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1. Study on the Cloud Point Extraction of Gd(III) with 8-Hydroxyquinoline

Author

Alain Favre-Réguillon, Micheline Draye, Denis Murat, Laboratoire de Génie des Procédés Catalytiques ( LGPC ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Génie des Procédés Catalytiques (LGPC), École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, Gadolinium, Analytical chemistry, chemistry.chemical_element, Filtration and Separation, 02 engineering and technology, 01 natural sciences, Micelle, [ CHIM ] Chemical Sciences, [ SDE ] Environmental Sciences, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Chelation, ComputingMilieux_MISCELLANEOUS, Cloud point, Chloroform, Process Chemistry and Technology, 010401 analytical chemistry, Extraction (chemistry), 8-Hydroxyquinoline, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Solvent, chemistry, [SDE]Environmental Sciences, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, 0210 nano-technology
Abstract

The extraction of gadolinium was studied using Cloud Point Extraction (CPE) with 8-hydroxyquinoline (8-HQ) as a chelating agent. The structure of the extracted Gd3+ complex with 8-HQ in the micelle of Triton X114 was determined using log-log analysis of the extraction data. A ratio of 8-HQ to Gd3+ of 3:1 was found. The CPE results were compared with those obtained by classical liquid-liquid extraction with chloroform as solvent. The parameters of the extraction process in both media were determined and compared. A quantitative extraction of Gd3+ at pH 5.5 was obtained by CPE using a 8-HQ/Gd3+ ratio of 10 although a 8-HQ/Gd3+ ratio of 500 was necessary for solvent extraction using chloroform as solvent, illustrating an increase of the mass action of extractants when using CPE instead of solvent extraction. Under those conditions, a higher extraction constant was determined for CPE compared with solvent extraction even if the formation of adducts in the CPE system could not be checked experimentally.

Published
2011
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2. Swift and efficient sono-hydrolysis of nitriles to carboxylic acids under basic condition: Role of the oxide anion radical in the hydrolysis mechanism

Author

Nathalie Kardos, Micheline Draye, Lydie Gravouil, Pascal Lignier, Julien Gazza, Emmanuel Naffrechoux, Julien Estager, Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Anions, Acoustics and Ultrasonics, Nitrile, Free Radicals, Sonication, Carboxylic acid, Oxide, Carboxylic Acids, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, Sonochemistry, Inorganic Chemistry, [ SDE ] Environmental Sciences, chemistry.chemical_compound, Hydrolysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Nitriles, Chemical Engineering (miscellaneous), Environmental Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Sodium Hydroxide, Radiology, Nuclear Medicine and imaging, Ultrasonics, ComputingMilieux_MISCELLANEOUS, Benzoic acid, chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Hydrogen-Ion Concentration, 0104 chemical sciences, chemistry, [SDE]Environmental Sciences, Organic synthesis, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, Oxidation-Reduction
Abstract

Carboxylic acids are promising candidates for new sustainable strategies in organic synthesis. In this paper, we ascertain the potential of ultrasound for the hydrolysis of nitriles into carboxylic acids through the study of key parameters of the reaction: pH, hydrolysis medium, reaction time and activation technique. The positive influence of ultrasound under basic conditions is due to more than mechanical effects of cavitation. Indeed, the rate of hydrolysis is dramatically increased under sonication in NaOH solutions. A radical mechanism involving the oxide anion radical O(*-) is proposed.

Published
2011
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3. Electrochemical and Spectral Properties of Ferrocene (Fc) in Ionic Liquid: 1-Butyl-3-methylimidazolium Triflimide, [BMIM][NTf2]. Concentration Effects

Author

Dmitry V. Konev, Michel Picquet, Veronika A. Zinovyeva, Laurent Gaillon, Cécile Rizzi, Mikhail A. Vorotyntsev, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)

Subjects
Inorganic chemistry, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, chemistry.chemical_compound, Materials Chemistry, Physical and Theoretical Chemistry, Acetonitrile, ComputingMilieux_MISCELLANEOUS, ionic liquid, Heptane, ferrocene, 021001 nanoscience & nanotechnology, Toluene, 0104 chemical sciences, Surfaces, Coatings and Films, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Ferrocene, electrochemistry, Absorption band, Ionic liquid, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, 0210 nano-technology
Abstract

Several earlier studies of the electrochemical oxidation of ferrocene (Fc) in room-temperature ionic liquids revealed an essentially nonlinear dependence of the oxidation current on the Fc concentration in its relatively dilute solutions, with its formally calculated diffusion coefficient strongly increasing with the concentration. Since no plausible mechanism leading to this very unusual finding had been proposed, our study of Fc solutions in 1-butyl-3-methylimidazolium triflimide, [BMIM][NTf(2)], was performed to verify whether the above observation originated from an incorrect determination of the dissolved Fc concentration. Our observations have demonstrated that reliable control of the Fc concentration in solution is complicated by factors such as the low amount of Fc used to prepare small-volume solutions or the great difficulty to dissolve completely a solid powder in a solvent with an extremely high viscosity. An unexpected additional complication is related to a sufficiently high volatility of Fc which manifests itself even at room temperature and especially at elevated temperatures or/and in the course of vacuum treatment of its solutions or its solid powder. Parallel measurements of electrochemical responses and UV-visible spectra for several series of Fc solutions of various concentrations (prepared with the use of different procedures) have shown a perfect parallelism between the peak current and the intensity of the absorption band in the range of 360-550 nm, leading us to the conclusion of a linear relationship between the oxidation current and the molecularly dissolved Fc concentration. The relations of these measured characteristics with the estimated Fc concentration in these solutions have demonstrated a much greater dispersion (attributed to the difficulty of a precise measurement of the latter) but without a significant deviation from the linearity in general. This finding has allowed us to estimate the diffusion coefficient of this species: D = (1.7 +/- 0.2) x 10(-7) cm(2)/s. The extinction coefficients for the maximum of the absorption band (at 440 nm) of Fc have been compared for a series of solvents: [BMIM][NTf(2)], acetonitrile, THF, heptane, CH(2)Cl(2), ethanol, and toluene. A simple method to estimate reliably the concentration of solute Fc in ionic liquids based on spectroscopic measurements has been proposed, owing to the proximity of Fc absorption properties for a great variety of solvents.

Published
2009
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4. Aggregation of Plate-like Colloids Induced by Charged Polymer Chains: Organization at the Nanometer Scale Tuned by Polymer Charge Density

Author

Laurent J. Michot, Pierre Levitz, Daniel Hermida Merino, Yasine Sakhawoth, Juliette Sirieix-Plénet, Natalie Malikova, Anne-Laure Rollet, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Physicochimie des Electrolytes, Colloïdes et Sciences Analytiques (PECSA), and Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, Materials science, Scale (ratio), 02 engineering and technology, 010402 general chemistry, complex mixtures, 01 natural sciences, Colloid, Electrochemistry, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS, Spectroscopy, chemistry.chemical_classification, Charge density, Surfaces and Interfaces, Polymer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical physics, Nanometre, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

International audience; We study the aggregation of charged plate-like colloids, Na-montmorillonite clays, in the presence of ionenes, oppositely charged polymer chains. The choice of the charged polymer allows tuning its linear charge density to match/mismatch the average charge separation on the clay surfaces. We assess the nanoscale structure of the aggregates formed by small-angle X-ray and neutron scattering. The nanoscale features of the formed clay aggregates are dominated by the presence of a stacking peak, giving clear evidence for the formation of clay tactoids, that is, a face-to-face aggregation geometry of the clay platelets. The chain charge density of ionenes influences not only the stacking repeat distance within the clay tactoids but also the extent of stacking and abundance of the tactoids. We may distinguish two regimes as a function of clay and ionene polymer charge densities (ρc and ρp, respectively). The first regime applies to ρp > ρc and ρp ≈ ρc, that is, for highly and “matching” charged chains. Under these conditions, the intercalated chains lie in a flat conformation within the tactoids, irrespective of the ionic strength (within the range studied, i.e., up to 0.05 M NaBr). For weakly charged chains, ρp < ρc, undulation of the ionene chains within the tactoid is seen. The degree of undulation increases with ionic strength due to the decreasing persistence length of the ionene chains. The extent of stacking (5–10 platelets per tactoid) is a general feature of all the systems, and its origin remains unknown. The system corresponding to the closest match in charge separations on the clay surface and on the polymer chain (ρp ≈ ρc) features the highest abundance of tactoids. This coincides with the highest macroscopic density as deduced from simple visual inspection of sediment volumes. This leads to the open question regarding the link between the density at the nanoscale and the macroscopic density and sedimentation behavior of the aggregate.

Published
2019
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5. Integrated microfluidic device for the separation, decomposition and detection of low molecular weight S-nitrosothiols

Author

José Alberto Fracassi da Silva, Fethi Bedioui, Abdulghani Ismail, Gerson F. Duarte-Junior, Wendell K. T. Coltro, Sophie Griveau, Fanny d’Orlyé, Anne Varenne, Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Universidade Federal de Goiás [Goiânia] (UFG), Universidade Estadual de Campinas (UNICAMP), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Bedioui, Fethi, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Estadual de Campinas = University of Campinas (UNICAMP)

Subjects
[CHIM.ANAL] Chemical Sciences/Analytical chemistry, Materials science, Microfluidics, Nanotechnology, 02 engineering and technology, 01 natural sciences, Biochemistry, Catalysis, Analytical Chemistry, Electrokinetic phenomena, Limit of Detection, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Lab-On-A-Chip Devices, Electrochemistry, Decomposition (computer science), Environmental Chemistry, Cysteine, Spectroscopy, S-Nitrosothiols, chemistry.chemical_classification, Detection limit, Biomolecule, 010401 analytical chemistry, Electrochemical Techniques, Microfluidic Analytical Techniques, 021001 nanoscience & nanotechnology, Potentiostat, Amperometry, 0104 chemical sciences, chemistry, S-Nitrosoglutathione, 0210 nano-technology, Copper
Abstract

International audience; S-nitrosothiols (RSNOs) are very important biomolecules that play crucial roles in many physiological and physiopathological processes. They act as NO-donors and are candidates for future medicines. Their identification and quantitation are therefore important for biomedical applications. One, two or more RSNOs can then be combined to design a drug and therefore, the quantification of each is important to establish an acceptable quality control process. Till date, miniaturized devices have been used to detect RSNOs based on their total quantitation without a preceding separation step. This study reports on an original and integrated microdevice allowing for the successive electrokinetic separation of low molecular weight RSNOs, their decomposition under metal catalysis, and their quantitation by amperometric detection of the produced nitrite in the end-channel arrangement, leading to their quantitation in a single run. For this purpose, a commercial SU-8/Pyrex microfluidic system was coupled to a portable and wireless potentiostat. Different operating and running parameters were optimized to achieve the best analytical data, allowing for an LOD equal to 20 μM. The simultaneous separation of S-nitrosoglutathione and S-nitrosocysteine was successfully obtained within 75 s. The proposed methodology using SU-8/Pyrex microfluidic devices opens new possibilities to investigate future drug candidates for NO-donors.

Published
2019
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6. Insights in uranium extraction from spent nuclear fuels using dicyclohexano-18-crown-6 – Fate of rhenium as technetium homolog

Author

Gérard Cote, Kenneth R. Czerwinsky, Micheline Draye, Alain Favre-Réguillon, Laboratoire de Génie des Procédés Catalytiques (LGPC), École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Laboratoire LCME / Equipe Chimie Verte (LCME_CV), Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Perrhenate, Extraction (chemistry), chemistry.chemical_element, Filtration and Separation, 02 engineering and technology, Rhenium, Uranium, 021001 nanoscience & nanotechnology, Technetium, Uranyl, 7. Clean energy, Analytical Chemistry, chemistry.chemical_compound, 020401 chemical engineering, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Nitric acid, [SDE]Environmental Sciences, 0204 chemical engineering, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Stoichiometry, Nuclear chemistry
Abstract

The single extraction of rhenium(VII) and uranium(VI) from nitric acid solution by dicyclohexano-18-crown-6 (DCH) solutions was investigated. The extraction of Re(VII), in the form of perrhenate (ReO4−) anion, was optimum for a nitric acid concentration of 3 M and was explained by the ion-pair extraction of perrhenate anions by the hydroxonium DCH complex. The stoichiometry of the Re(VII) complex was obtained from the distribution data by slope analysis and the extracted specie was identified as {ReO4−(DCH-H3O)+}. The uranyl extraction by DCH solutions was evaluated under the same conditions and the extracted specie was identified as {(NO3−)2(DCH-UO22+)} for a nitric acid concentration above 5 M. The extraction of rhenium(VII) from nitric acid solution by DCH solutions in the presence of large excess of uranium(VI) was then investigated. For a nitric acid concentration of 3 mol/L, the extraction efficiency of perrhenate was found to be almost independent of uranium concentration. Based on the chemical similarities between Re(VII) and Tc(VII), this suggests that DCH could be considered for the separation of technetium (VII)/uranium(VI) from nitric acid solution.

Published
2019
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7. Characterization of home-made graphite/PDMS microband electrodes for amperometric detection in an original reusable glass-NOA®-PDMS electrophoretic microdevice

Author

Fethi Bedioui, Jérémie Gouyon, Anne Varenne, Fanny d’Orlyé, Sophie Griveau, Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Agence de l'Environnement et de la Maîtrise de l'Energie (ADEME), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE - UMR 8587), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Unité de pharmacologie chimique et génétique et d'imagerie (UPCGI - UMR 8151 / UMR_S 1022 ), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse, électrochimie, imagerie et systèmes analytiques pour le Diagnostic (SEISAD), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), and GRIVEAU, SOPHIE

Subjects
Electrophoresis, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, Materials science, General Chemical Engineering, Microfluidics, Microchip, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Chronoamperometry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electrochemistry, Screen printing, Polydimethylsiloxane, 021001 nanoscience & nanotechnology, Amperometry, 0104 chemical sciences, Microelectrode, chemistry, Chemical engineering, Electrode, Cyclic voltammetry, 0210 nano-technology
Abstract

International audience; A new dismountable and reusable microchip for electrophoretic separation coupled to amperometric detection was developed. For this purpose, a new home made three-microbands electrode system was developed and microfabricated based on screen-printing for the inclusion of graphite/polydimethylsiloxane (C-PDMS) composite in microchannels down to 30 μm width. The composition of the composite as well as the fabrication methodology were optimized for an easy handling and an optimized electrochemical behavior. The electrochemical characterization of this composite material was first performed in bulk format (disc-shaped electrode, 6 mm diameter). It was then transposed to the micrometric scale for its integration in an original glass-NOA81®-PDMS microfluidic device allowing for reversible sealing. The microband electrodes were characterized by scanning electron microcopy and cyclic voltammetry, illustrating a good control of the microelectrode width. Then, the analytical performances of the C-PDMS composite microelectrodes were evaluated using Ru(NH3)63+ and FcMeOH as model electroactive molecules. The electrophoretic separation and quantitation of Ru(NH3)63+ were then performed in a background electrolyte made of hydrochloric acid and sodium chloride, leading to a LOD and a LOQ of 3.4 μmol L−1 and 11.3 μmol L−1, respectively. The re-openable NOA-based microdevice permits to regenerate the electrode surface by simply repositioning the microband on a new spot, allowing for robust analysis in a reusable system.

Published
2020
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8. Niobium and tantalum processing in oxalic-nitric media: Nb2O5·nH2O and Ta2O5·nH2O precipitation with oxalates and nitrates recycling

Author

Alexandre Chagnes, Denis Beltrami, David Bengio, Sarah Bélair, Gérard Cote, Gauthier J.-P. Deblonde, ERAMET RESEARCH, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), GeoRessources, Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL)-Centre de recherches sur la géologie des matières premières minérales et énergétiques (CREGU)-Institut national des sciences de l'Univers (INSU - CNRS), and Institut national des sciences de l'Univers (INSU - CNRS)-Centre de recherches sur la géologie des matières premières minérales et énergétiques (CREGU)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Metal ions in aqueous solution, Niobium, Oxalic acid, Tantalum, chemistry.chemical_element, Filtration and Separation, 02 engineering and technology, Precipitation, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Oxalate, Analytical Chemistry, chemistry.chemical_compound, 020401 chemical engineering, Recycling, 0204 chemical engineering, Solubility, Oxalates, Aqueous solution, Hydrometallurgy, Precipitation (chemistry), 021001 nanoscience & nanotechnology, 6. Clean water, chemistry, 0210 nano-technology, Nuclear chemistry
Abstract

International audience; Oxalate-based aqueous media represent one of the rare options for solubilizing macroscopic amount of niobium (Nb) and tantalum (Ta) without using toxic fluoride-based mixtures. Recent progress in the hydrometallurgy of Nb and Ta also highlighted the potential of oxalate-nitrate media for the separation of Nb and Ta. Nonetheless, the resulting purified aqueous solutions, containing Nb or Ta in HNO3-H2C2O4 mixtures, need to be further processed in order to yield Nb and Ta solid products that can be commercialized. Furthermore, oxalic acid is relatively expensive in the frame of the hydrometallurgy of Nb and its recycling is necessary. In this study, the precipitation of Nb and Ta, as well as their usual minor impurities (Ti and Fe), from oxalic-nitric acid solutions has been investigated for the first time. Neutralization of Nb-HNO3-H2C2O4 mixtures to pH 7-8 by concentrated NaOH or NH4OH was found to be effective at decomposing the oxalate complexes ([NbO(C2O4)3] 3-and [NbO(C2O4)2(H2O)]-) and precipitating Nb in the form of Nb2O5·nH2O while leaving the Page 2/27 oxalate ions in solution. Taking advantage of the solubility difference between nitrate and oxalate salts, the subsequent concentration of the filtrates yields to the recovery of the oxalates as Na2C2O4 or (NH4)2C2O4·H2O and a concentrated solution of sodium or ammonium nitrate. The developed method exhibits high precipitation yields (>99.9%) for Nb and Ta and high recovery yields (>99%) for the nitrates and oxalates. The process was optimized at the laboratory scale (~50 mL) and then validated on industrial Nb and Ta solutions (~225 L) with successful production of purified Nb2O5·nH2O and Ta2O5·nH2O, recovery of the oxalates in the form of Na2C2O4 or (NH4)2C2O4·H2O and a concentration solution of nitrates. Taking together, the proposed precipitation method and the fluoride-free liquid-liquid Nb-Ta separation recently reported pave the way for more suitable hydrometallurgical processes for Nb and Ta.

Published
2019
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9. A fluoride-free liquid-liquid extraction process for the recovery and separation of niobium and tantalum from alkaline leach solutions

Author

Denis Beltrami, Gérard Cote, Sarah Bélair, Alexandre Chagnes, David Bengio, Gauthier J.-P. Deblonde, ERAMET RESEARCH, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), GeoRessources, Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL)-Centre de recherches sur la géologie des matières premières minérales et énergétiques (CREGU)-Institut national des sciences de l'Univers (INSU - CNRS), and Institut national des sciences de l'Univers (INSU - CNRS)-Centre de recherches sur la géologie des matières premières minérales et énergétiques (CREGU)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Materials science, Extraction (chemistry), Inorganic chemistry, Tantalum, Niobium, chemistry.chemical_element, Salt (chemistry), Filtration and Separation, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, Diluent, Analytical Chemistry, chemistry.chemical_compound, 020401 chemical engineering, chemistry, Liquid–liquid extraction, 0204 chemical engineering, 0210 nano-technology, Fluoride, ComputingMilieux_MISCELLANEOUS, Refining (metallurgy)
Abstract

The production of high purity niobium (Nb) or tantalum (Ta) compounds still relies on processes that require highly acidic conditions and concentrated HF or NH4F solutions. Recent progress in the chemistry of group V elements, along with the evolution of the environmental concerns, call for the development of more sustainable industrial processes for these strategic elements. In sharp contrast with the historical fluoride approach chosen by the Nb and Ta refining industry, there has been a recent surge in the literature concerning the chemistry of these elements in diluted alkaline or oxalate media. We here propose an innovative liquid-liquid extraction process that is amenable to separate Nb and Ta from alkaline feed solutions, can be operated at low acidity and that does not require any fluoride-based chemical. The developed strategy is as follows: first, Nb and Ta are co-extracted from their alkaline solution (pH 12) using a quaternary ammonium salt (Aliquat® 336) dissolved in an organic diluent; then, Nb is selectively back-extracted in a mixture of diluted nitric and oxalic acids; and finally, Ta is stripped in a diluted nitric media. The process also affords purifying Nb from Ti, Fe and Na. Following an optimization at laboratory scale, the full process has been validated during continuous running tests (160 h at 1.4 L h−1) using industrial Nb-Ta caustic solutions coming from the development of the so-called Maboumine process. The developed process works at room temperature, low acidity ([H+] 20 wt% Ta) even when starting from a diluted feed (39 ppm Ta). The proposed strategy paves the way for new Nb and Ta hydrometallurgical processes operating under mild chemical environments and represents a concrete alternative to the current fluoride-intensive industrial methods.

Published
2019
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10. On the Stability Issues of TiO 2 -Based Composites in View of Fuel Cell Application: A Combined Experimental and Theoretical Investigation

Author

Chiara Ricca, Carlo Adamo, Michel Cassir, Armelle Ringuedé, Frédéric Labat, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Aquabio, and Laboratoire d'Hydrobiologie

Subjects
Materials science, Composite number, 02 engineering and technology, Electrolyte, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Stability (probability), 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Complex materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, General Energy, chemistry, Fuel cells, Carbonate, Physical and Theoretical Chemistry, Composite material, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Oxide–carbonate composite electrolytes are complex materials whose peculiar conductivity performances are yet to be fully understood. Stability issues, however, arise when the carbonate is combined...

Published
2019
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11. Cutting-edge multi-level analytical and structural characterization of antibody-drug conjugates: present and future

Author

Oscar Hernandez-Alba, Emmanuel Leize-Wagner, Alain Beck, Yannis François, Davy Guillarme, Szabolcs Fekete, Valentina D'Atri, Sarah Cianférani, Anthony Ehkirch, Rabah Gahoual, Centre d'Immunologie Pierre Fabre, CIPF, School of Pharmaceutical Science, Université de Lausanne (UNIL)-University of Geneva [Switzerland], Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Tectonique Moléculaire du Solide (TMS), Chimie de la matière complexe (CMC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de Coordination Organique, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), University of Geneva [Switzerland], Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA), Centre d'Immunologie Pierre Fabre (CIPF), PIERRE FABRE, University of Geneva [Switzerland]-Université de Lausanne (UNIL), 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), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Center of Immunology Pierre Fabre, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Descartes - Paris 5 (UPD5)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP), and Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Drug, Electrophoresis, Bioanalysis, Immunoconjugates, Computer science, media_common.quotation_subject, Nanotechnology, inotuzumab ozogamicin, Biochemistry, Inotuzumab ozogamicin, Sacituzumab govitecan, Mass Spectrometry, 03 medical and health sciences, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, gemtuzumab ozogamicin, [CHIM]Chemical Sciences, Humans, Gemtuzumab ozogamicin, Amino Acid Sequence, Molecular Biology, Trastuzumab emtansine, ComputingMilieux_MISCELLANEOUS, media_common, trastuzumab emtansine, ddc:615, Chromatography, 030102 biochemistry & molecular biology, small-protein fragment-DCs, 3. Good health, Characterization (materials science), body regions, 030104 developmental biology, 3G-ADCs, Brentuximab vedotin, Fragment-DCs, Small-protein, Hydrophobic and Hydrophilic Interactions, Conjugate
Abstract

International audience; Introduction : The development and optimization of antibody drug conjugates (ADCs) rely on improving their analytical and bioanalytical characterization, by assessing critical quality attributes (CQAs). Among the CQAs, the glycoprofile, drug load distribution (DLD), the amountof unconjugated antibody (D0), the average drug-to-antibody ratio (DAR), the drug conjugation sites and the residual drug-linker and related product proportions (SMDs) in addition to high and low molecular weight species (H/LMWS) are the most important ones.Areas covered : The analytical and structural toolbox for the characterization of 1st, 2d and 3d generation ADCs was significantly extended in the last 3 years. Here, we reviewed state-ofthe-art techniques, such as liquid chromatography, high resolution native and ion mobility mass spectrometry, multidimensional LC and capillary electrophoresis hyphenated to mass spectrometry, reported mainly since 2016.Expert commentary : These emerging techniques allow a deep insight into important CQAs that are related to ADC Chemistry Manufacturing and Control (CMC) as well as an improved understanding of in vitro and in vivo ADC biotransformations. This knowledge and the development of quantitative bioanalytical assays will continue to contribute to earlydevelopability assessment for the optimization of all the ADC components (i.e., antibody, drug, and linker) and help to bring next-generation candidate ADC into the clinic and hopefully to the marke

Published
2019
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12. A simple and low-cost chip bonding solution for high pressure, high temperature and biological applications

Author

Iago Pereiro, Jean-Louis Viovy, Ayako Yamada, Stéphanie Descroix, Marco Serra, Davide Ferraro, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie-Curie (PCC), Centre National de la Recherche Scientifique (CNRS)-Institut Curie [Paris]-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut Curie [Paris]-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hot Temperature, Materials science, Microfluidics, Biomedical Engineering, Bioengineering, Nanotechnology, 02 engineering and technology, Polymerase Chain Reaction, 01 natural sciences, Biochemistry, Seal (mechanical), [SPI]Engineering Sciences [physics], Adhesives, Materials Testing, Pressure, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Process engineering, ComputingMilieux_MISCELLANEOUS, SIMPLE (military communications protocol), business.industry, Chemistry (all), 010401 analytical chemistry, Process (computing), Ranging, General Chemistry, Microfluidic Analytical Techniques, 021001 nanoscience & nanotechnology, Chip, 0104 chemical sciences, Cell and molecular biology, High pressure, Plastics, 0210 nano-technology, business
Abstract

The sealing of microfluidic devices remains a complex and time-consuming process requiring specific equipment and protocols: a universal method is thus highly desirable. We propose here the use of a commercially available sealing tape as a robust, versatile, reversible solution, compatible with cell and molecular biology protocols, and requiring only the application of manually achievable pressures. The performance of the seal was tested with regards to the most commonly used chip materials. For most materials, the bonding resisted 5 bars at room temperature and 1 bar at 95 °C. This method should find numerous uses, ranging from fast prototyping in the laboratory to implementation in low technology environments or industrial production.

Published
2017
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13. Ligand exchange on CdSe nanoplatelets for the solar light sensitization of TiO2 and ZnO nanorod arrays

Author

Sandrine Ithurria, Alexandra Szemjonov, Mariana Tasso, Frédéric Labat, Th. Pauporté, Ilaria Ciofini, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Laboratoire de Physique et d'Etude des Matériaux (UMR 8213) (LPEM), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Passivation, Band gap, NANOPLATELETS, General Chemical Engineering, General Physics and Astronomy, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Light sensitization, 01 natural sciences, 7. Clean energy, CdSe, CDSE, LIGHT SENSITIZATION, purl.org/becyt/ford/1 [https], chemistry.chemical_compound, symbols.namesake, Monolayer, Química Coloidal, purl.org/becyt/ford/1.4 [https], ZNO, TiO2, [CHIM]Chemical Sciences, Bifunctional, ComputingMilieux_MISCELLANEOUS, [PHYS]Physics [physics], Ligand exchange, Chemistry, Nanoplatelets, Wide-bandgap semiconductor, Ciencias Químicas, General Chemistry, 021001 nanoscience & nanotechnology, LIGAND EXCHANGE, 0104 chemical sciences, Quantum dot, symbols, ZnO, TIO2, Nanorod, 0210 nano-technology, Raman spectroscopy, CIENCIAS NATURALES Y EXACTAS
Abstract

In quantum dot (QD) solar cells, the ex situ sensitization of wide band gap semiconductors (WBSCs) makes it possible to control the shape and the passivation of the nanosized sensitizer. Hence, ex situ techniques can be used to investigate how the band gap of the sensitizers affects the performance of quantum dot solar cells. The latter can be precisely controlled in 1D confined structures such as quasi-2D nanoplatelets (NPLs), the thickness of which is defined with an atomic precision. In this work, we tested and thoroughly characterized the attachment of 7, 9 and 11 monolayers thick CdSe NPLs (as well as QDs for the sake of comparison) to ZnO and to TiO2 nanorods. A crucial point of the ex situ techniques is the choice of bifunctional ligands that link the nanosized sensitizers to the WBSCs. Besides the well-known mercaptopropionic acid, we also studied two ‘atomic linkers’ (OH− and SH−) to minimize the distance between the sensitizer and the oxide. The as-prepared systems have been analyzed by UV/VIS absorption and Raman spectroscopy. Among them, SH− was found to be the most versatile linker that enabled the efficient attachment of all types of CdSe nanocrystals on ZnO and TiO2 nanorods. Fil: Szemjonov, A.. PSL Research University; Francia. Centre National de la Recherche Scientifique; Francia Fil: Tasso, Mariana Patricia. Laboratoire de Physique Et D'etude Des Materiaux; Francia. Centre National de la Recherche Scientifique; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Ithurria, S.. Laboratoire de Physique Et D'etude Des Materiaux; Francia Fil: Ciofini, I.. PSL Research University; Francia. Centre National de la Recherche Scientifique; Francia Fil: Labat, F.. PSL Research University; Francia. Centre National de la Recherche Scientifique; Francia Fil: Pauporté, T.. PSL Research University; Francia. Centre National de la Recherche Scientifique; Francia

Published
2019
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14. Extraction of tungsten as polyoxometalate anion using a layered double hydroxide: Selectivity and regeneration

Author

Aurélie Makolana, Grégory Lefèvre, Julie Lion, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ion exchange, Hydrotalcite, Chemistry, Process Chemistry and Technology, General Chemical Engineering, Extraction (chemistry), Inorganic chemistry, Filtration and Separation, 02 engineering and technology, General Chemistry, 010501 environmental sciences, 01 natural sciences, Chloride, chemistry.chemical_compound, Adsorption, 020401 chemical engineering, Tungstate, Polyoxometalate, medicine, Hydroxide, [CHIM]Chemical Sciences, 0204 chemical engineering, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, medicine.drug
Abstract

Extraction of tungstate species as highly charged polyoxometalates has been performed with hydrotalcite. An optimum pH around 5 has been determined, correlated with the stability domain of heptatungstate species. Two mechanisms have been shown from in situ infrared spectroscopy and zeta potential measurements: exchange of carbonate ions by heptatungstate species and adsorption as inner-sphere surface complexes. The presence of nitrate, chloride, and sulfate has no effect on the extracted fraction and it was concluded that the extraction is selective toward these anions. The regeneration of the solid was performed with a solution of carbonate sodium at pH 10.

Published
2018
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15. Microfluidic valve with zero dead volume and negligible back-flow for droplets handling

Author

Jean-Louis Viovy, Stéphanie Descroix, Marco Serra, Davide Ferraro, I. Ferrante, Laboratoire Physico-Chimie Curie [Institut Curie] (PCC), Institut Curie [Paris]-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Materials Chemistry Metals and Alloys, Microfluidics, Mechanical engineering, 3D printing, 02 engineering and technology, Microvalves, Droplet microfluidics, Microfabrication, Soft-lithography, Electronic, Optical and Magnetic Materials, Instrumentation, Condensed Matter Physics, Surfaces, Coatings and Films, 2506, Electrical and Electronic Engineering, 01 natural sciences, Soft lithography, Coatings and Films, Electronic, Materials Chemistry, Optical and Magnetic Materials, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, ComputingMilieux_MISCELLANEOUS, Backflow, business.industry, 010401 analytical chemistry, Metals and Alloys, 021001 nanoscience & nanotechnology, Dead volume, 0104 chemical sciences, Surfaces, Mechanical stability, 0210 nano-technology, business
Abstract

Droplet microfluidics allows the implementation of several biochemical and bioanalytical protocols in microfluidic devices. However, this integration typically requires the use of microfluidic valves, which allow the control of different operations on the same channels network. Unfortunately, the valves commercially available are almost exclusively suitable for-single phase flow, and only one valve system compatible with multi-phase systems has been presented so far in the literature. We present here a new pinch-like valve that withstands high pressures (tested up to 4 bar), allows droplet manipulation and combines the advantages of conventional pinch valves regarding the absence of dead volume, while making negligible the backflow generated (less than 2 nL). The conception and design of the presented valve, based on numerical simulations, is performed by an optimized microfabrication strategy, combining PDMS soft-lithography and 3D printing technologies. The valves had been tested regarding their mechanical stability and proving their capability of allowing droplets passing through them, without any perturbation. Finally, the very small back-flow volume generated during the actuation, has been exploited for various applications in droplets microfluidics, like droplet handling, droplet-on-demand generation and sorting.

Published
2018
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16. Influence of phosphate on tungstate sorption on hematite: A macroscopic and spectroscopic evaluation of the mechanism

Author

Grégory Lefèvre, Bryan Sallman, Sudipta Rakshit, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Environmental Engineering, Surface Properties, Health, Toxicology and Mutagenesis, Iron oxide, Oxyanion, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Ferric Compounds, Ion, Phosphates, chemistry.chemical_compound, Tungstate, Environmental Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Spectrum Analysis, Public Health, Environmental and Occupational Health, Sorption, General Medicine, General Chemistry, Hematite, Hydrogen-Ion Concentration, Tungsten Compounds, 021001 nanoscience & nanotechnology, Phosphate, Pollution, chemistry, Attenuated total reflection, visual_art, visual_art.visual_art_medium, Adsorption, 0210 nano-technology, Nuclear chemistry
Abstract

The environmental fate of the tungstate (VI) oxyanion [ e.g. mono tungstate and several polytungstate, generally expressed by W (VI)] is largely controlled by sorption on soil minerals, especially on iron oxide minerals. Molecular scale evaluation of W (VI) retention on iron oxides in the presence of competing oxyanions is scarce in literature. Here we report surface interaction mechanisms of W (VI) on hematite in the presence of phosphate (P) using macroscopic and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic experiments. Batch sorption experiments were conducted using 2 g L−1 hematite and 100 μM W (VI) and P, in single ion system and in binary mixtures as a function of pH (4–11). In situ ATR-FTIR spectroscopic evaluation of P and W (VI) sorption on hematite was also carried out. The results from macroscopic experiments indicated that W (VI) sorption on hematite was not affected by P when W (VI) was added first. The influence of P on W (VI) sorption was noticed when W (VI) & P were added simultaneously or P was added first. The in situ ATR-FTIR spectroscopic data corroborated these findings. In addition, the spectroscopic data revealed that in the presence of P, the surface complexation mode of W (VI) differed as noted from either the absence of W O antisymmetric infrared (IR) band or the W O W stretching band. This study provides useful information on molecular level understanding of W (VI) surface complexation on hematite in the presence of competing ions such as P.

Published
2018
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17. A chemically encoded timer for dual molecular delivery at tailored ranges and concentrations

Author

Raphaël Labruère, Thomas Le Saux, Silvia Serra, Raphaël Plasson, Steve Huvelle, Frédéric Schmidt, Ludovic Jullien, Ahmed Alouane, Chimie biologique des membranes et ciblage thérapeutique (CBMCT - UMR 3666 / U1143), Centre National de la Recherche Scientifique (CNRS)-Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nordic Institute for Theoretical Physics (NORDITA), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ANR Kituse [ANR-11-BS07-0021], INSERM (Photocancer project), LabEx LERMIT, École normale supérieure - Paris (ENS Paris)-École normale supérieure - Paris (ENS Paris)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Curie-Université Paris Descartes - Paris 5 (UPD5), nordita, Uppsala University, Institut Curie-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie - ENS Paris, and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Computer science, [SDV]Life Sciences [q-bio], Metals and Alloys, General Chemistry, DUAL (cognitive architecture), 010402 general chemistry, 01 natural sciences, release, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, kinetics, cathepsin-b, Materials Chemistry, Ceramics and Composites, Molecular distribution, systems, [CHIM]Chemical Sciences, Timer, energy propagation, Biological system, self-immolative spacers, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Spatiotemporal control of molecular distribution is much in demand in many fields of chemistry. To address this goal, we exploit a low molecular weight branched self-immolative architecture, which acts as a triggerable chemically encoded timer for autonomous sequential release of two chemicals. Using a light-activated model liberating two distinct fluorophores, we generated a tunable spatially contrasted molecular distribution.

Published
2018
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18. Electrochemical Behavior of Stainless Steels for Sudomotor Dysfunction Applications

Author

Armelle Ringuedé, Mamie Sancy, Michel Cassir, N. Vejar, José H. Zagal, X. Gonzalez, Virginie Lair, Sophie Griveau, Fethi Bedioui, Amandine Calmet, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Saclay (COmUE), Unité de pharmacologie chimique et génétique et d'imagerie (UPCGI - UMR 8151 / UMR_S 1022 ), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE - UMR 8587), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Dielectric spectroscopy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Composite material, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Sudomotor dysfunction
Abstract

AISI 304L is used in Sudoscan(TM) technology (Impeto Medical Inc.) for the early diagnosis of small fiber neuropathy caused by type-2 diabetes or cystic fibrosis. In a recent paper, several substitute electrodes were analyzed, among which the biocompatib

Published
2018
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19. First investigations for the characterization of glucosamine-6-phosphate synthase by capillary electrophoresis

Author

Pierre Gareil, Bernard Badet, Miriam Beneito-Cambra, Marie-Ange Badet-Denisot, Nathalie Delaunay, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS), Laboratoires Sciences Analytiques, Bioanalytiques et Miniaturisation, and Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris)

Subjects
0301 basic medicine, Dimer, Clinical Biochemistry, Random hexamer, 01 natural sciences, Biochemistry, Analytical Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Capillary electrophoresis, Biosynthesis, [CHIM]Chemical Sciences, Enzyme Inhibitors, ComputingMilieux_MISCELLANEOUS, Glutamine-Fructose-6-Phosphate Transaminase (Isomerizing), chemistry.chemical_classification, Chromatography, ATP synthase, biology, Escherichia coli Proteins, 010401 analytical chemistry, Electrophoresis, Capillary, Cell Biology, General Medicine, Phosphate, 0104 chemical sciences, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], 030104 developmental biology, Enzyme, chemistry, Ionic strength, biology.protein
Abstract

The enzyme glucosamine-6-phosphate synthase (GlmS) is an important point of metabolic control in biosynthesis of amino sugar-containing macromolecules and is therefore a potential target in order to design antibacterial and antifungal drugs. It has two oligomerization states, which are the active dimer and the inactive hexamer. For the first time, the potential of CE to separate and quantify the two forms was studied. After incubating GlmS with the d-glucosamine 6-phosphate (GlcN6P) inhibitor, an electrolyte based on sodium phosphate at pH 7.2 and an ionic strength of 100mM plus GlcN6P (either 2 or 20mM) allowed the hexamer-dimer separation. However, the displacement of the dimer/hexamer equilibrium during the analysis time prevented any improvement of the resolution when varying the effective separation length or the temperature of the analysis. Therefore, the use of a short-end CE method allowed the decrease in the analysis time to about 1min. Some parameters such as the temperature and the time of incubation and the ratio of the inhibitor and enzyme concentrations were studied. Then, it was also possible to test, very rapidly and with a very small amount, some molecules having an inhibition potential for the GlmS enzyme (arabinose-5-phosphate oxime, 2-amino-2-deoxy-d-glucitol 6-phosphate, and glucose-6-phosphate).

Published
2018
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20. Electrochemical behavior of electrode materials (nickel and stainless steels) for sudomotor dysfunction applications : a review

Author

José H. Zagal, Armelle Ringuedé, Michel Cassir, Sophie Griveau, Fethi Bedioui, Virginie Lair, Unité de pharmacologie chimique et génétique et d'imagerie (UPCGI - UMR 8151 / UMR_S 1022 ), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Universidad de Santiago de Chile [Santiago] (USACH), Bedioui, Fethi, Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE - UMR 8587), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Université d'Évry-Val-d'Essonne (UEVE)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, and Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)

Subjects
Clinical tests, Materials science, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, Electrochemistry, Chloride, Analytical Chemistry, 03 medical and health sciences, nickel, 0302 clinical medicine, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, medicine, Small Fiber Neuropathy, stainless steel, Electrode material, Metallurgy, fungi, electrochemical conductance, technology, industry, and agriculture, 021001 nanoscience & nanotechnology, 3. Good health, Nickel, sweat, chemistry, medical application, Electrode, sudomotor dysfynctions, 0210 nano-technology, 030217 neurology & neurosurgery, Sudomotor dysfunction, medicine.drug
Abstract

International audience; This is an overview of the electrochemical characterization of nickel and stainless steel as electrodes in medical devices for the early diagnosis of small fiber neuropathy that originates from type-2 diabetes or cystic fibrosis. The electrical current responses obtained during the clinical tests are related to the amount of chloride present on the sweat. Stainless steel electrodes are now used to replace nickel because this later not only presents problems with chloride sensitivity but its contact with skin can cause possible allergic reactions for some patients. For the above reasons, several types of stainless steels were studied. It was shown that some of them perform well and have lower costs than Ni electrodes. We discuss the state of the art of the electrochemical studies conducted with nickel and steels under physiological or biomimetic conditions and discuss the advantages of a particular steel over the others depending on the conditions, especially chloride concentration.

Published
2018
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21. Effect of Zn2+ and Cu2+ -bearing salts on the dissolution of silicate glasses

Author

Majérus, Odile, de Seauve, Victor, Alloteau, Fanny, Caurant, Daniel, Lefèvre, Grégory, Lehuédé, Patrice, Biron, Isabelle, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Centre de recherche et de restauration des musées de France (C2RMF), Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture et de la Communication (MCC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Caurant, Daniel, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Laboratoire d'Etude de la Corrosion Aqueuse (LECA), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, and Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM] Chemical Sciences, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

22. Adsorption of Uranium over NH2 -Functionalized Ordered Silica in Aqueous Solutions

Author

Grégory Lefèvre, Nadia Guignard, Sébastien Royer, Isabelle Batonneau-Gener, Jérémie Huynh, Emmanuel Tertre, Michael Descostes, Ruben Palacio, Fariba Safizadeh, Julie Rousseau, Lilian Eloy, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), AREVA e Business Group Mines, R&D Department, BAL 0414C-2, Tour AREVA, AREVA e Business Group Mines, R&D Department, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), 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), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille

Subjects
Aqueous solution, Materials science, Inorganic chemistry, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Mesoporous silica, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Uranyl, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Adsorption, Physisorption, chemistry, Surface modification, Moiety, General Materials Science, Fourier transform infrared spectroscopy, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

The aim of this work was to obtain an in-depth understanding of the U(VI) adsorption mechanism over amino-functionalized mesoporous silica SBA-15 and highlights its high efficiency in aqueous media for U(VI) removal and preconcentration. The samples were synthesized and functionalized by both grafting and co-condensation methods, using different alkyl-substituted amine groups and were characterized using X-ray diffraction, N2 physisorption, Fourier transform infrared spectroscopy, and elemental C–H–N–S analyses. The properties for U(VI) adsorption were evaluated under discontinuous conditions, with the determination of the effect of several parameters (initial pH, contact time, initial U(VI) concentration, functionalization method, and organic moiety composition). U(VI) adsorption over grafted materials reached equilibrium at around 30 min, with a maximum adsorption capacity of 573 mgU·gads–1 for the most efficient material at its optimal adsorption pH (equal to 6) at 20 °C. Functionalized materials by gr...

Published
2017
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23. Influence of hydroxybenzoic acids on the adsorption of Eu(III) onto $\alpha$,$\gamma$-Al$_2$O$_3$ particles in mildly acidic conditions: a macroscopic and spectroscopic study

Author

Pauline Moreau, Sonia Colette-Maatouk, Pierre Gareil, Pascal E. Reiller, Laboratoire de développement Analytique Nucléaire Isotopique et Elémentaire (LANIE), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by the RSTB program (RBPCH project) from CEA, and the French Direction Générale de l’Armement (DGA).

Subjects
Hydroxybenzoic acid, Inorganic chemistry, chemistry.chemical_element, 010501 environmental sciences, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Protocatechuic acid, chemistry.chemical_compound, Adsorption, Europium, Geochemistry and Petrology, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Environmental Chemistry, Binary system, 0105 earth and related environmental sciences, Ternary numeral system, Pollution, alumina, 0104 chemical sciences, Crystallography, chemistry, adsorption, TRLS, Ternary operation, Luminescence, phenolic acids
Abstract

International audience; The influence of hydroxybenzoic acids (HAH$_n$), namely $p$-hydroxybenzoic acid (4 hydroxybenzoic acid, HPhbH) and protocatechuic acid (3,4-dihydroxybenzoic acid, HProtoH2), on the adsorption of europium(III) onto $\alpha$,$\gamma$ Al$_2$O$_3$ particles is studied as a function of acid concentration. After measuring the adsorption edge of the Eu(III)/ $\alpha$,$\gamma$ Al$_2$O$_3$ binary system, and using the previously studied binary component system Eu(III)/HAH$_n$—Moreau et al. (2015) Inorg. Chim. Acta 432, 81—, and HAH$_n$/ $\alpha$,$\gamma$ Al$_2$O$_3$—Moreau et al. (2013) Colloids Surf. A 435, 97—, it is evidenced that HPhbH does not enhance Eu(III) adsorption onto $\alpha$,$\gamma$ Al$_2$O$_3$ in the Eu(III)/HPhbH/ $\alpha$,$\gamma$ Al$_2$O$_3$ ternary system. Conversely, HProtoH$_2$ enhances Eu(III) adsorption onto $\alpha$,$\gamma$ Al$_2$O$_3$ in the Eu(III)/HProtoH$_2$/ $\alpha$,$\gamma$ Al$_2$O$_3$ ternary system. Adsorption of the acids are also found higher in the Eu(III)/acid/ $\alpha$,$\gamma$ Al$_2$O$_3$ ternary systems as compared with the corresponding binary systems assessing synergetic effects. For high HPhbH concentrations a ternary surface species involving $\equiv$AlOH surface sites, Eu(III), and PhbH$^–$ is evidenced by time-resolved luminescence spectroscopy (TRLS). However, in the Eu(III)/HProtoH$_2$/ $\alpha$,$\gamma$ Al$_2$O$_3$ ternary system, chemical environment of Eu(III) is found to be very close to that in the Eu(III)/HProtoH2 binary system. Ternary surface species could not be evidenced in the Eu(III)/HProtoH$_2$/ $\alpha$,$\gamma$ Al$_2$O$_3$ ternary system with TRLS because of the very short decay time of Eu(III) in the presence of protocatechuic acid.

Published
2016
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24. Development and validation of a nonaqueous capillary electrophoretic method for the enantiomeric purity determination of a synthetic intermediate of new 3,4-dihydro-2,2-dimethyl-2H-1-benzopyrans using a single-isomer anionic cyclodextrin derivative and an ionic liquid

Author

Anne Rousseau, Bernard Pirotte, Anne-Catherine Servais, Xavier Florence, Patrice Chiap, Marianne Fillet, Anne Varenne, Jacques Crommen, Pierre Gareil, Didier Villemin, Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Department of Medicinal Chemistry, Natural and Synthetic Drugs Research Centre, Université de Liège, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Universitaire de Liège (CHU-Liège), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Le Havre Normandie (ULH), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Formic acid, Ionic Liquids, 02 engineering and technology, 01 natural sciences, Biochemistry, Analytical Chemistry, chemistry.chemical_compound, Capillary electrophoresis, Ammonium formate, Benzopyrans, Enantiomeric excess, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Cyclodextrins, Chromatography, Cyclodextrin, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010401 analytical chemistry, Organic Chemistry, Electrophoresis, Capillary, Stereoisomerism, General Medicine, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Ionic liquid, Enantiomer, 0210 nano-technology, Selectivity
Abstract

The enantiomeric purity determination of a synthetic intermediate of new 3,4-dihydro-2,2-dimethyl-2H-1-benzopyrans, i.e. 4-amino-2,2-dimethyl-6-ethoxycarbonylamino-3,4-dihydro-2H-1-benzopyran, was successfully carried out using an anionic cyclodextrin (CD) derivative combined with a chiral ionic liquid (IL). In order to obtain high resolution and efficiency values, the addition of a chiral IL, i.e. ethylcholine bis(trifluoromethylsulfonyl)imide (EtChol NTf(2)), to the background electrolyte containing heptakis(2,3-di-O-methyl-6-O-sulfo)-β-CD (HDMS-β-CD) was found to be essential. A simultaneous increase in separation selectivity and enantioresolution seems to indicate a synergistic effect of HDMS-β-CD and EtChol NTf(2). The best enantioseparation of the key intermediate was achieved using a methanolic solution of 0.75M formic acid, 10mM ammonium formate, 1.5mM HDMS-β-CD and 5mM EtChol NTf(2). Levamisole was selected as internal standard. The optimized conditions allowed the determination of 0.1% of each enantiomer in the presence of its stereoisomer using the method of standard additions. The NACE method was then fully validated with respect to selectivity, response function, trueness, precision, accuracy, linearity and limits of detection and quantification.

Published
2010
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25. Activity Coefficients at Infinite Dilution of Organic Compounds in 1-Butyl-3-methylimidazolium Tetrafluoroborate Using Inverse Gas Chromatography

Author

Roland Solimando, Mireille Turmine, Anne-Laure Revelli, Fabrice Mutelet, Jean-Noël Jaubert, Laboratoire de Thermodynamique des Milieux Polyphasés (LTMP), Institut National Polytechnique de Lorraine (INPL), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Activity coefficient, Tetrafluoroborate, General Chemical Engineering, Inorganic chemistry, Solvation, 02 engineering and technology, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Dilution, chemistry.chemical_compound, Adsorption, 020401 chemical engineering, chemistry, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Ionic liquid, Inverse gas chromatography, Polar, 0204 chemical engineering
Abstract

International audience; Activity coefficients at infinite dilution (γ∞) of organic compounds in the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate were determined using inverse gas chromatography from (303.35 to 332.55) K. Retention data were used to estimate the influence of gas−liquid and gas−solid interfacial adsorption on the value of activity coefficients at infinite dilution of solutes in this ionic liquid. Most of the polar solutes were retained largely by partition, while n-alkanes were retained predominantly by interfacial adsorption on the ionic liquid studied. The solvation characteristics of the ionic liquid were evaluated using the Abraham solvation parameter model.

Published
2008
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26. Theoretical Study of the Uranyl Complexation by Hydroxamic and Carboxylic Acid Groups

Author

Céline Bouvier-Capely, Carlo Adamo, B. Boulet, Laurent Joubert, Catherine Cossonnet, Gérard Cote, Institut de Radioprotection et de Sûreté Nucléaire (IRSN), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Coordination sphere, 010405 organic chemistry, Carboxylic acid, Coordination number, Inorganic chemistry, Alcohol, 010402 general chemistry, Uranyl, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Deprotonation, chemistry, Computational chemistry, [CHIM]Chemical Sciences, Molecule, Density functional theory, Physical and Theoretical Chemistry
Abstract

A theoretical study on the complexation of uranyl cation (UO 22+) by three different functional groups of a calix[6]arene cage, that is, two hydroxamic and a carboxylic acid function, has been carried out using density functional theory calculations. In particular, interaction energies between the uranyl and the functional groups have been used to determine their affinity toward uranyl, whereas pKa calculations give some information on the availability of the functional groups in the extraction conditions. On the one hand, calculations of the interaction energies have pointed out clearly a better affinity with the hydroxamic groups. The stabilization of this complex was rationalized in terms of a stronger electrostatic interaction between the uranyl cation and the hydroxamic groups. The presence of a water molecule in the first coordination sphere of uranyl does not destabilize the complex, and the most stable complex is obtained with two functional groups and two water molecules, leading to a coordination number of 8 for the central uranium atom. On the other hand, pKa theoretical evaluation shows that both hydroxamic (deprotonated on the oxygen site) and carboxylic groups are potential extradants in aqueous medium with a preference for carboxylic functions at low pH. Moreover, these data allowed to unambiguously identify the oxygen of the alcohol function as the favored deprotonation site on the hydroxamic function. © 2008 American Chemical Society.

Published
2008
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27. Complexation of europium(III) by hydroxybenzoic acids: a time-resolved luminescence spectroscopy study

Author

Pascal E. Reiller, Pauline Moreau, Pierre Gareil, Sonia Colette-Maatouk, Pierre Vitorge, Laboratoire de développement Analytique Nucléaire Isotopique et Elémentaire (LANIE), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Radiolyse et de la Matière Organique (LRMO), Service d'Etudes du Comportement des Radionucléides (SECR), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hydroxybenzoic acid, time-resolved luminescence spectroscopy, complexation, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Materials Chemistry, [CHIM]Chemical Sciences, lanthanides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate, Physical and Theoretical Chemistry, Spectroscopy, Quenching (fluorescence), Ligand, Euroium, 021001 nanoscience & nanotechnology, hydroxybenzoic acids, 0104 chemical sciences, chemistry, Stability constants of complexes, 0210 nano-technology, Luminescence, Europium, phenolic acids
Abstract

International audience; Complexation of Eu(III) by two hydroxybenzoic acids, namely p-hydroxybenzoic acid (4 dihydroxybenzoic, HPhbH), and protocatechuic acid (3,4-dihydroxybenzoic, HProtoH2), is studied by time-resolved luminescence spectroscopy (TRLS) in mildly acidic solution. Comparable formation constants are determined at 0.1 mol/L NaCl for EuPhbH[2+] – log10β°(EuPhbH[2+]) = 2.18 ± 0.09 (1sigma) – and 0.01 mol/L NaCl for EuProtoH2[2+] – log10β°(EuProtoH2[2+]) = 2.72 ± 0.07 (1sigma). The stoichiometry and carboxylate complexation of the EuProtoH2[2+] complex is ascertained by varying both pH and ligand concentration. The luminescence decay time of EuPhbH[2+] (τ = 107 ± 5 µs) is comparable with that of Eu(H2O)n[3+] (τ = 110 ± 3 µs), suggesting that luminescence quenching processes compensate the expected increase in decay time due to the dehydration associated with complexation. For EuProtoH2[2+], the luminescence decay time is even shorter (τ = 20 ± 5 µs), evidencing intricate quenching processes.

Published
2015
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28. Synthesis and characterization of LaNixCo1−xO3: Role of microstructure on magnetic properties

Author

R.F. Cienfuegos, Armelle Ringuedé, B. Medina-Lott, Michel Cassir, L. Chávez-Guerrero, M. A. Garza-Navarro, Moisés Hinojosa, Rose-Noëlle Vannier, Universidad Autonoma de Nuevo Leon [Mexique] (UANL), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, PIIT, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, 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), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
Thermogravimetric analysis, Materials science, Scanning electron microscope, chemistry.chemical_element, Mineralogy, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, Grain size, 0104 chemical sciences, 3. Good health, Crystallography, Ferromagnetism, chemistry, Geochemistry and Petrology, Lanthanum, [CHIM]Chemical Sciences, 0210 nano-technology, Cobalt, ComputingMilieux_MISCELLANEOUS, Perovskite (structure)
Abstract

Perovskite-type structures with the composition LaNi x Co 1− x O 3 ( x =0.3, 0.5, 0.7) were synthesized by a modified sol-gel method. Using transitional metal elements on the lanthanum base perovskites, properties could be tuned by doping the structure. Thermogravimetric analysis (TGA) evidenced a temperature of 350 °C as the start point of the perovskite-phase formation. Scanning electron microscopy (SEM) images showed the microstructure changes (grain size) of the cobalt-doped perovskite due to composition. In addition, it was shown that magnetic properties of the samples were dependent of cobalt content; experimental results pointed to the existence of disordered spins interactions, which were more evident with the decrease of cobalt content and the existence of ferromagnetic coupling among spins of the samples. These results showed the feasibility of producing a family of compounds with the desired properties, manipulating composition and therefore the microstructure.

Published
2015
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29. Electrical properties of thin bilayered YSZ/GDC SOFC electrolyte elaborated by sputtering

Author

Alain Billard, E. Gourba, C. Brahim, Armelle Ringuedé, Pascal Briois, Michel Cassir, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de science et génie des surfaces (LSGS), and Institut National Polytechnique de Lorraine (INPL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Inorganic chemistry, Oxide, Impedance spectroscopy, Energy Engineering and Power Technology, 02 engineering and technology, Electrolyte, 010402 general chemistry, 7. Clean energy, 01 natural sciences, chemistry.chemical_compound, Lanthanum manganite, Ionic conductivity, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Thin film, Yttria-stabilized zirconia, Intermediate temperature SOFC, Renewable Energy, Sustainability and the Environment, Sputtering, Thin layers, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dielectric spectroscopy, Chemical engineering, chemistry, Solid oxide fuel cell, 0210 nano-technology
Abstract

International audience; One of the present challenges for the commercialisation of planar solid oxide fuel cell is the reduction of its operating temperature, which requires the optimisation of the electrolyte nature and ionic conductivity. Thin layer technology seems suitable to decrease the electrolyte resistance at lower operating temperatures. Bilayered electrolytes are proposed and studied in terms of electrical performance. They are constituted of a gadolinia-doped ceria (GDC) layer (the most suitable candidates for IT solid oxide fuel cells (SOFC) in terms of ionic conductivity) protected by an ultra-thin YSZ layer (as electronic barrier). This work analyses the feasibility of bilayered GDC/YSZ electrolyte elaborated by DC magnetron spectroscopy. The bilayer was deposited on the state-of-the-art SOFC porous cathode, strontium-doped lanthanum manganite (LSM). The analysis of the electrical properties of such layers was performed by impedance spectroscopy. Experimental difficulties in order to obtain reliable results and interpretations are discussed.

Published
2006
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30. Sorption of sulfate ions onto hematite studied by attenuated total reflection-infrared spectroscopy: Kinetics and competition with other ions

Author

M. Fédoroff, G. Lefèvre, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ferric oxide, Perrhenate, Chemistry, Inorganic chemistry, ATR-IR, Infrared spectroscopy, Sorption, [CHIM.MATE]Chemical Sciences/Material chemistry, Inorganic ions, Uranyl, Selenate, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Geophysics, Adsorption, Geochemistry and Petrology, Attenuated total reflection, Sulfate, Spectroscopy
Abstract

In this paper, after a short discussion about the use of attenuated total reflection-infrared spectroscopy (ATR-IR) to study sorption of inorganic ions onto iron oxides, results of ATR-IR spectroscopy of surface complexes adsorbed on hematite are presented. Kinetics of sorption of sulfate ions was followed, showing an equilibrium after half an hour. The infrared band was assigned to a monodentate surface complex with a low contribution of a bidentate complex with help of second-derivative spectral analysis. The effect of several ions ( SeO 4 2 - , ReO 4 - , UO 2 2 + ) after sorption of sulfate (10 μM) was investigated. Selenate ions (10–100 μM) were shown to compete with sulfate ions, while perrhenate ions (1–100 μM) did not desorbed sulfate complexes. Experiments were also carried out in the hematite–sulfate (10 μM)–uranyl (10 μM) system, but no ternary complex was observed.

Published
2006
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31. Temperature-induced surfactant- mediated pre-concentration of uranium assisted by complexation

Author

Jacques Foos, Alain Favre-Réguillon, Gérard Cote, Denis Murat, Micheline Draye, Laboratoire de chimie organique (UMR 7084) (LCO), Synthèse organique et modélisation par apprentissage, Conservatoire National des Arts et Métiers [CNAM] (CNAM), 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)-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)-Conservatoire National des Arts et Métiers [CNAM] (CNAM), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Sciences nucléaires, 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), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Conservatoire National des Arts et Métiers [CNAM] (CNAM)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Conservatoire National des Arts et Métiers [CNAM] (CNAM)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris)

Subjects
General Chemical Engineering, Metal ions in aqueous solution, Inorganic chemistry, chemistry.chemical_element, cloud-point extraction, 010402 general chemistry, 010403 inorganic & nuclear chemistry, 01 natural sciences, uranium, Inorganic Chemistry, chemistry.chemical_compound, 8-hydroxyquinoline, [CHIM.GENI]Chemical Sciences/Chemical engineering, Pulmonary surfactant, Nitric acid, Phase (matter), Waste Management and Disposal, Triton X-114, Aqueous solution, Renewable Energy, Sustainability and the Environment, Organic Chemistry, Extraction (chemistry), 8-Hydroxyquinoline, Uranium, Pollution, 0104 chemical sciences, Fuel Technology, chemistry, Biotechnology
Abstract

Cloud-point extraction (CPE) was used with lipophilic chelating agent to extract uranium(VI) from aqueous solutions. The methodology used is based on the formation of metal complexes soluble in a micellar phase of a non-ionic surfactant, Triton X-114. The metal ions complexes are then extracted into the surfactant-rich phase at a temperature above the cloud-point temperature. The influence of surfactant concentration on extraction efficiency was studied and the advantage of adding 8-hydroxyquinoline (8HQ) as lipophilic chelating agent was evidenced. High extraction efficiency was observed, indicating the feasibility of extracting U(VI) using CPE. This study describes a four-step process—(1) extraction, (2) thermo-induced phase splitting, (3) back-extraction and (4) second phase splitting—for the recovery of uranium from water. In our conditions, the extraction yield is quantitative and the concentration factor obtained is superior to 100. After stripping with a diluted nitric acid solution (pH < 1), the system can be recycled through a new four-step cycle. Copyright © 2006 Society of Chemical Industry

Published
2006
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32. Properties of zirconia thin layers elaborated by high voltage anodisation in view of SOFC application

Author

Rose-Noëlle Vannier, Thierry Pauporté, Armelle Ringuedé, Michel Cassir, Xabier Montero, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallochimie et physicochimie du solide (LCPS), Université de Lille, Sciences et Technologies-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille

Subjects
Materials science, 020209 energy, Impedance spectroscopy, Energy Engineering and Power Technology, Mineralogy, chemistry.chemical_element, 02 engineering and technology, Solid oxide fuel cells, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 0202 electrical engineering, electronic engineering, information engineering, Cubic zirconia, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Composite material, Thin film, Yttria-stabilized zirconia, Zirconium, Thin layers, Renewable Energy, Sustainability and the Environment, Anodizing, Nb-doped zirconia, 021001 nanoscience & nanotechnology, Dielectric spectroscopy, Anodisation, chemistry, Zirconia, Solid oxide fuel cell, 0210 nano-technology
Abstract

In order to adapt the anodisation technique to SOFC application, zirconium and zirconium–niobium alloys were tested in various electrolytic media and applied potentials (up to 420 V). The elaborated ZrO 2 insulating layers were characterised in situ by electrochemical impedance spectroscopy and their thicknesses were determined as ranging up to 1 μm. The effect of thermal annealing treatment of layers prepared in various experimental conditions was investigated by X-ray diffraction (XRD) and solid-state electrochemical impedance spectroscopy in a planar configuration. The effect of the growing conditions on significant parameters such as zirconia crystallite size, zirconia conductivity and activation energy were deduced up to 800 °C. The possibility of using the anodisation process for fuel cell devices is discussed. This study demonstrates that it surely requires the use of more efficient dopants, such as yttria.

Published
2005
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33. In situ X-ray absorption spectroscopy study of lithium insertion into sputtered WO3 thin films

Author

Yvonne Soldo-Olivier, René Faure, Th. Pauporté, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI ), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Institut National Polytechnique de Grenoble (INPG)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Université Joseph Fourier - Grenoble 1 (UJF)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)

Subjects
Absorption spectroscopy, General Chemical Engineering, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Analytical Chemistry, law.invention, chemistry.chemical_compound, law, Electrochemistry, Crystallization, Thin film, X-ray absorption spectroscopy, Extended X-ray absorption fine structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Tungsten trioxide, 0104 chemical sciences, Amorphous solid, chemistry, Lithium, 0210 nano-technology, Lithium insertion
Abstract

International audience; We have performed an in situ X-ray absorption spectroscopy (XAS) study of the effect of Li+ electroinsertion into amorphous sputtered WO3 thin films. Three different potentials have been investigated, which are +0.66, −0.84 and −1.04 V vs SHE. We have estimated by electrochemical and chemical titration that they correspond in LixWO3 to x equal to 0, ca. 0.32 and ca. 0.45, respectively. Shifts of the tungsten LI and LIII-edge positions towards lower energies are observed with lithiation and attributed to the decrease of the W oxidation state. Significant modifications are also observed on the extended X-ray fine structure (EXAFS) spectra. The analysis of first oxygen shells clearly shows an increase of the mean W–O inter-atomic distances upon lithiation which is not due to a crystallization process induced by the cathodic reaction.

Published
2004
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34. Validation and assessment of an accurate approach to the correlation problem in density functional theory: The Kriger–Chen–Iafrate–Savin model

Author

Carlo Adamo, Andreas Savin, Julien Toulouse, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010304 chemical physics, Orbital-free density functional theory, General Physics and Astronomy, Hartree, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Hybrid functional, Fock space, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-COMP-PH]Physics [physics]/Physics [physics]/Computational Physics [physics.comp-ph], Set (abstract data type), Computational chemistry, 0103 physical sciences, Applied mathematics, Density functional theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Local-density approximation, Parametrization, Mathematics
Abstract

International audience; In the present paper, we validate and assess a correlation functional based on the so-called meta generalized gradient approximation, whose form and parameters are entirely derived only from first-principles criteria. In particular, we have carried out a detailed comparison with the most common, parametrized correlation functionals. Next, we propose a new model in which the correlation functional proposed by Kriger, Chen, Iafrate, and Savin is integrated in a hybrid Hartree-Fock/density functional theory scheme. In such approach only one, or two in the G2-optimized version, parameters are adjusted on experimental data, all the others being derived from purely theoretical considerations. The results obtained for a set of molecular properties, including H-bonded complexes, proton transfer model, SN2 reaction and magnetic properties, are satisfactory and comparable, if not better, with those delivered by the most common functionals including heavy parametrization. The way in which the whole functional is derived and the few empirical parameters used make the new exchange-correlation functional widely applicable.

Published
2002
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35. Reaction site-driven regioselective synthesis of AChE inhibitors

Author

Martin Weik, Olga A. Syzgantseva, Ludovic Jean, Laurent Joubert, Vincent Tognetti, Pierre-Yves Renard, Florian Nachon, Gianluca Santoni, Anthony Romieu, Emilia Oueis, Cyrille Sabot, Cyril Ronco, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre d'études prospectives et d'informations internationales (CEPII), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), 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), 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 Recherche Biomédicale des Armées [Brétigny-sur-Orge] (IRBA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 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), and Institut de Recherche Biomédicale des Armées (IRBA)

Subjects
Models, Molecular, Denticity, Stereochemistry, Ligands, Biochemistry, chemistry.chemical_compound, Humans, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Molecular Structure, Chemistry, Organic Chemistry, Regioselectivity, Stereoisomerism, Combinatorial chemistry, Acetylcholinesterase, Cycloaddition, Recombinant Proteins, Enzyme, Biological target, Cyclization, Click chemistry, Aminoquinolines, Click Chemistry, Cholinesterase Inhibitors, Selectivity
Abstract

The enzyme-directed synthesis is an emerging fragment-based lead discovery approach in which the biological target is able to assemble its own multidentate ligands from a pool of building blocks. Here, we report for the first time the use of the human acetylcholinesterase (AChE) as an enzyme for the design and synthesis of new potent heterodimeric huprine-based inhibitors. Both the specific click chemistry site within the protein and the regioselectivity of the Huisgen cycloaddition observed suggest promising alternatives in the design of efficient mono- and dimeric ligands of AChE. Finally, a detailed computational modelling of the click reaction was conducted to further understand the origin of this TGS selectivity.

Published
2014
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36. Modelisation of the SECMin molten salts environment

Author

C. Slim, S. Delpech, Dung Di Caprio, Janusz Stafiej, Marie-Francoise Lucas, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institute of Physical Chemistry (IPC), Polska Akademia Nauk = Polish Academy of Sciences (PAN), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)

Subjects
Surface (mathematics), Partial differential equation, Materials science, Substrate (electronics), Electrochemistry, 7. Clean energy, Corrosion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Electrode, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Coaxial, Composite material, Molten salt, ComputingMilieux_MISCELLANEOUS, Simulation
Abstract

We develop a cellular automata modelisation of SECM experiments to study corrosion in molten salt media for generation IV nuclear reactors. The electrodes used in these experiments are cylindrical glass tips with a coaxial metal wire inside. As the result of simulations we obtain the current approach curves of the electrodes with geometries characterized by several values of the ratios of glass to metal area at the tip. We compare these results with predictions of the known analytic expressions, solutions of partial differential equations for flat uniform geometry of the substrate. We present the results for other, more complicated substrate surface geometries e. g. regular saw modulated surface, surface obtained by Eden model process, ...

Published
2014
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37. Phase behavior under the averaging over disorder realizations

Author

E.V. Vakarin, W. Dong, J.P. Badiali, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Supérieur des Mécaniques et Matériaux Avancés (ISMANS CESI), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Statistics and Probability, Phase transition, Statistical Mechanics (cond-mat.stat-mech), Condensed matter physics, Phase (waves), FOS: Physical sciences, Sampling (statistics), Context (language use), Statistical mechanics, Condensed Matter Physics, 01 natural sciences, 010305 fluids & plasmas, Interpretation (model theory), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Mean field theory, 0103 physical sciences, Range (statistics), Statistical physics, 010306 general physics, ComputingMilieux_MISCELLANEOUS, Condensed Matter - Statistical Mechanics, Mathematics
Abstract

Effects of the averaging over disorder realizations (samples) on the phase behavior are analyzed in terms of the mean field approximation for the random field Ising model with infinite range interactions. It is found that the averaging is equivalent to a drastic modification in the statistics of the quenched variables. In its turn, this lowers the critical temperature of a second-order phase transition or, depending on the sampling, even suppresses the ordered phase. Possible first order transitions are shown to be softened by the sample averaging. Common issues and differences in the interpretation of these effects in the context of the simulation and experimental studies are discussed.

Published
2013
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38. Modelling the adsorption of phenolic acids onto $\alpha$,$\gamma$-alumina particles

Author

Pauline, Moreau, Collette-Maatouk, Sonia, Gareil, Pierre, Reiller, Pascal E., Laboratoire de développement Analytique Nucléaire Isotopique et Elémentaire (LANIE), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by the RSTB program (RBPCH project) from the CEA, and the French Direction Générale de l’Armement (DGA)

Subjects
Adorption, phenolic acid, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, [SDE.MCG]Environmental Sciences/Global Changes, dissolution, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, alumina, surface complexation model
Abstract

International audience; Adsorption of three phenolic acids, namely parahydroxybenzoic acid (4-hydroxybenzoic acid, H$_2$Phb), protocatechuic acid (3,4-dihydroxybenzoic acid, H$_2$Proto) and gallic acid (3,4,5-trihydroxybenzoic acid, H$_2$Gal) onto $\alpha$,$\gamma$-Al$_2$O$_3$ particles was studied vs. ligand concentration at pH 5.0, and vs. pH. The oxide surface was characterized with both potentiometric titrations and electrophoretic measurements; a difference in the point of zero salt effect (PZSE) and the isoelectric point (IEP) was evidenced, which could be attributed to the presence of impurities or to the heterogeneity of the oxide. The potentiometric titration experiments lead to the determination of a PZSE of 8.5. Moreover, the particular shape of the curves were fitted in the framework of the constant capacitance model (CCM), using FITEQL 4.0 software, to determine the oxide parameters (protolytic properties and site density). The electrophoretic measurements were fitted in the framework of the double diffuse layer model (DLM) and an IEP of 9.5 was determined. The constant-pH isotherms of the acids were fitted using the CCM. Constant-pH isotherms of H$_2$Gal and H$_2$Proto onto the Al$_2$O$_3$ surface sites at pH 5 were similar. Two adsorption sites of different affinities were clearly evidenced for H$_2$Gal and can also be proposed for H$_2$Proto. H$_2$Phb showed a lower affinity for the surface than the two other acids, as the logK$_{sorb}$ for H$_2$Phb is one and a half time lower than the one for H$_2$Proto when adsorption is described with one adsorption site. As expected for a carboxylic acid, adsorption of H$_2$Phb decreased with pH and experimental data were well fitted using three adsorbed species $\equiv$MOH$_2$H$_2$Phb$^+$, $\equiv$MHPhb$^−$, and $\equiv$MPhb$^−$). Adsorption of H$_2$Proto and H$_2$Gal did not change significantly upon increasing pH, meaning that the different functional groups on the aromatic ring (carboxylate and phenolate) were involved in adsorption as pH increases. Dissolution of the oxide was also estimated by measuring the amount of soluble aluminum at pH 5. Increasing acid concentration promoted dissolution, especially for the low concentration range ([acid] < 3 mmol L$^{−1}$), but higher acid concentration lowers the increase of the solubility increase, likely due to adsorption on surface of an aluminum-organic complex.

Published
2013
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39. Modeling charge transfer in fuel cells

Author

Mangiatordi, Giuseppe, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris VI, Carlo Adamo, and Bupmc, Theses

Subjects
Membrane à échange de protons (PEM), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Dynamique Moléculaire, Mécanisme de Grotthuss, Théorie du fonctionnelle de la densité (DFT), Imidazole, Réaction du transfert de proton
Abstract

The performances of Proton Exchange Membrane Fuel Cells (PEMFCs) are strongly influenced by the proton conductivity of the solid electrolyte. The azole-based polymers are among the most promising materials to improve the effectiveness of these systems. A theoretical study of proton transfer (PT) reaction in protonated imidazole, 1,2,3-triazole, and tetrazole dimers has been performed. The developed DFT protocol has been applied on more complex systems. The results obtained from the investigation performed on Poly(4-vinyl-imidazole) (P4VI) suggest that the commonly accepted (Grotthuss) conduction mechanism, based on a sequential proton transfer between imidazole moieties, could be impeded in this system because of the backbone constraint. Such a study, performed through a combined Density Functional Theory (DFT) / Molecular Dynamics simulations (MD) approach, allowed to hypothesize an alternative mechanism of conduction. A further study performed on phosphoric-acid (H3PO4) included models has revealed as low concentrations of H3PO4 could allow for the Grotthuss mechanism despite the polymeric constraint. The underpinning role played by the backbone topology on the conductivity has been then confirmed by the investigation carried out on a second polymer: the wire tethering position can strongly affect the mechanism of conduction. In short, the obtained simulations show how the polymeric matrix play a crucial role in the conductivity mechanism. The present research represents a first effort for a more systematic study of the relationship between backbone connectivity and efficiency of the charge transport, Les performances des piles à combustible à échange de protons (PEMFC) sont fortement influencées par la conductivité protonique de l'électrolyte solide. Les polymères à base d'azole sont parmi les matériaux les plus prometteurs pour améliorer l'efficacité de ces systèmes. Une étude théorique de réaction du transfert de protons (PT) en dimères protonée du imidazole, 1,2,3-triazole et tétrazole a été effectuée. Le protocole DFT mis au point a été appliqué sur des systèmes plus complexes. Les résultats obtenus à partir de l'étude réalisée sur le poly(4-vinyl-imidazole) (P4VI) suggèrent que le mécanisme de conduction communément admis (Grotthuss) pourrait être entravé dans ce système en raison de l'effet de la matrice polymérique. Cette étude, réalisée par le biais d'une approche combinée théorie du fonctionnelle de la densité (DFT) / simulations de Dynamique Moléculaire (MD), a permis de proposer un mécanisme alternatif de conduction. Une étude supplémentaire réalisée sur des modèles avec du acide phosphorique (H3PO4) a révélé que faibles concentrations de H3PO4 pourrait permettre le mécanisme de Grotthuss malgré la matrice polymérique. Le rôle crucial joué par la matrice polymérique sur la conductivité a été ensuite confirmée par l'étude menée sur un second polymère : la position d'attache du imidazole peut fortement affecter le mécanisme de conduction. En bref, les simulations obtenus montrent comment la matrice polymérique jouent un rôle crucial dans le mécanisme de la conductivité. La présente recherche représente une première tentative pour une étude plus systématique de la relation entre la connectivité de la matrice polymère et l'efficacité du transport de charge

Published
2012

40. Cloud point and solvent extraction study of uranium(VI) by 8-hydroxyquinoline

Author

Szymczak , Jonathan, Legeai , Sophie, Diliberto , Sebastien, Migot , Sylvie, Stein , Nicolas, Boulanger , Clotilde, Chatel , Grégory, Draye , Micheline, Favre-Reguillon , Alain, Murat , Denis, Cote , Gérard, Institut Jean Lamour ( IJL ), Université de Lorraine ( UL ) -Centre National de la Recherche Scientifique ( CNRS ), Leibniz Institute of Plant Genetics and Crop Plant Research, Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Génie des Procédés Catalytiques ( LGPC ), Université Claude Bernard Lyon 1 ( UCBL ), and Université de Lyon-Université de Lyon-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS )

Subjects
[ SDE ] Environmental Sciences, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, [ CHIM ] Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2012
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41. H2O2/NaHCO3-mediated enantioselective epoxidation of olefins in NTf2-based ionic liquids and under ultrasound

Author

Micheline Draye, Bruno Andrioletti, Anaïs Mirabaud, Gregory Chatel, Nathalie Kardos, Thomas Rossi, Catherine Goux-Henry, Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Catalyse Synthèse et Environnement (CASYEN), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires ( ICBMS ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon ( INSA Lyon ), Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 ( C2P2 ), Centre National de la Recherche Scientifique ( CNRS ) -École supérieure de Chimie Physique Electronique de Lyon ( CPE ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon, Catalyse Synthèse et Environnement ( CASYEN ), Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS ) -Université Claude Bernard Lyon 1 ( UCBL ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), and Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS )

Subjects
Epoxidation, 010402 general chemistry, 01 natural sciences, Peroxide, [ CHIM ] Chemical Sciences, Catalysis, [ SDE ] Environmental Sciences, chemistry.chemical_compound, Manganese porphyrin, Ultrasound, Organic chemistry, [CHIM]Chemical Sciences, Enantioselective catalysis, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Mn-porphyrin, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Enantioselective synthesis, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Ionic liquids, Ionic liquid, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry
Abstract

International audience; The bicarbonate-activated peroxide (BAP) system has been shown to constitute an excellent and versatile combination for the epoxidation of olefins. Herein, we demonstrate that the benign H2O2/NaHCO3 oxidative combination can be used for the enantioselective epoxidation of olefins using a chiral manganese porphyrin as a catalyst. This unprecedented result was made possible by the use of an ionic liquid with ultrasound, which leads to the activation of Mn-porphyrin catalysis.

Published
2012
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42. Ultrasound and ionic liquid: an efficient combination to tune the mechanism of alkenes epoxidation

Author

Nathalie Kardos, Gregory Chatel, Catherine Goux-Henry, Micheline Draye, Bruno Andrioletti, Joël Suptil, Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Catalyse Synthèse et Environnement (CASYEN), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires ( ICBMS ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon ( INSA Lyon ), Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Catalyse Synthèse et Environnement ( CASYEN ), Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS ) -Université Claude Bernard Lyon 1 ( UCBL ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), and Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS )

Subjects
Acoustics and Ultrasonics, Inorganic chemistry, Ionic Liquids, Alkenes, 010402 general chemistry, Photochemistry, Radiation Dosage, 01 natural sciences, Peroxide, [ CHIM ] Chemical Sciences, Catalysis, High-Energy Shock Waves, Inorganic Chemistry, Ultrasonic irradiation, [ SDE ] Environmental Sciences, chemistry.chemical_compound, Sonication, Chemical Engineering (miscellaneous), Environmental Chemistry, Imidazole, Radiology, Nuclear Medicine and imaging, ComputingMilieux_MISCELLANEOUS, Olefin fiber, 010405 organic chemistry, business.industry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Ultrasound, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, chemistry, Ionic liquid, Epoxy Compounds, Ultrasonic sensor, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, business
Abstract

International audience; In this proof of concept study, the advantageous properties of both H(2)O(2)/NaHCO(3)/imidazole/Mn(TPP)OAc oxidation system and MOPyrroNTf(2) ionic liquid have been combined under ultrasonic irradiation to give an exceptionally favorable environment for Mn(TPP)OAc catalyzed olefin oxidations. The results reveal the crucial role played by the ultrasonic irradiations that influence drastically the oxidation process. In MOPyrroNTf(2) and under ultrasonic irradiation, the mechanism probably involves an oxo-manganyl intermediate at the expense of the classical bicarbonate-activated peroxide route.

Published
2012
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43. Correlating the structure and composition of ionic liquids with their toxicity on Vibrio fischeri: A systematic study

Author

Micheline Draye, Nicolas Papaiconomou, Sylvie Viboud, Dominique Fontvieille, Aurélien Cortesi, Gregory Chatel, Centre Alpin de Recherche sur les Réseaux Trophiques et Ecosystèmes Limniques (CARRTEL), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut National de la Recherche Agronomique (INRA), Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Université Grenoble Alpes (UGA), Centre Alpin de Recherche sur les Réseaux Trophiques et Ecosystèmes Limniques ( CARRTEL ), Institut National de la Recherche Agronomique ( INRA ) -Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Liquides Ioniques et Interfaces Chargées ( LI2C ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -ESPCI ParisTech-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National de la Recherche Agronomique (INRA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), and Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])

Subjects
EXTRACTION, Environmental Engineering, Tetrafluoroborate, Luminescence, PHASE, Health, Toxicology and Mutagenesis, VISCOSITIES, Ionic Liquids, Vibrio fischeri, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, [ SDE ] Environmental Sciences, chemistry.chemical_compound, Structure-Activity Relationship, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, WATER, Environmental Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Imide, TEMPERATURE, Waste Management and Disposal, Dicyanamide, IMIDAZOLIUM, ComputingMilieux_MISCELLANEOUS, Tetraphenylborate, Toxicity, Thiocyanate, 021001 nanoscience & nanotechnology, Pollution, Aliivibrio fischeri, 0104 chemical sciences, EC50, ECOTOXICITY, chemistry, PHYSICOCHEMICAL PROPERTIES, Ionic liquid, ELECTRODEPOSITION, DICYANAMIDE ANION, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, Pyridinium, 0210 nano-technology, Water Pollutants, Chemical
Abstract

International audience; A systematic screening of the toxicity of ionic liquids (IL) towards Vibrio fischeri, a bioluminescent marine bacteria generally used in ecotoxicological bioassays, was carried out. The objectives of this work were to find hydrophilic or hydrophobic low toxicity IL and to investigate structure-toxicity relationship of IL Toxicity of 54 IL to V. fischeri have been measured, some referring to new IL based on quinuclidinol or tropinol and some to generic IL (i.e., imidazolium, pyridinium, pyrrolidinium or piperidinium). For 47 of them, toxicity values have not been reported elsewhere. Water-soluble IL containing hydrophilic anions halide, thiocyanate, dicyanamide, trifluoromethansulfonate were studied. Some IL were found to exhibit very low toxicity towards V. fisheri. Hydrophobic IL based on bis(trifluoromethanesulfonyl)imide, tetrafluoroborate tetraphenylborate and tetracyanoborate were also studied. Toxicity was measured in a consistent way starting from aqueous solutions saturated with IL. The least toxic hydrophobic IL found in this study was [EMIM][B(CN)(4)]. A multifactorial analysis was found to be convenient for finding relevant structure parameters influencing the toxicity of IL. From this analysis, the planarity of the cation ring appeared to be a relevant parameter. Finally, good linear correlations were found when toxicity of IL was plotted either against the number of aliphatic carbons surrounding a pyridinium cation or the total number of carbons of a cation. (C) 2012 Elsevier B.V. All rights reserved.

Published
2012
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44. Generalized gradient exchange functionals based on the gradient-regulated connection: a new member of the TCA family

Author

Carlo Adamo, Pietro Cortona, Éric Brémond, Henry Chermette, Diane Pilard, Ilaria Ciofini, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), CHEMOD - CHEmometry et MODélisation moléculaire (2011-2014), Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structures, Propriétés et Modélisation des solides (SPMS), Institut de Chimie du CNRS (INC)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)

Subjects
Physics, Generalized gradient, 010304 chemical physics, 0103 physical sciences, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Statistical physics, Physical and Theoretical Chemistry, Type (model theory), 010306 general physics, 01 natural sciences, Hybrid functional, Connection (mathematics)
Abstract

International audience; A new type of generalized gradient approximation exchange functional coupled with the TCA correlation model has been proposed. Based on gradient-regulated connection, this exchange functional is able to mix performances of a modified PBE for the bulk region, to those of the PW91 for the asymptotic one, leading to a significant improvement on the modelization of weak interacting systems, while keeping a good accuracy for the atomization energies.

Published
2012
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45. New insight into indium electrochemistry in a Tf2N-based room-temperature ionic liquid

Author

Szymczak , Jonathan, Legeai , Sophie, Diliberto , Sebastien, Migot , Sylvie, Stein , Nicolas, Boulanger , Clotilde, Chatel , Grégory, Draye , Micheline, Traoré , Youssouf, Arrachart , Guilhem, Pellet-Rostaing , Stéphane, Institut Jean Lamour ( IJL ), Université de Lorraine ( UL ) -Centre National de la Recherche Scientifique ( CNRS ), Leibniz Institute of Plant Genetics and Crop Plant Research, Laboratoire de Chimie Moléculaire et Environnement ( LCME ), Université Grenoble Alpes [Saint Martin d'Hères]-Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ), Laboratoire d'Electrochimie et de Chimie Analytique ( LECA ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL ( ENSCP ) -Centre National de la Recherche Scientifique ( CNRS ), Département de Chimie Moléculaire ( DCM ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Institut de Chimie Séparative de Marcoule ( ICSM - UMR 5257 ), Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires ( ICBMS ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon ( INSA Lyon ), and Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique ( CNRS )

Subjects
[ SDE ] Environmental Sciences, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, [ CHIM ] Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2011
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46. Packings of deformable spheres

Author

Jorge Peixinho, Shomeek Mukhopadhyay, Columbia University [New York], City College of New York [CUNY] (CCNY), City University of New York [New York] (CUNY), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
genetic structures, Biophysics, Geometry, Atomic packing factor, 01 natural sciences, Power law, 010305 fluids & plasmas, Stress (mechanics), Rheology, 0103 physical sciences, Pressure, Composite material, 010306 general physics, Fluorescent Dyes, Mathematics, Normal force, Water, Hydrogels, equipment and supplies, Faceting, Microscopy, Fluorescence, SPHERES, Stress, Mechanical, sense organs, Deformation (engineering), [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], Algorithms
Abstract

International audience; We present an experimental study of disordered packings of deformable spheres. Fluorescent hydrogel spheres immersed in water together with a tomography technique enabled the imaging of the three-dimensional arrangement. The mechanical behavior of single spheres subjected to compression is first examined. Then the properties of packings of a randomized collection of deformable spheres in a box with a moving lid are tested. The transition to a state where the packing withstands finite stresses before yielding is observed. Starting from random packed states, the power law dependence of the normal force versus packing fraction or strain at different velocities is quantified. Furthermore, a compression-decompression sequence at low velocities resulted in rearrangements of the spheres. At larger packing fractions, a saturation of the mean coordination number took place, indicating the deformation and faceting of the spheres.

Published
2011
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47. Density-functional calculations for large systems: can GGA functionals be competitive with hybrid functionals?

Author

Vincent Tognetti, Pietro Cortona, Carlo Adamo, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structures, Propriétés et Modélisation des solides (SPMS), and Institut de Chimie du CNRS (INC)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)

Subjects
Class (set theory), Mathematical optimization, Hot Temperature, Biophysics, Health Informatics, 01 natural sciences, General Biochemistry, Genetics and Molecular Biology, 0103 physical sciences, Computational Science and Engineering, Applied mathematics, Computer Simulation, 010306 general physics, Mathematics, Models, Statistical, 010304 chemical physics, Computational Biology, Reproducibility of Results, Hydrogen Bonding, Models, Theoretical, Computer Science Applications, Hybrid functional, Constraint (information theory), Minnesota Functionals, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Quantum Theory, Density functional theory, Local-density approximation, Algorithms, Software
Abstract

International audience; Two recently proposed correlation functionals, TCA and RevTCA, belonging to the generalized-gradient approximation (GGA) class, are briefly presented and their performances are discussed. The emphasis is put on the comparison with hybrid functionals, which are often the preferred ones for applications to molecular (but not to solid-state) systems. We show that the TCA and RevTCA performances are not far from those of hybrid functionals such as B3LYP or PBE0 when standard tests are performed and can be even better when less standard systems are considered. This is particularly interesting in view of applications to nano-scale systems or systems of biological interest, and, in general, in all the cases where the computer time requirements become an important constraint

Published
2010
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48. Photovoltaic energy: bolts and perspective

Author

Cramail, Henri, Hadziioannou, Georges, Hirsch, Lionel, Lincot, Daniel, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Laboratoire de l'intégration, du matériau au système (IMS), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université Sciences et Technologies - Bordeaux 1, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), and RICHARD, Dominique

Subjects
Solar cells, [CHIM.POLY] Chemical Sciences/Polymers, thin layers, [CHIM.POLY]Chemical Sciences/Polymers, active layer, conjugated polymers, silicon
Abstract

International audience; Photovoltaic energy: bolts and perspective This paper aims to present and compare the technologies used and envisaged to be used in the future for photovoltaic conversion. In addition to devices based on silicon (be they monocrystalline, polycrystalline, thin layer and so on), which have at least reached a certain industrial maturity, other emerging routes based on inorganic thin layer devices (such as CdTe and CIS types) and semi-conducting polymers are discussed. All these technologies are considered to be complementary and will be necessary to effectively confront the energy needs of the 21(st) century.

Published
2010

49. Procédés de conversion d'énergie : batteries, piles à combustible et procédés non électriques

Author

Lapicque, F., Cassir, M., Chartier, Thierry, Croguennec, L., Dirand, M., Geffroy, Pierre-Marie, Levasseur, A., Vannier, R.N., Laboratoire des Sciences du Génie Chimique (LSGC), Institut National Polytechnique de Lorraine (INPL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Axe 1 : procédés céramiques, Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Laboratoire de Thermodynamique des Milieux Polyphasés (LTMP), Institut National Polytechnique de Lorraine (INPL), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
Conversion d'énergie, batteries, récupération d'énergie, biomasse, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, piles à combustible, hydrogène, ComputingMilieux_MISCELLANEOUS
Abstract

National audience; Le monde de l'énergie et de sa conversion est un domaine qui intéresse fortement les ingénieurs chimistes, notamment quand cette conversion s'accompagne d'une transformation de la matière. Pour les exemples de technologies concernées - batteries, piles à combustible et procédés de récupération de l'énergie, hydrogène et biomasse -, deux approches des travaux entrepris dans les écoles de la Fédération Gay-Lussac sont décrites : les avancées en sciences chimique et des matériaux, et la contribution des sciences de l'ingénieur

Published
2010

50. How the Choice of a Computational Model Could Rule the Chemical Interpretation: The Ni(II) Catalyzed Ethylene Dimerization as a Case Study (pub)

Author

Tognetti, Vincent, Le Floch, Pascal, Adamo, Carlo, Laboratoire d'Electrochimie et de Chimie Analytique (LECA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétéroéléments et Coordination (DCPH), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Le Goff, Xavier

Subjects
[CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2010

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