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129 results on '"Dipartimento di Scienze Chimiche"'

1. Structural and Luminescent Properties of Homoleptic Silver(I), Gold(I), and Palladium(II) Complexes with nNHC0-tz NHC Heteroditopic Carbene Ligands

Author: Monticelli, Marco, Baron, Marco, Tubaro, Cristina, Bellemin-Laponnaz, Stéphane, Graiff, Claudia, Bottaro, Gregorio, Armelao, Lidia, Orian, Laura, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Dipartimento di Scienze Chimiche [Padova], Universita degli Studi di Padova, Dipartimento di Scienze Chimiche, University of Parma = Università degli studi di Parma [Parme, Italie], Institute of Condensed Matter Chemistry and Technologies for Energy (ICMATE), and Consiglio Nazionale delle Ricerche (CNR)
Subjects: heteroditopic ligands, [CHIM.CRIS]Chemical Sciences/Cristallography, dinuclear complexes, blue luminescence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, N-heterocyclic carbenes, relativistic TD-DFT calculations
Abstract: International audience; Novel silver(I), gold(I), and palladium(II) complexes were synthesized with bidentate heteroditopic carbene ligands that combine an imidazol-2-ylidene (nNHC) with a 1,2,3-triazol-5-ylidene (tzNHC) connected by a propylene bridge. The silver(I) and gold(I) complexes were dinuclear species, [M2(nNHC-tzNHC)2](PF6)2 (M = Ag or Au), with the two bidentate ligands bridging the metal centers, whereas in the palladium(II) complex [Pd(nNHC-tzNHC)2](PF6)2, the two ligands were chelated on the same metal center. Because of the presence of two different carbene units, isomers were observed for the gold(I) and palladium(II) complexes. The molecular structures of the head-to-tail isomer for gold(I) complexes, with a twisted or folded-syn conformation of the bridge between the carbene units, were determined by X-ray diffraction analysis. The study was completed with a systematic structural investigation through density functional theory (DFT) calculations. For palladium(II) species, the head-to-head form was structurally characterized. The dinuclear gold(I) complexes were emissive in the solid state in the blue region (PLQY up to 8%); time-dependent density functional theory (abbreviated as TD-DFT) calculations disclosed that the absorption bands have metal-to-ligand-charge-transfer character and evidenced that the emission occurs from the T1 level (phosphorescence).
Published: 2019

2. Middle Pennsylvanian vegetation of the San Giorgio Basin, southern Sardinia (Italy)

Author: Paola Pittau, Christopher J. Cleal, Evelyn Kustatscher, Giovanni Giuseppe Scanu, Carla Buosi, National Museum of Wales - Cardiff, Botanique et Modélisation de l'Architecture des Plantes et des Végétations (UMR AMAP), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut National de la Recherche Agronomique (INRA)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD [France-Sud]), Dipartimento di scienze Chimiche Universita di Cagliari, DIPARTIMENTO DI SCIENZE CHIMICHE, Dipartimento di Scienze Chimiche e Geologiche, Universita degli Studi di Cagliari [Cagliari], Universität München (Ludwig-Maximilians-Universität München and Bayerische Staatssammlung für Paläontologie und Geobiologie), and Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut National de la Recherche Agronomique (INRA)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut de Recherche pour le Développement (IRD [France-Sud])
Subjects: 010506 paleontology, Palaeobotany, Macrofossil, Biostratigraphy, Geology, Vegetation, Structural basin, [SDV.BV.BOT]Life Sciences [q-bio]/Vegetal Biology/Botanics, 010502 geochemistry & geophysics, Sardinia, [SDV.BID.SPT]Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, 01 natural sciences, Moscovian, Tectonics, Paleontology, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, Pennsylvanian, Paleobotany, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, 0105 earth and related environmental sciences
Abstract: The small, intramontane San Giorgio Basin in southwestern Sardinia has yielded plant macrofossils dominated by sphenophytes, but with subsidiary pteridosperms, ferns, (?)noeggerathians and cordaitanthaleans. They belong to the upper part of theCrenulopteris acadicaZone or possibly theOdontopteris cantabricaZone, indicating a late Asturian or Cantabrian (≡ late Moscovian) age. They therefore correlate with the post-Leonian deposits in northern Spain, the Nýřany Member in Western and Central Bohemia, and the Llantwit Beds in South Wales. The presence of post-tectonic deposits of this age is further evidence of the widespread influence of the Leonian Phase of tectonic activity in middle Asturian times, whose effect can be observed across Europe. The San Giorgio Basin is therefore a late Variscan rather than post-Variscan basin.
Published: 2017

3. Preparation of tocotrienol derivatives, pharmaceutical composition and method of use in 5-lipoxygenase related diseases

Author: Richomme, Pascal, Helesbeux, Jean-Jacques, Guilet, David, Seraphin, Denis, Stuppner, Hermann, Waltenberger, Birgit, Schuster, Daniela, Temmi, Veronika Sophie, Koeberle, Andreas, Werz, Oliver, Substances d'Origine Naturelle et Analogues Structuraux (SONAS), Université d'Angers (UA), Department of Pharmacology and Toxicology and Center for Molecular Biosciences Innsbruck (CMBI), Eberhard Karls Universität Tübingen = Eberhard Karls University of Tuebingen, Dipartimento di Scienze Chimiche, and DIPARTIMENTO DI SCIENZE CHIMICHE
Subjects: [CHIM]Chemical Sciences
Published: 2017

4. Effect of Chemical Composition on Molecular Mobility and Phase Coupling in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with Different Comonomer Contents

Author: Fosse, Clément, Esposito, Antonella, Lemechko, Pierre, Salim, Yoga Sugama, Causin, Valerio, Gaucher, Valérie, Bruzaud, Stéphane, Sudesh, Kumar, Delbreilh, Laurent, Dargent, Eric, Groupe de physique des matériaux (GPM), 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)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche Dupuy de Lôme (IRDL), École Nationale d'Ingénieurs de Brest (ENIB)-Université de Bretagne Sud (UBS)-Université de Brest (UBO)-École Nationale Supérieure de Techniques Avancées Bretagne (ENSTA Bretagne)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche [Padova], Università degli Studi di Padova = University of Padua (Unipd), Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Universiti Sains Malaysia (USM)
Subjects: [PHYS]Physics [physics], Environmental Engineering, Polymers and Plastics, Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; Two series of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) with different amounts of hydroxyvalerate (HV) and hydroxyhexanoate (HHx) units are compared. The influence of chemical composition on the molecular mobility in quenched samples is discussed, as well as the consequences on the aptitude to crystallize and the microstructures developed during cold-crystallization. In both quenched PHBHV and PHBHHx, Tg decreases as the content of comonomer unit increases. The HHx units (propyl side-groups) are better molecular spacers and produce a stronger Tg shift as compared to the HV units (ethyl side-groups). Copolymerization has no striking effect on the width of the glass transition and the cooperativity length in quenched samples, but in cold-crystallized samples the glass transition is dramatically broadened. When the fully amorphous copolymers are heated from the glassy state to room temperature, crystallization occurs but is largely disrupted, suggesting that the molecular environment in the amorphous phase is significantly changed. The HHx units, which are excluded from the host crystals, delay and slow down the crystallization kinetics in a stronger way as compared to the HV units, which can partially co-crystallize. The obtained crystalline phases are prone to reorganization and the residual amorphous phases appear to have strong differences in composition and large density fluctuations. A practical consequence is that microstructures with different coupling between phases, and thus different properties and stability over time, can be obtained by controlling the nature and content of the comonomer units.
Published: 2023

5. A Cenozoic-style scenario for the end-Ordovician glaciation

Author: Aicha Achab, Marie-Pierre Dabard, Thijs R.A. Vandenbroucke, Esther Asselin, André Desrochers, Jean-François Ghienne, Florentin Paris, Steven Wickson, Ján Veizer, Claude Farley, Alfredo Loi, Institut de physique du globe de Strasbourg (IPGS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Earth Sciences [Ottawa], University of Ottawa [Ottawa], Géosystèmes - UMR 8217 (Géosystèmes), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Sciences et Technologies, Centre Eau Terre Environnement [Québec] (INRS - ETE), Institut National de la Recherche Scientifique [Québec] (INRS), Tosca Consultants, PME, Géosciences Rennes (GR), Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Dipartimento di Scienze Chimiche e Geologiche, University of Ottawa, Dept. of Geology, Marion Hall, Ottawa , ON, Canada, Université de Lille, Sciences et Technologies-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Geological Survey of Canada [Québec] (GSC Québec), Geological Survey of Canada - Office (GSC), Natural Resources Canada (NRCan)-Natural Resources Canada (NRCan), Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, NSERC, Insu SYSTER, ANR-12-BS06-0014,SeqStrat-Ice,Les glaciations du passé: leçons pour un modèle de stratigraphie séquentielle dédié aux systèmes glaciaires(2012), Université de Strasbourg (UNISTRA)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Géosystèmes - UMR 8217, Université de Lille, Sciences et Technologies-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR), Université de Rennes (UR)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Cagliari = University of Cagliari (UniCa), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010506 paleontology, MASS EXTINCTION, ANTI-ATLAS, Paleozoic, General Physics and Astronomy, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Biology, 010502 geochemistry & geophysics, 01 natural sciences, MOROCCO, Article, General Biochemistry, Genetics and Molecular Biology, Paleontology, ISOTOPIC EVIDENCE, Phanerozoic, Deglaciation, Glacial period, 0105 earth and related environmental sciences, EARLY SILURIAN GLACIATION, Extinction event, CLIMATE-CHANGE, Multidisciplinary, Last Glacial Maximum, General Chemistry, ENVIRONMENTAL-CHANGES, ANTICOSTI ISLAND, SEA-LEVEL CHANGE, 13. Climate action, [SDU]Sciences of the Universe [physics], Earth and Environmental Sciences, Ordovician, Cenozoic, HIGH-RESOLUTION
Abstract: The end-Ordovician was an enigmatic interval in the Phanerozoic, known for massive glaciation potentially at elevated CO2 levels, biogeochemical cycle disruptions recorded as large isotope anomalies and a devastating extinction event. Ice-sheet volumes claimed to be twice those of the Last Glacial Maximum paradoxically coincided with oceans as warm as today. Here we argue that some of these remarkable claims arise from undersampling of incomplete geological sections that led to apparent temporal correlations within the relatively coarse resolution capability of Palaeozoic biochronostratigraphy. We examine exceptionally complete sedimentary records from two, low and high, palaeolatitude settings. Their correlation framework reveals a Cenozoic-style scenario including three main glacial cycles and higher-order phenomena. This necessitates revision of mechanisms for the end-Ordovician events, as the first extinction is tied to an early phase of melting, not to initial cooling, and the largest δ13C excursion occurs during final deglaciation, not at the glacial apex., Claims that the end-Ordovician Earth was characterized by giant ice sheets, yet paradoxically warm oceans and elevated CO2 levels are open to debate. Here, Ghienne et al. examine sedimentary records from low and high palaeolatitude settings and propose a revision of the mechanisms for end-Ordovician events.
Published: 2014

6. The unique photophysical properties of the Peridinin-Chlorophyll-a-Protein

Author: Riccardo Spezia, Marilena Di Valentin, Donatella Carbonera, Alberto Mezzetti, Dipartimento di Scienze Chimiche [Padova], Università degli Studi di Padova = University of Padua (Unipd), 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), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Service de Bioénergétique, Biologie Stucturale, et Mécanismes (SB2SM), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Universita degli Studi di Padova, Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Dipartimento di Scienze Chimiche, Universita degli Studi di Padova = University of Padua = Université de Padoue, 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 ), Laboratoire de Spectrochimie Infrarouge et Raman - UMR 8516 ( LASIR ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), Service de Bioénergétique, Biologie Stucturale, et Mécanismes ( SB2SM ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Biologie Intégrative de la Cellule ( I2BC ), and Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS )
Subjects: Energy transfer, Protozoan Proteins, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, peridinin-chlorophyll-protein, chemistry.chemical_compound, Molecular Biology, Chemistry, photoprotection, Cell Biology, General Medicine, Photochemical Processes, 021001 nanoscience & nanotechnology, light-harvesting, Carotenoids, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Peridinin, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, Dinoflagellida, peridinin, 0210 nano-technology
Abstract: Peridinin-Chlorophyll-a-Proteins (PCPs) are water-soluble light harvesting complexes from dinoflagellates. They have unique light-harvesting and energy transfer properties which have been studied in details in the last 15 years. This review aims to give an overview on all the main aspects of PCPs photophysics, with an emphasis on some aspects which have not been reviewed in details so far, such as vibrational spectroscopy studies, theoretical calculations, and magnetic resonance studies. A paragraph on the present development of PCPs towards technological applications is also included.
Published: 2014

7. The Astounding World of Glycans from Giant Viruses

Author: Immacolata Speciale, Anna Notaro, Chantal Abergel, Rosa Lanzetta, Todd L. Lowary, Antonio Molinaro, Michela Tonetti, James L. Van Etten, Cristina De Castro, Università degli Studi di Napoli 'Parthenope' = University of Naples (PARTHENOPE), Information génomique et structurale (IGS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Academia Sinica, Università degli studi di Genova = University of Genoa (UniGe), University of Nebraska–Lincoln, University of Nebraska System, European Project: 832601,Cells and giant viruses: a win-win co-evolution, University of Naples Federico II = Università degli studi di Napoli Federico II, Dipartimento di Scienze Chimiche, University of Alberta, University of Genova, University of Nebraska [Kearney] (UNK), Speciale, Immacolata, Notaro, Anna, Abergel, Chantal, Lanzetta, Rosa, Lowary, Todd L, Molinaro, Antonio, Tonetti, Michela, Van Etten, James L, and De Castro, Cristina
Subjects: Giant Viruse, Glycoside Hydrolases, Glycoside Hydrolase, Carbohydrates, Glycosyltransferases, General Chemistry, Genomics, Peptides and proteins, Viral Proteins, Polysaccharides, Giant Viruses, Viruses, [SDV.MP.VIR]Life Sciences [q-bio]/Microbiology and Parasitology/Virology, Viral Protein, Infectious diseases, Glycoprotein, Sugar, Sugars, Polysaccharide, Glycosyltransferase, Glycoproteins
Abstract: International audience; Viruses are a heterogeneous ensemble of entities, all sharing the need for a suitable host to replicate. They are extremely diverse, varying in morphology, size, nature, and complexity of their genomic content. Typically, viruses use host-encoded glycosyltransferases and glycosidases to add and remove sugar residues from their glycoproteins. Thus, the structure of the glycans on the viral proteins have, to date, typically been considered to mimick those of the host. However, the more recently discovered large and giant viruses differ from this paradigm. At least some of these viruses code for an (almost) autonomous glycosylation pathway. These viral genes include those that encode the production of activated sugars, glycosyltransferases, and other enzymes able to manipulate sugars at various levels. This review focuses on large and giant viruses that produce carbohydrate-processing enzymes. A brief description of those harboring these features at the genomic level will be discussed, followed by the achievements reached with regard to the elucidation of the glycan structures, the activity of the proteins able to manipulate sugars, and the organic synthesis of some of these virus-encoded glycans. During this progression, we will also comment on many of the challenging questions on this subject that remain to be addressed. CONTENTS AJ 4.2. Chlorovirus N-Glycans AJ 5. Conclusions and Future Perspectives AN Author Information
Published: 2022

8. Surface modification of plasma-treated polyamide-6 with fluorinated alcohols and azobenzene compounds using chlorinated phosphazenes as coupling agents

Author: Ahmed Mazzah, charafeddine Jama, Mario Gleria, Léon Gengembre, Roger De Jaeger, Roberto Milani, Alessandro Sassi, Dipartimento di Scienze Chimiche, Università degli Studi di Padova = University of Padua (Unipd), Istituto di Scienze e Tecnologie Molecolari del Consiglio Nazionale delle Ricerche, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Procédés d'Élaboration des Réactifs Fonctionnels (PERF), Ecole Nationale Supérieure de Chimie de Lille (ENSCL), 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), Laboratoire de catalyse de Lille - UMR 8010 (LCL), Université de Lille, Sciences et Technologies-Centrale Lille-Centre National de la Recherche Scientifique (CNRS), Universita degli Studi di Padova, Dipartimento di Scienze Chimiche dell'Universita di Padova, Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), 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, Istituto di Scienze e Tecnologie Molecolari (ISTM), Universita degli Studi di Padova-Consiglio Nazionale delle Ricerche [Roma] (CNR), Laboratoire des Procédés d'Elaboration des Rvêtements Fonctionnels (PERF), Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)-Università degli Studi di Padova = University of Padua (Unipd)
Subjects: Chemistry, Substrate (chemistry), 02 engineering and technology, General Chemistry, Plasma, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Grafting, 01 natural sciences, 0104 chemical sciences, Contact angle, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, X-ray photoelectron spectroscopy, Azobenzene, Polyamide, Polymer chemistry, Surface modification, General Materials Science, 0210 nano-technology
Abstract: International audience; A three-step procedure for surface functionalization of polyamide-6 plates is presented. The substrate was first treated with cold, low pressure Ar plasma to generate surface OH groups, which were successively reacted with chlorophosphazenes to ensure grafting of these mols. Substitution of the residual chlorines of the phosphazenes with fluorinated alcs. and 4-hydroxyazobenzene yielded the final surface modification. Characterization was performed by contact angle, XPS and UV-Vis techniques.
Published: 2007

9. Contribution of DFT to the optimization of Ni-based catalysts for dry reforming of methane: a review

Author: Oualid Alioui, Michael Badawi, Alessandro Erto, Mohammed A. Amin, Vineet Tirth, Byong-Hun Jeon, Saiful Islam, Marco Balsamo, Mirella Virginie, Barbara Ernst, Yacine Benguerba, Université Ferhat-Abbas Sétif 1 [Sétif] (UFAS1), Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Napoli 'Parthenope' = University of Naples (PARTHENOPE), Taif University (TU), Partenaires INRAE, King Khalid University [Abha], Hanyang University, Dipartimento di Scienze Chimiche, Complesso Universitario Monte Sant’Angelo, University of Naples Federico II = Università degli studi di Napoli Federico II, 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), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Alioui, O., Badawi, M., Erto, A., Amin, M. A., Tirth, V., Jeon, B. -H., Islam, S., Balsamo, M., Virginie, M., Ernst, B., and Benguerba, Y.
Subjects: Greenhouse ga, Received: 18 April 2021 Revised: 12 Novembre 2021 accepted: 15 Décembre 2021, density functional theory (DFT), Process Chemistry and Technology, dry reforming of methane (drm), methane dissociation, [CHIM]Chemical Sciences, General Chemistry, Ni-based catalyst, Catalysis
Abstract: International audience; In recent years, Density Functional Theory (DFT) simulations have been utilized to gain insight into the Dry Reforming of Methane (DRM) process. It enables new and improved management of current reactions, acquiring extra information about specific elements of the catalytic process, and developing practical methods for rational in silico catalyst design. This study covers the significance of DFT and current research on Ni-based catalysts in the DRM process, including the reaction mechanism, coke production, metal sintering, and metal support interactions. The DFT tool may explain the catalytic characteristics of Ni-based catalysts and their relationship with their catalytic performances, which are necessary tools for a rational design of appropriate catalytic systems for DRM applications.
Published: 2022

10. Redox behavior of CeO2-ZrO2 mixed oxides: I. Influence of redox treatments on high surface area catalysts

Author: Vidal, Hilario, Kaspar, Jan, Pijolat, Michèle, Colon, Gerardo, Cordon, Ana Maria, Perrichon, Vincent, Fally, Fabienne, Dipartimento di Scienze Chimiche, Università degli studi di Trieste, Departamento de Mecánica Estructural y Resistencia de Materiales, dipartimento di scienze chimiche, Laboratoire des Procédés en Milieux Granulaires (LPMG-EMSE), École des Mines de Saint-Étienne (Mines Saint-Étienne MSE), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Centre National de la Recherche Scientifique (CNRS), Centre Sciences des Processus Industriels et Naturels (SPIN-ENSMSE), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Département Procédés et évolution des systèmes avec solides (ProcESS-ENSMSE), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-SPIN, Laboratoire d'Application de la Chimie à l'Environnement (LACE), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Laboratoire Interdisciplinaire de Spectroscopie Electronique (LISE), Facultés Universitaires Notre Dame de la Paix (FUNDP), Università di Trieste, Universidad de Cádiz, Université Lyon 1 LACE UMR CNRS 5634, Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: Magnetic susceptibility, Oxygen storage capacity (OSC), Oxygen buffering capacity (OBC), Raman spectroscopy, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, CeO2-ZrO2 mixed oxides, Temperature-programmed reduction/oxidation (TPR/TPO), X-ray diffraction
Abstract: International audience; Redox and textural/structural properties of high surface area ceria-zirconia mixed oxides with composition ranging from 0 to 85 mol% of ZrO2, have been studied using Raman spectroscopy, X-ray diffraction, textural characterization, magnetic susceptibility measurements, temperature-programmed reduction and oxidation, oxygen storage and buffering capacity measurements. Special attention was given to the effects of aging under redox conditions. Correlation between chemical composition, textural, structural and redox properties of the oxides is reported. While for pure ceria almost no reducibility occurs below 773 K, mixed oxides, independently of their composition, exhibit an oxygen storage and buffering capacity at low temperature, which remains stable even after several oxidation/reduction cycles. This improvement with respect to CeO2 is remarkably high in the oxides with high zirconia content and is not affected by worsening of textural properties induced by redox-aging. Phase transformation and/or structural modification are detected as a consequence of the redox treatments, which could be at the origin of such effects
Published: 2000

11. Mechanochemical Rearrangements

Author: Francesco Delogu, David VIRIEUX, Felipe Garcia, Evelina Colacino, Andrea PORCHEDDU, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Dipartimento di Ingegneria Meccanica, Universita degli Studi di Cagliari [Cagliari], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, Institut d'Investigacions Biomèdiques August Pi i Sunyer (IDIBAPS), and Universitat de Barcelona (UB)
Subjects: Biological Products, 010405 organic chemistry, Organic Chemistry, [CHIM]Chemical Sciences, 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract: Molecular rearrangements are a powerful tool for constructing complex structures in an atom- and step-economic manner, translating multistep transformations into an intrinsically more sustainable process. Mechanochemical molecular rearrangements become an even more appealing eco-friendly synthetic approach, especially for preparing active pharmaceutical ingredients (APIs) and natural products. Still in their infancy, rearrangements promoted by mechanochemistry represent a promising approach for chemists to merge molecular diversity and green chemistry perspectives toward more selective and efficient syntheses with a reduced environmental footprint.
Published: 2021

12. Formation and Dispersal of Ash at Open Conduit Basaltic Volcanoes: Lessons From Etna

Author: Edwards, Matthew, Eychenne, Julia, Pioli, Laura, Université de Genève = University of Geneva (UNIGE), Laboratoire Magmas et Volcans (LMV), Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Recherche pour le Développement et la société-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA), Génétique, Reproduction et Développement (GReD), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA), Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari = University of Cagliari (UniCa), ANR-10-LABX-0006,CLERVOLC,Clermont-Ferrand centre for research on volcanism(2010), ANR-16-IDEX-0001,CAP 20-25,CAP 20-25(2016), Jouhannel, Sylvaine, Laboratoires d'excellence - Clermont-Ferrand centre for research on volcanism - - CLERVOLC2010 - ANR-10-LABX-0006 - LABX - VALID, and CAP 20-25 - - CAP 20-252016 - ANR-16-IDEX-0001 - IDEX - VALID
Subjects: volcanic hazard, [SDU.STU.VO] Sciences of the Universe [physics]/Earth Sciences/Volcanology, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, General Earth and Planetary Sciences, explosive volcanism, tephra dispersal, ash morphology, magma fragmentation
Abstract: co-auteur étranger; International audience; Open conduit volcanoes are characterized by frequent, small scale explosive eruptions, which have a significant impact. Ash-forming explosions are impacting over larger areas with respect to effusive or poorly explosive events and, consequently, are more significant for hazard assessments. Quantifying the hazard associated with them requires understanding the processes and parameters controlling explosive style, and tephra dispersal and obtaining a comprehensive dataset to constrain syn-eruptive dynamics and particle transport in the volcanic plume. We present a study focused on Etna volcano (Italy), which, despite its continuous outgassing through the summit vents, has very frequent explosive eruptions dispersing ash along the southern Mediterranean area. The goal of this study is to obtain a statistically valid dataset on ash morphology and texture and investigate how various particle types distribute spatially in the tephra blanket. We chose a small scale, ash-forming eruption occurred in May 2016, sampled a few hours after tephra deposition. Analyses of grainsize distribution were coupled with further data on tephra texture and morphology, and numerical simulations. Several components were identified based either on purely textural or purely shape characteristics. Shape parameters related to the form of the grains (aspect ratio) are consistent across grainsizes and components. However, roughness parameters (solidity, convexity, concavity index) vary non-uniformly with particle size and componentry. Ash was formed through complex fragmentation of heterogenous magma, starting in the conduit, extending to the explosion jet, and resulting into a large variability of particle shapes, density and textures which distribute non-uniformly across grainsizes. This variability determines variable traveling potential within the volcanic plume and thus non uniform distribution in the deposit. Componentry variations along the dispersal axis suggest that density is the most effective parameter in controlling particle settling. However, extreme shapes, such as very elongated particles formed by surface tension instabilities in the jet, have the largest potential of being transported in the plume and can disperse downwind up to tens of km. Our results suggest that heterogeneities in textures and morphologies of particles are fundamental characteristics of tephra from frequently erupting volcanoes and should be accounted for plume dispersal modelling and hazard assessment.
Published: 2021

13. An update of the Worldwide Integrated Assessment (WIA) on systemic insecticides. Part 1: new molecules, metabolism, fate, and transport

Author: Giorio, Chiara, Safer, Anton, Sánchez-Bayo, Francisco, Tapparo, Andrea, Lentola, Andrea, Girolami, Vincenzo, van Lexmond, Maarten Bijleveld, Bonmatin, Jean-Marc, Department of Chemistry (Cambridge], University of Cambridge [UK] (CAM), Laboratoire Chimie de l'environnement (LCE), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The University of Sydney, Dipartimento di Scienze Chimiche [Padova], Università degli Studi di Padova = University of Padua (Unipd), Task force on systemic pesticides, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universita degli Studi di Padova, and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Worldwide Integrated Assessment of the Impact of Systemic Pesticides on Biodiversity and Ecosystems, Insecticides, Systemic insecticides, [SDV]Life Sciences [q-bio], Remediation, Residues, Review, Bees, Invertebrates, Pollution, Soil, Neonicotinoids, Synergy, Mode of action, Health, Metabolites, Animals, Fipronil, Environmental Chemistry, Health, Toxicology and Mutagenesis, Toxicology and Mutagenesis, Ecosystem
Abstract: International audience; With the exponential number of published data on neonicotinoids and fipronil during the last decade, an updated review of literature has been conducted in three parts. The present part focuses on gaps of knowledge that have been addressed after publication of the Worldwide Integrated Assessment (WIA) on systemic insecticides in 2015. More specifically, new data on the mode of action and metabolism of neonicotinoids and fipronil, and their toxicity to invertebrates and vertebrates, were obtained. We included the newly detected synergistic effects and/or interactions of these systemic insecticides with other insecticides, fungicides, herbicides, adjuvants, honeybee viruses, and parasites of honeybees. New studies have also investigated the contamination of all environmental compartments (air and dust, soil, water, sediments, and plants) as well as bees and apicultural products, food and beverages, and the exposure of invertebrates and vertebrates to such contaminants. Finally, we review new publications on remediation of neonicotinoids and fipronil, especially in water systems. Conclusions of the previous WIA in 2015 are reinforced; neonicotinoids and fipronil represent a major threat worldwide for biodiversity, ecosystems, and all the services the latter provide.
Published: 2021

14. The Mechanochemical Beckmann Rearrangement: An Eco-efficient 'Cut-and-Paste' Strategy to Design the 'Good Old Amide Bond'

Author: Andrea Porcheddu, Lidia De Luca, Evelina Colacino, Rita Mocci, Francesco Delogu, Claudia Fattuoni, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Universita degli Studi di Cagliari [Cagliari], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, Dipartimento di Ingegneria Meccanica, and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Green chemistry, Renewable Energy, Sustainability and the Environment, General Chemical Engineering, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Oxime, 01 natural sciences, 12. Responsible consumption, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Mechanochemistry, Amide, Beckmann rearrangement, Green metrics, Environmental Chemistry, Organic chemistry, Peptide bond, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Discovered over a century ago, Beckmann rearrangement is still today fully compliant with all the green chemistry principles and consistent with the key aspects of sustainable development. Herein, ...
Published: 2021

15. Magma fragmentation and particle size distributions in low intensity mafic explosions: the July/August 2015 Piton de la Fournaise eruption

Author: Edwards, Matthew J., Pioli, Laura, Harris, Andrew J. L., Gurioli, Lucia, Thivet, Simon, Université de Genève = University of Geneva (UNIGE), Università degli Studi di Cagliari = University of Cagliari (UniCa), Laboratoire Magmas et Volcans (LMV), Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), ANR-10-LABX-0006,CLERVOLC,Clermont-Ferrand centre for research on volcanism(2010), ANR-16-IDEX-0001,CAP 20-25,CAP 20-25(2016), Département des Sciences de la Terre, Université de Genève, Dipartimento di Scienze Chimiche e Geologiche, Università Degli Studi di Cagliari, Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), and Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS)
Subjects: lcsh:R, Natural hazards, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, lcsh:Medicine, Volcanology, lcsh:Q, lcsh:Science, Article
Abstract: Co-auteur étranger; International audience; Understanding magma fragmentation mechanisms in explosive eruptions is a key requirement for volcanic hazard assessment, eruption management and risk mitigation. This paper focuses on a type case small explosivity eruption (July–August 2015 eruption of Piton de la Fournaise). These eruptions, despite being often overlooked, are exceedingly frequent on local-to-global scales and constitute a significant hazard in vent-proximal areas, which are often populated by guides, tourists and, indeed, volcanologists due to their accessibility. The explosions presented here are ideal cases for the study of the dynamics of magma fragmentation and how it relates to the size distribution of scoria generated at the vent. We documented these events visually and thermally, and characterised the products through sample-return. This allowed us to describe small-scale gas bursts sending ejecta up to 30 m during intermittent lava fountains. Surface tension instabilities and inertial forces played a major role in fragmentation processes and generated particles with coarse-skewed distributions and median diameters ranging from − 8 to − 10 ϕ. However, with time distributions of particles in the most energetic fountains shifted towards more symmetrical shapes as median grains sizes became finer. Analyses of sequences of images demonstrate that the evolution of particle size distributions with time is due to instability of magma droplets and (in-flight) fragmentation.
Published: 2020

16. Mechanochemical Preparation of Active Pharmaceutical Ingredients Monitored by In Situ Raman Spectroscopy

Author: Andrea Porcheddu, Ivan Halasz, Evelina Colacino, Anita Dogan, Fabien Caron, Ernest Meštrović, Irena Sović, Thomas Perilli, Francesco Delogu, Pier Carlo Ricci, Stipe Lukin, Rudjer Boskovic Institute [Zagreb], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, Dipartimento di Ingegneria Meccanica, Universita degli Studi di Cagliari [Cagliari], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Active ingredient, 010405 organic chemistry, Chemistry, General Chemical Engineering, Pharmacy, General Chemistry, 010402 general chemistry, Silver sulfadiazine, 01 natural sciences, Ammonia, Raman spectroscopy, Chemical reactions, Pharmaceuticals : Silver, 0104 chemical sciences, In situ raman spectroscopy, medicine, [CHIM]Chemical Sciences, QD1-999, Nuclear chemistry, medicine.drug
Abstract: International audience; The mechanochemical preparation of silver sulfadiazine and dantrolene, two marketed active pharmaceutical ingredients, was investigated by in situ Raman spectroscopy. For the first time, the mechanochemical transformations involving highly fluorescent compounds could be studied in situ with a high-resolution Raman system combined with a unique suitable Raman probe. Moreover, the kinetic features of the mechanochemical process were examined by a mathematical model allowing to describe the chemical changes under mechanical stress. This approach is promising both to broaden the scope of Raman in situ investigations that would otherwise be impossible and for process optimization at any scale.
Published: 2020

17. Sodium diffusion in ionic liquid-based electrolytes for Na-ion batteries: the effect of polarizable force fields

Author: Jocasta Avila, Claudio Gerbaldi, Arianna Massaro, Agilio A. H. Padua, Kateryna Goloviznina, Michele Pavone, Ivan Rivalta, Margarida F. Costa Gomes, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Massaro, A., Avila, J., Goloviznina, K., Rivalta, I., Gerbaldi, C., Pavone, M., Costa Gomes, M. F., Padua, A. A. H., Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Dipartimento di Scienze Chimiche [Naples], Complesso Universitario Monte Sant'Angelo, Università di Napoli Federico II, Dipartimento di Chimica Industriale 'Toso Montanari', Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Politecnico di Torino = Polytechnic of Turin (Polito), Massaro A., Avila J., Goloviznina K., Rivalta I., Gerbaldi C., Pavone M., Costa Gomes M.F., Padua A.A.H., 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), University of Naples Federico II = Università degli studi di Napoli Federico II, and ANR-16-IDEX-0005,IDEXLYON,IDEXLYON(2016)
Subjects: sodium battery, post lithium battery, room temperature ionic liquid, sodium electrolyte, modelling, Ions transport, ionic liquids, sodium-ion batteries, molecular dynamics, polarizable force field, Materials science, Sodium, General Physics and Astronomy, chemistry.chemical_element, Ionic bonding, Thermodynamics, 02 engineering and technology, Electrolyte, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Ion, chemistry.chemical_compound, Molecular dynamics, [CHIM.GENI]Chemical Sciences/Chemical engineering, Physical and Theoretical Chemistry, Polarization (electrochemistry), ComputingMilieux_MISCELLANEOUS, Solvation, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Ionic liquid, 0210 nano-technology
Abstract: Understanding the transport of sodium ions in ionic liquids is key to designing novel electrolyte materials for sodium-ion batteries. In this work, we combine molecular dynamics simulation and experiments to study how molecular interactions and local ordering affect relevant physico-chemical properties. Ionic transport and local solvation environments are investigated in electrolytes composed of sodium bis(fluorosulfonyl)imide, (Na[FSI]), in N,N-methylpropylpyrrolidinium bis(fluorosulfonyl)imide, [C3C1pyr][FSI], at different salt concentrations. The electrolyte systems are modelled by means of molecular dynamic simulations using a polarizable force field. We show that including polarization effects explicitly in the molecular simulations is required in order to attain a reliable description of the transport properties of sodium in the [C3C1pyr][FSI] electrolyte. The validation of the computational results upon comparison with experimental data allows us to assess the suitability of polarizable force fields in describing and interpreting the structure and dynamics of the sodium salt-ionic liquid system, which is essential to enable the application of IL-based electrolytes in novel energy-storage technologies.
Published: 2020

18. Origin of oceanic ferrodiorites by injection of nelsonitic melts in gabbros at the Vema Lithospheric Section, Mid Atlantic Ridge

Author: Brunelli, Daniele, Sanfilippo, Alessio, Bonatti, Enrico, Skolotnev, Sergei, Escartin, Javier, Ligi, Marco, Ballabio, Giorgia, Cipriani, Anna, Dipartimento di scienze chimiche e geologiche, University of Pavia, Istituto di Scienze Marine [Bologna] (ISMAR), Istituto di Science Marine (ISMAR ), Consiglio Nazionale delle Ricerche (CNR)-Consiglio Nazionale delle Ricerche (CNR), Institut de Physique du Globe de Paris (IPGP), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS.PHYS.PHYS-GEO-PH]Physics [physics]/Physics [physics]/Geophysics [physics.geo-ph], Oceanic lower crust Gabbro Oxide gabbro Axial magma chamber Nelsonite Vema fracture zone, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2020

19. Arene vs. Alkene Substrates in Ru-Catalyzed Olefin Metathesis: a DFT Investigation

Author: Poater, Albert, D'Alterio, Massimo Christian, Talarico, Giovanni, Chauvin, Rémi, Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Dipartimento di Scienze Chimiche, Università degli studi di Napoli Federico II, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Ministerio de Ciencia e Innovación (MICINN) of Spain : project PGC2018-097722-B-I00, and Università degli Studi di Napoli (Ricerca di Ateneo 2017, DR_409_2017).
Subjects: Pyran, Aromaticity, Olefin metathesis, Metallacycles, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Ruthenium
Abstract: International audience; DFT calculations have been performed to compare metathesis of olefin, diene, and arene substrates catalyzed by a 2nd generation Ru(SIMes)-based complex. A large screening of modified substrates has been performed with the intention to explore the energetic gaps between acyclically conjugated alkenes and arenes in metathesis processes. The results are analyzed through the effects of conjugation vs. aromaticity, as quantified by the HOMA and NICS aromaticity indices, as well as the effects of non-covalent interactions between coplanar rings and/or any ring with functional groups nearby.
Published: 2020

20. TurboRVB: a many-body toolkit for ab initio electronic simulations by quantum Monte Carlo

Author: Claudio Genovese, Kousuke Nakano, Emanuele Coccia, Claudio Attaccalite, Mario Dagrada, Andrea Zen, Sandro Sorella, Guglielmo Mazzola, Matteo Barborini, Ye Luo, Michele Casula, Luca Capriotti, Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Nakano, K., Attaccalite, C., Barborini, M., Capriotti, L., Casula, M., Coccia, E., Dagrada, M., Genovese, C., Luo, Y., Mazzola, G., Zen, A., Sorella, S., Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche e Farmaceutiche, University of Trieste, via Giorgieri 1, 34127 Trieste, Italy, and Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS)
Subjects: Quantum Monte Carlo, Gaussian, General Physics and Astronomy, FOS: Physical sciences, 010402 general chemistry, Energy minimization, 01 natural sciences, Settore FIS/03 - Fisica della Materia, symbols.namesake, Condensed Matter - Strongly Correlated Electrons, [PHYS.QPHY]Physics [physics]/Quantum Physics [quant-ph], Physics - Chemical Physics, 0103 physical sciences, [CHIM]Chemical Sciences, Statistical physics, Physical and Theoretical Chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], many body theory, Ansatz, Physics, Chemical Physics (physics.chem-ph), [PHYS]Physics [physics], Condensed Matter - Materials Science, 010304 chemical physics, Strongly Correlated Electrons (cond-mat.str-el), Materials Science (cond-mat.mtrl-sci), [CHIM.MATE]Chemical Sciences/Material chemistry, Computational Physics (physics.comp-ph), 0104 chemical sciences, 3. Good health, symbols, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Slater determinant, Diffusion Monte Carlo, Density functional theory, Variational Monte Carlo, [PHYS.COND.CM-SCE]Physics [physics]/Condensed Matter [cond-mat]/Strongly Correlated Electrons [cond-mat.str-el], Physics - Computational Physics, correlated methods
Abstract: TurboRVB is a computational package for {\it ab initio} Quantum Monte Carlo (QMC) simulations of both molecular and bulk electronic systems. The code implements two types of well established QMC algorithms: Variational Monte Carlo (VMC), and Diffusion Monte Carlo in its robust and efficient lattice regularized variant. A key feature of the code is the possibility of using strongly correlated many-body wave functions. The electronic wave function (WF) is obtained by applying a Jastrow factor, which takes into account dynamical correlations, to the most general mean-field ground state, written either as an antisymmetrized geminal product with spin-singlet pairing, or as a Pfaffian, including both singlet and triplet correlations. This wave function can be viewed as an efficient implementation of the so-called resonating valence bond (RVB) ansatz, first proposed by L. Pauling and P. W. Anderson in quantum chemistry and condensed matter physics, respectively. The RVB ansatz implemented in TurboRVB has a large variational freedom, including the Jastrow correlated Slater determinant as its simplest, but nontrivial case. Moreover, it has the remarkable advantage of remaining with an affordable computational cost, proportional to the one spent for the evaluation of a single Slater determinant. The code implements the adjoint algorithmic differentiation that enables a very efficient evaluation of energy derivatives, comprising the ionic forces. Thus, one can perform structural optimizations and molecular dynamics in the canonical NVT ensemble at the VMC level. For the electronic part, a full WF optimization is made possible thanks to state-of-the-art stochastic algorithms for energy minimization. The code has been efficiently parallelized by using a hybrid MPI-OpenMP protocol, that is also an ideal environment for exploiting the computational power of modern GPU accelerators., 41 pages, 21 figures, 3 tables
Published: 2020

21. Base-controlled product switch in the ruthenium-catalyzed protodecarbonylation of phthalimides: a mechanistic study

Author: Massimo Christian D'Alterio, Rafael Gramage-Doria, Christian Bruneau, Yu-Chao Yuan, Albert Poater, Giovanni Talarico, Dipartimento di Scienze Chimiche, University of Naples Federico II = Università degli studi di Napoli Federico II, Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PGC2018-097722-B-I00, Ministerio de Ciencia e Innovación, UNGI08-4E-003, European Regional Development Fund, Centre National de la Recherche Scientifique, China Scholarship Council, Agence Nationale de la Recherche, Université de Rennes 1, European Cooperation in Science and Technology, Università degli studi di Napoli Federico II, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), D'Alterio, M. C., Yuan, Y. -C., Bruneau, C., Talarico, G., Gramage-Doria, R., and Poater, A.
Subjects: Phthalimides, Reaction mechanism, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, Transition state, 0104 chemical sciences, Phthalimide, chemistry.chemical_compound, Catalytic cycle, Polymer chemistry, Reactivity (chemistry), Chemoselectivity
Abstract: International audience; The whole reaction mechanism of the ruthenium-catalyzed protodecarbonylation of N-substituted phthalimides into secondary amides was unravelled by a combined experimental and theoretical study. The chemoselectivity of the reaction, which is catalyzed by para-cymene coordinated Ru(II) species all over the catalytic cycle, is exclusively controlled by the unique roles of the bases. Meanwhile, in the presence of K2CO3 or KOH at high temperatures, the same product (benzamide) is mainly formed, whereas at low temperatures, KOH led to an unexpected side-product (phthalamic acid) and no reactivity was observed with K2CO3. The non-covalent interactions between the potassium cations and the different carbonyl groups in the molecules are key to providing a thermodynamically favourable pathway with energetically accessible transition states. The unexpected formation of carbon dioxide (CO2) in the course of the reaction originates from the phthalimide substrate and the base K2CO3 in two different elementary steps, respectively.
Published: 2020

22. Heteroleptic NIR-Emitting Yb III /Anilate-Based Neutral Coordination Polymer Nanosheets for Solvent Sensing

Author: Mariangela Oggianu, Suchithra Ashoka Sahadevan, Carla Cannas, Andrea Mura, Daniela Marongiu, Maria Laura Mercuri, Noemi Monni, Michele Saba, Narcis Avarvari, Francesco Quochi, Giovanni Bongiovanni, Alexandre Abhervé, Valentina Mameli, Universita degli Studi di Cagliari [Cagliari], MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche, and Università di Cagliari
Subjects: chemistry.chemical_classification, Materials science, nanosheets, 010405 organic chemistry, Coordination polymer, anilates, NIR-emitting lanthanides, carboxylates, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Solvent, Coordination polymers, chemistry.chemical_compound, chemistry, Polymer chemistry, [CHIM]Chemical Sciences, General Materials Science, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate, Linker, photophysics
Abstract: International audience; Nanosheets of two mixed linker (anilate/carboxylate)/YbIII-based two-dimensional (2D) layered coordination polymers (CPs) are herein reported. Bulky sized CPs, formulated as [Yb4(ClCNAn)5(DOBDC)1(DMSO)10]n·(DMSO)2 (1) and [Yb2(ClCNAn)2(F4BDC)(DMSO)6]n (2), are formed by two-dimensional neutral polymeric networks based on YbIII ions, heterosubstituted ClCNAn2– anilate, and dicarboxylate linkers (DOBDC2– in 1; F4BDC2– in 2): in 1, neighbor layers are eclipsed and form six-membered rings showing either hexagonal cavities, formed by ClCNAn2– and YbIII ions or rectangular cavities formed by ClCNAn2–, DOBDC2–, and YbIII while distorted square-like cavities formed by ClCNAn2–, F4BDC2–, and YbIII are obtained in 2. The 1 and 2 nanosheets, that is, 1-NS and 2-NS, are produced by exfoliation of bulk CPs by the well-known top-down approach and characterized by atomic force microscopy and high resolution transmission electron microscopy. The 1-NS and 2-NS show thickness in the range of 1–5 nm, whereas the lateral dimensions are in the micrometer scale and the presence of well-defined lattice fringes, key evidence of their robustness. Remarkably the powder X-ray diffraction (PXRD) patterns highlight that the crystallinity is retained at the nanoscale level. Nanosheets photophysics are investigated by an innovative Multiprobe Approach where lifetime, photoluminescence (PL) and integrated PL are simultaneously measured in order to study how these parameters can be affected by the presence of the different ligands. These advanced photophysical studies pave the way to challenging luminescent sensing applications and to contribute to the ongoing research on fabricating robust and crystalline hybrid (organic/inorganic) lanthanide sheetlike 2D nanomaterials.
Published: 2020

23. Dichroïsme magnéto-chiral : un terrain de jeu pour la chimie moléculaire

Author: Atzori, Matteo, G.L.J.A., Rikken, TRAIN, Cyrille, Dipartimento di Scienze Chimiche e Geologiche, Laboratoire national des champs magnétiques intenses - Toulouse (LNCMI-T), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire national des champs magnétiques intenses - Grenoble (LNCMI-G ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and ANR-18-CE09-0032,MONAFER,Approche Moléculaire de composés multiferroïques nanostructurés(2018)
Subjects: [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2020

24. Designing expanded bipyridinium as redox and optical probes for DNA

Author: Emanuela Trovato, Antonino Giannetto, Francesco Nastasi, Fausto Puntoriero, Grégory Dupeyre, Maria Letizia Di Pietro, Sebastiano Campagna, Philippe P. Lainé, Universita degli Studi di Messina, Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche e Ambientali, Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)
Subjects: Guanine, Ultraviolet Rays, Pyridinium Compounds, 010402 general chemistry, Photochemistry, 01 natural sciences, Redox, Photoinduced electron transfer, chemistry.chemical_compound, Animals, Physical and Theoretical Chemistry, Fluorescent Dyes, Spectroscopy, Near-Infrared, Molecular Structure, 010405 organic chemistry, Optical Imaging, DNA, 0104 chemical sciences, chemistry, Polynucleotide, Picosecond, Cattle, Luminescence, DNA Probes, [CHIM.OTHE]Chemical Sciences/Other, Sensing system, Oxidation-Reduction
Abstract: International audience; We report on the light-switch behaviour of two head-to-tail expanded bipyridinium species as a function of their interaction with calf thymus DNA and polynucleotides. In particular, both DNA and polynucleotides containing exclusively adenine or guanine moieties quench the luminescence of the fused expanded bipyridinium species. This behaviour has been rationalized demonstrating that a reductive photoinduced electron transfer process takes place involving both adenine or guanine moieties. The charge separated state so produced recombines in the tens of picoseconds. These results could help on designing new organic substrates for application in DNA probing technology and lab on chip-based sensing systems.
Published: 2020

25. A Chiral Prussian Blue Analogue Pushes Magneto-Chiral Dichroism Limits

Author: Katsuya Inoue, Matteo Atzori, Ivan Breslavetz, Geert L. J. A. Rikken, Cyrille Train, Kévin Paillot, Dipartimento di Scienze Chimiche, Università di Cagliari, Laboratoire national des champs magnétiques intenses - Grenoble (LNCMI-G ), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire des champs magnétiques intenses (LCMI-GHMFL), and Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Prussian blue, Absolute configuration, General Chemistry, Dichroism, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Spectral line, 0104 chemical sciences, Magnetization, Crystallography, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Ferrimagnetism, [CHIM]Chemical Sciences, Néel temperature, ComputingMilieux_MISCELLANEOUS, Visible spectrum
Abstract: Here we report on magneto-chiral dichroism (MChD) detected with visible light on the chiral Prussian Blue Analogue [MnII(X-pnH)(H2O)][CrIII(CN)6]·H2O (X = S, R; pn = 1,2-propanediamine). Single crystals suitable for magneto-optical measurements were grown starting from enantiopure chiral ligands. X-ray diffraction and magnetic measurements confirmed the 2D-layered structure of the material, its absolute configuration, and its ferrimagnetic ordered state below a critical temperature TC of 38 K. Absorption and MChD spectra were measured between 450 and 900 nm from room temperature down to 4 K. At 4 K the electronic spectrum features spin-allowed and spin-forbidden transitions of CrIII centers, spin-forbidden transitions of the MnII centers, and metal-to-metal charge transfer bands. The MChD spectra below the magnetic ordering temperature exhibit intense absolute configuration-dependent MChD signals. The temperature dependence of these signals closely follows the material magnetization. Under a magnetic fiel...
Published: 2019

26. Dysprosium Chlorocyanoanilate-Based 2D-Layered Coordination Polymers

Author: Suchithra Ashoka Sahadevan, Guido Ennas, Narcis Avarvari, Alexandre Abhervé, Masahiro Yamashita, Noemi Monni, Maria Laura Mercuri, Mariangela Oggianu, Goulven Cosquer, Instituto de Ciencia Molecular, Universitat de València (UV)-Instituto de Ciencia Molecular, Department of Chemistry, Graduate School of Science Tohoku University, Tohoku University [Sendai], MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche e Geologiche, B18030, State Administration of Foreign Experts Affairs, B18030, Ministry of Education of the People's Republic of China, Centre National de la Recherche Scientifique, Universite Angers, RFI Regional project LUMOMAT, Fondazione di Sardegna ? Convenzione triennale tra la Fondazione di Sardegna e gli Atenei Sardi, Regione Sardegna, INSTM, and SULCIS 820947, ?SENSORI LUMINESCENTI AD EFFETTO PLASMONICO PER IL RILEVAMENTO DEI METALLI PESANTI NELLE ACQUE?, REGIONE AUTONOMA DELLA SARDEGNA
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Cationic polymerization, chemistry.chemical_element, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Solvent, Thermogravimetry, Crystallography, Differential scanning calorimetry, chemistry, Polymorphism (materials science), Dysprosium, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Thermal analysis, ComputingMilieux_MISCELLANEOUS
Abstract: A series of two-dimensional (2D)-layered coordination polymers (CPs) based on the heterosubstituted anilate ligand ClCNAn2- derived from 3-chloro-6-cyano-2,5-dihydroxybenzoquinone and DyIII are reported. By changes in the synthetic methods (layering technique, solvothermal or conventional one-pot reactions) and conditions (solvent, concentration, etc.), different types of 2D extended networks could be prepared and structurally characterized. Compounds 1 and 1', two polymorphs with the formula [Dy2(ClCNAn)3(DMSO)6]n·(H2O)x [x = 7 (1), 0 (1')], were prepared by a conventional one-pot reaction and recrystallized at different concentrations. Compound 2, formulated as [Dy2(ClCNAn)3(DMF)6]n, was prepared by a layering technique, while compound 3, formulated as {(Me2NH2)2[Dy2(ClCNAn)4(H2O)2]·(DMF)2·(H2O)5}n, was obtained by a solvothermal method. Compounds 1 and 2 are neutral 2D CPs of the ClCNAn2- ligand and DyIII ions, while 3 presents 2D anionic layers of [Dy2(ClCNAn)4(H2O)2]2- alternating with cationic layers of Me2NH2+ ions. These compounds show very diverse networks, with compound 1 forming 2D (8,3) and (4,3) topology with eight- and four-membered rings with square cavities, 1' and 2, respectively, a 2D (6,3) topology with six-membered rings (a rectangular cavity for 1' and a regular hexagonal cavity for 2), and 3 a 2D (4,4) topology with distorted square cavities. In this respect, 1 and 1' represent the first examples of polymorphism in the family of anilate-based CPs. Thermal analysis measurements (differential scanning calorimetry and thermogravimetry) show an exothermic polymorphic transformation from the kinetically stable 1' phase to the thermodynamically stable phase 1. The magnetic behavior of 1-3 very likely indicates depopulation of the mJ levels, while the presence of weak antiferromagnetic coupling between the DyIII centers mediated by the anilate bridge cannot be excluded.
Published: 2019

27. Deciphering the roles of environment and development in the evolution of a Late Triassic assemblage of conodont elements

Author: Manuel Rigo, Pauline Guenser, Michele Mazza, Sylvain Dolédec, Louise Souquet, Nicolas Goudemand, Laboratoire d'Ecologie des Hydrosystèmes Naturels et Anthropisés (LEHNA), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Nationale des Travaux Publics de l'État (ENTPE), Institut de Génomique Fonctionnelle de Lyon (IGFL), École normale supérieure - Lyon (ENS Lyon)-Institut National de la Recherche Agronomique (INRA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche e Geologiche, CNR Istituto di Geoscienze e Georisorse [Pisa] (IGG-CNR), Consiglio Nazionale delle Ricerche [Pisa] (CNR PISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Nationale des Travaux Publics de l'État (ENTPE)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)-École normale supérieure - Lyon (ENS Lyon), Consiglio Nazionale delle Ricerche (CNR), École normale supérieure de Lyon (ENS de Lyon)-Institut National de la Recherche Agronomique (INRA)-Université Claude Bernard Lyon 1 (UCBL), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)
Subjects: 0106 biological sciences, Morphometrics, 010506 paleontology, Ecology, Resistance (ecology), Paleontology, Biology, biology.organism_classification, Triassic, 010603 evolutionary biology, 01 natural sciences, Intraspecific competition, Taxon, Evolutionary biology, Abundance (ecology), evolution, Assemblage (archaeology), [SDE.BE]Environmental Sciences/Biodiversity and Ecology, General Agricultural and Biological Sciences, Conodont, conodont, Ecology, Evolution, Behavior and Systematics, Deep time, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences
Abstract: To assess evolutionary processes in deep time, it is essential to understand the roles of development and environment, both recorded through the morphological variability of fossil assemblages. Thanks to their great abundance and the high temporal resolution of their fossil record, conodont elements are ideal to address this issue. In this paper, we present the first quantitative study of a Carnian–Norian (Late Triassic) assemblage of closely related P1 conodont elements. Using geometric morphometrics (landmarks, sliding landmarks, and elliptic Fourier analysis), we explore the main axes of phenotypic variation and relate them to classically used taxonomic characters. We show that some important taxonomic features follow laws of covariation, hence highlighting developmental constraints. Furthermore, the intraspecific variation within all considered species, either Carnian or Norian forms, is similarly restricted, emphasizing, for the first time in conodont P1 elements, a common line of least resistance to evolution, which means that similar intrinsic (developmental) factors were acting on these taxa and likely biased the evolutionary trajectories of all these taxa in a similar way. Because the evolution between Carnian and Norian forms is known to have followed a trajectory that is significantly different from the line of least resistance, strong extrinsic pressures, such as environmental disturbances, were probably at play around the Carnian/Norian boundary to counteract the effects of these intrinsic, developmental constraints.
Published: 2019

28. From enabling technologies to medicinal mechanochemistry: an eco-friendly access to hydantoin-based active pharmaceutical ingredients

Author: Evelina Colacino, Andrea Porcheddu, Francesco Delogu, Clarence Charnay, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Universita degli Studi di Cagliari [Cagliari], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, and Dipartimento di Ingegneria Meccanica
Subjects: Fluid Flow and Transfer Processes, Active ingredient, Engineering, 010405 organic chemistry, business.industry, Process Chemistry and Technology, Hydantoin, 010402 general chemistry, 01 natural sciences, Environmentally friendly, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Chemistry (miscellaneous), Mechanochemistry, Chemical Engineering (miscellaneous), [CHIM]Chemical Sciences, Biochemical engineering, Activation method, business, Pharmaceutical industry
Abstract: International audience; The preparation of hydantoin scaffolds using modern non-conventional activation methods is herein described. Special attention is devoted to the preparation of hydantoin-based Active Pharmaceutical Ingredients (APIs) by mechanochemistry, highlighting its advantages compared to classical solution procedures, opening new perspectives in the sustainable preparation of useful scaffolds for the pharmaceutical industry.
Published: 2019

29. Stability Is Not Everything: The Case of the Cyclisation of a Thrombin‐Binding Aptamer

Author: Albert Meyer, Luigi Paduano, Jean-Jacques Vasseur, Irene Russo Krauss, François Morvan, Daniela Montesarchio, Claudia Riccardi, Rosario Oliva, Luigi Petraccone, Centre de Droit Pénal et de Criminologie (CDPC), Université Paris Nanterre (UPN), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche, Complesso Universitario Monte Sant’Angelo, University of Naples Federico II = Università degli studi di Napoli Federico II, Department of Chemical Sciences, Università degli studi di Napoli Federico II, University of Naples Federico II, Riccardi, Claudia, Meyer, Albert, Vasseur, Jean-Jacque, Russo Krauss, Irene, Paduano, Luigi, Oliva, Rosario, Petraccone, Luigi, Morvan, Francoi, and Montesarchio, Daniela
Subjects: cyclization, Aptamer, aptamers, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, G-quadruplex, 01 natural sciences, Biochemistry, Proof of Concept Study, Molecular recognition, Thrombin, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, medicine, Humans, Transition Temperature, [CHIM]Chemical Sciences, Thermal stability, Molecular Biology, Thrombin-binding aptamer, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Circular Dichroism, Organic Chemistry, Aptamers, Nucleotide, Combinatorial chemistry, G-quadruplexes, Cycloaddition, 0104 chemical sciences, click chemistry, Click chemistry, Molecular Medicine, molecular recognition, Aptamers * Cyclization * Click Chemistry * G-quadruplexes * Molecular Recognition, medicine.drug
Abstract: International audience; With the aim of developing a new approach to obtain improved aptamers, a cyclic thrombin-binding aptamer (TBA) analogue (cycTBA) has been prepared by exploiting a copper(I)-assisted azide-alkyne cycloaddition. The markedly increased serum resistance and exceptional thermal stability of the G-quadruplex versus TBA were associated with halved thrombin inhibition, which suggested that some flexibility in the TBA structure was necessary for protein recognition.
Published: 2019

30. Na+ diffusion in IL-based electrolytes for Na-ion batteries: the effect of polarizable force fields

Author: Massaro, Arianna, Rivalta, Ivan, Pavone, Michele, Costa Gomes, Margarida, Pádua, Agílio, Dipartimento di Scienze Chimiche [Naples], University of Naples Federico II = Università degli studi di Napoli Federico II, 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), Complesso Universitario Monte Sant'Angelo, Università di Napoli Federico II, 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: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS, molecular simulation, ionic liquid
Abstract: International audience
Published: 2019

31. Stochastic modeling of macromolecules in solution. II. Spectral densities

Author: Daniel Abergel, Mirco Zerbetto, Antonino Polimeno, Dipartimento di Scienze Chimiche [Padova], and Universita degli Studi di Padova
Subjects: Physics, Coupling, 010304 chemical physics, Stochastic process, Degrees of freedom (physics and chemistry), General Physics and Astronomy, Dissipation, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Simple (abstract algebra), Orientation (geometry), 0103 physical sciences, Relaxation (approximation), Statistical physics, Physical and Theoretical Chemistry, Brownian motion
Abstract: In Paper I [Polimeno et al., J. Chem. Phys. 150, 184107 (2019)], we proposed a general approach for interpreting relaxation properties of a macromolecule in solution, derived from an atomistic description. A simple scheme (the semiflexible Brownian, SFB, model) has been defined for the case of limited internal flexibility, but retaining full coupling with external degrees of freedom, inclusion of all of the momenta, and dissipation. Here we discuss the application of the SFB model to the practical evaluation of orientation spectral densities, based on two complementary computational treatments.
Published: 2019

32. Real-Time Geophysical Monitoring of Particle Size Distribution During Volcanic Explosions at Stromboli Volcano (Italy)

Author: Laura Pioli, Andrew J. L. Harris, Département des Sciences de la Terre, Université de Genève, Dipartimento di Scienze Chimiche e Geologiche, Laboratoire Magmas et Volcans (LMV), Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS), ANR-10-LABX-0006,CLERVOLC,Clermont-Ferrand centre for research on volcanism(2010), ANR-16-IDEX-0001,CAP 20-25,CAP 20-25(2016), Université de Genève = University of Geneva (UNIGE), Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), and Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)
Subjects: Volcanic hazards, 010504 meteorology & atmospheric sciences, Explosive material, Strombolian explosion, 010502 geochemistry & geophysics, 01 natural sciences, Physics::Geophysics, volcanic hazard, mass discharge rate, Impact crater, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, lcsh:Science, 0105 earth and related environmental sciences, geography, geography.geographical_feature_category, Geophysics, Lapilli, Strombolian eruption, magma fragmentation, Plume, Volcano, 13. Climate action, Particle-size distribution, General Earth and Planetary Sciences, thermal infrared, lcsh:Q, Geology
Abstract: Co-auteur étranger; International audience; Of all the key parameters needed to inform forecast models for volcanic plumes,real-time tracking particle size distribution (PSD) of pyroclasts leaving the vent coupledwith plume modeling has probably the highest potential for effective managementof volcanic hazard associated with plume dispersal and sedimentation. This paperpresents a novel algorithm capable of providing syn-emission horizontal size and velocityof particles in real time, converted in mass discharge rates, and its evolution during anexplosion, using thermal infrared videos. We present data on explosions that occurredat the SW crater of Stromboli volcano (Italy) in 2012. PSDs and mass eruption rate(MER) data, collected at frequencies of 40 Hz, are then coupled with particle and gasspeed data collected with traditional image analysis techniques. The dataset is usedto quantify for the first time the dynamics of the explosions and the regime of magmafragmentation. We find that explosive evacuation of magma from a Strombolian conduitduring a single explosion proceeds at a constant rate while the explosive dynamicsare marked by a pattern that includes an initial transient and short phase until thesystem stabilizes at equilibrium. These stationary conditions dominate the emission. Allexplosions begin with a gas jet (onset phase), with maximum recorded vertical velocitiesabove 150 m/s. These high velocities are for small particles carried by the faster movinggas or pressure wave, and larger particles typically have slower velocities. The gas jetsare followed by a particle-loaded plume. The particles increase in number until theexplosion dynamics become almost constant (in the stationary phase). MER is eitherstable or increases during the onset to become stable in the stationary phase. Theshearing at the interface between the magma and the gas jets controls fragmentationdynamics and particles sizes. Quantification of the Reynolds and Weber numberssuggests that the fragmentation regime changes during an explosion to affect particleshape. The algorithm proposed requires low-cost thermal monitoring systems, and lowprocessing capability, but is robust, powerful, and accurate and is able to provide datawith unprecedented accuracy. In general terms, its applicability is limited by the size ofindividual pixels recorded by the camera, which depends on the detector, the recordingdistance, and the optical system, particle temperature, which has to be significantlyhigher than the background.
Published: 2019

33. Meteorological Data-Based Optimal Control Strategy for Microalgae Cultivation in Open Pond Systems

Author: Riccardo De-Luca, Fabrizio Bezzo, Quentin Béchet, Olivier Bernard, Biological control of artificial ecosystems (BIOCORE), Inria Sophia Antipolis - Méditerranée (CRISAM), Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de la Recherche Agronomique (INRA)-Laboratoire d'océanographie de Villefranche (LOV), Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de la Mer de Villefranche (IMEV), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de la Mer de Villefranche (IMEV), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche [Padova], Universita degli Studi di Padova, Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria)-Laboratoire d'océanographie de Villefranche (LOV), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Riccardo De-Luca and Fabrizio Bezzo acknowledge thesupport of Project PRIN 2012 Improving Biofuels and HighAdded Value Molecules Production from Unicellular Algae (2012XSAWYM)., ANR-14-CE04-0011,Phycover,Durabilité des productions microalgales par recyclage du phosphore et de l'azote des eaux résiduaires : vers la station d'épuration du futur(2014), and Università degli Studi di Padova = University of Padua (Unipd)
Subjects: Article Subject, [INFO.INFO-AU]Computer Science [cs]/Automatic Control Engineering, lcsh:Electronic computers. Computer science, lcsh:QA75.5-76.95
Abstract: International audience; Outdoor biofuel production from microalgae is a complex dynamical process submitted to climatic variations. Controlling andoptimizing such a nonlinear process strongly influenced by weather conditions is therefore tricky, but it is crucial to make thisprocess economically sustainable. The strategy investigated in this study uses weather forecast coupled to a detailed predictivemodel of algal productivity for online optimization of the rates of fresh medium injection and culture removal into and from thepond. This optimization strategy was applied at various climatic conditions and significantly increased productivity compared to astandard operation with constant pond depth and dilution rate, by up to a factor of 2.2 in a Mediterranean climate in summer. Athorough analysis of the optimizer strategy revealed that the increase of productivity in summer was achieved by finding a trade-off between algal concentration to optimally distribute light and pond temperature to get closer to optimal growth temperature.This study also revealed that maintaining the temperature as high as possible is the best strategy to maximize productivity in coldclimatic conditions
Published: 2019

34. Sr, Nd, Pb and trace element systematics of the New Caledonia harzburgites: Tracking source depletion and contamination processes in a SSZ setting

Author: Dominique Cluzel, Arianna Secchiari, Alessandra Montanini, Delphine Bosch, Patrizia Macera, Dipartimento di Scienze Chimiche,della Vita e della Sostenibilità Ambientale, University of Parma = Università degli studi di Parma [Parme, Italie], Géosciences Montpellier, Institut national des sciences de l'Univers (INSU - CNRS)-Université de Montpellier (UM)-Université des Antilles (UA)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze della Terra [Pisa], University of Pisa - Università di Pisa, Institut de sciences exactes et appliquées (ISEA), and Université de la Nouvelle-Calédonie (UNC)
Subjects: Intra-oceanic arcs, 010504 meteorology & atmospheric sciences, Mantle wedge, Geochemistry, engineering.material, 010502 geochemistry & geophysics, 01 natural sciences, Mantle (geology), [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, New Caledonia ophiolite, Plagioclase, Subduction zones, Metasomatism, 0105 earth and related environmental sciences, Peridotite, Radiogenic nuclide, Olivine, Fore-ac harzburgites, Settore GEO/07 - Petrologia e Petrografia, lcsh:QE1-996.5, Trace element, Sr-Nd-Pb isotopes, Depleted mantle sections, lcsh:Geology, 13. Climate action, engineering, General Earth and Planetary Sciences, Geology
Abstract: The New Caledonia ophiolite (Peridotite Nappe) consists primarily of harzburgites, locally overlain by mafic-ultramafic cumulates, and minor spinel and plagioclase lherzolites. In this study, a comprehensive geochemical data set (major and trace element, Sr-Nd-Pb isotopes) has been obtained on a new set of fresh harzburgites in order to track the processes recorded by this mantle section and its evolution.The studied harzburgites are low-strain tectonites showing porphyroclastic textures, locally grading into protomylonitic textures. They exhibit a refractory nature, as attested by the notable absence of primary clinopyroxene, very high Fo content of olivine (91–93 mol.%), high Mg# of orthopyroxene (0.91–0.93) and high Cr# of spinel (0.44–0.71). The harzburgites are characterised by remarkably low REE concentrations (
Published: 2019

35. Tunable and Reversible Gelatin‐Based Bonding for Microfluidic Cell Culture

Author: Antoine Riaud, Valérie Taly, Claudio Nastruzzi, Gabriele Pitingolo, TALY, Valerie, Médecine Personnalisée, Pharmacogénomique, Optimisation Thérapeutique (MEPPOT - U1147), Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), Dipartimento di Scienze Chimiche e Farmaceutiche [Ferrara, Italy], Università degli Studi di Ferrara = University of Ferrara (UniFE), This work was supported by the Ministère de l’Enseignement Supérieur et de la Recherche, the Université Paris-Descartes, the Centre National de la Recherche Scientifique (CNRS), the Institut National de la Santé et de la Recherche Médicale (INSERM), the Institut National du Cancer (INCA) and canceropole Ile-de-France (no. 2016-1-EMERG-54-UP 5–1), the SIRIC CARPEM, the Fondation de la Recherche Medicale (SPF20160936257), the ligue nationale contre le cancer (LNCC, Program 'Equipe labelisée LIGUE', no. EL2016.LNCC/VaT). The authors acknowledges the financial support of HTE Program-HetColi network, INSERM Physicancer program (no. PC201423) and the SIRIC CARPEM. Financial supports from CAMPUS FRANCE (no. 39525QJ) and Università Italo-Francese (no. G18_208) are gratefully acknowledged. This work was carried out with the support of the Pierre-Gilles de Gennes Institute equipment ('Investissements d’Avenir' program, reference: ANR 10-NANO 0207)., and Università degli Studi di Ferrara (UniFE)
Subjects: Materials science, food.ingredient, [SDV]Life Sciences [q-bio], Microfluidics, Nanotechnology, 02 engineering and technology, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, microfluidic chip, 01 natural sciences, Gelatin, gelatin, food, microfluidic cell culture, reversible bonding, General Materials Science, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, 010401 analytical chemistry, Ambientale, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [SDV] Life Sciences [q-bio], Microfluidic chip, Cell culture, 0210 nano-technology
Abstract: International audience; The development of novel bonding techniques could enable new applications and uses of plastics in microfluidic cell culture, complementing the omnipresent polydimethylsiloxane (PDMS). In this respect, the present paper describes a reversible gelatin-based method (named GEL-D) for bonding microfluidic chip parts, constituted of different materials. The herein introduced method enables the bonding of the most of the commonly used materials in microfluidics such as PMMA, PDMS, glass and NOA. Notably, the fabricated chips resist to pressure up to 0.7 MPa, to organic solvent exposure and temperature up to 70 C. To show the versatility of the described method, microchips with different sizes, materials, and geometries were bonded, including microchannel down to 200mm (width x depth) and round microstructures. The bonded chips are suitable to microfluidic cell culture procedures, including formation of microtissues, cells viability analysis and confocal microscopy. Therefore, the room-temperature bonding method appear to be highly efficient for cell culture on plastic chips, where in situ analysis of the seeded cells is required after microchip de-bonding.
Published: 2019

36. Origin of the spinel-pyroxene symplectites in the harzburgites from the New Caledonia Peridotite

Author: Dominique Cluzel, Arianna Secchiari, Alessandra Montanini, delphine bosch, Patrizia Macera, Dipartimento di Scienze Chimiche,della Vita e della Sostenibilità Ambientale, University of Parma = Università degli studi di Parma [Parme, Italie], Géosciences Montpellier, Institut national des sciences de l'Univers (INSU - CNRS)-Université de Montpellier (UM)-Université des Antilles (UA)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze della Terra [Pisa], University of Pisa - Università di Pisa, and Université de la Nouvelle-Calédonie (UNC)
Subjects: spinel-pyroxene clusters, symplectites, spinel-pyroxem clusters, harzburgites, Settore GEO/07 - Petrologia e Petrografia, New Caledonia Ophiolite, [SDU.STU.PE]Sciences of the Universe [physics]/Earth Sciences/Petrography, Harzburgites, Melt-rock reactions, Spinel-pyroxene clusters, Subduction zones, Symplectites, melt-rock reactions, subduction zones
Abstract: The New Caledonia ophiolite (Peridotite Nappe) hosts one of the largest and best-exposed mantle section worldwide, providing an exceptional insight into upper mantle processes. The Peridotite Nappe is mostly dominated by harzburgites, locally overlain by mafic-ultramafic cumulates, but also includes minor spinel and plagioclase lherzolites, cropping out in the northern part of the island. The New Caledonia harzburgites are low-strain tectonites, showing dominant porphyroclastic textures. The main mantle paragenesis is constituted by olivine (~ 75-85 vol%), orthopyroxene (~ 15-25 vol%) and spinel (< 1 vol%), while primary clinopyroxene is notably absent. An important textural feature of these mantle rocks is represented by the common occurrence of spinel-pyroxene symplectitic aggregates.In this work, we present a petrographical, textural and major element chemical characterization of the spinel-pyroxene symplectitic intergrowths occurring in the New Caledonia harzburgites (Kopeto, Central Massif, and Yaté, Massif du Sud). Based on textures, size and relationships with the other mineral phases, these spinel-pyroxene clusters have been divided into two types, named type-A and type-B.Type-A symplectites occur in the Kopeto harzburgites and are composed of spinel-orthopyroxene (± clinopyroxene) intergrowths. In type-A symplectites, symplectitic spinel (Spl2) occurs as abundant vermicular shaped grains, ranging in size from ~ 0.5 to 2 mm. By contrast, spinel of the porphyroclastic assemblage (Spl1) shows smaller size (in the range of few m) and notably lower abundances (< 1%). Type-A symplectites develop exclusively on porphyroclastic olivine, which in turn displays evidence of chemical disequilibrium and corroded outlines. Bulk major element composition reconstructed for type-A symplectites rule out a derivation from a pre-existing garnet phase, as the model garnet compositions do not satisfy garnet stoichiometry, being characterized by Si deficiency. By contrast, major element chemical variations of the symplectitic phases, coupled with the high abundance of Spl2 and olivine resorption, suggest an origin from reactive percolation of opx-saturated hydrous melts or slab-derived fluids in a subduction zone setting.Type-B symplectites are found in Yaté sample and consist of spinel-orthopyroxene (± clinopyroxene). They are characterized by smaller size (few hundreds of m, i.e. “micro-symplectites”) and different shapes compared to type-A symplectites, growing as vermicular, “myrmekite-like” intergrowths at the rims of porphyroclastic orthopyroxene. Major element chemical compositions of type-B symplectites are consistent with an origin as “cooling textures”. These structures may derive from unmixing of a high-T, Al-Cr rich, orthopyroxene due to the decreased solubility of the Cr-Al component (CrMgTs) during post-melting lithospheric cooling at T < 900°C.
Published: 2019

37. Multistimuli‐responsive materials from benzothiadiazole‐based charge‐transfer chromophores: Interdependence of optical properties and aggregation

Author: Brunella Bardi, Sonia Ladeira, Marine Tassé, Kathleen I. Moineau-Chane Ching, Anna Painelli, Chunxiang Dall’Agnese, Francesca Terenziani, Dipartimento di Scienze Chimiche,della Vita e della Sostenibilità Ambientale, University of Parma = Università degli studi di Parma [Parme, Italie]-Dipartimento di Chimica, Università degli studi di Parma, University of Parma = Università degli studi di Parma [Parme, Italie], Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Aggregates, Materials science, Theoretical modelling, Energy transfer, Organic Chemistry, Charge (physics), 02 engineering and technology, Chromophore, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Fluorescence, Stimuli responsiveness, 0104 chemical sciences, Analytical Chemistry, Chemical physics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; A family of multipolar V‐shaped chromophores bearing an A′‐D‐A‐D‐A′ structure were investigated, where 2,1,3‐benzothiadiazole, acting as the central electron acceptor (A), is linked to two thiophene‐based electron‐donating moieties (D) end‐capped with alkyl‐cyanoacetate substituents (A′). The spectroscopic properties of thin films and powders were investigated and were compared to solutions and nanoaggregates. The optical properties strongly depended on the aggregation state and could be tuned by means of thermal treatment (annealing) of the films and through mechanical treatment (grinding) of the powders, demonstrating that these materials are multistimuli responsive. The spectroscopic analysis revealed the partial formation of J‐aggregates both in the films and in powders, despite the weak luminescence. This behavior was interpreted as due to the partial formation of poorly fluorescent red‐shifted aggregates acting as a sink in an efficient excitation energy‐transfer process from J‐aggregates.
Published: 2018

38. Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks

Author: Bruno J. C. Vieira, José Ramón Galán-Mascarós, Suchithra Ashoka Sahadevan, El-Eulmi Bendeif, Noemi Monni, Enric Canadell, Maria Laura Mercuri, Cristina Sáenz de Pipaón, Narcis Avarvari, Pere Alemany, Sébastien Pillet, Pascale Auban-Senzier, João C. Waerenborgh, Alexandre Abhervé, Universita degli Studi di Cagliari [Cagliari], MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular, Universitat de València (UV)-Instituto de Ciencia Molecular, Barcelona Institute of Science and Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Instituto Superior Técnico, Universidade Técnica de Lisboa (IST), Centro de Cien̂cias e Tecnologias Nucleares, Universidade de Lisboa (ULISBOA), Laboratoire de Physique des Solides (LPS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Universitat de Barcelona (Diagonal 647), Universitat de Barcelona (UB), Instituto de Ciencia de Materiales de Aragón [Saragoza, España] (ICMA-CSIC), University of Zaragoza - Universidad de Zaragoza [Zaragoza], Dipartimento di Scienze Chimiche e Geologiche, IMPACT N4S, ANR-15-IDEX-0004,LUE,Isite LUE(2015), Centre National de la Recherche Scientifique (France), Université d’Angers, Région des Pays de la Loire, Université de Lorraine (France), Regione Autonoma della Sardegna, Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, and Fundação para a Ciência e a Tecnologia (Portugal)
Subjects: Anions, Coordination polymer, 02 engineering and technology, Iron compounds, 010402 general chemistry, Polaron, Ligands, 01 natural sciences, Biochemistry, Catalysis, Hydrogen bonds, Magnetic susceptibility, chemistry.chemical_compound, Colloid and Surface Chemistry, Electric conductivity, Oxalic acid, PolaronsPolymers, Oxidation state, Mössbauer spectroscopy, [CHIM]Chemical Sciences, Magnetic materials, ComputingMilieux_MISCELLANEOUS, Valence (chemistry), Hydrogen bond, Ligand, 2D coordination polymers, General Chemistry, Conductivitat elèctrica, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, Coordination polymers, Crystallography, Lligands, chemistry, Electron delocalization, 0210 nano-technology
Abstract: The mixed-valence FeIIFeIII 2D coordination polymer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2− = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [FeIIFeIII(ClCNAn)3]− establish in the ab plane, with an intralayer metal−metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe−O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C3 symmetry to the structure and engages in intermolecular N−H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10−3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type FeIIFeIII 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones., The work in France was supported by the CNRS, the University of Angers, the Erasmus program (mobility grant to N.M.), the RFI Regional project LUMOMAT (grant to A.A., project ASCO MMM), and the PIA project “Lorraine Université d'Excellence” (reference ANR-15-IDEX-04-LUE). This work was supported in Italy by the Fondazione di Sardegna-Convenzione triennale tra la Fondazione di Sardegna e gli Atenei Sardi, Regione Sardegna-L.R. 7/2007 annualità 2016-DGR 28/21 del 17.05.2015 “Innovative Molecular Functional Materials for Environmental and Biomedical Applications” and INSTM. Work in Spain was supported by the Spanish Ministerio de Economi ́ a y Competitividad (Grants FIS2012-37549-C05-05, FIS2015-64886-C5-4-P, CTQ2015- 64579-C3-3-P, and CTQ2015-71287-R) and Generalitat de Catalunya (2014SGR301, 2017SGR797, and XRQTC and the CERCA program). E.C. acknowledges support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under Grant SEV-2015-0496. J.C.W. and B.J.C.V. acknowledge Fundaca̧ o para a Cie ̃ ncia e a Tecnologia (FCT, ̂ Portugal) through the project UID/Multi/04349/2013.
Published: 2018

39. Nanosheets of Two-Dimensional Neutral Coordination Polymers Based on Near-Infrared-Emitting Lanthanides and a Chlorocyananilate Ligand

Author: Antonio Andrea Mura, Carla Cannas, Valerio Sarritzu, Nicola Sestu, Daniela Marongiu, Suchithra Ashoka Sahadevan, Francesco Quochi, Maria Laura Mercuri, Alexandre Abhervé, Giovanni Bongiovanni, Michele Saba, Narcis Avarvari, Noemi Monni, Universita degli Studi di Cagliari [Cagliari], Instituto de Ciencia Molecular, Universitat de València (UV)-Instituto de Ciencia Molecular, MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche, and Università di Cagliari
Subjects: Lanthanide, chemistry.chemical_classification, Solid-state chemistry, Materials science, Ligand, General Chemical Engineering, Near-infrared spectroscopy, 02 engineering and technology, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Exfoliation joint, 0104 chemical sciences, Characterization (materials science), Crystallography, chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: The synthesis, structural characterization, photophysical studies, and exfoliation of two-dimensional (2D) layered coordination polymers, formulated as {[Ln2(ClCNAn)3(DMF)6]·(DCM)x}n (Ln(III) = Yb(...
Published: 2018

40. Processing and Investigation Methods in Mechanochemical Kinetics

Author: Andrea Porcheddu, Pier Carlo Ricci, Evelina Colacino, Maria Carta, Francesco Delogu, Giorgio Pia, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Universita degli Studi di Cagliari [Cagliari], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, Università di Cagliari, and Dipartimento di Ingegneria Meccanica
Subjects: Work (thermodynamics), 010405 organic chemistry, business.industry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Scale (chemistry), Kinetics, Context (language use), General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Article, 0104 chemical sciences, Broad spectrum, Investigation methods, Transformation kinetics, Process engineering, business, Material properties, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; The present work focuses on the challenges that emerge inconnection with the kinetics of mechanically activated transformations. This isan important topics to comprehend to enable the full exploitation ofmechanical processing in a broad spectrum of areas related to chemistry andmaterials science and engineering. Emerging challenges involve a number offacets regarding materials and material properties, working principles of ballmills and milling conditions, and local changes occurring in series in processedmaterials. Within this context, it is highly desirable to relate the nature andrate of observed mechanochemical transformations to individual collisions andthen to the processes induced by mechanical stresses on the molecular scale.Hence, it is necessary to characterize the milling regimes that can establish inball mills regarding frequency and energy of collisions, map the relationshipbetween milling dynamics and transformation kinetics, and obtain mechanisticinformation through proper time-resolved investigations in situ. A few specific hints are provided in this respect.
Published: 2018

41. Dynamic Nuclear Polarization-Enhanced Biomolecular NMR Spectroscopy at High Magnetic Field with Fast Magic-Angle Spinning

Author: Olivier Ouari, Diane Cala de Paepe, Inara Akopjana, Svetlana Kotelovica, G. Pintacuda, Anne Lesage, Andrea Pica, Andrew J. Pell, Kristaps Jaudzems, Andrea Bertarello, Sachin Rama Chaudhari, Emeline Barbet-Massin, Kaspars Tars, David Gajan, Biological Solid-State NMR Methods - Méthodes de RMN à l'état solide en biologie, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Dipartimento di Scienze Chimiche, Università degli studi di Napoli Federico II, Department of Materials and Environmental Chemistry - Arrhenius Laboratory, Biomed Res & Study Ctr, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We acknowledge financial support from the CNRS, the EQUIPEX (contract ANR-10-EQPX-47-01), the Agence Nationale de la Recherche (contract ANR15-CE29-002202), and the People Programme of the European Union's FP7 (FP7- PEOPLE-2012-ITN no. 317127 'pNMR'). K.J. is supported by a MC incoming fellowship (REA grant agreement no. 661175 'virus-DNP-NMR'). A.P. is supported by Fondazione con il Sud (grant 2011-PDR-19)., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project: 317127,EC:FP7:PEOPLE,FP7-PEOPLE-2012-ITN,PNMR(2013), 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), and University of Naples Federico II = Università degli studi di Napoli Federico II
Subjects: Materials science, magic-angle spinning, 010405 organic chemistry, General Medicine, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Polarization (waves), 01 natural sciences, Molecular physics, Catalysis, Spectral line, 0104 chemical sciences, NMR spectra database, dynamic nuclear polarization, Paramagnetism, Magic angle spinning, [CHIM]Chemical Sciences, biomolecular NMR, solid-state NMR spectroscopy, High magnetic field, Coherence (physics)
Abstract: International audience; Dynamic nuclear polarization (DNP) is a powerful way to overcome the sensitivity limitation of magic-angle-spinning (MAS) NMR experiments. However, the resolution of the DNPNMR spectra of proteins is compromised by severe line broadening associated with the necessity to perform experiments at cryogenic temperatures and in the presence of paramagnetic radicals. High-quality DNP-enhanced NMR spectra of the Acinetobacter phage 205 (AP205) nucleocapsid can be obtained by combining high magnetic field (800MHz) and fast MAS (40kHz). These conditions yield enhanced resolution and long coherence lifetimes allowing the acquisition of resolved 2D correlation spectra and of previously unfeasible scalar-based experiments. This enables the assignment of aromatic resonances of the AP205 coat protein and its packaged RNA, as well as the detection of long-range contacts, which are not observed at room temperature, opening new possibilities for structure determination.
Published: 2018

42. Overview of atmospheric composition in Western Mediterranean during PEACETIME cruise

Author: Desboeufs, Karine, Doussin, Jean-Francois, Giorio, Chiara, Triquet, Sylvain, Fu, Yinghe, Riffault, Véronique, Dulac, François, Féron, Anaïs, Maisonneuve, Franck, Siour, Guillaume, Zapf, Pascal, Guieu, Cecile, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Laboratoire Chimie de l'environnement (LCE), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche [Padova], Università degli Studi di Padova = University of Padua (Unipd), Centre for Energy and Environment (CERI EE - IMT Nord Europe), Ecole nationale supérieure Mines-Télécom Lille Douai (IMT Nord Europe), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Ecole nationale supérieure Mines-Télécom Lille Douai (IMT Lille Douai), Institut Mines-Télécom [Paris] (IMT), Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'océanographie de Villefranche (LOV), Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de la Mer de Villefranche (IMEV), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Riffault, Véronique, Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC), Universita degli Studi di Padova, Centre for Energy and Environment (CERI EE), and Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)
Subjects: [SDE] Environmental Sciences, [PHYS]Physics [physics], [SDU.OCEAN]Sciences of the Universe [physics]/Ocean, Atmosphere, [SDU.OCEAN] Sciences of the Universe [physics]/Ocean, Atmosphere, [CHIM] Chemical Sciences, [SDE]Environmental Sciences, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, [PHYS] Physics [physics]
Abstract: International audience
Published: 2018

43. Crystal structures ofLymphocytic choriomeningitis virusendonuclease domain complexed with diketo-acid ligands

Author: Saez-Ayala, Magali, Yekwa, Elsie, Carcelli, Mauro, Canard, Bruno, ALVAREZ, Karine, Ferron, Francois, Architecture et fonction des macromolécules biologiques (AFMB), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Università degli studi di Parma = University of Parma (UNIPR), European Virus Bioinformatics Center [Jena], ANR-11-BSV8-0019,ArenaBunya-L,Structures, mecanismes, et conception d'inhibiteurs des protéines L des Bunyavirus et Arenavirus(2011), ANR-10-INBS-0005,FRISBI,Infrastructure Française pour la Biologie Structurale Intégrée(2010), and Dipartimento di Scienze Chimiche, della Vita, della Sostenibilita`Ambientale, Universita`Di Parma
Subjects: metal chelation, viruses, compound optimization, [SDV]Life Sciences [q-bio], Lymphocytic choriomeningitis virus, diketo acids, LCMV, Arenaviridae, endonucleases, compounds optimization, endonuclease
Abstract: International audience; The Arenaviridae family is one of the three negative stranded RNA viral families encoding an endonuclease in their genome, together with Bunyaviridae and Orthomyxoviridae. The endonuclease domain is carried at the N-terminal of the L protein, a multifunctional protein that includes the RNA dependent RNA polymerase. The synthesis of mRNA in arenaviruses is a process that is primed by capped nucleotides stolen from the cellular mRNA by the endonuclease domain in cooperation with other domains of L protein. This molecular mechanism had been demonstrated earlier by our group on the endonuclease of the prototype Lymphocytic ChorioMeningitis virus (LCMV). However, the mode of action of this enzyme is not fully understood as the original structure did not contain the catalytic metal ions. The pivotal role played by the cap-snatching process in the life cycle of the virus and the highly conserved nature of the endonuclease domain makes it a target of choice for the development of novel antiviral therapy. Here we evaluated using biophysical methods the binding affinity of two diketo acids (DKAs) compounds (DPBA (1) and L-742,001 (2)) onto the LCMV endonuclease domain. We have determined the X-ray structures of LCMV endonuclease domain with catalytic ions in complex with these two compounds, and assessed their efficacy in an in vitro endonuclease activity assay. Based on these data and computational simulation, we synthesized two new DKAs. The LCMV endonuclease exhibits a good affinity for these DKAs making them a good starting point for the design of arenavirus endonuclease inhibitors. Beside being the first example of an arenavirus endonuclease X-ray structure incorporating a ligand, this study is a proof of concept that the design of optimized inhibitors against the arenavirus endonuclease is possible.
Published: 2018

44. Mineralizations and transition metal mobility driven by organic carbon during low-temperature serpentinization

Author: Valerio Pasini, Daniele Brunelli, François Guyot, Karim Benzerara, Bénédicte Ménez, Sylvain Bernard, Institut de Physique du Globe de Paris (IPGP), Centre National de la Recherche Scientifique (CNRS)-Université de La Réunion (UR)-Université Paris Diderot - Paris 7 (UPD7)-IPG PARIS-Institut national des sciences de l'Univers (INSU - CNRS), Dipartimento di scienze chimiche e geologiche, Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Istituto di Scienze del Mare, Consiglio Nazionale delle Ricerche [Roma] (CNR), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)
Subjects: 010504 meteorology & atmospheric sciences, Geochemistry, Biomass, 010502 geochemistry & geophysics, 01 natural sciences, Hydrothermal circulation, Extracellular polymeric substance, Geochemistry and Petrology, Oceanic crust, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Ecosystem, Organic carbon, 0105 earth and related environmental sciences, Metal mobility, Total organic carbon, geography, geography.geographical_feature_category, Supergene ore formation, Mid-Ocean ridges, Organomineralization, Serpentinization, Biofilm, Geology, Mid-ocean ridge, 13. Climate action, Environmental chemistry, [SDU.STU.MI]Sciences of the Universe [physics]/Earth Sciences/Mineralogy
Abstract: Serpentinization is known to provide substantial amounts of energy in the form of molecular hydrogen along with a suite of abiotic organic compounds of low molecular weight (mainly as short chain alkanes and carboxylic acids), all sustaining the development of microbial ecosystems in the mantle-derived crust. The latter have a cryptoendolithic life style and are responsible for (i) the local formation of biomass and of organic metabolic byproducts and (ii) the production of extracellular polymeric substances which organize the community in the form of a biofilm at the surface of the rock-forming minerals. In accordance, whatever their origin, organic compounds can be diverse and widespread in the shallow oceanic crust where they undergo hydrothermal degradation and remobilization through fluid circulations. Here we show that organic carbon is directly involved in low temperature serpentinization reactions (< 200 degrees C). Fine scale investigations of microbial niches hosted in serpentinites from the Mid-Atlantic ridge were performed using scanning and transmission electron microscopy along with scanning transmission X-ray microscopy. They suggest that organic coatings at mineral surfaces may influence the nature and structure of the serpentinization products as well as the mobility and speciation of transition metals as the reaction progresses. This likely constitutes an efficient yet poorly considered mechanism in active serpentinizing systems with possible implications for ore formation associated with the alteration of ophiolitic massifs and subsurface storage. (C) 2018 Elsevier B.V. All rights reserved.
Published: 2018

45. Bradyrhizobium Lipid A: Immunological Properties and Molecular Basis of Its Binding to the Myeloid Differentiation Protein-2/Toll-Like Receptor 4 Complex

Author: Luigi Lembo-Fazio, Jean-Marc Billod, Flaviana Di Lorenzo, Ida Paciello, Mateusz Pallach, Sara Vaz-Francisco, Aurora Holgado, Rudi Beyaert, Manuel Fresno, Atsushi Shimoyama, Rosa Lanzetta, Koichi Fukase, Djamel Gully, Eric Giraud, Sonsoles Martín-Santamaría, Maria-Lina Bernardini, Alba Silipo, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Centro de Investigaciones Biológicas (CIB), Dipartimento di Scienze Chimiche, Complesso Universitario Monte Sant’Angelo, University of Naples Federico II = Università degli studi di Napoli Federico II, Diomune SL, Partenaires INRAE, Flanders Institute for Biotechnology, Department of Biomedical Molecular Biology, Universiteit Gent = Ghent University (UGENT), Osaka University, Laboratoire des symbioses tropicales et méditerranéennes (UMR LSTM), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Université Montpellier 1 (UM1)-Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Université Montpellier 2 - Sciences et Techniques (UM2)-Université de Montpellier (UM)-Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Spanish MINECO [CTQ2014-57141-R, CTQ2017-88353-R], European Project: 642157,H2020,H2020-MSCA-ITN-2014,TOLLerant(2015), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Università degli studi di Napoli Federico II, Universiteit Gent = Ghent University [Belgium] (UGENT), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), Lembo-Fazio, Luigi, Billod, Jean-Marc, Di Lorenzo, Flaviana, Paciello, Ida, Pallach, Mateusz, Vaz-Francisco, Sara, Holgado, Aurora, Beyaert, Rudi, Fresno, Manuel, Shimoyama, Atsushi, Lanzetta, Rosa, Fukase, Koichi, Gully, Djamel, Giraud, Eric, Martín-Santamaría, Sonsole, Bernardini, Maria-Lina, and Silipo, Alba
Subjects: 0301 basic medicine, INTERFERON-BETA, Lipopolysaccharide, AIRWAY INFLAMMATION, inflammatory cytokines, Biodiversité et Ecologie, myeloid differentiation protein-2/toll-like receptor 4, Lipid A, ACTIVATION, chemistry.chemical_compound, Medicine and Health Sciences, Immunology and Allergy, Bradyrhizobium lipid A, Inflammatory cytokines, Innate immunity, Molecular modeling, Myeloid differentiation protein-2/toll-like receptor 4, Immunology, Receptor, innate immunity, Original Research, Toll-like receptor, PROPOSED STRUCTURE, biology, lipopolysaccharide, Biochemistry, differentiation protein-2toll-like receptor 4, lipids (amino acids, peptides, and proteins), myeloid, réponse immunitaire innée, lcsh:Immunologic diseases. Allergy, LPS, Inflammatory cytokine, 030106 microbiology, BIOLOGICAL-ACTIVITIES, Bradyrhizobium, Biodiversity and Ecology, 03 medical and health sciences, Immune system, propriété immunologique, molecular modeling, differentiation protein-2/toll-like receptor 4, modélisation, ANTAGONIST, Innate immune system, bradyrhizobium, lps, RECOGNITION, Biology and Life Sciences, biology.organism_classification, 030104 developmental biology, chemistry, TLR4, FORCE-FIELD, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, lcsh:RC581-607
Abstract: International audience; Lipopolysaccharides (LPS) are potent activator of the innate immune response through the binding to the myeloid differentiation protein-2 (MD-2)/toll-like receptor 4 (TLR4) receptor complexes. Although a variety of LPSs have been characterized so far, a detailed molecular description of the structure-activity relationship of the lipid A part has yet to be clarified. Photosynthetic Bradyrhizobium strains, symbiont of Aeschynomene legumes, express distinctive LPSs bearing very long-chain fatty acids with a hopanoid moiety covalently linked to the lipid A region. Here, we investigated the immunological properties of LPSs isolated from Bradyrhizobium strains on both murine and human immune systems. We found that they exhibit a weak agonistic activity and, more interestingly, a potent inhibitory effect on MD-2/TLR4 activation exerted by toxic enterobacterial LPSs. By applying computational modeling techniques, we also furnished a plausible explanation for the Bradyrhizobium LPS inhibitory activity at atomic level, revealing that its uncommon lipid A chemical features could impair the proper formation of the receptorial complex, and/or has a destabilizing effect on the pre-assembled complex itself.
Published: 2018

46. Homo- and co-polymerization of ethylene with cyclic olefins catalyzed by phosphine adducts of (imido)vanadium(IV) complexes

Author: Fabio Bertini, Giuseppe Leone, Laure Vendier, Giorgia Zanchin, Christian Lorber, Ivana Pierro, Giovanni Ricci, Istituto per lo Studio delle Macromolecole, ISMAC, Consiglio Nazionale delle Ricerche [Roma] (CNR), Dipartimento di Chimica, Università degli Studi di Milano [Milano] (UNIMI), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Scienze Chimiche, and Università degli studi di Napoli Federico II
Subjects: Ethylene, 010405 organic chemistry, Comonomer, Organic Chemistry, Vanadium, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Dicyclopentadiene, ethylene copolymerization, vanadium catalysts, norbornene, Polymer chemistry, Copolymer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Phosphine, Norbornene
Abstract: International audience; The synthesis and the characterization of a series of phosphine adducts of (imido)vanadium(IV) dichloride complexes of the type V(═NR)Cl2(PMe2Ph)2 [R = 2,6-Cl2-Ph (1), 2,6-iPr2-Ph (2), and tBu (3)] and V(═NtBu)Cl2(PMe3)2 (3′) are reported. The solid-state structures of 1 and 3′ were determined by X-ray crystallography. The complexes present a geometry around the metal center between a distorted trigonal-bipyramid and a square pyramid, with an almost linear N–V–C bond. Complexes 1–3 were evaluated as catalyst precursors for the polymerization of ethylene and ethylene copolymerization with various cyclic olefins (i.e., norbornene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene). In combination with Et2AlCl (500 equiv to V) and Cl3CCO2Et (ETA, 10 equiv to V), 1–3 are versatile and promising catalysts for the synthesis of high molecular weight linear poly(ethylene)s and alternating copolymers with efficient comonomer incorporation, unimodal molecular weight distributions, and uniform composition under mild conditions. Differences in the homo- and copolymerization of ethylene regarding the activity, stability over temperature, reactivity toward the target comonomers, and (co)polymer chain growth were investigated to probe the effects of imido ligand substitution. The introduction of more electron-donating groups led to an increase in polymers molecular weight and provided increased stability over temperature to the catalysts, particularly for 3. Both of these effects are likely because the tert-butyl imido moiety in 3 strengthens the V–N bond, thus improving the stability of the active intermediate. The steric shielding of the tert-butyl group may also contribute to inhibit the associative chain transfer. Control over the molecular weight of the resultant copolymers proved to be possible also by varying the ETA loading. ETA acts as a reoxidant, restarting the catalytic cycle, but it behaves also like a chain transfer agent and to a different extent strongly depending on the type of imido ligand.
Published: 2018

47. New Sulfur-Containing Polyarsenicals from the New Caledonian Sponge Echinochalina bargibanti

Author: Petri Tähtinen, Giacomo Saielli, Edouard Hnawia, Cécile Debitus, Graziano Guella, Ines Mancini, University of Turku, Università degli Studi di Trento (UNITN), Dipartimento di Scienze Chimiche [Padova], Universita degli Studi di Padova, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD), Laboratoire Insulaire du Vivant et de l'Environnement (LIVE), Université de la Nouvelle-Calédonie (UNC), Università degli Studi di Padova = University of Padua (Unipd), and Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Circular dichroism, Magnetic Resonance Spectroscopy, extracts, compound, natural products, Pharmaceutical Science, arsenical, 01 natural sciences, arsenicin, Arsenicals, Mass Spectrometry, Anti-Infective Agents, Computational chemistry, antibacterial, calculated NMR spectrum, density functional theory, NMR spectroscopy, structure elucidation, sulfur metabolite, Drug Discovery3003 Pharmaceutical Science, spin coupling-constants, Drug Discovery, ta116, lcsh:QH301-705.5, Pharmacology, Toxicology and Pharmaceutics (miscellaneous), density-functional calculations, arsenosugars, complexes, biology, Chemistry, Circular Dichroism, Nuclear magnetic resonance spectroscopy, Porifera, Antibacterial, Arsenical, Calculated NMR spectrum, Density functional theory, Natural products, Structure elucidation, Sulfur metabolite, orbitals, Echinochalina, Staphylococcus aureus, shifts, in-vitro, 010402 general chemistry, Article, Animals, 010405 organic chemistry, ACL, Carbon-13 NMR, Sulfur containing, biology.organism_classification, 0104 chemical sciences, Sponge, lcsh:Biology (General), Mass spectrum, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Sulfur
Abstract: Isolated from a New Caledonian collection of the poecilosclerid sponge Echinochalina bargibanti, arsenicin A (C3H6As4O3) was described as the first natural organic polyarsenic compound. Continuing on bioassay guided fractionation of the organic extracts of this sponge, we describe here the isolation and structural elucidation of the first sulfur-containing organic polyarsenicals ever found in nature. The novel metabolites, called arsenicin B and arsenicin C, are built on a noradamantane type framework and they further distinguish from the adamantane type framework of arsenicin A by a different heteroatom composition and by the presence of an unusual As-As bonding. Extensive 1D and 2D-NMR measurements, in combination with tandem APCI mass spectra, allowed to establish the structure of arsenicin B (C3H6As4S2) as 2. The scarcity of arsenicin C and and its intrinsic chemical instability, only allowed to collect partial spectral data which prevented the full structural definition. After extensive computational testing of several putative structures, structure 3 for arsenicin C (C3H6As4OS) was inferred by comparing experimental with DFT-calculated 1H and 13C NMR spectra. Finally, the absolute configuration of 2 and 3 were determined with a combined use of experimental and TD-DFT calculated ECD spectra and observed specific rotations. These findings pose great challenges for both the biosynthesis of these metabolites and the cycle of Arsenic in nature. Arsenicin B and arsenicin C showed strong antifungal and antibacterial activities, especially against S. aureus comparable to the antibiotic gentamycin.
Published: 2018

48. Ball-milling and cheap reagents breathe green life into the one hundred-year-old Hofmann reaction

Author: Rita Mocci, Francesco Delogu, Evelina Colacino, Andrea Porcheddu, Lidia De Luca, Sergio Murgia, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Ingegneria Meccanica, Universita degli Studi di Cagliari [Cagliari], Dipartimento di Scienze Chimiche e Geologiche Centro Grandi Strumenti and INSTM unit, and Università di Cagliari
Subjects: Green chemistry, Green Chemistry, Chloroform, Primary (chemistry), 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Isocyanide, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Environmentally friendly, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Carbylamine reaction, Reagent, Mechanochemistry, Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: The Hofmann carbylamine reaction is a very attractive route for preparing isocyanides directly from primary amines. However, its environmentally friendly potential is reduced by the use of hazardous chloroform in large excess. Herein, we report an innovative and very efficient mechanically activated synthesis of isocyanides based on the reaction of amines with chloroform in the presence of solid NaOH and without extra-solvent addition.
Published: 2018

49. Mannosylcalix[n]arenes as multivalent ligands for DC-SIGN

Author: Andrea Magini, Alessandro Casnati, Vanessa Porkolab, Ilaria Morbioli, Francesco Sansone, Franck Fieschi, Dipartimento di Scienze Chimiche, Università degli studi di Parma = University of Parma (UNIPR), 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), University of Parma = Università degli studi di Parma [Parme, Italie], Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Dendrimers, Stereochemistry, Glycocalixarenes, Receptors, Cell Surface, HIV Envelope Protein gp120, 010402 general chemistry, 01 natural sciences, Biochemistry, DC-SIGN, Dendritic cells, Analytical Chemistry, Tetramer, Dendrimer, Calixarene, Humans, Lectins, C-Type, Surface plasmon resonance, Receptor, biology, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], 010405 organic chemistry, Chemistry, Organic Chemistry, Glycoside cluster effect, General Medicine, Surface Plasmon Resonance, Envelope glycoprotein GP120, 0104 chemical sciences, 3. Good health, Membrane, biology.protein, Multivalency, Peptides, Cell Adhesion Molecules
Abstract: International audience; DC-SIGN is a receptor protruded from the membrane of immature dendritic cells (DCs) that participates in the activation of the immune response through the recognition of pathogen-associated molecular patterns (PAMPs). On the other hand, HIV exploits the interaction between high-mannose structures of its envelope glycoprotein gp120 and DC-SIGN to be transported towards and infect T-cells. DC-SIGN is involved in the recognition process in the form of a tetramer and the multiple exposition of carbohydrate recognition sites (CRSs) is amplified by the formation on the DCs membrane of patches of tetramers. DC-SIGN is then considered an interesting target to fight the virus and multivalent systems exposing multiple copies of ligating units for its CRSs are becoming valuable tools to reach this goal. We herein prepared four mannosylated calix[n]arenes (1a-d) and tested them by Surface Plasmon Resonance (SPR) competition assays as inhibitors of the binding between DC-SIGN and a mannosylated BSA used as model of HIV gp120. IC50s in the μM range were found evidencing in particular for compound 1a that, although rather moderate, a multivalent effect is taking place in the inhibition activity of this cluster. A relative potency (rp/n) around 4, respect to the monovalent methyl α-mannoside and normalized for the number of monosaccharide on the scaffold, was observed. This result, compared with previously reported data relative to dendrimers with the same valency, indicates the calixarene as a promising scaffold to build efficient inhibitors for DC-SIGN and, in perspective, for HIV.
Published: 2017

50. Synthesis and Physical Properties of Purely Organic BEDT-TTF-Based Conductors Containing Hetero-/Homosubstituted Cl/CN-Anilate Derivatives

Author: Suchithra Ashoka Sahadevan, Noemi Monni, Maria Laura Mercuri, Narcis Avarvari, Alexandre Abhervé, Enric Canadell, Pascale Auban-Senzier, Universita degli Studi di Cagliari [Cagliari], Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Dipartimento di Scienze Chimiche, Università di Cagliari, MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (France), Université d’Angers, Regione Autonoma della Sardegna, Ministerio de Economía y Competitividad (España), and Generalitat de Catalunya
Subjects: Stereochemistry, 02 engineering and technology, Activation energy, Conductivity, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Anilate, Inorganic Chemistry, chemistry.chemical_compound, Group (periodic table), [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, BEDT-TTF, ComputingMilieux_MISCELLANEOUS, Chemistry, business.industry, Mott insulator, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Electrocrystallization, Crystallography, Semiconductor, Radical ion, Mott Insulator, 0210 nano-technology, business, Tetrathiafulvalene, Monoclinic crystal system
Abstract: Radical cation salts composed of a bis(ethylenedithio)- tetrathiafulvalene (ET) donor with homo-/heterosubstituted Cl/CN anilic acids as purely organic molecular conducting materials formulated as [BEDTTTF]2[HClCNAn] (1) and [BEDT-TTF][HCl2An] (2) have been prepared by electrocrystallization. Compounds 1 and 2 crystallized in the monoclinic space group P2/c for 1 and I2/a for 2, showing segregated donor-anion layers arranged in a α′-type donor packing pattern (1) and twisted parallel columns (2), respectively. Single-crystal conductivity measurements show that 1 is a semiconductor with room-temperature conductivity of 10−2 S cm−1 and an activation energy Ea of 1900 K., This work was supported in France by the CNRS, the University of Angers, the Erasmus program (mobility grant to N.M.), and the RFI Regional project LUMOMAT (grant to A.A.). The work in Italy was supported by the Fondazione di Sardegna-Convenzione triennale tra la Fondazione di Sardegna e gli Atenei Sardi, Regione Sardegna-L.R. 7/2007 annualità 2016-DGR 28/21 del 17.05.2015 “Innovative Molecular Functional Materials for Environmental and Biomedical Applicatons” and INSTM. Special thanks are due to Dr. Walter Marchione and Stefano Gai, HORIBA Italia S.r.l., for Raman measurements. E.C. acknowledges support by the MINECO (Spain) through Grant FIS2015-64886-C5-4-P and the Severo Ochoa Centers of Excellence Program (Grant SEV-2015-0496) as well as by Generalitat de Catalunya (2014SGR301).
Published: 2017

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