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535 results on '"[ CHIM ] Chemical Sciences"'

1. Control of Spatial Organization of Electrospun Fibers in a Carbon Felt for Enhanced Bioelectrode Performance

Author: David Cornu, Adriana Both Engel, Mikhael Bechelany, Aziz Cherifi, Sophie Tingry, Institut Européen des membranes ( IEM ), Centre National de la Recherche Scientifique ( CNRS ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM ), SICaPS ( SICaPS ), Département Plateforme ( PF I2BC ), Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Institut Européen des membranes (IEM), Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), SICaPS (SICaPS), Département Plateforme (PF I2BC), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Intégrative de la Cellule (I2BC), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, 020209 energy, Carbon fibers, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, Electrochemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, [ CHIM ] Chemical Sciences, Electrospinning, 0104 chemical sciences, Cathodic protection, Carbon felt, Electrical resistivity and conductivity, visual_art, Electrode, visual_art.visual_art_medium, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, Composite material, Cyclic voltammetry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Electrospun carbon fiber electrodes showing high performance for bio-electrochemical applications were developed. Easy to handle and manipulate aligned and unaligned carbon fibers with a mean diameter of (330±50) nm were synthesized through an electrospinning technique. Electrical resistivity measurements, which are a challenge that has not been much explored in the case of fibrous materials, were realized through two different techniques, and a study of contact resistances between electrical clips and the carbon fibers was performed. To target the creation of a bioelectrode, carbon fibers were characterized electrochemically by cyclic voltammetry. After being modified with the enzyme laccase, its response to oxygen electroreduction was studied. Aligned fibers present a cathodic current that is 30 % higher than that of randomly distributed fibers. Overall, the results show that aligned fibers are more appropriate for bio-electrochemical applications when exploiting anisotropic spatial organization.
Published: 2020
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2. 1,3-Dipolar cycloadditions with azomethine ylide species generated from aminocyclopropanes

Author: Justyna A. Kowalska-Six, Yvan Six, Andrzej Wolan, Holisoa Rajerison, Marie Cordier, Michèle Cesario, Institut de Chimie des Substances Naturelles ( ICSN ), Centre National de la Recherche Scientifique ( CNRS ), Nicolaus Copernicus University [Toruń], Centre de Recherche en Cancérologie / Nantes - Angers ( CRCNA ), CHU Angers-Centre hospitalier universitaire de Nantes ( CHU Nantes ) -Hôtel-Dieu de Nantes-Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Hôpital Laennec-Centre National de la Recherche Scientifique ( CNRS ) -Faculté de Médecine d'Angers, Laboratoire de chimie moléculaire ( LCM ), École polytechnique ( X ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de synthèse organique ( DCSO ), École polytechnique ( X ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Laboratoire de synthèse organique (DCSO), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Six, Yvan, and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nucleophilic conjugate addition, Azomethine ylide, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Medicinal chemistry, Pyrrolidine, Microwave-assisted synthesis, Cyclopropane, 3-Dipolar cycloaddition, chemistry.chemical_compound, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, [CHIM] Chemical Sciences, Drug Discovery, Pyrrolizidine, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Titanium, Bicyclic molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Diastereomer, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Cycloaddition, 0104 chemical sciences
Abstract: International audience; Two types of bicyclic N-cyclopropyl glycine ester derivatives have been prepared and put under scrutiny as possible precursors of azomethine ylides. The results demonstrate that they can indeed participate in 1,3-dipolar cycloaddition reactions with dipolarophiles, as illustrated in the cases of phenyl vinyl sulfone, N-phenylmaleimide, diethyl fumarate and diethyl maleate. The relative configurations of the major diastereoisomers produced are consistent with the predicted generation of azomethine ylide species, reacting in concerted cycloaddition processes. This unprecedented way of generating such 1,3-dipoles provides access to functionalised pyrrolizidine and pyrrolidine derivatives, that would be difficult to make directly by more classic methods. It was also found that using phenyl vinyl sulfone or N-phenylmaleimide as the dipolarophile reactant, a domino nucleophilic conjugate addition/1,3-dipolar cycloaddition process may operate competitively.
Published: 2018
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3. Scaling law for excitons in 2D perovskite quantum wells

Author: Aditya D. Mohite, Jared Crochet, Claudine Katan, G. T. Noe, Mikael Kepenekian, Hsinhan Tsai, Fumiya Katsutani, Sergei Tretiak, Boubacar Traore, Constantinos C. Stoumpos, Mercouri G. Kanatzidis, Andreas V. Stier, Scott A. Crooker, Laurent Pedesseau, Wanyi Nie, Junichiro Kono, Jacky Even, Jean-Christophe Blancon, Los Alamos National Laboratory ( LANL ), Rice University [Houston], Northwestern University [Evanston], Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Fonctions Optiques pour les Technologies de l'informatiON ( FOTON ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Institut National des Sciences Appliquées - Rennes ( INSA Rennes ) -École Nationale Supérieure des Sciences Appliquées et de Technologie ( ENSSAT ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Bretagne Loire ( UBL ) -IMT Atlantique Bretagne-Pays de la Loire ( IMT Atlantique ), ANR-15-CE05-0018-01,TRANSHYPERO, Los Alamos National Laboratory (LANL), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), ANR-15-CE05-0018,TRANSHYPERO,Vers une compréhension des propriétés de transport électronique des cellules solaires basées sur les pérovskites hybrides(2015), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Exciton, Science, Binding energy, General Physics and Astronomy, Physics::Optics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, Article, General Biochemistry, Genetics and Molecular Biology, Condensed Matter::Materials Science, [CHIM]Chemical Sciences, lcsh:Science, Spectroscopy, Scaling, Quantum well, Perovskite (structure), [PHYS]Physics [physics], Condensed Matter::Quantum Gases, Multidisciplinary, [ PHYS ] Physics [physics], Condensed matter physics, Condensed Matter::Other, business.industry, General Chemistry, Reduced mass, 021001 nanoscience & nanotechnology, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, 0104 chemical sciences, Semiconductor, lcsh:Q, Condensed Matter::Strongly Correlated Electrons, 0210 nano-technology, business
Abstract: Ruddlesden–Popper halide perovskites are 2D solution-processed quantum wells with a general formula A2A’n-1MnX3n+1, where optoelectronic properties can be tuned by varying the perovskite layer thickness (n-value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free carriers) and the exciton reduced mass, and their scaling with quantum well thickness, which are critical for designing efficient optoelectronic devices, remain unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modeling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with both exciton reduced masses and binding energies decreasing, respectively, from 0.221 m0 to 0.186 m0 and from 470 meV to 125 meV with increasing thickness from n equals 1 to 5. Based on this study we propose a general scaling law to determine the binding energy of excitons in perovskite quantum wells of any layer thickness., Hybrid 2D layered perovskites are solution-processed quantum wells whose optoelectronic properties are tunable by varying the thickness of the inorganic slab. Here Blancon et al. work out a general behavior for dependence of the excitonic properties in layered 2D perovskites.
Published: 2018
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4. Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Author: Franck Camerel, Embarek Bentouhami, Olivier Jeannin, Loïc J. Charbonnière, Jérémy Salaam, Lilia Tabti, Sylvana Bahamyirou, Sarah Cianférani, Oscar Hernandez Alba, Alexandre Lecointre, Aline Nonat, Institut Pluridisciplinaire Hubert Curien ( IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Sciences Analytiques et Interactions Ioniques et Biomoléculaires ( DSA-IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), University of Ferhat Abbas Setif 1, CNRS, Centre National de la Recherche Scientifique, Université de Strasbourg, GIS, Genome Institute of Singapore, Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Ferhat-Abbas Sétif 1 [Sétif] (UFAS1), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)
Subjects: pyridine, Lanthanide, lanthanide, Hydrogen, 010405 organic chemistry, Chemistry, Hydrogen bond, Ligand, Quantum yield, chemistry.chemical_element, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Phosphonate, 0104 chemical sciences, Inorganic Chemistry, polynuclear assemblies, Crystallography, chemistry.chemical_compound, luminescence, phosphonate, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence, Stoichiometry
Abstract: International audience; A series of polynuclear assemblies based on ligand L (1,4,7-tris[hydrogen (6-methylpyridin-2-yl)phosphonate]-1,4,7-triazacyclononane) has been developed. The coordination properties of ligand L with LnIII (Ln = La, Eu, Tb, Yb, Lu) have been studied in water (pH = 7.0) and in D2O (pD = 7.0) by UV-absorption spectrometry, spectrofluorimetry, 1H and 31P NMR, DOSY, ESI-mass spectrometry, and X-ray diffraction. This nonadentate ligand forms highly stable mononuclear complexes in water and provides a very efficient shielding of the Ln cations, as emphasized by the very good luminescence properties of the Yb complex in D2O, especially regarding its lifetime (τD2O = 10.2 μs) and quantum yield (φD2O = 0.42%). In the presence of excess LnIII cation, polynuclar complexes of [(LnL)2Lnx] stoichiometry (x = 1 and x = 2) are observed in solution. In the solid state, a dinuclear complex of La could be isolated and structurally characterized by X-ray diffraction, unraveling the presence of strong hydrogen bonding interactions between a La(H2O)9 3+ cation and the [LaL]3- complex. © 2018 American Chemical Society.
Published: 2018
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5. Environmental scenarii for the degradation of oxo-polymers

Author: Jacques Lemaire, S. Bonhomme, Martine Sancelme, D. Fromageot, Anne-Marie Delort, Martin Leremboure, Mounir Traïkia, Boris Eyheraguibel, J. Lacoste, Institut de Chimie de Clermont-Ferrand - Clermont Auvergne ( ICCF ), Sigma CLERMONT ( Sigma CLERMONT ) -Université Clermont Auvergne ( UCA ) -Centre National de la Recherche Scientifique ( CNRS ), CNEP, Institut de Chimie de Clermont-Ferrand (ICCF), SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE34-0007,OXOMAR,Dégradation abiotique et biotique et toxicité des plastiques oxo-biodégradables en mer(2016)
Subjects: Magnetic Resonance Spectroscopy, Time Factors, Environmental Engineering, Health, Toxicology and Mutagenesis, Diffusion, 02 engineering and technology, 010501 environmental sciences, Photochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Mass Spectrometry, Acetone, chemistry.chemical_compound, [CHIM]Chemical Sciences, Environmental Chemistry, Molecule, 0105 earth and related environmental sciences, chemistry.chemical_classification, Chloroform, Extraction (chemistry), Public Health, Environmental and Occupational Health, Water, NMR MS, Polymer aging, General Medicine, General Chemistry, Polymer, Models, Theoretical, Biodegradation, 021001 nanoscience & nanotechnology, Pollution, Molecular characterization, Molecular Weight, Biodegradation, Environmental, chemistry, 13. Climate action, Oligomers, Solvents, Polyethylenes, 0210 nano-technology, Oxidation-Reduction, Macromolecule
Abstract: International audience; The fate of oxo-polymers in nature is strongly dependent on environmental conditions, mainly on the intensity and duration of sunshine, which vary with the season and the climate. In this work, we report the effect of different scenarii on the production and the molecular composition of oligomers released from oxo-biodegradable HDPE films. Under our experimental conditions, the duration of accelerated weathering corresponded to a period of 3 months to 3 years of exposure to outside conditions under temperate climate. In addition, the oligomers were extracted in three different solvents: i) water to mimics the natural environment; ii) acetone and chloroform to identify oligomers trapped in the polymer matrix. The combination of high-resolution mass spectrometry and 1H NMR spectroscopy gives an extensive picture of the relative concentrations and the structural compositions of the extracted oligomers in the different tested conditions. In particular, the masses, the number of oxygen and carbon atoms could be determined for up to 2283 molecules. Globally the concentration and the size of oligomers increased with the duration of extraction, the level of aging of the polymer and the use of non-polar solvents. Surprisingly, the presence of highly oxidized molecules in acetone and chloroform extract, suggested an important swelling of HPDE films in these solvents and a better diffusion of these oligomers in the matrix. In nature, the biodegradability of oligomers could result from processes occurring both at the molecular (oxidation) and the macromolecular (diffusion and release) levels.
Published: 2018
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6. Ionic-to-Electronic Conductivity Crossover in CdTe–AgI–As2Te3 Glasses: An 110mAg Tracer Diffusion Study

Author: Eugene Bychkov, Mohammad Kassem, D. Le Coq, I. Alekseev, Maria Bokova, Laboratoire de Physico-Chimie de l'Atmosphère ( LPCA ), Université du Littoral Côte d'Opale-Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), ANR, Agence Nationale de la Recherche, ANR-15-ASTR-0016-01, Campus France, EC, European Commission, Laboratoire de Physico-Chimie de l'Atmosphère (LPCA), Université du Littoral Côte d'Opale (ULCO)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-15-ASTR-0016,VOIR,Verres pour l'Optique dans l'InfraRouge long(2015), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Diffusion activation energy, Chalcogenide, Diffusion, Nonmonotonic behaviors, Semiconducting cadmium telluride, Oxide, Analytical chemistry, Ionic bonding, 02 engineering and technology, Activation energy, Conductivity, Ion transports, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, chemistry.chemical_compound, Electric conductivity, Semiconducting tellurium compounds, Materials Chemistry, Cadmium telluride, Orders of magnitude (data), Metal ions, Tracer diffusion, Physical and Theoretical Chemistry, II-VI semiconductors, [CHIM.MATE]Chemical Sciences/Material chemistry, Silver halides, 021001 nanoscience & nanotechnology, Cadmium telluride photovoltaics, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic transport, Orders of magnitude, Electronic conductivity, chemistry, Chalcogenide glass, Glass, Semiconducting silver compounds, 0210 nano-technology
Abstract: International audience; Conductivity isotherms of (CdTe)x(AgI)0.5-x/2(As2Te3)0.5-x/2 glasses (0.0 ≤ x ≤ 0.15) reveal a nonmonotonic behavior with increasing CdTe content reminiscent of mixed cation effect in oxide and chalcogenide glasses. Nevertheless, the apparent similarity appears to be partly incorrect. Using 110mAg tracer diffusion measurements, we show that semiconducting CdTe additions produce a dual effect (i) decreasing the Ag+ ion transport by a factor of ≈ 200 with a simultaneous increase of the diffusion activation energy and (ii) increasing the electronic conductivity by 1.5 orders of magnitude. Consequently, the conductivity minimum at x = 0.05 reflects an ionic-to-electronic transport crossover; the silver-ion transport number decreases by 3 orders of magnitude with increasing x. © 2018 American Chemical Society.
Published: 2018
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7. Steel: The Resurrection of a Forgotten Water-Splitting Catalyst

Author: Helmut Schäfer, Marian Chatenet, Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces ( LEPMI ), and Université Grenoble Alpes ( UGA ) -Université Joseph Fourier - Grenoble 1 ( UJF ) -Institut National Polytechnique de Grenoble ( INPG ) -Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ) -Institut polytechnique de Grenoble - Grenoble Institute of Technology ( Grenoble INP ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: Materials science, Hydrogen, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrocatalyst, Heterogeneous catalysis, [ CHIM ] Chemical Sciences, 01 natural sciences, 7. Clean energy, Catalysis, law.invention, [CHIM.GENI]Chemical Sciences/Chemical engineering, law, Materials Chemistry, ComputingMilieux_MISCELLANEOUS, Electrolysis, [ PHYS ] Physics [physics], Renewable Energy, Sustainability and the Environment, business.industry, Metallurgy, Fossil fuel, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Solar energy, 0104 chemical sciences, Fuel Technology, chemistry, Chemistry (miscellaneous), Water splitting, 0210 nano-technology, business
Abstract: Because of the limited availability of fossil fuels, the splitting of water into oxygen and hydrogen upon exploitation of solar energy becomes an increasingly important clean energy production and storage technique. Despite its early use as a hydrogen-evolution catalyst in alkaline electrolysis, steel was until very recently supposed to be neither an active and stable water-splitting catalyst nor an interesting scientific subject at all. The authors of this contribution not only have shown in recent papers the potential of steel in terms of pure material properties but also have revealed the qualities of steel as a striking scientific topic. They herewith review what is known about the water-splitting properties of untreated and surface-modified steel and try to determine a potential transfer to a broader application of modified steels in heterogeneous catalysis. The synopsis is basically limited to the usage of steel as a real electrocatalyst, thus presenting the catalytic active species itself.
Published: 2018
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8. Octahedral bis(2-thenoyltrifluoroacetonato)-ethylenediamine Co(II), Ni(II) and Cu(II) complexes: Synthetic, structural, electrochemical, and theoretical studies

Author: Carolina Manzur, Thierry Roisnel, Jean-Yves Saillard, Ricardo Córdova, Samia Kahlal, Guillermo Ahumada, Jean-René Hamon, David Carrillo, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratorio de Quimica Inorganica, Pontificia Universidad Católica de Valparaíso (PUCV), 1140903, Fondo Nacional de Desarrollo Científico y Tecnológico, Pontificia Universidad Católica de Valparaíso, Centre National de la Recherche Scientifique, Université de Rennes 1, 21120098, Comisión Nacional de Investigación Científica y Tecnológica, FONDEQUIP, Vicerrectoría de Investigación y Estudios Avanzados, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic chemistry, 2-Thenoyltrifluoroacetone, chemistry.chemical_element, Ethylenediamine, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Redox, Octahedral complexes, Inorganic Chemistry, Metal, chemistry.chemical_compound, Diamine, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010405 organic chemistry, DFT and TDDFT calculations, Copper, 0104 chemical sciences, Crystallography, chemistry, Octahedron, 13. Climate action, visual_art, visual_art.visual_art_medium, Single crystal X-ray structure, Derivative (chemistry)
Abstract: International audience; We report the synthesis of three new octahedral bis(2-thenoyltrifluoroacetonato)-ethylenediamine metal(II) complexes [M(TTA)2(en)] (M = Co, 2a; Ni, 2b; Cu, 2c) resulting from the coordination of the diamine onto the bis(β-diketonate) precursors [Co(TTA)2(CH3OH)2] (1a), [Ni(TTA)2(H2O)2] (1b) and [Cu(TTA)2] (1c), respectively. The six-coordinate paramagnetic complexes 2a-c have been isolated as neutral, air and thermally stable solids in high yields (andgt;80%) and have been fully characterized by elemental analysis, ESI+ HRMS, FT-IR and UV–vis spectroscopy. Single-crystal X-ray diffraction studies indicate that the metal(II) ion sits in a pseudo-octahedral environment; the copper derivative 2c showing a significant elongation along the O–Cu–O axis due to Jahn-Teller distorsion associated with the “eg” electron occupation of the dz2-type MO. The three complexes 2a-c display similar cyclic voltammetric behavior exhibiting two irreversible anodic waves, tentatively assigned to the M(II)/M(III) redox couples and to the oxidation of soluble short oligomeric species generated during the first redox process, respectively. No deposits of polymeric species on the electrode surface occured. The electronic structures of 2a-c and their cations have been analysed through DFT calculations, allowing providing a consistent view of their structure and properties. TDDFT calculations have been used to interpret the major features of their UV–vis spectra. © 2017 Elsevier B.V.
Published: 2018
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9. A protocol for quantifying hydrogen evolution by dye-sensitized molecular photocathodes and its implementation for evaluating a new covalent architecture based on an optimized dye-catalyst dyad

Author: Murielle Chavarot-Kerlidou, Vincent Artero, Julien Massin, Christopher D. Windle, Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: Aqueous solution, Materials science, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Acceptor, Photocathode, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Electrode, Thiophene, [CHIM]Chemical Sciences, 0210 nano-technology, Faraday efficiency, Hydrogen production
Abstract: International audience; A protocol that combines gas chromatography and a high-sensitivity micro Clark-type electrode is described to quantify hydrogen production across gas and solution phases for systems operating at very low currents such as dye-sensitized H2-evolving photocathodes. Data indicate that a significant fraction of H2 remains in aqueous solution even after several hours of experiments. Using this protocol, re-evaluation of a dye-sensitized H2-evolving photocathode based on a dye-catalyst dyad showed a reproducible 66% increase of the faradaic efficiency compared with previously reported headspace GC measurements [Kaeffer et al., J. Am. Chem. Soc., 2016, 138, 12308-12311]. This dyad was based on an organic push-pull dye where donor and acceptor are separated by one thiophene group. Insertion of a second thiophene group between the donor and acceptor led to a more efficient system with 30% improved faradaic efficiency for H2 evolution.
Published: 2018
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10. Phosphorescent cationic iridium(<scp>iii</scp>) complexes bearing a nonconjugated six-membered chelating ancillary ligand: a strategy for tuning the emission towards the blue

Author: Véronique Guerchais, Claus Hierlinger, Denis Jacquemin, David B. Cordes, Alexandra M. Z. Slawin, Eli Zysman-Colman, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of St Andrews [Scotland], 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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 278845, H2020 European Research Council, EP/M02105X/1, Engineering and Physical Sciences Research Council, European Project: 278845,EC:FP7:ERC,ERC-2011-StG_20101014,MARCHES(2012), EPSRC, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, University of St Andrews. Organic Semiconductor Centre, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), and Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: 010405 organic chemistry, Ligand, Aryl, chemistry.chemical_element, DAS, QD Chemistry, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Bipyridine, chemistry.chemical_compound, chemistry, Pyridine, QD, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Iridium, Phosphorescence, HOMO/LUMO, Diimine
Abstract: C.H. acknowledges the Région Bretagne, France for funding. D.J. acknowledges the European Research Council and the Région des Pays de la Loire for financial support in the framework of a Starting Grant (Marches - 278845) and the LUMOMAT RFI project, respectively. E.Z.-C. acknowledges the University of St Andrews and EPSRC (EP/M02105X/1) for financial support. This study concerns an assessment of the impact of the interruption of the electronic crosstalk between the pyridine rings in the ancillary ligand on the photoluminescence properties of the corresponding iridium(III) complexes. Two new cationic Ir(III) complexes, [Ir(dFmesppy)2(pmdp)]PF6, 1 , and [Ir(mesppy)2(pmdp)]PF6, 2 , [where dFmesppy is 2-(2,4- difluorophenyl)-4-mesitylpyridinato, mesppy is 4-mesityl-2-phenylpyridinato and pmdp is 2,2'-(phenylmethine)dipyridine, L1 ] possessing sterically congested cyclometalating ligands combined with the nonconjugated diimine ancillary N^N ligand are reported and their solution-state and thin film photophysical properties analyzed by both experimental and theoretical methods. The crystal structure of 1 confirms the formation of a six-membered chelate ring by the N^N ligand and illustrates the pseudo-axial configuration of the phenyl substituents. Upon photoexcitation in acetonitrile, both complexes exhibit a ligand-centered emission profile in the blue-green region of the visible spectrum. A significant blue-shift is observed in solution at room temperature compared to the analogous reference Ir(III) complexes ( R1 and R2 ) bearing 4,4'-di-tert-butyl-2,2'-bipyridine (dtBubpy) as the N^N ligand. The computational investigation demonstrates that the HOMO is mainly centered on the metal and on both cyclometalating aryl rings of the C^N ligands, whereas the LUMO is principally localized on the pyridyl rings of the C^N ligands. The photoluminescence quantum yield is reduced compared to the reference complexes, a probable consequence of the greater flexibility of the ancillary ligand. Postprint
Published: 2018
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11. Stabilization of synthetic heme-superoxo complexes by hydrogen bonding: a still on-going quest

Author: Stéphane Le Gac, Bernard Boitrel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique, Ministère de l'Education Nationale, de l'Enseignement Superieur et de la Recherche, Agence Nationale de la Recherche, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Autoxidation, 010405 organic chemistry, Hydrogen bond, Stereochemistry, General Chemistry, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Binding constant, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Adduct, chemistry.chemical_compound, chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Binding site, Heme
Abstract: International audience; Selected synthetic heme complexes designed during the past half century for O2 binding studies are analyzed. Efficient O2 carriers must avoid the autooxidation process upon O2 binding and must lead to stable O2 adducts. Several strategies have been successful in achieving this paramount property through the peripheral functionalization of the heme by pickets, straps, caps and tripods. The affinity of the complex for O2 is generally investigated in solution by its binding constant, either measured or calculated, and the [Fe-O2] species characterized by its spectroscopic (vibrational) data. When achieved, the stability of the O2 adduct has been very often attributed to a possible hydrogen bond with a H-bond donor supplied by the chemical dressing around the binding site of the model. However, solid-state evidence remains to come, so far. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Published: 2018
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12. Synthesis, characterization, and thermal properties of N,N,N′,N′-tetramethyl guanidinium tribromidocadmate(II) exhibiting an unusual coordination geometry

Author: Sylvie Pourchet, Laurent Plasseraud, Hélène Cattey, Mamadou Ndiaye, Libasse Diop, Abdoulaye Samb, Laboratoire des Produits Naturels [Université Cheikh Anta Diop, Dakar], Université Cheikh Anta Diop [Dakar, Sénégal] (UCAD), Laboratoire de Chimie Minérale et Analytique (LACHIMIA), 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), Université Cheikh Anta Diop Dakar, Laboratoire de Chimie Minérale et Analytique ( LACHIMIA ), Université Cheikh Anta Diop ( UCAD ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), and Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: Thermogravimetric analysis, nqr, compound, polymer, Inorganic chemistry, diffraction, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, Differential scanning calorimetry, condensed anion structure, Thermal, Materials Chemistry, [CHIM]Chemical Sciences, bromocadmate(ii), QD1-999, x-ray crystallography, Coordination geometry, ray-structure analysis, thermogravimetric analysis, Chemistry, ligands, phase-transitions, Metals and Alloys, crystal-structure, organic-inorganic hybrid materials, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Characterization (materials science), n-h···br interaction, Crystallography, X-ray crystallography, differential scanning calorimetry, 0210 nano-technology, complex
Abstract: International audience; The reaction of N,N,N′,N′-tetramethyl guanidine, NHC(N(CH3)2)2 (TMGD) and CdBr2·4H2O in ethanol led to the formation of [TMGDH][CdBr3] (1), which crystallizes in the monoclinic space group Cc with Z=4, a=8.9079(7) Å, b=18.5810(14) Å, c=8.1637(6) Å, β=107.953(3)°, and V=1285.44(17) Å3. In the crystal lattice, 1 is organized in one-dimensional anionic chains of CdBr4 tetrahedra sharing two corners. To our knowledge, this is the first evidence of such a coordination geometry described for a bromocadmate derivative. The negative charges are compensated by monoprotonated N,N,N′,N′-tetramethyl guanidinium cations (TMGDHs), which are in N-H hydrogen bonding interaction with the terminal bromide atoms of the anionic chain. The title compound was also characterized by middle and far-infrared spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The elemental analysis corroborates as well the X-ray elucidation. Multinuclear solution nuclear magnetic resonance (NMR) spectroscopic measurements (1H, 13C{1H}) were conducted in D2O.
Published: 2017
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13. Coupled Effects of Spreading Solvent Molecules and Electrostatic Repulsions on the Behavior of PS-b-PAA Monolayers at the Air–Water Interface

Author: Patrick Perrin, Fabrice Cousin, Philippe Fontaine, Denis Limagne, Michel Goldmann, Zineb Guennouni, Marie-Claude Fauré, Institut des Nanosciences de Paris (INSP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Physico-chimie et dynamique des surfaces (INSP-E6), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Faculté des Sciences Fondamentales et Biomédicales (UPD5 Sciences), Université Paris Descartes - Paris 5 (UPD5), Sciences et Ingénierie de la Matière Molle (SIMM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Nanosciences de Paris ( INSP ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), 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, Synchrotron SOLEIL ( SSOLEIL ), Centre National de la Recherche Scientifique ( CNRS ), Physico-chimie et dynamique des surfaces ( INSP-E6 ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Université Paris Descartes - Faculté des Sciences Fondamentales et Biomédicales ( UPD5 Sciences ), Université Paris Descartes - Paris 5 ( UPD5 ), Sciences et Ingénierie de la Matière Molle ( SIMM ), Centre National de la Recherche Scientifique ( CNRS ) -PSL Research University ( PSL ) -ESPCI ParisTech-Université Pierre et Marie Curie - Paris 6 ( UPMC ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), and Centre National de la Recherche Scientifique (CNRS)-PSL Research University (PSL)-ESPCI ParisTech-Université Pierre et Marie Curie - Paris 6 (UPMC)
Subjects: Langmuir, Chemistry, Scattering, Spinodal decomposition, Analytical chemistry, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Surface pressure, [ CHIM ] Chemical Sciences, 01 natural sciences, 0104 chemical sciences, Solvent, Monolayer, Electrochemistry, [CHIM]Chemical Sciences, Grazing-incidence small-angle scattering, Molecule, General Materials Science, 0210 nano-technology, Spectroscopy
Abstract: International audience; We describe the surface behavior of PS-b-PAA monolayers at the air/water interface using N,N-dimethyformamide (DMF) as spreading solvent. At low pH, when the PAA blocks are neutral, the surface pressure versus molecular area isotherm shows a pseudoplateau associated with the presence of remaining solvent spreading molecules in the monolayer, as we described in a former study (Guennouni et al, Langmuir, 2016). We show here that the width of the plateau decreases when increasing pH up to its complete disappearance at high pH, when PAA blocks are fully charged, although there still exist two regimes of compressibilities on the isotherm. A refined structural study at pH 9 combining Specular Neutron Reflectivity (SNR), Grazing-Incidence Small-Angle X-rays Scattering (GISAXS) and Atomic Force Microscopy (AFM) in liquid measurements show that: (i) PAA blocks are stretched in solution, as expected from polyelectrolyte brushes in osmotic regime; (ii) the system undergoes a spinodal decomposition during deposit at the air/water interface in presence of DMF. Upon compression, the Qxy* position of the peak associated with the spinodal structure remains almost constant but its intensity evolves strongly and passes through a maximum at intermediate pressures. This reveals two operating processes in the system: strong electrostatic repulsions between chains that prevent in-plane reorganizations and force such reorganizations to occur from the surface to the volume and progressive expulsion of the DMF molecules from the monolayer. These processes have antagonist effects on the intensity of the peak: the increase of the repulsions makes it more pronounced whereas the expulsion of solvent makes it vanish due to the loss of contrast.
Published: 2017
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14. Mediator reduction of bromate anion at rotating disk electrode under steady-state conditions for high current densities

Author: A. E. Antipov, Mikhail A. Vorotyntsev, Lomonosov Moscow State University ( MSU ), Mendeleev University of Chemical Technology of Russia, Institute for Problems of Chemical Physics, Russian Academy of Sciences - Chernogolovka, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Russian Science Foundation 15-13-20038, Lomonosov Moscow State University (MSU), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), and Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Br-2/Br- redox couple, comproportionation, Analytical chemistry, mechanism, 02 engineering and technology, 010402 general chemistry, Kinetic energy, bromide reaction, [ CHIM ] Chemical Sciences, 01 natural sciences, Molecular physics, symbols.namesake, chemistry.chemical_compound, Electrochemistry, [CHIM]Chemical Sciences, Nernst equation, Diffusion (business), Rotating disk electrode, Steady state, Chemistry, Comproportionation, 021001 nanoscience & nanotechnology, Bromate, electroreduction, 0104 chemical sciences, bromate anion, kinetics, redox-mediator autocatalysis, Electrode, ions, symbols, 0210 nano-technology, belousov-zhabotinskii reaction
Abstract: Theoretical study of the bromate anion reduction under steady-state conditions is performed for rotating disk electrode. Transport of the components in solution is described within the framework of the Nernst stagnant layer model. Numerical calculations carried out recently for the same system confirmed the validity of our previous approximate analytical approaches for the weak current and thin kinetic layer regimes for small and moderate values of the principal parameters of the system: ratio of the diffusion and kinetic layer thicknesses, x dk = z d/z k, for the whole range of possible currents. At the same time, these numerical results showed a pronounced change of the calculated concentration distributions, compared to the predictions of the thin kinetic layer model, for very large values of the x dk parameter. A new theoretical analysis performed in this study provides approximate analytical expressions for the concentration distributions under conditions of very strong current exceeding the bromate diffusion-limited one. These expressions demonstrate that the passing of such currents results in a cardinal change of the kinetic layer structure, compared to that for weaker currents. The comproportionation reaction takes place mainly inside a layer near the electrode surface for moderate current densities while for strong currents a BrO3 −-free layer is formed near the surface, so that the reaction is localized within a narrow “reaction zone” displaced from the electrode surface.
Published: 2017
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15. Selective Nanomaterials for Glucose-to-Gluconate Oxidation in an Electrochemical Energy Converter: Cogenerating Organic Electrosynthesis

Author: Yaovi Holade, Kouakou Boniface Kokoh, Teko W. Napporn, Karine Servat, Institut Européen des membranes ( IEM ), Centre National de la Recherche Scientifique ( CNRS ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM ), Catalyse en chimie organique ( LACCO ), Université de Poitiers-Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie des Milieux et Matériaux de Poitiers ( IC2MP ), ANR, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC)
Subjects: Materials science, 020209 energy, ELECTROCATALYTIC OXIDATION, ELECTROACTIVITY, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Electrosynthesis, Electrocatalyst, Electrochemistry, MEMBRANE FUEL-CELLS, ELECTRICITY, [ CHIM ] Chemical Sciences, 01 natural sciences, Nanomaterials, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, NANOCATALYSTS, business.industry, GLYCEROL, ELECTROOXIDATION, Electrochemical energy conversion, Nanomaterial-based catalyst, 0104 chemical sciences, Anode, Renewable energy, BROMIDE ANION-EXCHANGE, GOLD NANOPARTICLES, ACID, business
Abstract: Glucose is an environmentally friendly and sustainable carbohydrate that is actually a cyclized aldehyde in aqueous solution i.e. a hemiacetal. Its selective oxidation by the anomeric carbon in C1-position without any function protection is of great interest for cogeneration because the electrochemical process enables converting this highly functionalized organic molecule into electricity, heat and added-value chemicals. For this objective, we decided to synthesize effective nanomaterials towards glucose conversion at the anode and the oxygen reduction reaction (ORR) in the cathodic side of a fuel cell. The physical characterizations of the prepared materials and their electrochemical analysis at each half-cell, permitted to optimize the activity of the electrodes according to their elemental composition and structure. Furthermore, a constructed direct glucose fuel cell (DGFC) delivered an open-circuit voltage of 1.1 V in 0.5 mol L‒1 NaOH and an outstanding output power of 2 mW cm‒2 in 0.5 M KOH (Figure 1a). Complementary analytical techniques were employed to quantify the reaction processes involved in each compartment, to determine the reaction products resulted from the glucose transformation and thereby, to understand reaction mechanisms of the glucose oxidation and the ORR over the synthesized electrode materials used in alkaline medium. As results, the identification of gluconate as the sole reaction product in the anodic side showed a selective 2-electron conversion of glucose (Figure 1b), while the ORR proceeded through a 4-electron pathway over the designed cathode catalyst (Figure 1c). Figure 1: (a) Fuel cell polarization curves for different concentrations of glucose in a single fuel cell. Anode: 20 wt.% Au/C (0.18 mgAu cm‒2); cathode 20 wt.% Pt/C (0.17 mgPt cm‒2); Fumatech AEM. Anode: 0.5 mol L‒1 KOH + glucose (deoxygenated by N2); cathode: 0.5 mol L‒1 KOH + O2. (b) LC–MS negative ionization mass spectrum (M-1) of the product. (c) Electrochemical durability tests: Comparison of the ORR polarization curves (at 5 mV s−1) before (black) and after 1000 CVs (red); insets show the normalized specific electrochemical active surface area (SECSA) decay over the 1000 cycles from 0.05 to 1.1 V vs. RHE at 50 mV s−1. Acknowledgments The authors gratefully acknowledge financial support from the French National Research Agency ANR-ChemBio-Energy References 1. Y. Holade et al., ChemSusChem, 9, 252 (2016). Figure 1
Published: 2017
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16. ALD Al2O3‑Coated TiO2 Nanotube Layers as Anodes for Lithium-Ion Batteries

Author: Girish D. Salian, Raul Zazpe, Jan Prikryl, Jan M. Macak, Thierry Djenizian, Ludek Hromadko, Hanna Sopha, University of Pardubice, Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre Microélectronique de Provence - Site Georges Charpak (CMP-GC) (CMP-ENSMSE), École des Mines de Saint-Étienne (Mines Saint-Étienne MSE), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), University Pardubice, Matériaux divisés, interfaces, réactivité, électrochimie ( MADIREL ), Aix Marseille Université ( AMU ) -Centre National de la Recherche Scientifique ( CNRS ), Centre Microélectronique de Provence - Site Georges Charpak (CMP-GC) ( CMP-ENSMSE ), École des Mines de Saint-Étienne ( Mines Saint-Étienne MSE ), Institut Mines-Télécom [Paris]-Institut Mines-Télécom [Paris], ANR-11-IDEX-0001-02/11-IDEX-0001,Amidex,Amidex ( 2011 ), and Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)
Subjects: Nanotube, Materials science, General Chemical Engineering, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, engineering.material, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, [ CHIM ] Chemical Sciences, Article, lcsh:Chemistry, Atomic layer deposition, Coating, [CHIM]Chemical Sciences, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Anode, Chemical engineering, chemistry, lcsh:QD1-999, Electrode, engineering, Lithium, 0210 nano-technology, Faraday efficiency
Abstract: International audience; The utilization of the anodic TiO 2 nanotube layers, with uniform Al 2 O 3 coatings of different thicknesses (prepared by atomic layer deposition, ALD), as the new electrode material for lithium-ion batteries (LIBs), is reported herein. Electrodes with very thin Al 2 O 3 coatings (∼1 nm) show a superior electrochemical performance for use in LIBs compared to that of the uncoated TiO 2 nanotube layers. A more than 2 times higher areal capacity is received on these coated TiO 2 nanotube layers (∼75 vs 200 μAh/cm 2) as well as higher rate capability and coulombic efficiency of the charging and discharging reactions. Reasons for this can be attributed to an increased mechanical stability of the TiO 2 nanotube layers upon Al 2 O 3 coating, as well as to an enhanced diffusion of the Li + ions within the coated nanotube layers. In contrast, thicker ALD Al 2 O 3 coatings result in a blocking of the electrode surface and therefore an areal capacity decrease. ■ INTRODUCTION During the last decade, TiO 2 nanomaterials have widely been studied as an alternative electrode material for lithium-ion batteries (LIBs). 1−15 TiO 2 has a higher lithiation potential (∼1.6 V vs Li/Li +) compared to that of the negative electrodes, such as graphite (∼0.1 V vs Li/Li +), and therefore enhances safety of the cells and provides a good capacity retention on cycling and a low self-discharge. 1−4 Furthermore, TiO 2 shows low volume changes of less than 4% upon reversible insertion and extraction of Li + in the lattice. However, TiO 2 also has a poor electrical conductivity and shows limited Li + uptake and slow Li + insertion kinetics. 1−4 To overcome these drawbacks, nanostructured TiO 2 , such as mesoporous microspheres, 5 nanowires, 6,7 nanoparticles, 8 nanoflakes, 9 or TiO 2 nano-tubes, 1−4,10 produced via different methods have been considered as anodes due to the larger specific surface area. Although most of these structures are randomly oriented and have to be deposited on the back contact of the electrode, self-organized TiO 2 nanotube layers produced by electrochemical anodization of the Ti substrates consist of straight and vertically aligned nanotubes in direct electrical contact with the underlying Ti substrate. 16 Another advantage of the vertically aligned nanotube layers is a direct diffusion path for the Li + ions, resulting in a superior electrochemical performance. 11 To further increase the capacity and conductivity of the TiO 2 nanotubes for their use in LIBs, they have been decorated or coated with other metals and metal oxides, with higher conductivities and capacities, for example, Ag, 17 Cu 6 Sn 5 , 18 Fe 2 O 3 , 19 SnO, 20 SnO 2 , 21,22 or ZnO. 23 Another advantage of these composite structures is that due to their hollow tubular architecture they can bear volume variations upon battery cycling without mechanical failure. Among the various methods that can be used for the coating and decoration of the TiO 2 nanotube layers, atomic layer deposition (ALD) has been the only method that creates uniform coatings of the nanotube walls from inside as well as outside, with a precise control of the coating thickness according to the deposition cycles. 24−26 However, although several reports can be found on utilization of the ALD coatings of different materials to modify the electrodes for lithium-ion battery application, 27−33 only one publication reports on the use of ALD to coat an anode prepared from an anodic TiO 2 nanotube layer with ZnO. 23 Usually, passivation layers on the electrode surfaces (solid electrolyte interphase (SEI)) are formed via decomposition of
Published: 2017
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17. Metabolic changes in Medaka fish induced by cyanobacterial exposures in mesocosms: an integrative approach combining proteomic and metabolomic analyses

Author: Hélène Huet, Gérard Lacroix, BenoÃ®t. Sotton, Alexis Millot, Qin Qiao, Alain Paris, Alain Blond, Arnaud Catherine, Joëlle Vinh, Sophie Labrut, Benjamin Marie, Charlotte Duval, Séverine Le Manach, Giovanni Chiapetta, Sotton, Benoît, Molécules de Communication et Adaptation des Micro-Organismes (MCAM), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Xénobiotiques, Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Vétérinaire de Toulouse (ENVT), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Biogéochimie et écologie des milieux continentaux (Bioemco), Centre National de la Recherche Scientifique (CNRS)-AgroParisTech-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Recherche Agronomique (INRA)-École normale supérieure - Paris (ENS Paris), CEREEP-Ecotron Ile de France (UMS 3194), Centre National de la Recherche Scientifique (CNRS)-Département de Biologie - ENS Paris, École normale supérieure - Paris (ENS Paris)-École normale supérieure - Paris (ENS Paris), École nationale vétérinaire d'Alfort (ENVA), Molécules de Communication et Adaptation des Micro-organismes (MCAM), Ecole Nationale Vétérinaire Agroalimentaire et de l'Alimentation Nantes Atlantique (ONIRIS), Unité de Spectrométrie de Masse Biologique et Protéomique, ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), Museum d'Histoire Naturelle, Biogéosciences [UMR 6282] [Dijon] (BGS), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Université Pierre et Marie Curie - Paris 6 (UPMC)-AgroParisTech-Centre National de la Recherche Scientifique (CNRS), Département de Biologie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), École nationale vétérinaire - Alfort (ENVA), Spectrométrie de Masse Biologique et Protéomique (USR3149 / FRE2032) (SMBP), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Biogéosciences [UMR 6282] (BGS), Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Universites 'DANCE', Sorbonne Universites 'Procytox', CNRS (Defi ENVIROMICS 'Toxcyfish' ), PLANAQUA, [ANR-10-EQPX-13-01], [ANR-11-INBS-0001], Molécules de Communication et Adaptation des Micro-Organismes ( MCAM ), Muséum National d'Histoire Naturelle ( MNHN ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National de la Recherche Agronomique ( INRA ) -Ecole Nationale Vétérinaire de Toulouse, Biogéochimie et écologie des milieux continentaux ( Bioemco ), École normale supérieure - Paris ( ENS Paris ) -Institut National de la Recherche Agronomique ( INRA ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -AgroParisTech-Université Paris-Est Créteil Val-de-Marne - Paris 12 ( UPEC UP12 ) -Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique ( CNRS ) -Département de Biologie - ENS Paris, École normale supérieure - Paris ( ENS Paris ) -École normale supérieure - Paris ( ENS Paris ), École nationale vétérinaire d'Alfort ( ENVA ), UMR 7245 - Molécules de Communication et Adaptation des Micro-organismes (MCAM) ( MCAM ), Ecole Nationale Vétérinaire Agroalimentaire et de l'Alimentation Nantes Atlantique ( ONIRIS ), ESPCI ParisTech-Centre National de la Recherche Scientifique ( CNRS ), Biogéosciences [Dijon] ( BGS ), Université de Bourgogne ( UB ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Centre National de la Recherche Scientifique ( CNRS ), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Centre National de la Recherche Scientifique (CNRS)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, Cyanobacteria, Oryzias, [SDV]Life Sciences [q-bio], Science, Computational biology, 010501 environmental sciences, 01 natural sciences, [ CHIM ] Chemical Sciences, Article, Mesocosm, 03 medical and health sciences, Metabolomics, Metabolome, [CHIM]Chemical Sciences, Microcystis aeruginosa, 14. Life underwater, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Multidisciplinary, biology, [ SDV ] Life Sciences [q-bio], Ecology, Aquatic ecosystem, biology.organism_classification, 030104 developmental biology, Proteome, Medicine
Abstract: Author Correction: The original version of this Article contained an error in the spelling of the author Giovanni Chiappetta, which was incorrectly given as Giovanni Chiapetta. This error has now been corrected in the HTML and PDF versions of the Article, and in the accompanying Supplementary Information document. https://doi.org/10.1038/s41598-018-20638-0; International audience; Cyanobacterial blooms pose serious threats to aquatic organisms and strongly impact the functioning of aquatic ecosystems. Due to their ability to produce a wide range of potentially bioactive secondary metabolites, so called cyanotoxins, cyanobacteria have been extensively studied in the past decades. Proteomic and metabolomic analyses provide a unique opportunity to evaluate the global response of hundreds of proteins and metabolites at a glance. In this study, we provide the first combined utilization of these methods targeted to identify the response of fish to bloom-forming cyanobacteria. Medaka fish (Oryzias latipes) were exposed for 96 hours either to a MC-producing or to a non-MC-producing strain of Microcystis aeruginosa and cellular, proteome and metabolome changes following exposure to cyanobacteria were characterized in the fish livers. The results suggest that a short-term exposure to cyanobacteria, producing or not MCs, induces sex-dependent molecular changes in medaka fish, without causing any cellular alterations. Globally, molecular entities involved in stress response, lipid metabolism and developmental processes exhibit the most contrasted changes following a cyanobacterial exposure. Moreover, it appears that proteomic and metabolomic analyses are useful tools to verify previous information and to additionally bring new horizons concerning molecular effects of cyanobacteria on fish.
Published: 2017
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18. Protonation and Electrochemical Properties of Pyridyl- and Sulfonatophenyl-Substituted Porphyrins in Nonaqueous Media

Author: Nicolas Desbois, Karl M. Kadish, Yan Cui, Lihan Zeng, Yuanyuan Fang, Yi Chang, Jialiang Zhu, Claude P. Gros, Mario L. Naitana, Department of Chemistry and Chemical Engineering, Jiangsu University, JiangSu University, Department of Chemistry [University of Houston], University of Houston, 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), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), and Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: 010405 organic chemistry, Chemistry, Protonation, 010402 general chemistry, Photochemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Medicinal chemistry, Porphyrin, Redox, Catalysis, 0104 chemical sciences, Solvent, chemistry.chemical_compound, PEG ratio, Trifluoroacetic acid, [CHIM]Chemical Sciences, Titration
Abstract: International audience; The protonation and electrochemical properties of positively charged and negatively charged porphyrins are reported in up to five different nonaqueous solvents. The positively charged porphyrins are represented by mono- and di-pyridyl derivatives having the formula Pyx(PhMe)4-xPM, where P=the dianion of the porphyrin macrocycle, PhMe is a meso-tolyl group, Py a meso-pyridyl group, x=1 or 2, and M=H2, NiII, CuII, ZnII, or CoII. The negatively charged porphyrins are comprised of meso-tetrasulfonato derivatives having the formula [(R)4(TPPS)H2]4−(X+)4, where [(TPPS)H2]4− represents the porphyrin with four SO3− groups on the meso-phenyl substituents of the macrocycle, R=H or PEG (PEG=C7H15O4) and X+=H+ or Na+. Each pyridylporphyrin was shown to undergo an initial protonation of the meso-pyridyl group(s) upon addition of acid to the porphyrin solutions and, in the case of the free-base derivatives, this was followed in a second step by a simultaneous protonation of the two core nitrogen atoms on the macrocycle. Two central nitrogen atoms of the sulfonatophenyl porphyrins are also protonated in a single-step process, and the constants for each protonation reaction of Pyx(PhMe)4-xPM and [(R)4(TPPS)H2]4−(X+)4 were determined through spectral titration with trifluoroacetic acid in DMF, DMSO, CH2Cl2, or PhCN, after which the data were related to solvent properties, the measured redox potentials, and the mechanisms for electroreduction under the same solution conditions.
Published: 2017
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19. Random Structural Modification of a Low-Band-Gap BODIPY-Based Polymer

Author: Léo Bucher, Paul-Ludovic Karsenti, Pierre D. Harvey, Claude P. Gros, Nicolas Desbois, Shawkat M. Aly, 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), Département de chimie [Sherbrooke] (UdeS), Faculté des sciences [Sherbrooke] (UdeS), Université de Sherbrooke (UdeS)-Université de Sherbrooke (UdeS), Natural Sciences and Engineering Research Council of Canada (NSERC) le 'Fonds Québecois de la Recherche sur la Nature et les Technologies (FQRNT)' Centre d’Études des Matériaux Optiques et Photoniques de FUniversité de Sherbrooke (CEMOPUS) Centre National de la Recherche Scientifique 6302 CNRS Université de Bourgogne Franche-ComtéConseil Régional de Bourgogne Consulat Général de France au Québec, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Département de Chimie, Université de Sherbrooke, and Université de Sherbrooke [Sherbrooke]
Subjects: Materials science, Band gap, thin-film transistors, 02 engineering and technology, 010402 general chemistry, Photochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, chemistry.chemical_compound, molecular-orbital methods, organometallic compounds, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, density-functional theory, Absorption (electromagnetic radiation), valence basis-sets, distyryl-boradiazaindacenes, chemistry.chemical_classification, Polymer modified, field-effect transistors, pi-conjugated copolymers, [CHIM.MATE]Chemical Sciences/Material chemistry, Polymer, Chromophore, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Wavelength, solar-cells, General Energy, chemistry, [ CHIM.MATE ] Chemical Sciences/Material chemistry, extended basis-sets, BODIPY, 0210 nano-technology
Abstract: International audience; A BODIPY thiophene polymer modified by extending conjugation of the BODIPY chromophore is reported. This modification induces tunability of energy levels and therefore absorption wavelengths in order to target lower energies.
Published: 2017
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20. Expression and purification of native and functional influenza A virus matrix 2 proton selective ion channel

Author: Lorraine Benier, Sebastien Balme, Stéphane Audebert, Aurélien Traversier, Elodie Desuzinges Mandon, Anne Champagne, Emmanuel Dejean, Manuel Rosa Calatrava, Anass Jawhari, Centre International de Recherche en Infectiologie ( CIRI ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ), Centre de Recherche en Cancérologie de Marseille ( CRCM ), Aix Marseille Université ( AMU ) -Institut Paoli-Calmettes-Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Européen des membranes ( IEM ), Centre National de la Recherche Scientifique ( CNRS ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM ), CALIXAR, Virpath-Grippe, de l'émergence au contrôle -- Virpath-Influenza, from emergence to control (Virpath), Centre International de Recherche en Infectiologie - UMR (CIRI), Institut National de la Santé et de la Recherche Médicale (INSERM)-École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de biologie et chimie des protéines [Lyon] (IBCP), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Centre de Recherche en Cancérologie de Marseille (CRCM), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Paoli-Calmettes, Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Aix Marseille Université (AMU), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Aix Marseille Université (AMU)-Institut Paoli-Calmettes, Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre International de Recherche en Infectiologie (CIRI), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, Lysine, Oligomeric state, Gene Expression, Biology, medicine.disease_cause, [ CHIM ] Chemical Sciences, Ion Channels, Virus, Madin Darby Canine Kidney Cells, Lipid bilayer, Viral Matrix Proteins, 03 medical and health sciences, Dogs, Influenza A Virus, H1N1 Subtype, Viral envelope, Influenza A virus, medicine, [CHIM]Chemical Sciences, Animals, Humans, Purification, ComputingMilieux_MISCELLANEOUS, Ion channel, Native solubilization, 030102 biochemistry & molecular biology, Influenza infection, Proton selective ion channel, Cell Membrane, Matrix 2 influenza, Recombinant Proteins, 3. Good health, AMDCK expression, 030104 developmental biology, Membrane protein, Biochemistry, Current/voltage, Ion channel blocker, Biotechnology
Abstract: International audience; Influenza A virus displays one of the highest infection rates of all human viruses and therefore represents a severe human health threat associated with an important economical challenge. Influenza matrix protein 2 (M2) is a membrane protein of the viral envelope that forms a proton selective ion channel. Here we report the expression and native isolation of full length active M2 without mutations or fusions. The ability of the influenza virus to efficiently infect MDCK cells was used to express native M2 protein. Using a Calixarene detergents/surfactants based approach; we were able to solubilize most of M2 from the plasma membrane and purify it. The tetrameric form of native M2 was maintained during the protein preparation. Mass spectrometry shows that M2 was phosphorylated in its cytoplasmic tail (serine 64) and newly identifies an acetylation of the highly conserved Lysine 60. ELISA shows that solubilized and purified M2 was specifically recognized by M2 antibody MAB65 and was able to displace the antibody from M2 MDCK membranes. Using a bilayer voltage clamp measurement assay, we demonstrate a pH dependent proton selective ion channel activity. The addition of the M2 ion channel blocker amantadine allows a total inhibition of the channel activity, illustrating therefore the specificity of purified M2 activity. Taken together, this work shows the production and isolation of a tetrameric and functional native M2 ion channel that will pave the way to structural and functional characterization of native M2, conformational antibody development, small molecules compounds screening towards vaccine treatment.
Published: 2017
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21. Proton-Detected Solid-State NMR Spectroscopy of a Zinc Diffusion Facilitator Protein in Native Nanodiscs

Author: Bersch, Beate, Dörr, Jonas M, Hessel, Audrey, Killian, J Antoinette, Schanda, Paul, Sub Membrane Biochemistry & Biophysics, Membrane Biochemistry and Biophysics, Institut de biologie structurale (IBS - UMR 5075), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS), Utrecht University [Utrecht], Institut de biologie structurale ( IBS - UMR 5075 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Institut de biologie structurale (IBS - UMR 5075 ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), European Project: 311318,EC:FP7:ERC,ERC-2012-StG_20111109,PROTDYN2FUNCTION(2013), European Project: 317371,EC:FP7:PEOPLE,FP7-PEOPLE-2012-ITN,MANIFOLD(2012), European Project : 311318,EC:FP7:ERC,ERC-2012-StG_20111109,PROTDYN2FUNCTION ( 2013 ), European Project : 317371,EC:FP7:PEOPLE,FP7-PEOPLE-2012-ITN,MANIFOLD ( 2012 ), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Sub Membrane Biochemistry & Biophysics, and Membrane Biochemistry and Biophysics
Subjects: 0301 basic medicine, NMR spectoscopy, Proteolipids, Proton Magnetic Resonance Spectroscopy, membrane proteins, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Article, Catalysis, Diffusion, 03 medical and health sciences, NMR spectroscopy, Bacterial Proteins, nanodiscs, copolymers, [CHIM]Chemical Sciences, Integral membrane protein, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], biology, Cupriavidus metallidurans, Chemistry, Cupriavidus, Peripheral membrane protein, Maleates, Nanodiscs, Membrane Transport Proteins, Biological membrane, General Chemistry, biology.organism_classification, solis-state NMR, coplymers, Nanostructures, 0104 chemical sciences, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], Zinc, Crystallography, 030104 developmental biology, Membrane, Solid-state nuclear magnetic resonance, Membrane protein, solid-state NMR, Polystyrenes, Protons, [ SDV.BBM.BS ] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], Cation diffusion facilitator
Abstract: International audience; The structure, dynamics and function of membrane proteins are intimately linked to the properties of the membrane environment in which the proteins are embedded. For structural and biophysical characterization, membrane proteins generally need to be extracted from the membrane, and reconstituted in a suitable membrane-mimicking environment. Ensuring functional and structural integrity in these environments is often a major concern. The styrene/maleic acid co-polymer has recently been shown to be able to extract lipid/membrane protein patches directly from native membranes, forming nanosize discoidal proteolipid particles, also referred to as native nanodiscs. Here we show, for the first time, that high-resolution solid-state NMR spectra can be obtained from an integral membrane protein in native nanodiscs, as exemplified with the 2 x 34 kDa-large bacterial cation diffusion facilitator CzcD from Cupriavidus metallidurans CH34.
Published: 2017
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22. A Dual Functional Electroactive and Fluorescent Probe for Coupled Measurements of Vesicular Exocytosis with High Spatial and Temporal Resolution

Author: Sylvie Maurin, Jérôme Delacotte, Laurence Grimaud, François Darchen, Manon Guille-Collignon, Eric Labbé, Olivier Buriez, Frédéric Lemaître, Xiaoqing Liu, Damien Quinton, Alexandra Savy, Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Laboratoire de Neurophotonique (UMR 8250), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris ( ENS Paris ), Laboratoire de Neurophotonique ( UMR 8250 ), and Centre National de la Recherche Scientifique ( CNRS ) -Université Paris Descartes - Paris 5 ( UPD5 )
Subjects: Nanotechnology, 02 engineering and technology, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Exocytosis, Fluorescence, Catalysis, Cell Line, 03 medical and health sciences, 0302 clinical medicine, Microscopy, Humans, [CHIM]Chemical Sciences, Electrodes, Fluorescent Dyes, Neurotransmitter Agents, Total internal reflection fluorescence microscope, Chemistry, Electrochemical Techniques, General Chemistry, General Medicine, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Amperometry, Indium tin oxide, 0104 chemical sciences, Spectrometry, Fluorescence, Microscopy, Fluorescence, Temporal resolution, Electrode, Biophysics, 0210 nano-technology, 030217 neurology & neurosurgery
Abstract: International audience; In this work, Fluorescent False Neurotransmitter 102 (FFN102), a synthesized analogue of biogenic neurotransmit-ters, was demonstrated to show both pH-dependent fluores-cence and electroactivity. To study secretory behaviors at the single-vesicle level, FFN102 was employed as a new fluores-cent/electroactive dual probe in a coupled technique (amper-ometry and total internal reflection fluorescence microscopy (TIRFM)). We used N13 cells, a stable clone of BON cells, to specifically accumulate FFN102 into their secretory vesicles, and then optical and electrochemical measurements of vesic-ular exocytosis were experimentally achieved by using indium tin oxide (ITO) transparent electrodes. Upon stimulation, FFN102 started to diffuse out from the acidic intravesicular microenvironment to the neutral extracellular space, leading to fluorescent emissions and to the electrochemical oxidation signals that were simultaneously collected from the ITO electrode surface. The correlation of fluorescence and ampero-metric signals resulting from the FFN102 probe allows real-time monitoring of single exocytotic events with both high spatial and temporal resolution. This work opens new possibilities in the investigation of exocytotic mechanisms.
Published: 2017
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23. Stochastic modeling for biotechnologies Anaerobic model AM2b

Author: Campillo , Fabien, Chebbi , Mohsen, Toumi , Salwa, Mathématiques pour les Neurosciences (MATHNEURO), Inria Sophia Antipolis - Méditerranée (CRISAM), Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria), Ecole Nationale d'Ingénieurs de Tunis (ENIT), Université de Tunis El Manar (UTM), and Institut National des Sciences Appliquées et de Technologie - Carthage (INSAT Carthage)
Subjects: [ MATH ] Mathematics [math], pure jump process, modèle AM2b, [ SDV ] Life Sciences [q-bio], [SDV]Life Sciences [q-bio], diffusion approximation, approximation diffusion, ordinary differential equation, stochastic differential equation, AM2b model, [ CHIM ] Chemical Sciences, processus de saut pur, équation différentielle stochastique, équation différentielle ordinaire, [CHIM]Chemical Sciences, [MATH]Mathematics [math]
Abstract: Le modèle AM2b est classiquement représenté par un système d'équations différentielles. Toutefois ce modèle n'est valide qu'en grande population et notre objectif est d'établir plusieurs mo-dèles stochastiques à différentes échelles. À l'échelle microscopique, on propose un modèle sto-chastique de saut pur que l'on peut simuler de fa con exacte. Mais dans la plupart des situations ce genre de simulation n'est pas réaliste, et nous proposons des méthodes de simulation approchées de type poissonnien ou de type diffusif. La méthode de simulation de type diffusif peut être vue comme une discrétisation d'une équation différentielle stochastique. Nous présentons enfin de fa con infor-melle un résultat de type loi des grands nombres/théorème central limite fonctionnelle qui démontre la convergence de ses modèles stochastiques vers le modèles déterministe initial., The model AM2b is conventionally represented by a system of differential equations. However, this model is valid only in a large population context and our objective is to establish several stochastic models at different scales. At a microscopic scale, we propose a pure jump stochastic model that can be simulated exactly. But in most situations this exact simulation is not feasible, and we propose approximate simulation methods of Poisson type and of diffusive type. The diffusive type simulation method can be seen as a discretization of a stochastic differential equation. Finally, we formally present a result of law of large numbers and of functional central limit theorem which demonstrates the convergence of these stochastic models towards the initial deterministic models.
Published: 2019

24. Aluminum oxide nanowires as safe and effective adjuvants for next-generation vaccines

Author: Tetiana Dumych, Solomiya Paryzhak, Gleb Yushin, Alexandre Barras, Kostiantyn Turcheniuk, Rabah Boukherroub, Rostyslav Bilyy, Sabine Szunerits, Fujia Wang, Danylo Halytskiy Lviv National Medical University, Institut de biologie de Lille - IBL (IBLI), Université de Lille, Sciences et Technologies-Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Droit et Santé, Institut d’Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520 (IEMN), Ecole Centrale de Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), Georgia Institute of Technology [Atlanta], Institut d’Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520 ( IEMN ), Ecole Centrale de Lille-Institut supérieur de l'électronique et du nunérique (ISEN)-Université Polytechnique Hauts-de-France ( UPHF ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), European Project : 690836,H2020,H2020-MSCA-RISE-2015,PANG ( 2016 ), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), NanoBioInterfaces - IEMN (NBI - IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), European Project: 690836,H2020,H2020-MSCA-RISE-2015,PANG(2016), Ecole Centrale de Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Laboratoire International associé sur les phénomènes Critiques et Supercritiques en électronique fonctionnelle, acoustique et fluidique (LIA LICS/LEMAC), and Ecole Centrale de Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-Ecole Centrale de Lille-Université de Lille-Université Polytechnique Hauts-de-France (UPHF)-Université Polytechnique Hauts-de-France (UPHF)
Subjects: medicine.medical_treatment, [SDV]Life Sciences [q-bio], Nanowire, Nanotechnology, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 02 engineering and technology, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, chemistry.chemical_compound, Immune system, Antigen, medicine, [ SDV.IMM ] Life Sciences [q-bio]/Immunology, [CHIM]Chemical Sciences, General Materials Science, Aluminum oxide, ComputingMilieux_MISCELLANEOUS, [ SDV ] Life Sciences [q-bio], Chemistry, Alum, Mechanical Engineering, [ CHIM.THER ] Chemical Sciences/Medicinal Chemistry, Neutrophil extracellular traps, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 3. Good health, 0104 chemical sciences, Mechanics of Materials, [ CHIM.MATE ] Chemical Sciences/Material chemistry, [ SDV.IMM.VAC ] Life Sciences [q-bio]/Immunology/Vaccinology, [SDV.IMM]Life Sciences [q-bio]/Immunology, [SDV.IMM.VAC]Life Sciences [q-bio]/Immunology/Vaccinology, 0210 nano-technology, Adjuvant
Abstract: Improving efficiency of an adjuvant, material that enhances the body’s immune response to an antigen, has become vital for the development of safer, cheaper, and more effective next-generation vaccines. Commercial vaccines typically use aluminum salt-based adjuvant particles, most commonly aluminum oxyhydroxide (AlOOH) and aluminum hydroxide (Al(OH)3) based, often referred to as “alum”. Despite their broad use, their adjuvant properties are rather moderate. This is even worse in the case of aluminum oxide (Al2O3)-based adjuvant. While being more robust and less cytotoxic, Al2O3 is a significantly less effective adjuvant than above-mentioned Al compounds and is consequently not commonly used. Here, we report on the remarkably enhanced adjuvant properties of Al2O3 when produced in the form of nanowires (NWs). Based on recent advances in understanding neutrophil activation by inert nanoscaffolds, we have created ultra-long Al2O3 NWs with a high aspect ratio of ∼1000. These NWs showed strong humoral immune response with no damaging effect on the microvasculature. Since only the change of shape of Al adjuvants is responsible for the excellent adjuvant properties, our finding holds great promise for rapid implementation as safer and more effective adjuvant alternative for human vaccines. The mechanism behind human blood-derived neutrophil activation with Al2O3 NWs was found to be sequestering of Al2O3 NWs by neutrophils via formation of neutrophil extracellular traps (NETs).
Published: 2019
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25. Biotransformation of herbicides by aquatic microbial communities associated to submerged leaves

Author: Isabelle Batisson, Pascale Besse-Hoggan, Muriel Joly, Louis Carles, Joan Artigas, Florent Rossi, Laboratoire Microorganismes : Génome et Environnement - Clermont Auvergne ( LMGE ), Université Clermont Auvergne ( UCA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie de Clermont-Ferrand - Clermont Auvergne ( ICCF ), Sigma CLERMONT ( Sigma CLERMONT ) -Université Clermont Auvergne ( UCA ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire Microorganismes : Génome et Environnement (LMGE), Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])
Subjects: medicine.drug_class, Health, Toxicology and Mutagenesis, Microorganism, 010501 environmental sciences, Zea mays, [ CHIM ] Chemical Sciences, 01 natural sciences, Mesotrione, chemistry.chemical_compound, Biotransformation, Botany, medicine, [CHIM]Chemical Sciences, Environmental Chemistry, Ecotoxicology, 0105 earth and related environmental sciences, 2. Zero hunger, Herbicides, Leaf-associated microorganisms Biodegradation Mesotrione Nicosulfuron S-metolachlor Herbicide mixture, fungi, Water, food and beverages, 04 agricultural and veterinary sciences, General Medicine, 15. Life on land, Biodegradation, Pesticide, Pollution, Sulfonylurea, 6. Clean water, Plant Leaves, chemistry, 13. Climate action, 040103 agronomy & agriculture, 0401 agriculture, forestry, and fisheries, Water Microbiology, Xenobiotic
Abstract: International audience; Leaf microbial communities possess a large panel of enzymes permitting the breakdown of leaf polymers as well as the transformation of organic xenobiotic compounds present in stream waters. This study aims to assess the potential of leaf microbial communities, exhibiting different exposure histories to pesticides (upstream versus downstream), to biotransform three maize herbicides (mesotrione, S-metolachlor, and nicosulfuron) in single and cocktail molecule exposures. The results showed a high dissipation of nicosulfuron (sulfonylurea herbicide) (from 29.1 ± 10.8% to 66 ± 16.2%, day 40) in both single and cocktail exposures, respectively, but not of mesotrione and S-metolachlor. The formation of nicosulfuron metabolites such as ASDM (2-(aminosulfonyl)-N,N-dimethyl-3-pyridinecarboxamide) and ADMP (2-amino-4,6-dimethoxypyrimidine) and the weak sorption (
Published: 2016
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26. Immobilization of Monolayers Incorporating Cu Funnel Complexes onto Gold Electrodes. Application to the Selective Electrochemical Recognition of Primary Alkylamines in Water

Author: Ivan Jabin, Gaël De Leener, Yann R. Leroux, Ana Gabriela Porras-Gutierrez, Corinne Lagrost, Diana Over, Philippe Hapiot, Nicolas Le Poul, Olivia Reinaud, Jeremy Mertens, François Reniers, Ferdinand Evoung-Evoung, Yves Le Mest, Angélique Lascaux, Laboratoire de Chimie Organique, Université Libre de Bruxelles [Bruxelles] ( ULB ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Université libre de bruxelles, Service de chimie analytique et chimie des interfaces (CHANI), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Fonds de la Recherche Scientifique-FNRS [FRFC 2.4.617.10.F], Agence Nationale de la Recherche [ANR10-BLAN-714], De Brouckere-Solvay fund, Michel Kaisin fund, Université libre de Bruxelles (ULB), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Service de chimie analytique et chimie des interfaces (CHANI), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université Libre de Bruxelles [Bruxelles] (ULB), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université Paris Diderot - Paris 7 (UPD7), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: aqueous-solution, Inorganic chemistry, Alkyne, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Redox, Catalysis, beta-cyclodextrin, active-sites, Colloid and Surface Chemistry, aliphatic-amines, Monolayer, neutral molecules, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, copper complex, chemistry.chemical_classification, Aqueous solution, Chemistry, metal-surfaces, self-assembled monolayers, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Copper, 0104 chemical sciences, alkyl amines, induced electroclick, Electrode, Cyclic voltammetry, 0210 nano-technology
Abstract: International audience; The immobilization of a copper calix[6]azacryptand funnel complex on gold-modified electrodes is reported. Two different methodologies are described. One is based on alkyne-terminated thiol self assembled monolayers. The other relies on the electrografting of a calix[4]arene platform bearing diazonium functionalities at its large rim and carboxylic functions at its small rim, which is post-functionalized with alkyne moieties. In both cases, the CuAAC electroclick methodology proved to be the method of choice for grafting the calix[6]azacryptand onto the monolayers. The surface-immobilized complex was fully characterized by surface spectroscopies and electrochemistry in organic and aqueous solvents. The Cu complex display a well-defined quasi-reversible system in cyclic voltammetry associated with the Cu(II)/Cu(I) redox process. Remarkably, this-redox process triggers a powerful selective detection of primary alkylamines in water at a micromolar level, based on a cavitary recognition process.
Published: 2016
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27. Mechanism of O2 diffusion and reduction in FeFe hydrogenases

Author: Philippe Soucaille, Matteo Sensi, Christophe Léger, Isabelle Meynial-Salles, Charles Gauquelin, Carole Baffert, Jochen Blumberger, Laure Saujet, Robert B. Best, David De Sancho, Adam Kubas, Christophe Orain, Hervé Bottin, Vincent Fourmond, Kubas, A, Orain, C, Sancho, D, Saujet, L, Sensi, M, Gauquelin, C, Meynial-Salles, I, Soucaille, P, Bottin, H, Baffert, C, Fourmond, V, Best, R, Blumberger, J, Léger, C, Department of Physics and Astronomy [UCL London], University College of London [London] ( UCL ), Bioénergétique et Ingénierie des Protéines ( BIP ), Aix Marseille Université ( AMU ) -Centre National de la Recherche Scientifique ( CNRS ), Department of Chemistry [Cambridge, UK], University of Cambridge [UK] ( CAM ), Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Institut de Biologie et de Technologies de Saclay ( IBITECS ), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), Laboratoire d'Ingénierie des Systèmes Biologiques et des Procédés ( LISBP ), Institut National de la Recherche Agronomique ( INRA ) -Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), and Institut de Microbiologie de la Méditerranée ( IMM )
Subjects: Hydrogenase, General Chemical Engineering, Mutant, Nanotechnology, Molecular Dynamics Simulation, Molecular Dynamics, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Catalysis, Diffusion, Molecular dynamics, Metalloproteins, Site-Directed, Clostridium, CHIM/03 - CHIMICA GENERALE E INORGANICA, chemistry.chemical_classification, biology, 010405 organic chemistry, Chemistry, Mutagenesis, Active site, Electrochemical Techniques, General Chemistry, 0104 chemical sciences, Oxygen, CHIM/02 - CHIMICA FISICA, Enzyme mecanisms, Enzyme, Hydrogen, Mutagenesis, Site-Directed, Oxidation-Reduction, Quantum Theory, Density functional theory, Electrocatalysis, Enzyme mechanisms, Metalloproteins, Molecular dynamics, Density functional theory, Biophysics, biology.protein, Electrocatalysis, Cysteine
Abstract: International audience; FeFe hydrogenases are the most efficient H2-producing enzymes. However, inactivation by O2 remains an obstacle that prevents them being used in many biotechnological devices. Here, we combine electrochemistry, site-directed mutagenesis, molecular dynamics and quantum chemical calculations to uncover the molecular mechanism of O2 diffusion within the enzyme and its reactions at the active site. We propose that the partial reversibility of the reaction with O2 results from the four-electron reduction of O2 to water. The third electron/proton transfer step is the bottleneck for water production, competing with formation of a highly reactive OH radical and hydroxylated cysteine. The rapid delivery of electrons and protons to the active site is therefore crucial to prevent the accumulation of these aggressive species during prolonged O2 exposure. These findings should provide important clues for the design of hydrogenase mutants with increased resistance to oxidative damage.
Published: 2016
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28. Non-linear optical, electrochemical and spectroelectrochemical properties of amphiphilic inner salt porphyrinic systems

Author: Jean-François Nicoud, Karl M. Kadish, Frédéric Bolze, Koen Clays, Lihan Zeng, Nicolas Desbois, Yuanyuan Fang, Claude P. Gros, Yan Cui, Colin Lopez, Hoang Minh Ngo, Griet Depotter, Clément Michelin, Isabelle Ledoux, 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), University of Leuven Department of Chemistry, Université Catholique de Louvain = Catholic University of Louvain (UCL), Department of Chemistry [University of Houston], University of Houston, Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Conception et application de molécules bioactives (CAMB), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), 'Centre National de la Recherche Scientifique' (ICMUB) UMR CNRS 6302, Robert A. Welch Foundation (KMK) E-680, CNRS, the 'Universite de Bourgogne', 'Conseil Regional de Bourgogne' through the 3MIM integrated project ('Marquage de Molecules par les Metaux pour l'Imagerie Medicale'), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Université Catholique de Louvain ( UCL ), Laboratoire de Photonique Quantique et Moléculaire ( LPQM ), École normale supérieure - Cachan ( ENS Cachan ) -CentraleSupélec-Centre National de la Recherche Scientifique ( CNRS ), Conception et application de molécules bioactives ( CAMB ), and Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: design, Inorganic chemistry, Substituent, amphiphilic inner salt, 02 engineering and technology, 010402 general chemistry, Electrochemistry, Photochemistry, [ CHIM ] Chemical Sciences, electron-accepting moieties, 01 natural sciences, non-linear optical property, chemistry.chemical_compound, Amphiphile, chromophores, [CHIM]Chemical Sciences, Molecule, Chemistry, frequency dispersion, Second-harmonic generation, spectroelectrochemistry, dipolar complexes, General Chemistry, 021001 nanoscience & nanotechnology, Porphyrin, Fluorescence, 0104 chemical sciences, 2nd-harmonic generation, electrochemistry, microscopy, charge-transfer, fluorescence, Absorption (chemistry), hyper-rayleigh scattering, 0210 nano-technology
Abstract: Three zwitterionic meso-substituted A3B- and AB2C-porphyrins containing one sulfonato alkylpyridinium substituent and three or two alkoxy-substituted phenyl groups were synthesized in good yield and fully characterized as to their physicochemical properties by a variety of techniques. This new series of inner salt donor-acceptor meso-substituted porphyrin derivatives were prepared for possible application as amphiphilic probes for membrane insertion in the area of combined second-harmonic and two-photon fluorescence cellular microscopy. To this end, the linear and nonlinear optical properties of the compounds were characterized, together with their electrochemical and spectroelectrochemical properties in non-aqueous media. The neutral design of such molecules enabled us to determine their second order non-linear properties, both by Electric Field Induced Second Harmonic Generation and Hyper–Rayleigh Scattering. Two-photon absorption cross sections of these dyes were also measured by the two-photon induced fluorescence method. The zwitterionic nature of the inner salt results in very specific solvent-dependent redox-properties, which could be rationalized in terms of solvent-dependent ion-pairing. The overall data electrochemical and photophysical data indicates that these new porphyrinic systems should be good probes for membrane potential sensing.
Published: 2016
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29. Preparation of cobalt polyporphine and its catalytic properties in oxygen electroreduction

Author: Dmitry V. Konev, D. K. Khairullina, Mikhail A. Vorotyntsev, K. V. Lizgina, M. A. Shamraeva, Charles H. Devillers, Mendeleev University of Chemical Technology of Russia, Institute for Problems of Chemical Physics, Russian Academy of Sciences - Chernogolovka, Lomonosov Moscow State University ( MSU ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Russian Scientific Foundation 14-13-01244, Lomonosov Moscow State University (MSU), 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), Institute of Problems of Chemical Physics of RAS, Russian Academy of Sciences [Moscow] (RAS), and Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)
Subjects: metal porphines, polymer-modified electrodes, oxidation, Inorganic chemistry, chemistry.chemical_element, reduction, 02 engineering and technology, porphyrins, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Catalysis, [ CHIM.CATA ] Chemical Sciences/Catalysis, chemistry.chemical_compound, porphine, oxygen electroreduction, Trifluoroacetic acid, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, conductive polymer, polymers, chemistry.chemical_classification, Conductive polymer, metalloporphyrins, Ion exchange, Magnesium, electropolymerization, [CHIM.CATA]Chemical Sciences/Catalysis, Polymer, electrochemical properties, 021001 nanoscience & nanotechnology, bandgap, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, films, pyropolymer, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology, Cobalt
Abstract: International audience; A new member of the polyporphine series-cobalt polyporphine of type I (pCoP-I)-was prepared from the starting magnesium polyporphine of type I (pMgP-I) by ion exchange, i.e. by sequential processing of the pMgP-I polymer film on the electrode surface with solutions of trifluoroacetic acid (forming metalfree polyporphine of type I, pH(2)P-I) and cobalt(II) acetate in organic solvents. The completeness of each stage of ion exchange can be judged from the change in the electrochemical and spectral characteristics of the obtained polymer films of unsubstituted porphine (?H2P-I) and cobalt porphine (pCoP-I) of type I. Oxidative transformation of this polyporphine pCoP-I was performed, which led to the formation of additional bonds between the neighboring porphine units in the polymer film (transition of polymer of type I into polymer of type II, pCoP-II). The behavior of the polymer films of cobalt polyporphine of types I and II in oxygen electroreduction was studied. The films showed catalytic activity in this process.
Published: 2016
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30. Triorganotin carboxylates – synthesis and crystal structure of 2-methyl-1H-imidazol-3-ium catena-O,O′-oxalatotriphenylstannate

Author: Hélène Cattey, Laurent Plasseraud, Mouhamadou Birame Diop, Libasse Diop, Laboratoire de Chimie Minérale et Analytique, Université Cheikh Anta Diop, Université Cheikh Anta Diop ( UCAD ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Université Cheikh Anta Diop [Dakar, Sénégal] (UCAD), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), and Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: organotin (IV) carboxylates, Crystal structure, anticancer, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Medicinal chemistry, oxalate ligand, esters, Materials Chemistry, [CHIM]Chemical Sciences, QD1-999, X-ray crystallography, oxalate, dicarboxylic-acids, 010405 organic chemistry, Chemistry, Metals and Alloys, self-assembly, General Chemistry, Condensed Matter Physics, 3. Good health, 0104 chemical sciences, triphenyltin, organotin compounds
Abstract: The reaction of bis(2-methyl-1H-imidazol-3-ium) oxalate, [C4H7N2]2[C2O4], and bis(triphenyltin) oxalate, [(Ph3Sn)2(C2O4)], in methanol at room temperature yielded the formation of 2-methyl-1H-imidazol-3-ium catena-O,O′-oxalatotriphenylstannate, [C4H7N2][Ph3Sn(C2O4)] (1), which crystallizes in the monoclinic space group P21/c with Z=8, a=16.9334(14) Å, b=17.3251(14) Å, c=14.5114(10) Å, β=90.590(2)°, and V=4257.0(6) Å3. The oxalate ligand of 1 displays a bridging coordination mode and thus links two SnPh3 moieties through an axial coordination leading to the propagation of infinite polymeric chains along the c axis. All Sn(IV) atoms exhibit a trigonal bipyramid geometry. The negative charge of [Ph3Sn(C2O4)]- moieties is compensated by the presence of surrounding noncoordinating 2-methyl-1H-imidazol-3-ium cations. From a supramolecular point of view, the Sn-based chains are connected to one another through N-H···O hydrogen bond interactions involving oxalate ligands of distinct strands and doubly by the [C4H7N2]+ cations. The topology of the resulting crystal packing can be described as a two-dimensional layer network.
Published: 2016
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31. When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure

Author: Johann Lüder, Niklas Mårtensson, Cesare Grazioli, Nadine Witkowski, Carla Puglia, Marcel Bouvet, Barbara Brena, Ieva Bidermane, Sareh Ahmadi, Department of Physics and Astronomy [Uppsala], Uppsala University, Materialfysik, KTH-Electrum, Laboratorio TASC ( IOM CNR ), Consiglio Nazionale delle Ricerche ( CNR ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Nanosciences de Paris ( INSP ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Swedish Research Council (VR), European Research Council under the European Union 321319, Gender Equality Group, Department of Physics and Astronomy, Uppsala University, Knut and Alice Wallenberg Foundation KAW-2013.0020, Swedish Research Council 2014-3776, European Project : 321319,ERC 321319, Laboratorio TASC (IOM CNR), Consiglio Nazionale delle Ricerche (CNR), 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), Institut des Nanosciences de Paris (INSP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), European Project: 321319,ERC 321319, and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)
Subjects: lutetium bi-phthalocyanine, Silicon, XAS, Atom and Molecular Physics and Optics, STM, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, DFT, [ CHIM ] Chemical Sciences, 01 natural sciences, Si(100), law.invention, Adsorption, X-ray photoelectron spectroscopy, scanning tunneling microscope, law, basis-set, XPS, [CHIM]Chemical Sciences, surface, Molecule, Physical and Theoretical Chemistry, Basis set, metal-free phthalocyanine, field-effect transistors, Phthalocyanine, bis-phthalocyanine, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, total-energy calculations, General Energy, Electronic Structure, chemistry, si(001), Chemical physics, thin-films, augmented-wave method, Atom- och molekylfysik och optik, Density functional theory, Scanning tunneling microscope, Absorption (chemistry), 0210 nano-technology
Abstract: International audience; A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus of the biphthalocyanine are not affected in the same manner upon the adsorption onto the silicon surface. This finding can be of particular importance in the implementation of organic molecules in hybrid devices.
Published: 2016
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32. Crystal structure of the triphenyltin(IV) chloride dimethyl N-cyanodithioiminocarbonate adduct

Author: Yaya Sow, Libasse Diop, Laurent Plasseraud, Hélène Cattey, Mouhamadou Birame Diop, Laboratoire de Chimie Minérale et Analytique, Université Cheikh Anta Diop, Université Cheikh Anta Diop [Dakar, Sénégal] (UCAD), 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), Université Cheikh Anta Diop ( UCAD ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), and Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: cyanodithioimidocarbonate, Stereochemistry, coordination complex, Crystal structure, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Adduct, Coordination complex, Materials Chemistry, [CHIM]Chemical Sciences, Moiety, cyanamide derivative, QD1-999, X-ray crystallography, chemistry.chemical_classification, complexes, ligands, 010405 organic chemistry, Ligand, Metals and Alloys, General Chemistry, Nuclear magnetic resonance spectroscopy, Condensed Matter Physics, 0104 chemical sciences, Chemistry, Crystallography, Trigonal bipyramidal molecular geometry, chemistry, triphenyltin, N-ligand, Monoclinic crystal system
Abstract: Reaction of dimethyl N-cyanodithioiminocarbonate, NCNC(SCH3)2 (L), and SnPh3Cl led to the formation of [ClPh3SnNCNC(SCH3)2] (1) which crystallizes in the monoclinic space group C2/c with Z=8, a=19.152(2) Å, b=12.8659 (16) Å, c=19.063(3) Å, β=108.608(3) and V=4451.6(10) Å3. The structure of 1 consists of a SnPh3 moiety trans-coordinated in apical positions by one L ligand, N-coordinated, and one chlorine atom involving a trigonal bipyramid geometry around the Sn(IV) atom. To our knowledge, this is the first isolation of a discrete triorganotin(IV) complex with a N-cyanodithioiminocarbonate adduct. The structural characterization of 1 was completed by infrared and nuclear magnetic resonance spectroscopy, and elemental analysis which confirm the X-ray elucidation.
Published: 2016
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33. Ferrocenyl Quinone Methide-Thiol Adducts as New Antiproliferative Agents: Synthesis, Metabolic Formation from Ferrociphenols, and Oxidative Transformation

Author: Patrick M. Dansette, Anne Vessières, Daniel Mansuy, Yong Wang, Pascal Pigeon, Gérard Jaouen, Siden Top, Marie-Aude Richard, Université Pierre et Marie Curie - Paris 6 ( UPMC ), Chimie ParisTech, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Université Pierre et Marie Curie - Paris 6 (UPMC), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Stereochemistry, [SDV.CAN]Life Sciences [q-bio]/Cancer, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Glutathion, Catalysis, [ SDV.CAN ] Life Sciences [q-bio]/Cancer, chemistry.chemical_compound, Nucleophile, Michael-Addition, [CHIM]Chemical Sciences, Moiety, Reactivity (chemistry), Tumortherapeutika, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, General Medicine, General Chemistry, Lebermikrosome, Organometallverbindungen, Quinone methide, 0104 chemical sciences, Quinone, Electrophile, Michael reaction, Thiol
Abstract: International audience; Ferrociphenols (FCs) and their oxidized, electrophilic quinone methide metabolites (FC-QMs) are organometallic compounds related to tamoxifen that exhibit strong antiproliferative properties. To evaluate the reactivity of FC-QMs towards cellular nucleophiles, we studied their reaction with selected thiols. A series of new compounds resulting from the addition of these nucleophiles, the FC-SR adducts, were thus synthesized and completely characterized. Such conjugates are formed upon metabolism of FCs by liver microsomes in the presence of NADPH and thiols. Some of them exhibit antiproliferative properties comparable to those of their FC precursors. Under oxidizing conditions they either lead to their FC-QM precursors or to new quinone methides containing the SR moiety, FC-SR-QM. These results not only provide interesting data about the reactivity and mechanism of antiproliferative effects of FCs, but also open the way towards new series of organometallic anti-tumor compounds.
Published: 2016
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34. Antibacterial activity against methicillin-resistantStaphylococcus aureusof five essential oils from Algerian medicinal plants (Lamiaceae)

Author: Isabelle Bombarda, Abdelaziz Touati, Fahima Bekka-Hadji, Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Université Abderrahmane Mira [Béjaïa], Institut méditerranéen de biodiversité et d'écologie marine et continentale ( IMBE ), Université d'Avignon et des Pays de Vaucluse ( UAPV ) -Aix Marseille Université ( AMU ) -Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique ( CNRS ), and Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS)
Subjects: Traditional medicine, 010401 analytical chemistry, General Chemistry, Origanum, Biology, biology.organism_classification, [ CHIM ] Chemical Sciences, 01 natural sciences, Fenchone, 0104 chemical sciences, 3. Good health, Microbiology, 010404 medicinal & biomolecular chemistry, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Lamiaceae, Carvacrol, Mentha pulegium, Pulegone, Thymol, Lavandula stoechas, ComputingMilieux_MISCELLANEOUS
Abstract: The susceptibility of two methicillin-resistant Staphylococcus Aureus (MRSA) and one methicillin-sensitive Staphylococcus Aureus (MSSA) to essential oils (EOs) extracted from five Algerian medicinal plants (Lamiaceae) was evaluated. Thymus fontanesii and Thymus numidicus EOs revealed a carvacrol chemical profile (62.7 and 46.8%, respectively) whereas Origanum glandulosum EO was characterized by high contents of carvacrol and thymol. Mentha pulegium was characterized by a high content of pulegone (74.8%) never put in evidence. The major components of Lavandula stoechas L. were fenchone (48.0%) and camphor (21.1%). Antibacterial activities against MRSA and MSSA were evaluated by disk diffusion method and microdilution broth assay. This is the first report on the antibacterial activity against MRSA for EOs from the species T. fontanesii and T. numidicus and for M. pulegium from Algeria. EOs were found to be strongly bactericidal (MIC from 0.3 μL/mL to 4.7 μL/mL) which suggests an additional option to...
Published: 2016
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35. Synthesis and characterization of new M(II) carbonyl complexes (M = Fe or Ru) including an η1-N-maleimidato ligand. Reactivity studies with biological thiols

Author: Aleksandra Kubicka, Sławomir Wojtulewski, Agnieszka J. Rybarczyk-Pirek, Bogna Rudolf, Marcin Palusiak, Michèle Salmain, Chemical Biology ( CHEMBIO ), Institut Parisien de Chimie Moléculaire ( IPCM ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Chemical Biology (CHEMBIO), 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)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Steric effects, Reaction mechanism, [SDV]Life Sciences [q-bio], chemistry.chemical_element, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Medicinal chemistry, Inorganic Chemistry, chemistry.chemical_compound, Cyclopentadienyl complex, Materials Chemistry, [CHIM]Chemical Sciences, Organic chemistry, Reactivity (chemistry), Physical and Theoretical Chemistry, Maleimide, ComputingMilieux_MISCELLANEOUS, [ SDV ] Life Sciences [q-bio], 010405 organic chemistry, Hydrogen bond, Ligand, Organic Chemistry, 3. Good health, 0104 chemical sciences, Ruthenium, chemistry
Abstract: Herein we report the preparation and characterization of the iron and ruthenium organometallic maleimides (η5-Cp*)Fe(CO)2(η1-maleimidato) (Cp* = pentamethyl cyclopentadienyl) and (η5-Cp)Ru(CO)2(η1-maleimidato). The molecular structure of the ruthenium complex was confirmed by X-ray diffraction study. The reactivity of the metallocarbonyl maleimide derivatives toward biologically meaningful thiols, namely cysteine ethyl ester hydrochloride, glutathione (GSH) and human serum albumin (HSA) was investigated. To get better insight into the reaction mechanism, kinetic studies of the reaction with GSH and HSA were performed as well as quantum-chemical calculations and QTAIM analysis. We found out that the reactivity of the organometallic maleimides towards thiols depended on: 1) the metal present in the structure, 2) the nature of the capping aromatic ligand due to differences in electron donating capabilities and steric demands and 3) additional interactions like hydrogen bonding in (η5-Cp*)Fe(CO)2(η1-maleimidato) and carbonyl … carbonyl interactions in (η5-Cp)Ru(CO)2(η1-maleimidato).
Published: 2016
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36. Low doses of bioherbicide favour prion aggregation and propagation in vivo

Author: Maria-Teresa Alvarez-Martinez, Elisabeth Huetter, Mike Robitzer, Thibaut Imberdis, Pierre-André Lafon, Nathalie Chevallier, Jianfeng Liu, Véronique Perrier, Catherine Desrumaux, Joan Torrent, Yunyun Wang, Laurent Givalois, Mécanismes moléculaires dans les démences neurodégénératives ( MMDN ), École pratique des hautes études ( EPHE ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier ( ICGM ICMMM ), Université Montpellier 1 ( UM1 ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Microbiologie et Pathologie Cellulaire Infectieuse, Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ), Université Grenoble Alpes - UFR Pharmacie ( UGA UFRP ), Université Grenoble Alpes ( UGA ), Lipides - Nutrition - Cancer (U866) ( LNC ), Université de Bourgogne ( UB ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Ecole Nationale Supérieure de Biologie Appliquée à la Nutrition et à l'Alimentation de Dijon ( ENSBANA ), Laboratoire de génomique fonctionnelle ( LGF ), Centre National de la Recherche Scientifique ( CNRS ), Mécanismes moléculaires dans les démences neurodégénératives (MMDN), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut National de la Santé et de la Recherche Médicale (INSERM)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Cellular Signaling Laboratory [Hubei, China] (College of Life Science and Technology), Huazhong University of Science and Technology [Wuhan] (HUST), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), BioCampus Montpellier (BCM), Université Montpellier 1 (UM1)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Biomécanique cellulaire et respiratoire (BCR), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), This study was supported by grants from INSERM (Institut National de la Santé et de la Recherche Médicale), from Alliance Biosecure (AAP 2010, AAP 2012) and the Agence Nationale de la Recherche (ANR) under the program ‘Investissements d’Avenir’ with reference ANR-11-LABX-0021-LipSTIC. WY is the recipient of a fellowship from the China Scholarship Council under the PHC CAI YUANPEI 2014–16 project n° 32106RD. We are very grateful to Pr. Jean-Michel Verdier for supporting this project. We thank Drs. Baskakov and Makarava for the gif of the Hamster R- and S-PrP fbrils and their help for fuorescence studies. We thank J-D Arnaud (CECEMA of Montpellier) for his support in animal care., ANR-11-LABX-0021,Lipstic,Lipoprotéines et santé : prévention et traitement des maladies inflammatoires non vasculaires et du(2011), École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), BioCampus (BCM), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0021,Lipstic,Lipoprotéines et santé : prévention et traitement des maladies inflammatoires non vasculaires et du cancer(2011), Perrier, Véronique, Laboratoires d'excellence - Lipoprotéines et santé : prévention et traitement des maladies inflammatoires non vasculaires et du cancer - - Lipstic2011 - ANR-11-LABX-0021 - LABX - VALID, Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Université de Montpellier (UM)-École pratique des hautes études (EPHE), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 2 - Sciences et Techniques (UM2)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire de génomique fonctionnelle (LGF), and Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, animal diseases, lcsh:Medicine, [ CHIM ] Chemical Sciences, Article, Prion Diseases, 03 medical and health sciences, Human health, Mice, Neuroblastoma, In vivo, [SDV.MHEP.MI]Life Sciences [q-bio]/Human health and pathology/Infectious diseases, Tumor Cells, Cultured, Animals, Humans, PrPC Proteins, Prion protein, Pesticides, lcsh:Science, ComputingMilieux_MISCELLANEOUS, 2. Zero hunger, Multidisciplinary, Dose-Response Relationship, Drug, Chemistry, Low dose, lcsh:R, Brain, Pesticide, In vitro, 3. Good health, nervous system diseases, Mice, Inbred C57BL, Biopesticide, 030104 developmental biology, Pyrimidines, Biochemistry, 13. Climate action, [SDV.MHEP.MI] Life Sciences [q-bio]/Human health and pathology/Infectious diseases, [SDV.NEU]Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC], Female, lcsh:Q, Bioherbicide
Abstract: Public concerns over the use of synthetic pesticides are growing since many studies have shown their impact on human health. A new environmental movement in occidental countries promoting an organic agriculture favours the rebirth of botanical pesticides. These products confer an effective alternative to chemical pesticides such as glyphosate. Among the biopesticides, the α-terthienyls found in the roots of Tagetes species, are powerful broad-spectrum pesticides. We found that an α-terthienyl analogue with herbicidal properties, called A6, triggers resistant SDS oligomers of the pathogenic prion protein PrPSc (rSDS-PrPSc) in cells. Our main question is to determine if we can induce those rSDS-PrPSc oligomers in vitro and in vivo, and their impact on prion aggregation and propagation. Using wild-type mice challenged with prions, we showed that A6 accelerates or slows down prion disease depending on the concentration used. At 5 mg/kg, A6 is worsening the pathology with a faster accumulation of PrPSc, reminiscent to soluble toxic rSDS-PrPSc oligomers. In contrast, at 10 and 20 mg/kg of A6, prion disease occurred later, with less PrPSc deposits and with rSDS-PrPSc oligomers in the brain reminiscent to non-toxic aggregates. Our results are bringing new openings regarding the impact of biopesticides in prion and prion-like diseases.
Published: 2018
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37. Detection of semi-volatile compounds in cloud waters by GC×GC-TOF-MS. Evidence of phenols and phthalates as priority pollutants

Author: Anne-Marie Delort, Isabelle Canet, Dmitrii M. Mazur, Laurent Deguillaume, Mickaël Vaitilingom, O. V. Polyakova, Audrey Lallement, Albert T. Lebedev, Viatcheslav B. Artaev, Lomonosov Moscow State University (MSU), LECO Corporation, Institut de Chimie de Clermont-Ferrand (ICCF), SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Météorologie Physique (LaMP), Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), Lomonosov Moscow State University ( MSU ), Institut de Chimie de Clermont-Ferrand - Clermont Auvergne ( ICCF ), Sigma CLERMONT ( Sigma CLERMONT ) -Université Clermont Auvergne ( UCA ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Météorologie Physique - Clermont Auvergne ( LaMP ), and Institut national des sciences de l'Univers ( INSU - CNRS ) -Université Clermont Auvergne ( UCA ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: 010504 meteorology & atmospheric sciences, Cloud water, Health, Toxicology and Mutagenesis, GC-HRMS, Phthalic Acids, 010501 environmental sciences, Toxicology, [ CHIM ] Chemical Sciences, 01 natural sciences, Gas Chromatography-Mass Spectrometry, chemistry.chemical_compound, Phthalates, Phenols, [CHIM]Chemical Sciences, Organic matter, Puy de Dôme, Volume concentration, Gc tof ms, Hrgc hrms, 0105 earth and related environmental sciences, Pollutant, chemistry.chemical_classification, Air Pollutants, Volatile Organic Compounds, Small sample, General Medicine, GC×GC-MS, Pollution, Dibutyl Phthalate, chemistry, 13. Climate action, Environmental chemistry, Environmental science, Organic pollutants, France, Environmental Monitoring
Abstract: International audience; Although organic species are transported and efficiently transformed in clouds, more than 60% of this organic matter remains unspeciated. Using GCxGC-HRMS technique we were able to detect and identify over 100 semi-volatile compounds in 3 cloud samples collected at the PUY station (puy de Dôme mountain, France) while they were present at low concentrations in a very small sample volume (
Published: 2018
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38. Cellular responses of Pacific oyster ( Crassostrea gigas ) gametes exposed in vitro to polystyrene nanoparticles

Author: Mathieu Berchel, Ika Paul-Pont, Philippe Soudant, Kevin Tallec, Arnaud Huvet, Nelly Le Goïc, Christophe Lambert, Carmen González-Fernández, Marc Suquet, Laboratoire des Sciences de l'Environnement Marin (LEMAR) ( LEMAR ), Institut de Recherche pour le Développement ( IRD ) -Institut Français de Recherche pour l'Exploitation de la Mer ( IFREMER ) -Université de Brest ( UBO ) -Institut Universitaire Européen de la Mer ( IUEM ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Français de Recherche pour l'Exploitation de la Mer - Brest ( IFREMER ), Institut Français de Recherche pour l'Exploitation de la Mer ( IFREMER ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, French doctoral research grant from Ifremer (50%), Region Bretagne (50%), ANR-15-CE34-0006-02,NANO,ANR-15-CE34-0006-02, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Français de Recherche pour l'Exploitation de la Mer - Brest (IFREMER Centre de Bretagne), Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), ANR-15-CE34-0006,Nanoplastics,Microplastiques, nanoplastiques dans l'environnement marin: caractérisation, impacts et évaluation des risques sanitaires.(2015), and Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, Oyster, Environmental Engineering, [SDV]Life Sciences [q-bio], Health, Toxicology and Mutagenesis, Gametes, 010501 environmental sciences, 01 natural sciences, [ CHIM ] Chemical Sciences, [ SDE ] Environmental Sciences, 03 medical and health sciences, Oysters, biology.animal, [CHIM]Chemical Sciences, Environmental Chemistry, Animals, 14. Life underwater, Crassostrea, 0105 earth and related environmental sciences, biology, [ SDV ] Life Sciences [q-bio], Chemistry, ACL, Public Health, Environmental and Occupational Health, technology, industry, and agriculture, Cellular responses, General Medicine, General Chemistry, Adhesion, Pacific oyster, biology.organism_classification, Pollution, Sperm, In vitro, Polystyrene nanoparticles, 030104 developmental biology, Germ Cells, [SDE]Environmental Sciences, Toxicity, Biophysics, Nanoparticles, Polystyrenes, Nanoplastics, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Plastics, Water Pollutants, Chemical
Abstract: International audience; While the detection and quantification of nano-sized plastic in the environment remains a challenge, the growing number of polymer applications mean that we can expect an increase in the release of nanoplastics into the environment by indirect outputs. Today, very little is known about the impact of nano-sized plastics on marine organisms. Thus, the objective of this study was to investigate the toxicity of polystyrene nanoplastics (NPs) on oyster (Crassostrea gigas) gametes. Spermatozoa and oocytes were exposed to four NPs concentrations ranging from 0.1 to 100 mg L−1 for 1, 3 and 5 h. NPs coated with carboxylic (PS-COOH) and amine groups (PS-NH2) were used to determine how surface properties influence the effects of nanoplastics. Results demonstrated the adhesion of NPs to oyster spermatozoa and oocytes as suggested by the increase of relative cell size and complexity measured by flow-cytometry and confirmed by microscopy observations. A significant increase of ROS production was observed in sperm cells upon exposure to 100 mg L−1 PS-COOH, but was not observed with PS-NH2, suggesting a differential effect according to the NP-associated functional group. Altogether, these results demonstrate that the effects of NPs occur rapidly, are complex and are possibly associated with the cellular eco-corona, which could modify NPs behaviour and toxicity.
Published: 2018
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39. NIR spectroscopy for the quality control of Moringa oleifera (Lam.) leaf powders: Prediction of minerals, protein and moisture contents

Author: Isabelle Bombarda, Inès Pany, Catherine Rébufa, Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Institut méditerranéen de biodiversité et d'écologie marine et continentale ( IMBE ), Université d'Avignon et des Pays de Vaucluse ( UAPV ) -Aix Marseille Université ( AMU ) -Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique ( CNRS ), and Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS)
Subjects: Quality Control, Food industry, [ CHIM ] Chemical Sciences, 01 natural sciences, Analytical Chemistry, Moringa, 0404 agricultural biotechnology, Nutrient, Partial least squares regression, [CHIM]Chemical Sciences, Food science, Least-Squares Analysis, Water content, ComputingMilieux_MISCELLANEOUS, Plant Proteins, Moringa oleifera, Minerals, Spectroscopy, Near-Infrared, Moisture, Chemistry, business.industry, 010401 analytical chemistry, Near-infrared spectroscopy, Temperature, Water, Sorption, 04 agricultural and veterinary sciences, General Medicine, 040401 food science, 0104 chemical sciences, Plant Leaves, Powders, business, Food Science
Abstract: A rapid methodology was developed to simultaneously predict water content and activity values (aw) of Moringa oleifera leaf powders (MOLP) using near infrared (NIR) signatures and experimental sorption isotherms. NIR spectra of MOLP samples (n = 181) were recorded. A Partial Least Square Regression model (PLS2) was obtained with low standard errors of prediction (SEP of 1.8% and 0.07 for water content and aw respectively). Experimental sorption isotherms obtained at 20, 30 and 40 °C showed similar profiles. This result is particularly important to use MOLP in food industry. In fact, a temperature variation of the drying process will not affect their available water content (self-life). Nutrient contents based on protein and selected minerals (Ca, Fe, K) were also predicted from PLS1 models. Protein contents were well predicted (SEP of 2.3%). This methodology allowed for an improvement in MOLP safety, quality control and traceability.
Published: 2018
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40. Physicochemical, textural, rheological and microstructural properties of protein isolate gels produced from European eel ( Anguilla anguilla ) by heat-induced gelation process

Author: Warfak Taktak, Moncef Nasri, Rim Nasri, Laura G. Gómez-Mascaraque, Amparo López-Rubio, Maha Karra-Chaâbouni, Suming Li, Marwa Hamdi, IATA, Novel Material and Nanotechnology Group, Spanish National Research Council (CSIC), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), École Nationale d'Ingénieurs de Sfax | National School of Engineers of Sfax (ENIS), Spanish National Research Council ( CSIC ), Institut Européen des membranes ( IEM ), Centre National de la Recherche Scientifique ( CNRS ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM ), École Nationale d'Ingénieurs de Sfax | National School of Engineers of Sfax ( ENIS ), and Ministère de l’Enseignement Supérieur et de la Recherche Scientifique (Tunisie)
Subjects: 0106 biological sciences, Heat induced, Gelation, pH-shift process, General Chemical Engineering, Textural and rheological properties, 01 natural sciences, [ CHIM ] Chemical Sciences, Protein isolate gel, Pigment, 0404 agricultural biotechnology, Rheology, 010608 biotechnology, [CHIM]Chemical Sciences, Protein secondary structure, Microstructure, ComputingMilieux_MISCELLANEOUS, Chromatography, Chemistry, Protein isolate, 04 agricultural and veterinary sciences, General Chemistry, Alkali metal, 040401 food science, Ionic strength, visual_art, visual_art.visual_art_medium, Food Science
Abstract: This study investigates the preparation and characterization of a protein isolate extracted from European eel (Anguilla anguilla) and its ability to generate protein gel. European eel protein isolate (EPI) was extracted from European eel muscle by a pH-shifting process. European eel protein isolate gels (EPIGs) were prepared by heat treatment of EPI with varying gelling parameters. The influences of pH value (2.0 and 10.0), EPI concentration (7 and 10%) and ionic strength on biochemical, textural, rheological and microstructural properties of EPIGs were studied. Textural and physicochemical analysis demonstrated a different gel forming mechanism for acidic and alkaline-treated gels. Results showed that whiteness of EPIGs increased with decreasing of EPI concentration and pH values. Moreover, EPIGs prepared under alkaline conditions were characterized by higher water holding capacity and total pigment content. In addition, the acid EPIGs exhibited poorer gelling ability compared to alkali EPIGs. Thus, a more compacted gel-protein arrangement was formed under alkaline condition. Furthermore, addition of salt slightly improved the elasticity of EPIGs at 2% wt. concentration. FT-IR analysis of EPIGs revealed more irregular secondary structure and higher hydration level in the acid EPIGs compared to alkaline EPIGs. Thus, this study shows the potential of protein isolate gels from A. anguilla as food texture enhancers., This study was funded by the Ministry of Higher Education and Scientific Research, Tunisia. Authors would also like to thank the Central Support Service for Experimental Research (SCSIE) of the University of Valencia for the electronic microscopy service.
Published: 2018
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41. New chemotype of essential oil of Achillea santolina L. collected from different regions of Algeria

Author: Tayeb Berramdane, Nadhir Gourine, Isabelle Bombarda, Mohamed Yousfi, Université Amar Telidji - Laghouat, Laboratoire des Sciences fondamentales (LSF), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale d'Ingénieurs de Sousse (ENISo), Mechanics surfaces and materials processing (MSMP), Arts et Métiers Sciences et Technologies, HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM), Mechanics surfaces and materials processing ( MSMP ), and HESAM Université (HESAM)-HESAM Université (HESAM)
Subjects: Chemotype, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemical Engineering, Achillea santolina, 15. Life on land, Biology, [ CHIM ] Chemical Sciences, 01 natural sciences, Industrial and Manufacturing Engineering, 0104 chemical sciences, law.invention, 010404 medicinal & biomolecular chemistry, Horticulture, Camphor, chemistry.chemical_compound, chemistry, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Safety, Risk, Reliability and Quality, Essential oil, ComputingMilieux_MISCELLANEOUS, Food Science
Abstract: Chemical composition of essential oil (EO) obtained by hydrodistillation of the aerial parts of Achillea santolina L. was analysed using GC and GC–MS. Especially, this study involved a large scale investigation, using different regions in which, five flowering wild growing populations collected from the high plateau of Algeria were engaged. Unlike previous reports, the current investigation showed very high EO yields for this plant (up to 1.7% w/w “dw”). The main result of the current study was the occurrence of a new chemotype rich in camphor (39.54–67.86%) and 1,8-cineole (7.14–8.57%).
Published: 2018
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42. A Theoretical Outlook on the Stereoselectivity Origins of Isoselective Zirconocene Propylene Polymerization Catalysts

Author: Ludovic Castro, Laurent Maron, Jean-François Carpentier, Jean-Michel Brusson, Gabriel Therukauff, Luc Haspeslagh, Alexandre Welle, Aurélien Vantomme, Evgueni Kirillov, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Total Research & Technology Center Feluy, TOTAL S.A., TOTAL France S.A., Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de physique et chimie des nano-objets ( LPCNO ), Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Université Paul Sabatier - Toulouse 3 ( UPS ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: metallocene catalysts, 010402 general chemistry, stereoselectivity, 01 natural sciences, [ CHIM ] Chemical Sciences, Catalysis, chemistry.chemical_compound, Tacticity, Polypropylene, 010405 organic chemistry, Chemistry, Organic Chemistry, Migratory insertion, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, polymerization, DFT study, Physical chemistry, Stereoselectivity, Polymerization catalysts, Metallocene, polypropylene
Abstract: International audience; The first three insertion steps of propylene for isoselective metallocenes from the one-carbon-bridged cyclopentadienyl-fluorenyl {Cp/Flu} and silicon-bridged ansa-bis(indenyl) {SBI} families were computed by using a theoretical method implementing the B3PW91 functional in combination with solvent corrections incorporated with the Solvation Model based on Density (SMD) continuum model. For C -symmetric {Cp/Flu}-type metallocenes, two mechanisms of stereocontrol were validated theoretically: more facile and more stereoselective chain "stationary" insertion (or site epimerization backskip) and less stereoselective alternating mechanisms. For the C -symmetric {SBI}-type system, the computation results were in complete agreement with the sole operating chain migratory insertion mechanism. The thermochemical data obtained through the study were used to predict microstructures of polypropylenes by using three-parameter and one-parameter statistical models for the two metallocene systems, respectively. The calculated meso/rac pentad distributions were found to be in good agreement with those determined experimentally for isotactic polypropylene samples obtained at different polymerization temperatures.
Published: 2018
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43. Spectrally narrow exciton luminescence from monolayer MoS 2 and MoSe 2 exfoliated onto epitaxially grown hexagonal BN

Author: Courtade, Emmanuel, Han, B., Nakhaie, S., Robert, Cédric, Marie, Xavier, Renucci, Pierre, Taniguchi, T., Watanabe, K., Geelhaar, L., Lopes, J., Urbaszek, B., Laboratoire de physique et chimie des nano-objets ( LPCNO ), Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Université Toulouse III - Paul Sabatier ( UPS ), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique ( CNRS ), Paul-Drude-Institut für Festkörperelektronik, National Institute for Materials Science ( NIMS ), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Paul-Drude-Institut für Festkörperelektronik (PDI), National Institute for Materials Science (NIMS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Microscopy, [ PHYS.PHYS.PHYS-OPTICS ] Physics [physics]/Physics [physics]/Optics [physics.optics], Semiconductors, Photoluminescence spectroscopy, Dielectric properties, Transition metal chalcogenides, [CHIM]Chemical Sciences, Heterostructures, Excitons, [ CHIM ] Chemical Sciences, Epitaxy
Abstract: International audience; The strong light-matter interaction in transition metal dichalcogenide (TMD) monolayers (MLs) is governed by robust excitons. Important progress has been made to control the dielectric environment surrounding the MLs, especially through hexagonal boron nitride (hBN) encapsulation which drastically reduces the inhomogeneous contribution to the exciton linewidth. Most studies use exfoliated hBN from high quality flakes grown under high pressure. In this work, we show that hBN grown by molecular beam epitaxy (MBE) over a large surface area substrate has a similarly positive impact on the optical emission from TMD MLs. We deposit MoS2 and MoSe2 MLs on ultrathin hBN films (few MLs thick) grown on Ni/MgO(111) by MBE. Then, we cover them with exfoliated hBN to finally obtain an encapsulated sample: exfoliated hBN/TMD ML/MBE hBN. We observe improved optical quality of our samples compared to TMD MLs exfoliated directly on SiO2 substrates. Our results suggest that hBN grown by MBE could be used as a flat and charge-free substrate for fabricating TMD-based heterostructures on a larger scale.
Published: 2018

44. d -Amino acids in molecular evolution in space – Absolute asymmetric photolysis and synthesis of amino acids by circularly polarized light

Author: Kenji Hamase, Uwe J. Meierhenrich, Cornelia Meinert, Nykola C. Jones, Laurent Nahon, Søren Vrønning Hoffmann, Yoshinori Takano, Haruna Sugahara, Institut de Chimie de Nice ( ICN ), Centre National de la Recherche Scientifique ( CNRS ) -Université Nice Sophia Antipolis ( UNS ), Université Côte d'Azur ( UCA ) -Université Côte d'Azur ( UCA ), Synchrotron SOLEIL ( SSOLEIL ), Centre National de la Recherche Scientifique ( CNRS ), Department of Physics and Astronomy [Aarhus], Aarhus University [Aarhus], 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 ), JSPS Overseas Research Fellowships, Grant-in-Aid for Scientific Research on Innovative Areas (Research Project on Evolution of Molecules in Space, No. 25108006, Agence National de la Recherche under grant number ANR-16-C829-0015, Agence National de la Recherche, Investissement d'Avenir UCAJEDI (ANR-15-IDEX-01), ANR-15-IDEX-0001,UCA JEDI,Université Côte d'Azur Joint, Excellent and Dynamic Initiative ( 2016 ), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Kyushu University [Fukuoka], Japan Agency for Marine-Earth Science and Technology (JAMSTEC), ANR-15-IDEX-0001,UCA JEDI,Idex UCA JEDI(2015), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), and COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)
Subjects: Extraterrestrial Environment, Light, Biophysics, Stereoisomerism, Homochirality, 010402 general chemistry, 01 natural sciences, Biochemistry, [ CHIM ] Chemical Sciences, Analytical Chemistry, Astrobiology, Evolution, Molecular, 0103 physical sciences, Extraterrestrial delivery, 010303 astronomy & astrophysics, Molecular Biology, [ SDU.ASTR ] Sciences of the Universe [physics]/Astrophysics [astro-ph], chemistry.chemical_classification, Photolysis, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Photodissociation, Enantioselective synthesis, Asymmetric synthesis, Circularly polarized light, 0104 chemical sciences, Amino acid, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Extraterrestrial life, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, Amino acids, Asymmetric photolysis, Chirality (chemistry)
Abstract: International audience; Living organisms on the Earth almost exclusively use l-amino acids for the molecular architecture of proteins. The biological occurrence of d-amino acids is rare, although their functions in various organisms are being gradually understood. A possible explanation for the origin of biomolecular homochirality is the delivery of enantioenriched molecules via extraterrestrial bodies, such as asteroids and comets on early Earth. For the asymmetric formation of amino acids and their precursor molecules in interstellar environments, the interaction with circularly polarized photons is considered to have played a potential role in causing chiral asymmetry. In this review, we summarize recent progress in the investigation of chirality transfer from chiral photons to amino acids involving the two major processes of asymmetric photolysis and asymmetric synthesis. We will discuss analytical data on cometary and meteoritic amino acids and their potential impact delivery to the early Earth. The ongoing and future ambitious space missions, Hayabusa2, OSIRIS-REx, ExoMars 2020, and MMX, are scheduled to provide new insights into the chirality of extraterrestrial organic molecules and their potential relation to the terrestrial homochirality. This article is part of a Special Issue entitled: d-Amino acids: biology in the mirror, edited by Dr. Loredano Pollegioni, Dr. Jean-Pierre Mothet and Dr. Molla Gianluca.
Published: 2018
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45. Controlling the Sulfidation Process of Iron Nanoparticles: Accessing Iron−Iron Sulfide Core-Shell Structures

Author: Dominikus Heift, Pier-Francesco Fazzini, Bruno Chaudret, Pierre Lecante, Lise-Marie Lacroix, Laboratoire de physique et chimie des nano-objets ( LPCNO ), Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Université Toulouse III - Paul Sabatier ( UPS ), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique ( CNRS ), Department of Chemistry [Durham, UK], Durham University, Centre d'élaboration de matériaux et d'études structurales ( CEMES ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Toulouse III - Paul Sabatier ( UPS ), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Surfaces, Interfaces et Nano-Objets ( CEMES-SINanO ), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Surfaces, Interfaces et Nano-Objets (CEMES-SINanO), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse)
Subjects: Materials science, Sulfide, Hydrogen sulfide, Sulfidation, Energy Engineering and Power Technology, Nanoparticle, Iron sulfide, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, Physics::Geophysics, sulfidation, Biomaterials, chemistry.chemical_compound, iron, Mössbauer spectroscopy, Materials Chemistry, [CHIM]Chemical Sciences, chemistry.chemical_classification, Zerovalent iron, Renewable Energy, Sustainability and the Environment, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Decomposition, 0104 chemical sciences, Chemical engineering, chemistry, nanoparticles, magnetic properties, 0210 nano-technology
Abstract: International audience; Iron sulfide nanocomposites have been prepared through reactions of bis[bis(trimethylsilyl)amido]iron(II) or zerovalent iron nanoparticles (NPs) with hydrogen sulfide gas. The chemical composition of these materials was analyzed by TEM, XRD, WAXS and Mössbauer measurements. Decomposition of bis[bis(trimethylsilyl)amido]iron(II) under an H2S atmosphere in the presence of palmitic acid produces thin iron sulfide nanoflakes, which seemingly consist of Fe2S2 and Fe7S8. The sulfidation of 9 nm zerovalent iron NPs with H2S yields thin nano flakes exhibiting the same iron sulfide phases and residual iron. Remarkably, treatment of slightly larger iron NPs (13 nm) with H2S (or alternatively benzylthiol) yields well‐shaped iron–iron sulfide core‐shell particles. These particles exhibit a crystalline iron core and an amorphous iron sulfide shell, which likely consists of Fe2S2, Fe7S8 and Fe1−XS. Magnetic measurements on these core‐shell particles show a decrease of the total magnetization (compared to bulk iron) coming along with the sulfidation process. Owing to the partially preserved ferromagnetic character these iron–iron sulfide core‐shell particles were found to have magnetic heating properties.
Published: 2018
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46. Photochromic DTE-Substituted-1,3-di(2-pyridyl)benzene Platinum(II) Complexes: Photo-modulation of Luminescence and Second-order Nonlinear Optical Properties

Author: Eleonora Garoni, Alessia Colombo, Julien Boixel, Daniele Marinotto, Véronique Guerchais, Dominique Roberto, Stefania Righetto, Hong Zhao, Denis Jacquemin, Claudia Dragonetti, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Dipartimento di Chimica, Università degli Studi di Milano [Milano] (UNIMI), ISTM CNR, Milano, 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), Centre National de la Recherche Scientifique, INSTMMI012, National Interuniversity Consortium of Materials Science and Technology, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Università degli studi di Milano [Milano], ISTM CNR, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Milano = University of Milan (UNIMI), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Photoluminescence, Photoisomerization, 010405 organic chemistry, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), Photochemistry, Photochromism, 01 natural sciences, [ CHIM ] Chemical Sciences, Fluorescence, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, closed-ring isomer, chemistry, Moiety, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Platinum, Luminescence, Isomerization
Abstract: International audience; We disclose a new family of photochromic cyclometalated platinum(II) complexes (PtDTE1 and PtDTE2), where a dithienylethene (DTE) unit is connected at the para-position of the central phenyl ring of (N^C^N) cyclometalated ligand, through two different linkages. Their syntheses are presented along with the X-ray characterizations of both the open and closed isomers of PtDTE1. The investigation of their photophysical properties is made, including absorption, photochromism, emission, and second-order nonlinear properties. We report a quantitative photo-isomerization for both PtDTE1 and PtDTE2, irrespective of the nature of the connecting mode between the DTE unit and the platinum(II) moiety. The efficient photochromism allows a significant NLO photo-modulation, both in solution and in thin films. In addition, we show that the photoluminescence of the PtDTE1 and PtDTE2 can be controlled by the open/closed isomerization of the DTE unit.
Published: 2018
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47. Design principles for electronic charge transport in solution-processed vertically stacked 2D perovskite quantum wells

Author: Hsinhan Tsai, Wanyi Nie, Aditya D. Mohite, Constantinos C. Stoumpos, Reza Asadpour, Muhammad A. Alam, Mercouri G. Kanatzidis, Pulickel M. Ajayan, Jacky Even, Jean-Christophe Blancon, Los Alamos National Laboratory ( LANL ), Purdue University [West Lafayette], Fonctions Optiques pour les Technologies de l'informatiON ( FOTON ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Institut National des Sciences Appliquées - Rennes ( INSA Rennes ) -École Nationale Supérieure des Sciences Appliquées et de Technologie ( ENSSAT ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Bretagne Loire ( UBL ) -IMT Atlantique Bretagne-Pays de la Loire ( IMT Atlantique ), Northwestern University [Evanston], Rice University [Houston], Los Alamos National Laboratory (LANL), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Science, Exciton, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, Elementary charge, [ CHIM ] Chemical Sciences, 01 natural sciences, 7. Clean energy, Article, General Biochemistry, Genetics and Molecular Biology, law.invention, law, Photovoltaics, Solar cell, [CHIM]Chemical Sciences, lcsh:Science, Quantum well, Perovskite (structure), [PHYS]Physics [physics], Photocurrent, [ PHYS ] Physics [physics], Multidisciplinary, business.industry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Semiconductor, Optoelectronics, lcsh:Q, 0210 nano-technology, business
Abstract: State-of-the-art quantum-well-based devices such as photovoltaics, photodetectors, and light-emission devices are enabled by understanding the nature and the exact mechanism of electronic charge transport. Ruddlesden–Popper phase halide perovskites are two-dimensional solution-processed quantum wells and have recently emerged as highly efficient semiconductors for solar cell approaching 14% in power conversion efficiency. However, further improvements will require an understanding of the charge transport mechanisms, which are currently unknown and further complicated by the presence of strongly bound excitons. Here, we unambiguously determine that dominant photocurrent collection is through electric field-assisted electron–hole pair separation and transport across the potential barriers. This is revealed by in-depth device characterization, coupled with comprehensive device modeling, which can self-consistently reproduce our experimental findings. These findings establish the fundamental guidelines for the molecular and device design for layered 2D perovskite-based photovoltaics and optoelectronic devices, and are relevant for other similar quantum-confined systems., Solution-processed two-dimensional perovskite quantum-well-based optoelectronic devices have attracted great research interest but their electrical transport is poorly understood. Tsai et al. reveal that the potential barriers of the quantum wells dominate the transport properties in solar cell devices.
Published: 2018
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48. Sanctis A–C Three Racemic Procyanidin Analogues from The Lichen Parmotrema sancti-angelii

Author: Duong , T.-H., Ha , X.-P., Chavasiri , W., Beniddir , M.A., Genta-Jouve , G., Boustie , J., Chollet-Krugler , M., Ferron , S., Nguyen , H.-H., Yamin , B.M., Huynh , B.-L.-C., Le Pogam , P., Nguyen , K.-P.-P., Chulalongkorn University [Bangkok], Ho Chi Minh City University of Science (HCMUS), Biomolécules : Conception, Isolement, Synthèse (BioCIS), Université Paris-Sud - Paris 11 (UP11)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Equipe C-TAC (UMR 8638), Chimie Organique, Médicinale et Extractive et Toxicologie Expérimentale (COMETE - UMR 8638), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chulalongkorn University, Ho Chi Minh City University of Science ( HCMUS ), Laboratory BIOCIS, Université Paris Sud-Centre National de la Recherche Scientifique ( CNRS ), Equipe C-TAC ( UMR 8638 ), Chimie Organique, Médicinale et Extractive et Toxicologie Expérimentale ( COMETE - UMR 8638 ), Centre National de la Recherche Scientifique ( CNRS ) -Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Paris Descartes - Paris 5 ( UPD5 ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Université Paris-Seine-Université Paris-Seine-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Natural products, Cytotoxicity, Procyanidin analogues, Structure elucidation, [CHIM]Chemical Sciences, Biosynthesis, [ CHIM ] Chemical Sciences
Abstract: International audience; The phytochemical investigation of the lichen Parmotrema sancti-angelii afforded three racemic compounds, sanctis A–C, which feature an original dibenzo-2,8-dioxabicyclo[3.3.1]nonane scaffold. These compounds were structurally characterized by extensive NMR spectroscopy analyses, comparison between experimental and theoretical NMR spectroscopic data, and X-ray crystallography. These metabolites are similar to procyanidin A and display a methyl group instead of a pendant aromatic ring at C-9, a so far unprecedented structural feature. A biosynthetic route to sanctis A–C is proposed. © 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim
Published: 2018
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49. Unravelling light-induced degradation of layered perovskite crystals and design of efficient encapsulation for improved photostability

Author: Jianting Ye, Jacky Even, Graeme R. Blake, Hong-Hua Fang, Sampson Adjokatse, Maria Antonietta Loi, Machteld E. Kamminga, Shuxia Tao, Jie Yang, Center for Computational Energy Research, Computational Materials Physics, Zernike Institute for Advanced Materials, University of Groningen [Groningen], Eindhoven University of Technology [Eindhoven] (TU/e), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), 306983, European Research Council, 15CST04-2, Stichting voor Fundamenteel Onderzoek der Materie, Nederlandse Organisatie voor Wetenschappelijk Onderzoek, Computational Sciences for Energy Research, Eindhoven University of Technology [Eindhoven] ( TU/e ), Fonctions Optiques pour les Technologies de l'informatiON ( FOTON ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Institut National des Sciences Appliquées - Rennes ( INSA Rennes ) -École Nationale Supérieure des Sciences Appliquées et de Technologie ( ENSSAT ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Bretagne Loire ( UBL ) -IMT Atlantique Bretagne-Pays de la Loire ( IMT Atlantique ), Photophysics and OptoElectronics, Device Physics of Complex Materials, Solid State Materials for Electronics, École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)
Subjects: In situ, Photoluminescence, Materials science, surface reactions, 2D heterostructures, Halide, 02 engineering and technology, 010402 general chemistry, photostability, 01 natural sciences, [ CHIM ] Chemical Sciences, Biomaterials, Crystal, Electrochemistry, Fluorescence microscope, [CHIM]Chemical Sciences, Perovskite (structure), [PHYS]Physics [physics], [ PHYS ] Physics [physics], 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Photoexcitation, Chemical engineering, layered semiconductors, Light induced, encapsulation, 0210 nano-technology
Abstract: Layered halide perovskites have recently shown extraordinary potential for low-cost solution-processable optoelectronic applications because of their superior moisture stability over their 3D counterparts. However, few studies have investigated the effect of light on layered hybrid perovskites. Here, the mechanically exfoliated nanoflakes of the 2D perovskite (PEA) 2PbI 4 (PEA, 2-phenylethylammonium) are used as a model to investigate their intrinsic photostability. The light-induced degradation of the flakes is investigated by using in situ techniques including confocal laser scanning microscopy, wide-field fluorescence microscopy, and atomic force microscopy. Under resonant photoexcitation, (PEA) 2PbI 4 degrades to PbI 2. It is clearly shown that this process is initiated at the crystal edges and from the surface. As a consequence, the photoluminescence of (PEA) 2PbI 4 is progressively quenched by surface traps. Importantly, the light-induced degradation can be suppressed by encapsulation using hexagonal boron nitride (hBN) flakes and/or polycarbonates. This report sheds light on a specific mechanism of light-induced degradation in layered perovskites and proposes a new encapsulation method to improve their photostability.
Published: 2018
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50. Biodegradation of Ammonium Ions and Formate During Ammonium Formate Metabolism by Yarrowia lipolytica and Pichia guilliermondii in a Batch Reactor

Author: M. Heran, B. Mohammadou, G. J. Kayem, G. P. Kofa, M. N. Nsoe, K. S. Ndi, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Européen des membranes ( IEM ), and Centre National de la Recherche Scientifique ( CNRS ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Université de Montpellier ( UM )
Subjects: Yarrowia lipolytica, Environmental Engineering, Batch reactor, Rubber wastewater, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, [ CHIM ] Chemical Sciences, Article, chemistry.chemical_compound, 020401 chemical engineering, Ammonium formate, Environmental Chemistry, [CHIM]Chemical Sciences, Ammonium, Formate, 0204 chemical engineering, Pichia guilliermondii, 0105 earth and related environmental sciences, Water Science and Technology, Pichia, biology, Ecological Modeling, Yarrowia, Biodegradation, Inhibitor substrat, biology.organism_classification, Pollution, chemistry, 13. Climate action, Nuclear chemistry
Abstract: International audience; The use of microorganisms for the biodegradation of pollutants is increasingly being studied. But at high concentrations, these pollutants become rather inhibitors for the metabolism of microorganisms. In this study, the biodegradation of ammonium formate at various concentrations (1.59-7.94 mM) by Yarrowia Lipolytica and Pichia guilliermondii isolated from the rubber effluent is studied by following the variation of ammonium ions and formate. A fitting of eight models of substrate inhibition was performed and the parameters were determined by nonlinear regression using MATLAB 8.5 A (c). The R (2) and the RSME allow to choose the best model. The results show that ammonium ions (3.17 mM ammonium formate) are used as substrate; no inhibition is observed. But beyond this concentration, the inhibition effect begins to be observed with the specific rates of ammonium biodegradation which decrease. Formate monitoring reveals that is used as the main source of energy and does not inhibit the growth of yeasts. The models of Luong and Webb seem to be more appropriate for predicting the observed phenomena of inhibition. For Yarrowia lipolytica, R (2) = 0.958 and 0.998 with RSME = 0.005342 and 0.003433, for Pichia guillermondii, R (2) = 0.999 and 0.992 with RSME = 0.0005121 and 0.001212.
Published: 2018
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