carbon, CSIC-Oviedo, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aragón Institute of Engineering Research [Zaragoza] (I3A), University of Zaragoza - Universidad de Zaragoza [Zaragoza], and Universidad Pablo de Olavide [Sevilla] (UPO)
Subjects: Hydrogen, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Hydrogen adsorption, Adsorption, Physisorption, Computational chemistry, Physical and Theoretical Chemistry, Zeolite, Quantum, ComputingMilieux_MISCELLANEOUS, Energy carrier, [SDE.IE]Environmental Sciences/Environmental Engineering, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Microporous material, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, Chemical physics, 0210 nano-technology
Abstract: Physisorption on microporous materials has emerged as a promising strategy to store hydrogen for use as an energy carrier. Here, we investigate adsorption of hydrogen in all-silica zeolites ITQ-29 and MFI at low temperatures using molecular simulations. Out of five existing models for hydrogen and its interactions with the zeolite, we determine that a model with hydrogen as a single uncharged Lennard-Jones center best reproduces experimental adsorption isotherms. We present a new set of Lennard-Jones parameters for this model and find that small variations in the parameters have a large impact on computed hydrogen adsorption at 77 K. Preferential adsorption sites of hydrogen in the two zeolite structures are analyzed. We investigate the effect of incorporating quantum corrections via use of a Feynman–Hibbs effective interaction potential and determine that quantum corrections are important at 25 K.
Published: 2013

47. Structural Relaxation Dynamics and Annealing Effects of Sodium Silicate Glass

Author: Francesco Piazza, Yann Vaills, Aurélien Canizares, Guillaume Guimbretière, Mohamed Naji, Département des sciences de la Terre, Faculté des sciences de Rabat, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)
Subjects: Length scale, [SDV]Life Sciences [q-bio], Sodium silicate, 02 engineering and technology, 01 natural sciences, Annealing (glass), symbols.namesake, chemistry.chemical_compound, Nuclear magnetic resonance, 0103 physical sciences, Materials Chemistry, Physical and Theoretical Chemistry, 010306 general physics, Molecular Structure, Chemistry, Silicates, Relaxation (NMR), 021001 nanoscience & nanotechnology, Surfaces, Coatings and Films, Brillouin zone, Homogeneous, Chemical physics, symbols, Thermodynamics, Glass, 0210 nano-technology, Glass transition, Raman spectroscopy
Abstract: International audience; Here we report high--precision measurements of structural relaxation dynamics in the glass transition range at the intermediate and short length scale for a strong sodium silicate glass during long annealing times. We evidence for the first time the heterogeneous dynamics at the intermediate range order by probing the acoustic longitudinal frequency in the GHz region by Brillouin light scattering spectroscopy. Or, from \textit{in--situ} Raman measurements we show that relaxation is indeed homogenous at the interatomic length scale. Our results show that the dynamics at the intermediate range order contains two distinct relaxation time scales, a fast and a slow component, differing by about a tenfold factor below $T_{g}$ and approaching to one another past the glass transition. The slow relaxation time agrees with the shear relaxation time, proving that Si--O bond breaking constitutes the primary control of structural relaxation at the intermediate range order.
Published: 2013

48. Toward a Transferable Set of Charges to Model Zeolitic Imidazolate Frameworks: Combined Experimental–Theoretical Research

Author: Freek Kapteijn, Conchi O. Ania, Jorge Gascon, José B. Parra, Juan José Gutiérrez Sevillano, Said Hamad, Sofia Calero, Universidad Pablo de Olavide [Sevilla] (UPO), Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto Nacional del Carbon, CSIC-Oviedo, Reactor and Catalysis Engineering, Delft University of Technology (TU Delft), Davy Faraday Research Laboratory, and The Royal Institution of Great Britain
Subjects: [SDE.IE]Environmental Sciences/Environmental Engineering, Thermodynamics, Theoretical research, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Co2 adsorption, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Set (abstract data type), chemistry.chemical_compound, General Energy, Adsorption, chemistry, Computational chemistry, Imidazolate, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Zeolitic imidazolate framework
Abstract: In a combined experimental and theoretical study, the first transferable set of charges of imidazolate linkers has been derived specifically to model zeolitic imidazolate frameworks (ZIFs). The validity of the charges is demonstrated by comparing experimental and computed results of CH4 and CO2 adsorption on ZIF-7, ZIF-8, ZIF-69, and ZIF-71. The sets of charges obtained with this method provide values of isosteric heats of adsorption and adsorption isotherms of similar accuracy as those obtained using specific sets of charges derived for each individual structure, with the great advantage of being readily transferable to a wide range of ZIFs.
Published: 2012

49. Improved Accuracy of Low Affinity Protein–Ligand Equilibrium Dissociation Constants Directly Determined by Electrospray Ionization Mass Spectrometry

Author: Fabienne Saab, Martine Cadene, Lucie Jaquillard, Françoise Schoentgen, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-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 minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, Spectrometry, Mass, Electrospray Ionization, Electrospray ionization, Kinetics, Analytical chemistry, Ligands, 010402 general chemistry, Mass spectrometry, Kinetic energy, MESH: Spectrometry, Mass, Electrospray Ionization, 01 natural sciences, Dissociation (chemistry), Structural Biology, MESH: Ligands, Animals, Humans, MESH: Protein Binding, MESH: Animals, MESH: Proteins, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Spectroscopy, MESH: Gases, MESH: Humans, MESH: Kinetics, Nucleotides, Ligand, Chemistry, 010401 analytical chemistry, MESH: Chickens, Proteins, MESH: Nucleotides, 0104 chemical sciences, Dissociation constant, MESH: Cattle, Cattle, Gases, Chickens, MESH: Models, Molecular, Protein Binding, Protein ligand
Abstract: International audience; There is continued interest in the determination by ESI-MS of equilibrium dissociation constants (K(D)) that accurately reflect the affinity of a protein-ligand complex in solution. Issues in the measurement of K(D) are compounded in the case of low affinity complexes. Here we present a K(D) measurement method and corresponding mathematical model dealing with both gas-phase dissociation (GPD) and aggregation. To this end, a rational mathematical correction of GPD (f(sat)) is combined with the development of an experimental protocol to deal with gas-phase aggregation. A guide to apply the method to noncovalent protein-ligand systems according to their kinetic behavior is provided. The approach is validated by comparing the K(D) values determined by this method with in-solution K(D) literature values. The influence of the type of molecular interactions and instrumental setup on f(sat) is examined as a first step towards a fine dissection of factors affecting GPD. The method can be reliably applied to a wide array of low affinity systems without the need for a reference ligand or protein.
Published: 2012

50. Supramolecular Assemblies of Histidinylated α-Cyclodextrin in the Presence of DNA Scaffold during CDplexes Formation

Author: Olivier R. Martin, Patrick Midoux, Véronique Bennevault-Celton, Chantal Pichon, Philippe Guégan, Allan Urbach, Laboratoire Matériaux Polymères aux Interfaces (MPI), Université d'Évry-Val-d'Essonne (UEVE), Institut de Chimie Organique et Analytique (ICOA), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université d'Orléans (UO)-Institut de Chimie du CNRS (INC), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-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: alpha-Cyclodextrins, Stereochemistry, Static Electricity, Biomedical Engineering, Supramolecular chemistry, Pharmaceutical Science, Bioengineering, 02 engineering and technology, Transfection, 010402 general chemistry, DNA condensation, 01 natural sciences, MESH: Histidine, chemistry.chemical_compound, MESH: Plasmids, Humans, Imidazole, Histidine, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, A-DNA, MESH: Static Electricity, Pharmacology, MESH: Humans, MESH: Transfection, Organic Chemistry, MESH: DNA, MESH: alpha-Cyclodextrins, DNA, 021001 nanoscience & nanotechnology, 0104 chemical sciences, HEK293 Cells, chemistry, MESH: HEK293 Cells, Polylysine, 0210 nano-technology, Plasmids, Biotechnology
Abstract: International audience; α-Cyclodextrin was transformed in a cationic unit after per substitution with histidine (His-α-CD) and lysine (Lys-α-CD) molecules on the primary face. His-α-CD and Lys-α-CD were used to form electrostatic complexes (CDplexes) with a plasmid DNA encoding luciferase gene, and the ability of CDplexes to transfect mammalian cells was examined using HEK293-T7 cells. The luciferase activity in cells transfected with His-α-CDplexes was 8-fold higher than that obtained Lys-α-CDplexes. When the transfection was carried out in the presence of chloroquine, the luciferase activity with His-α-CDplexes and Lys-α-CDplexes increased 6 and 25 times, respectively. The lower enhancement with His-α-CDplexes confirmed that histidine induced a proton sponge effect inside endosomes upon imidazole protonation, favoring DNA delivery in the cytosol. At the same time, we found that the condensation of DNA with His-α-CD was unexpectedly stronger than that obtained with the lysyl-α-CD counterpart. Moreover, it was as strong as that observed with high molecular weight polylysine. NMR (ROESY and DOSY) investigations in the absence of DNA showed that an inclusion complex is formed between the imidazole ring of histidine and the hydrophobic cavity of CD but no His-α-CD polymers can be formed by intermolecular interactions. These results suggest that intermolecular interactions between imidazole and His-α-CD cavity could be involved to form supramolecular assemblies in the presence of a DNA scaffold leading to DNA condensation into low diameter particles.
Published: 2011

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