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4,035 results on '"Université d'Orléans (UO)"'

1. Synthesis of Heterospirocycles through Gold‐(I) Catalysis: Useful Building Blocks for Medicinal Chemistry

Author

Kossi Efouako Soklou, Hamid Marzag, Karen Plé, Sylvain Routier, Béatrice Vallée, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), PLE, Karen, Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and 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
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nitrogen heterocycles, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Molecular Diversity, Gold catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Synthetic methods, Organic chemistry, Spiro Compounds
Abstract

International audience; Gold-(I) catalysis was used for the intramolecular cyclization of tertiary alcohols with terminal alkynes to form diverse aza-spirocycles. The reaction was carried out with low catalyst loading under microwave irradiation to give both sulfonylated and acylated spirocyclic nitrogen derivatives. Gram scale spirocyclization was carried out and demonstrates the robustness of the reaction. An intramolecular Mizoroki-Heck reaction was performed to give several tetracyclic spirocycles. Double bond reduction and selective protecting group manipulation gave spiropiperazine and spiromorpholine derivatives. These compounds were incorporated into biologically relevant scaffolds to give the first selective spirocyclic inhibitors of LIMK.

Published
2021

2. Geotechnical Behavior and Physico-Chemical Changes of Lime-Treated and Cement-Treated Silty Soil

Author

Muzahim Al-Mukhtar, Mylène Martin, Naima Belayachi, Kévin Beck, Fawzi Bouras, Nouffou Tapsoba, Serge Sabio, Génie Civil (GC), Laboratoire de Mécanique Gabriel Lamé (LaMé), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)

Subjects
Ettringite, Materials science, Aluminate, 0211 other engineering and technologies, Soil Science, 02 engineering and technology, engineering.material, 010502 geochemistry & geophysics, complex mixtures, 01 natural sciences, chemistry.chemical_compound, Architecture, Ultimate tensile strength, ComputingMilieux_MISCELLANEOUS, 021101 geological & geomatics engineering, 0105 earth and related environmental sciences, Lime, Cement, [SPI.GCIV.GEOTECH]Engineering Sciences [physics]/Civil Engineering/Géotechnique, Metallurgy, Geology, California bearing ratio, Geotechnical Engineering and Engineering Geology, 6. Clean water, Compressive strength, chemistry, engineering, Pozzolanic reaction
Abstract

An investigation performed on the interactions of silty soil treated with cement or lime demonstrates the strong relationship between microstructural phenomena and their engineering behavior. Cement hydration induces a rapid improvement in soil properties while the progressive pozzolanic reaction of lime leads to long-term improvement. Moreover, the cement-treated soil presents better mechanical properties (California bearing ratio and unconfined compressive strength). X-ray diffraction tests and thermo-gravimetric analyses show calcium aluminate hydrates in lime-treated soil and ettringite in cement-treated soil. Mineralogical changes and new hydrates formed in the treated soil demonstrate their positive effect on the engineering behavior of the soil. Swelling and indirect tensile strength indicate the soil suitability for treatment with specific amounts of binders. Cement-treated soil resists the immersion test, as ettringite and new calcium aluminate hydrate are detected by XRD after immersion, whereas dissolution of the unreacted lime and part of the calcium hydrates during the immersion test imply a low resistance to immersion of lime-treated soil.

Published
2021

3. Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

Author

L. Gatuingt, S. Rossano, J.-D. Mertz, C. Fourdrin, O. Rozenbaum, Q. Lemasson, S. Reguer, N. Trcera, B. Lanson, Laboratoire Géomatériaux et Intéractions Environnementales (GERS-LGIE), Université Gustave Eiffel, Laboratoire de recherche des monuments historiques (LRMH), Centre de Recherche sur la Conservation (CRC ), Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Contrôle de la Réponse Immune B et des Lymphoproliférations (CRIBL), Institut Génomique, Environnement, Immunité, Santé, Thérapeutique (GEIST), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut des Sciences de la Terre (ISTerre), Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Gustave Eiffel-Université Grenoble Alpes (UGA), Géomatériaux et Intéractions Environnementales (GERS-GIE), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut Génomique, Environnement, Immunité, Santé, Thérapeutique (GEIST), and Université de Limoges (UNILIM)-Université de Limoges (UNILIM)

Subjects
Birnessite, 010504 meteorology & atmospheric sciences, Chemistry, Geochemistry, 010502 geochemistry & geophysics, Mineralogy, 01 natural sciences, Natural (archaeology), Characterization (materials science), Natural phenomenon, Dissolution, 0105 earth and related environmental sciences, [SDU.STU.MI]Sciences of the Universe [physics]/Earth Sciences/Mineralogy, QE351-399.2
Abstract

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

Published
2021

4. Novel markers to early detect degradation on cellulose nitrate-based heritage at the submicrometer level using synchrotron UV–VIS multispectral luminescence

Author

Maria Elvira Callapez, Maria João Melo, Artur Neves, Ana M. Ramos, Mathieu Thoury, Robert Friedel, Matthieu Réfrégiers, LAQV@REQUIMTE, DCR - Departamento de Conservação e Restauro, DQ - Departamento de Química, Refregiers, Matthieu, Laboratorio Associado para a Quimica Verde (LAQV), Requimte, Universidade do Porto = University of Porto-Departamento de Química (DQ), Faculdade de Ciências e Tecnologia = School of Science & Technology (FCT NOVA), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Faculdade de Ciências e Tecnologia = School of Science & Technology (FCT NOVA), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade do Porto = University of Porto-Departamento de Química (DQ), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Centro Interuniversitário de História das Ciências e da Tecnologia [Caparica] (CIUHCT), University of Maryland [Baltimore], 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), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut photonique d'analyse non-destructive européen des matériaux anciens (IPANEMA), Muséum national d'Histoire naturelle (MNHN)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), This work was supported by the European Union’s Horizon 2020 Research and Innovation Programme (H2020-NMBP‐35‐2017), Grant agreement no 76081, Project NEMOSINE, 'Innovative packaging solutions for storage and conservation of 20th century cultural heritage of artefacts based on cellulose derivatives, and Fundação para a Ciência e a Tecnologia, Ministério da Ciência Tecnologia e Ensino Superior (FCT/MCTES), Portugal, through doctoral programme CORES-PD/00253/2012, PhD Grant PD/BD/136678/2018 (Artur Neves) and Associate Laboratory for Green Chemistry- LAQV financed by national funds (UIDB/ 50006/2020 and UIDP/50006/2020)., Universidade do Porto-Departamento de Química (DQ), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade Nova de Lisboa = NOVA University Lisbon (NOVA)-Universidade do Porto-Departamento de Química (DQ), 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
Materials science, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, Photochemistry, Science, Multispectral image, Nanotechnology, 02 engineering and technology, 01 natural sciences, Article, law.invention, Celluloid, chemistry.chemical_compound, Ultraviolet visible spectroscopy, Nitrate, SDG 3 - Good Health and Well-being, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, History of chemistry, Cellulose, General, Multidisciplinary, 010401 analytical chemistry, [SHS.ART]Humanities and Social Sciences/Art and art history, 021001 nanoscience & nanotechnology, Synchrotron, 0104 chemical sciences, Optics and photonics, Physical chemistry, chemistry, visual_art, visual_art.visual_art_medium, Degradation (geology), Medicine, [SHS.ART] Humanities and Social Sciences/Art and art history, 0210 nano-technology, Luminescence
Abstract

20200316 H2020-NMBP‐35‐2017 CORES-PD/00253/2012 PD/BD/136678/2018 UIDB/ 50006/2020 UIDP/50006/2020 Cellulose nitrate (CN) is an intrinsically unstable material that puts at risk the preservation of a great variety of objects in heritage collections, also posing threats to human health. For this reason, a detailed investigation of its degradation mechanisms is necessary to develop sustainable conservation strategies. To investigate novel probes of degradation, we implemented deep UV photoluminescence micro spectral-imaging, for the first time, to characterize a corpus of historical systems composed of cellulose nitrate. The analysis of cinematographic films and everyday objects dated from the nineteenth c./early twentieth c. (Perlov's collection), as well as of photo-aged CN and celluloid references allowed the identification of novel markers that correlate with different stages of CN degradation in artworks, providing insight into the role played by plasticizers, fillers, and other additives in stability. By comparison with photoaged references of CN and celluloid (70% CN and 30% camphor), it was possible to correlate camphor concentration with a higher rate of degradation of the cinematographic films. Furthermore, the present study investigates, at the sub-microscale, materials heterogeneity that correlates to the artworks' history, associating the different emission profiles of zinc oxide to specific color formulations used in the late nineteenth and early twentieth centuries. publishersversion published

Published
2021

5. Zinc isotopic fractionation between aqueous fluids and silicate magmas: An experimental study

Author

Fei Wu, Fang Huang, Haihao Guo, Ying Xia, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Magma - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Bayerisches Geoinstitut (BGI), Universität Bayreuth, CAS Key Laboratory of Crust–Mantle Materials and Environments [Hefei], School of Earth and Space Sciences [Hefei], University of Science and Technology of China [Hefei] (USTC)-University of Science and Technology of China [Hefei] (USTC)-Chinese Academy of Sciences [Beijing] (CAS), State Key Laboratory of Geological Processes and Mineral Resources [Wuhan] (GPMR), and China University of Geosciences [Wuhan] (CUG)

Subjects
Incompatible element, 010504 meteorology & atmospheric sciences, Inorganic chemistry, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, chemistry.chemical_element, Fractionation, Zinc, 010502 geochemistry & geophysics, 01 natural sciences, Silicate, Equilibrium fractionation, chemistry.chemical_compound, Igneous rock, Isotope fractionation, chemistry, [SDU]Sciences of the Universe [physics], 13. Climate action, Geochemistry and Petrology, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, Igneous differentiation, 0105 earth and related environmental sciences
Abstract

International audience; Fluids in magmas play a key role in magma differentiation and transportation of economic metals for ore deposits. As a chalcophile and incompatible element, zinc and its isotopes have been increasingly applied to study the magmatic-hydrothermal processes. However, zinc isotopic fractionation between aqueous fluids and magmas has not been well constrained. Here we experimentally determined equilibrium fractionation factors of Zn isotopes between aqueous fluids and silicate magmas (Δ66Znfluid-magma= δ66Znfluid - δ66Znmagma). The results reveal that aqueous fluids are isotopically heavier than the coexisting silicate magmas. No correlation between Δ66Znfluid-magma and temperature or chlorine contents in fluids is observed under our experimental conditions. Instead, Δ66Znfluid-magma is negatively corresponded with NBO/T of the melt (the ratio of non-bridge oxygen and tetrahedron ions), and positively correlated with the molar ratio of Al/(0.5K+Ca+Fe) in the bulk magmas, suggesting the controlling of silicate composition on Zn isotope fractionation. Our data therefore indicate that the isotopically heavier Zn in the fluids exsolved from magmas may account for the higher δ66Zn of pegmatites and high-silica granitic rocks. Moreover, involvement of magmatic fluids can explain the highly variable and remarkably heavier Zn isotopic signatures of fumaroles, thermal spring waters, and seafloor hydrothermal fluids compared to the igneous rocks. This study provides information that can be used to guide research using Zn isotopes to trace fluid activity and magmatism.

Published
2021

6. Doxorubicin‐Sensitized Luminescence of NIR‐Emitting Ytterbium Liposomes: Towards Direct Monitoring of Drug Release

Author

Sara Lacerda, Éva Tóth, Frédéric Szeremeta, Sandra Même, Anthony Delalande, Célia S. Bonnet, Stéphane Petoud, Agnès Pallier, Chantal Pichon, Svetlana V. Eliseeva, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Frapart, Isabelle

Subjects
Ytterbium, Luminescence, Materials science, Infrared Rays, [SDV]Life Sciences [q-bio], chemistry.chemical_element, Breast Neoplasms, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Polyethylene Glycols, Mice, Cell Line, Tumor, medicine, Animals, Chelation, Doxorubicin, Liposome, Antibiotics, Antineoplastic, Molecular Structure, General Medicine, General Chemistry, 021001 nanoscience & nanotechnology, Magnetic Resonance Imaging, 3. Good health, 0104 chemical sciences, [SDV] Life Sciences [q-bio], Drug Liberation, chemistry, Liposomes, Drug delivery, Nanomedicine, Female, 0210 nano-technology, Preclinical imaging, medicine.drug
Abstract

International audience; Drug-loaded liposomes are typical examples of nanomedicine. We show here that doxorubicin, the anti-cancer agent in the liposomal drug Doxil ® , can sensitize Ytterbium (Yb 3+ ) and generate its near infrared (NIR) emission. When doxorubicin and amphiphilic Yb 3+ chelates are incorporated into liposomes, the sensitized emission of Yb 3+ is dependent on the integrity of the particles which can be used to monitor drug release. We also established the first demonstration that the NIR Yb 3+ emission signal is observable in living mice following intratumoral injection of the Yb 3+ -doxorubicin-liposomes, using a commercial macroscopic setup equipped with a near-infrared camera.

Published
2021

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

Author

Cécile Genevois, Michael J. Pitcher, Yannick Ledemi, Sandra Ory, Younes Messaddeq, Marina Boyer, Mathieu Allix, Haytem Bazzaoui, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), and Université Laval [Québec] (ULaval)

Subjects
02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, metastability, Inorganic Chemistry, Tetragonal crystal system, law, luminescence, Ceramic, Physical and Theoretical Chemistry, Crystallization, STEM-HAADF, Chemistry, Melilite, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Gallate melilite, 0104 chemical sciences, Crystallography, visual_art, visual_art.visual_art_medium, engineering, Orthorhombic crystal system, Crystallite, 0210 nano-technology, Luminescence, Superstructure (condensed matter), cation ordering
Abstract

International audience; SrREGa3O7 melilite ceramics with large rare-earth elements (RE = La to Y) are famous materials especially known for their luminescence properties. Using an innovative approach, the full and congruent crystallization from glass process, SrREGa3O7 transparent polycrystalline ceramics with small rare earth elements (RE = Dy-Lu and Y) have been successfully synthesized and characterized. Interestingly, compared to the classic tetragonal (P-421m) melilite structure composed of mixed Sr/RE cationic sites, these compositions can crystallize in a 3 x 1 x 1 orthorhombic (P21212) superstructure. A detailed study of the superstructure, investigated by different techniques (synchrotron and neutron powder diffraction, STEM-HAADF imaging and EDS mapping), highlights the existence of a Sr/RE cation ordering favored by a large Sr/RE size mismatch and a sufficiently small RE cation. An appropriate control of the synthesis conditions through glass crystallization enables the formation of the desired polymorphs, either ordered or disordered. The influence of this tailored cationic ordering/disordering on the RE luminescent spectroscopic properties have been investigated. A stronger structuration of the RE emission band is observed in the ordered ceramic compared to the disordered ceramic and the glass, whose band shapes are very similar, indicating that the RE environment in the glass and disordered ceramic are close.

Published
2021

8. Observation and modelling of ozone-destructive halogen chemistry in a passively degassing volcanic plume

Author

L. Surl, T. Roberts, S. Bekki, Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), STRATO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Chemistry [Aberdeen], School of Natural and Computing Sciences, and University of Aberdeen-University of Aberdeen

Subjects
Atmospheric Science, Ozone, 010504 meteorology & atmospheric sciences, QC1-999, chemistry.chemical_element, 010502 geochemistry & geophysics, Atmospheric sciences, 01 natural sciences, Methane, Atmosphere, chemistry.chemical_compound, Chlorine, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, QD1-999, 0105 earth and related environmental sciences, [PHYS.PHYS.PHYS-AO-PH]Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph], geography, Bromine, geography.geographical_feature_category, Physics, Plume, Chemistry, chemistry, Volcano, 13. Climate action, Halogen
Abstract

Volcanoes emit halogens into the atmosphere that undergo complex chemical cycling in plumes and cause destruction of ozone. We present a case study of the Mount Etna plume in the summer of 2012, when the volcano was passively degassing, using aircraft observations and numerical simulations with a new 3D model “WRF-Chem Volcano” (WCV), incorporating volcanic emissions and multi-phase halogen chemistry. Measurements of SO2 – an indicator of plume intensity – and ozone were made in the plume a few tens of kilometres from Etna, revealing a strong negative correlation between ozone and SO2 levels. From these observations, using SO2 as a tracer species, we estimate a mean in-plume ozone loss rate of 1.3×10−5 molecules of O3 per second per molecule of SO2. This value is similar to observation-based estimates reported very close to Etna's vents, indicating continual ozone loss in the plume up to at least tens of kilometres downwind. The WCV model is run with nested grids to simulate the plume close to the volcano at 1 km resolution. The focus is on the early evolution of passively degassing plumes aged less than 1 h and up to tens of kilometres downwind. The model is able to reproduce the so-called “bromine explosion”: the daytime conversion of HBr into bromine radicals that continuously cycle in the plume. These forms include the radical BrO, a species whose ratio with SO2 is commonly measured in volcanic plumes as an indicator of halogen ozone-destroying chemistry. The species BrO is produced in the ambient-temperature chemistry, with in-plume BrO / SO2 ratios on the order of 10−4 mol/mol, similar to those observed previously in Etna plumes. Wind speed and time of day are identified as non-linear controls on this ratio. Sensitivity simulations confirm the importance of near-vent radical products from high-temperature chemistry in initiating the ambient-temperature plume halogen cycling. Heterogeneous reactions that activate bromine also activate a small fraction of the emitted chlorine; the resulting production of chlorine radical Cl strongly enhances the methane oxidation and hence the formation of formaldehyde (HCHO) in the plume. Modelled rates of ozone depletion are found to be similar to those derived from aircraft observations. Ozone destruction in the model is controlled by the processes that recycle bromine, with about three-quarters of this recycling occurring via reactions between halogen oxide radicals. Through sensitivity simulations, a relationship between the magnitude of halogen emissions and ozone loss is established. Volcanic halogen cycling profoundly impacts the overall plume chemistry in the model, notably hydrogen oxide radicals (HOx), nitrogen oxides (NOx), sulfur, and mercury chemistry. In the model, it depletes HOx within the plume, increasing the lifetime of SO2 and hence slowing sulfate aerosol formation. Halogen chemistry also promotes the conversion of NOx into nitric acid (HNO3). This, along with the displacement of nitrate out of background aerosols in the plume, results in enhanced HNO3 levels and an almost total depletion of NOx in the plume. The halogen–mercury model scheme is simple but includes newly identified photo-reductions of mercury halides. With this set-up, the mercury oxidation is found to be slow and in near-balance with the photo-reduction of the plume. Overall, the model findings demonstrate that halogen chemistry has to be considered for a complete understanding of sulfur, HOx, reactive nitrogen, and mercury chemistry and of the formation of sulfate particles in volcanic plumes.

Published
2021

9. Oxidation of C 5 esters: Influence of the position of the ester function

Author

Philippe Dagaut, Sébastien Thion, Guillaume Dayma, Zeynep Serinyel, Maxence Lailliau, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), European Project: 291049,EC:FP7:ERC,ERC-2011-ADG_20110209,2G-CSAFE(2011), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS)

Subjects
oxidation, Butyl formate, 020209 energy, chemistry.chemical_element, 02 engineering and technology, butyl formate, Mole fraction, Biochemistry, ethyl propanoate, Inorganic Chemistry, chemistry.chemical_compound, 020401 chemical engineering, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, Organic chemistry, Reactivity (chemistry), 0204 chemical engineering, Physical and Theoretical Chemistry, chemistry.chemical_classification, Chemistry, Alkene, Organic Chemistry, Ethyl propanoate, kinetic modeling, methyl butanoate, Product distribution, Propyl acetate, jet-stirred reactor, propyl acetate, Carbon
Abstract

International audience; The oxidation of esters has been extensively studied over the past 15 years, mainly focusing on methyl- and ethyl-esters. Recently, the oxidation of esters produced from higher alcohols has received more and more attention. In this work, we report experiments and modeling on the oxidation of a series of four esters with five carbon atoms, namely, methyl butanoate, ethyl propanoate, propyl acetate, and butyl formate. The oxidation of these esters was performed in a jet-stirred reactor under the same experimental conditions (tau = 700 ms, p = 10 atm, phi = 1, and X-fuel,X- initial = 1000 ppm). The mole fraction profiles obtained from these experiments were used to develop a unique detailed kinetic mechanism for the oxidation of these four esters, which performs well against our experimental data and on data from the literature. Although these esters are isomers, this work highlights the influence of the position of the ester function in terms of global reactivity and product distribution. In particular, this comparison shows the strong impact of the nature of the products (i.e., acid + alkene) formed by the different molecular decomposition reactions during the oxidation process of these esters.

Published
2021

10. DNA nuclear targeting sequences for enhanced non-viral gene transfer: An in vitro and in vivo study

Author

Tristan Montier, Philippe Guégan, Sandrine Quemener, Kévin Pluchon, Juliette Ropars, Chantal Pichon, Tanguy Haute, Yann Thierry Le Guen, Tony Le Gall, Patrick Midoux, Gestionnaire, Hal Sorbonne Université, monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes. - - VINP2017 - ANR-17-CE18-0015 - AAPG2017 - VALID, Génétique, génomique fonctionnelle et biotechnologies (UMR 1078) (GGB), EFS-Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Chimie des polymères (LCP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Parisien de Chimie Moléculaire (IPCM), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires (RNMCD - U1011), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), This work was funded by grants from the AFM – Association Française contre les Myopathies (project no. AFM2017#20609, AFM, Evry, France), the ANR – Agence Nationale de la Recherche (project no. ANR-17-CE18-0015-03, 'monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes', ANR, Paris, France), the Association de Transfusion Sanguine et de Biogénétique Gaétan Saleün (Brest, France), and the Région Bretagne (France). The Service Général des Plateformes, Animalerie Commune (Brest, France) and SynNanoVect (Brest-Rennes, France) are also acknowledged. Y.T.L.G. was a recipient of a PhD fellowship from the French Ministry of Higher Education, Research and Innovation., ANR-17-CE18-0015,VINP,monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes.(2017), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-EFS-Institut National de la Santé et de la Recherche Médicale (INSERM), 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), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires - U1011 (RNMCD)

Subjects
0301 basic medicine, [SDV]Life Sciences [q-bio], RM1-950, NF-κB, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, plasmid DNA, In vivo, Drug Discovery, skeletal muscle, Transcription factor, hydrodynamic limb vein injection, Transfection, nuclear import, In vitro, Cell biology, [SDV] Life Sciences [q-bio], 030104 developmental biology, chemistry, transfection, Cell culture, 030220 oncology & carcinogenesis, Nucleic acid, Molecular Medicine, Therapeutics. Pharmacology, Nuclear transport, DNA
Abstract

International audience; An important bottleneck for non-viral gene transfer commonly relates to translocation of nucleic acids into the nuclear compartment of target cells. So-called 3NFs are optimized short nucleotide sequences able to interact with the transcription factor nuclear factor κB (NF-κB), which can enhance the nuclear import of plasmid DNA (pDNA) carrying such motifs. In this work, we first designed a consistent set of six pDNAs featuring a common backbone and only varying in their 3NF sequences. These constructions were then transfected under various experimental settings. In vitro, cationic polymer-assisted pDNA delivery in five human-derived cell lines showed the potential advantage of 3NF carrying pDNA in diverse cellular contexts. In vivo, naked pDNAs were hydrodynamically delivered to muscle hindlimbs in healthy mice; this direct accurate comparative (in the absence of any gene carrier) revealed modest but consistent trends in favor of the pDNAs equipped with 3NF. In summary, the results reported emphasize the implications of various parameters on NF-κB-mediated pDNA nuclear import; under specific conditions, 3NF can provide modest to substantial advantages for pDNA gene transfer, in vitro as well as in vivo. This study thus further underscores the potential of optimized nuclear import for more efficient non-viral gene transfer applications.

Published
2021

11. Determinism of nonadditive litter mixture effect on decomposition: Role of the moisture content of litters

Author

Fabien Leroy, Sébastien Gogo, Renata Zocatelli, Fatima Laggoun-Défarge, Adrien Jacotot, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), PIVOTS (ARD 2020, CPER, FEDER), Service National d'Observation Tourbières (French Peatland Observatory), accredited by the INSU/CNRS, and ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010)

Subjects
0106 biological sciences, Litter (animal), Biomass, Context (language use), litter decomposition, 010603 evolutionary biology, 01 natural sciences, Decomposer, Nutrient, Sphagnum, Ecosystem, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, QH540-549.5, Ecology, Evolution, Behavior and Systematics, Nature and Landscape Conservation, Original Research, nonadditive effect, Ecology, Chemistry, Soil organic matter, 04 agricultural and veterinary sciences, 15. Life on land, Decomposition, Agronomy, Molinia caerulea, [SDU]Sciences of the Universe [physics], 040103 agronomy & agriculture, 0401 agriculture, forestry, and fisheries, litter water content, peatland
Abstract

The mechanisms behind the plant litter mixture effect on decomposition are still difficult to disentangle. To tackle this issue, we used a model that specifically addresses the role of the litter moisture content. Our model predicts that when two litters interact in terms of water flow, the difference of evaporation rate between two litters can trigger a nonadditive mixture effect on decomposition. Water flows from the wettest to the driest litter, changing the reaction rates without changing the overall litter water content. The reaction rate of the litter receiving the water increases relatively more than the decrease in the reaction rate of the litter supplying the water, leading to a synergistic effect. Such water flow can keep the microbial biomass of both litter in a water content domain suitable to maintain decomposition activity. When applied to experimental data (Sphagnum rubellum and Molinia caerulea litters), the model is able to assess whether any nonadditive effect originates from water content variation alone or whether other factors have to be taken into account., The mechanisms behind the plant litter mixture effect on decomposition are still difficult to disentangle. The model proposed in this article predicts that when two litters interact in terms of water flow, the difference of evaporation rate between two litters can trigger a nonadditive mixture effect on decomposition. Water flows from the wettest to the driest litter, changing the reaction rates without changing the overall litter water content.

Published
2021

12. Molecular Aspects concerning the Use of the SARS-CoV-2 Receptor Binding Domain as a Target for Preventive Vaccines

Author

Yury Valdés-Balbín, Fabrizio Chiodo, Lila Castellanos-Serra, Françoise Paquet, Belinda Sánchez Ramírez, Yanet Climent, Sonsire Fernández, Laura Rodriguez, Kalet León, Vicente Verez-Bencomo, Daniel G. Rivera, Guang-Wu Chen, Darielys Santana-Mederos, Raine Garrido, Dagmar García-Rivera, Tays Hernández, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Molecular cell biology and Immunology, and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, [SDV]Life Sciences [q-bio], Biology, 010402 general chemistry, 01 natural sciences, Epitope, Neutralization, Virus, law.invention, Immune system, Antigen, law, Neutralizing antibody, QD1-999, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, General Chemistry, Virology, 3. Good health, 0104 chemical sciences, Chemistry, chemistry, Recombinant DNA, biology.protein, Glycoprotein, Outlook
Abstract

The development of recombinant COVID-19 vaccines has resulted from scientific progress made at an unprecedented speed during 2020. The recombinant spike glycoprotein monomer, its trimer, and its recombinant receptor-binding domain (RBD) induce a potent anti-RBD neutralizing antibody response in animals. In COVID-19 convalescent sera, there is a good correlation between the antibody response and potent neutralization. In this review, we summarize with a critical view the molecular aspects associated with the interaction of SARS-CoV-2 RBD with its receptor in human cells, the angiotensin-converting enzyme 2 (ACE2), the epitopes involved in the neutralizing activity, and the impact of virus mutations thereof. Recent trends in RBD-based vaccines are analyzed, providing detailed insights into the role of antigen display and multivalence in the immune response of vaccines under development., SARS-CoV-2 receptor-binding domain (RBD)-specific antibodies are crucial for neutralizing efficacy. Emerging mutations, the quality of the IgG response, and the benefit of multivalent display are analyzed here for RBD subunit vaccines.

Published
2021

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

Author

Didier Gourier, Luidgi Giordano, Bruno Viana, Mathieu Allix, Cyrille Richard, Victor Castaing, Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Institut de Chimie du CNRS (INC)-Université de Paris (UP)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ORANGE, Colette

Subjects
MECHANISM, LONG-PERSISTENT, Materials science, Infrared, EUROPIUM, chemistry.chemical_element, Phosphor, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Photochromism, Persistent luminescence, NANOPARTICLES, Ceramic, Physical and Theoretical Chemistry, TRAP DEPTH, [CHIM.MATE] Chemical Sciences/Material chemistry, SPECTROSCOPY, business.industry, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, General Energy, chemistry, visual_art, visual_art.visual_art_medium, 2-PHOTON EXCITATION, Optoelectronics, VISIBLE-LIGHT, 0210 nano-technology, business, Europium, PEROVSKITE PHOSPHOR, STORAGE, Visible spectrum
Abstract

International audience; Persistent luminescence and photochromism are two fascinating optical properties that involve charge trapping via defects and their release due to an external stimulation. In both processes, it is possible to define 1 (or on) and 0 (or off) optical states. Consequently, materials with one of these phenomena find major interest in view of designing smart, anticounterfeiting, and optical information storage devices. Combining both processes within a single material can lead to a new generation of information storage phosphors, in which it may be possible to obtain three different optical states by playing on the external stimulations applied on the material. For that purpose, the elaboration of nickel-doped ZnGa2O4 spinet transparent nano-glassceramics is presented in this work. The short-wave infrared (SWIR) emission, a broad band located at ca. 1275 nm, arises from Ni2+ cations located in gallium octahedral sites. SWIR persistent luminescence, arising from the same doping ion transition, can also be monitored after UV charging. Interestingly, UV irradiation not only leads to persistent luminescence charging but also to a reversible photochromism effect. By means of a complete optical characterization study combined with electron paramagnetic resonance measurements, the origins of both the persistent luminescence emission and the photochromism are explored. Finally, a discussion on the advantages of such a material combining both persistent luminescence and photochromism properties, leading to three possible optical states of the material, is dressed in view of possible optical memory systems.

Published
2021

14. Transport properties in molten carbonates: self-diffusion and conductivity measurements at high temperature

Author

V. Sarou-Kanian, L. del Campo, Lionel Cosson, A. Zhadan, Mohammed Malki, Catherine Bessada, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Université d'Orléans (UO)

Subjects
Self-diffusion, Materials science, Energy Engineering and Power Technology, Thermodynamics, 02 engineering and technology, PFG NMR, Conductivity, 010402 general chemistry, 7. Clean energy, 01 natural sciences, high temperature, Atmosphere, chemistry.chemical_compound, Electrical resistivity and conductivity, Eutectic system, electrical conductivity, Molten carbonates, Renewable Energy, Sustainability and the Environment, selfdiffusion, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Fuel Technology, chemistry, 13. Climate action, Fuel cells, Carbonate, CO2, 0210 nano-technology, Pulsed field gradient
Abstract

International audience; A better understanding and use of molten carbonate fuel cells (MCFCs) requires more detailed consideration on transport properties in melt. The combination of different methodological developments can be one solution to improve our comprehension. Here we present 23 Na and 7 Li self-diffusion coefficients measured by pulsed field gradient (PFG) NMR technique combined with electrical conductivity obtained by a 4-electrod set up, in the eutectic mixture Li2CO3-Na2CO3 (52:48 %mol) at high temperature (up to 1050 K), and under pure CO2 atmosphere. The results were compared with known experimental data from literature obtained by radiotracers techniques and 2-electrod set up and also with some calculations of the transport properties.

Published
2021

15. Tumour angiogenesis normalized by myo‐inositol trispyrophosphate alleviates hypoxia in the microenvironment and promotes antitumor immune response

Author

Klaudia Brodaczewska, Aleksandra Majewska, Bouchra El Hafny-Rahbi, Claudine Kieda, Anthony Delalande, Guillaume Collet, Catherine Grillon, Krzysztof Klimkiewicz, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Faculty of Material Science and Engineering (WIM), Warsaw University of Technology [Warsaw], Medical University of Warsaw - Poland, Frapart, Isabelle, and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, CD31, Stromal cell, Angiogenesis, Inositol Phosphates, [SDV]Life Sciences [q-bio], Mice, Nude, Antineoplastic Agents, B7-H1 Antigen, immune response, Immune tolerance, Mice, angiogenesis, 03 medical and health sciences, 0302 clinical medicine, Immune system, Cell Line, Tumor, Tumor Cells, Cultured, Tumor Microenvironment, oxygen partial pressure (pO2), Animals, cancer, Lymphocytes, vessel normalization, Mice, Inbred BALB C, myo-inositol trispyrophosphate, Neovascularization, Pathologic, hypoxia, Chemistry, Macrophages, CD47, PTEN Phosphohydrolase, myo‐inositol trispyrophosphate, Original Articles, Cell Biology, Programmed Cell Death 1 Ligand 2 Protein, microenvironment, Cell Hypoxia, 3. Good health, Oxygen tension, [SDV] Life Sciences [q-bio], Mice, Inbred C57BL, 030104 developmental biology, 030220 oncology & carcinogenesis, Cancer research, Molecular Medicine, Original Article, CD8
Abstract

International audience; Pathologic angiogenesis directly responds to tumour hypoxia and controls the molecular/cellular composition of the tumour microenvironment, increasing both immune tolerance and stromal cooperation with tumour growth. Myo-inositol-trispyrophosphate (ITPP) provides a means to achieve stable normalization of angiogenesis. ITPP increases intratumour oxygen tension (pO2) and stabilizes vessel normalization through activation of endothelial Phosphatase-and-Tensin-homologue (PTEN). Here, we show that the tumour reduction due to the ITPP-induced modification of the tumour microenvironment by elevating pO2 affects the phenotype and properties of the immune infiltrate. Our main observations are as follows: a relative change in the M1 and M2 macrophage-type proportions, increased proportions of NK and CD8+T cells, and a reduction in Tregs and Th2 cells. We also found, in vivo and in vitro, that the impaired access of PD1+NK cells to tumour cells is due to their adhesion to PD-L1+/PD-L2+ endothelial cells in hypoxia. ITPP treatment strongly reduced PD-L1/PD-L2 expression on CD45+/CD31+ cells, and PD1+ cells were more numerous in the tumour mass. CTLA-4+ cell numbers were stable, but level of expression decreased. Similarly, CD47+ cells and expression were reduced. Consequently, angiogenesis normalization induced by ITPP is the mean to revert immunosuppression into an antitumor immune response. This brings a key adjuvant effect to improve the efficacy of chemo/radio/immunotherapeutic strategies for cancer treatment.

Published
2021

16. Regulation of the conserved <scp>3′</scp> ‐ <scp>5′</scp> exoribonuclease <scp>EXOSC10</scp> / <scp>Rrp6</scp> during cell division, development and cancer

Author

Anne Fernandez, Michael Primig, Igor Stuparević, A. Rachid Rahmouni, Ned J.C. Lamb, Ana Novačić, University of Zagreb, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de génétique humaine (IGH), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de recherche en santé, environnement et travail (Irset), Université d'Angers (UA)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), Croatian Science Foundation [UIP-2017-05-4411], La Ligue Contre le CancerLigue nationale contre le cancer, Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Angers (UA)-Université de Rennes (UR)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), and Chard-Hutchinson, Xavier

Subjects
0106 biological sciences, Saccharomyces cerevisiae Proteins, Cell division, Exosome complex, [SDV]Life Sciences [q-bio], RNA exosome, EXOSC10, Saccharomyces cerevisiae, Biology, 010603 evolutionary biology, 01 natural sciences, 5-fluorouracil, General Biochemistry, Genetics and Molecular Biology, Protein–protein interaction, 03 medical and health sciences, chemistry.chemical_compound, Transcription (biology), Neoplasms, Exoribonuclease, Rrp6, Gene expression, loss-of-function allele, Humans, 030304 developmental biology, 0303 health sciences, Exosome Multienzyme Ribonuclease Complex, RNA, 3. Good health, Cell biology, [SDV] Life Sciences [q-bio], chemistry, Exoribonucleases, General Agricultural and Biological Sciences, Cell Division, DNA
Abstract

International audience; The conserved 3 '-5 ' exoribonuclease EXOSC10/Rrp6 processes and degrades RNA, regulates gene expression and participates in DNA double-strand break repair and control of telomere maintenance via degradation of the telomerase RNA component. EXOSC10/Rrp6 is part of the multimeric nuclear RNA exosome and interacts with numerous proteins. Previous clinical, genetic, biochemical and genomic studies revealed the protein's essential functions in cell division and differentiation, its RNA substrates and its relevance to autoimmune disorders and oncology. However, little is known about the regulatory mechanisms that control the transcription, translation and stability of EXOSC10/Rrp6 during cell growth, development and disease and how these mechanisms evolved from yeast to human. Herein, we provide an overview of the RNA- and protein expression profiles of EXOSC10/Rrp6 during cell division, development and nutritional stress, and we summarize interaction networks and post-translational modifications across species. Additionally, we discuss how known and predicted protein interactions and post-translational modifications influence the stability of EXOSC10/Rrp6. Finally, we explore the idea that different EXOSC10/Rrp6 alleles, which potentially alter cellular protein levels or affect protein function, might influence human development and disease progression. In this review we interpret information from the literature together with genomic data from knowledgebases to inspire future work on the regulation of this essential protein's stability in normal and malignant cells.

Published
2021

17. Crystal structure of Dictyoglomus thermophilum β-d-xylosidase DtXyl unravels the structural determinants for efficient notoginsenoside R1 hydrolysis

Author

Pierre Lafite, René de Vaumas, Richard Daniellou, Damien Bretagne, Arnaud Pâris, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Extrasynthese, ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), LAFITE, Pierre, and Synthèse Organique : des molécules au vivant - - SYNORG2011 - ANR-11-LABX-0029 - LABX - VALID

Subjects
0301 basic medicine, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Ginsenosides, Stereochemistry, Crystal structure, Crystallography, X-Ray, Biochemistry, 03 medical and health sciences, Hydrolysis, Bacterial Proteins, Glycoside hydrolase, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Bacteria, 030102 biochemistry & molecular biology, biology, Chemistry, Active site, Substrate (chemistry), Biological activity, General Medicine, biology.organism_classification, [SDV.BIO] Life Sciences [q-bio]/Biotechnology, Xylosidases, 030104 developmental biology, Biocatalysis, biology.protein, Dictyoglomus thermophilum
Abstract

International audience; $Dictyoglomus\ thermophilum$ β-d-xylosidase DtXyl is attractive as a potential thermostable biocatalyst able to produce biologically active ginsenosides intermediates from β-(1,2)-D-xylosylated compounds, including Notoginsenoside-R1. DtXyl was expressed as an active N-terminal His-tagged protein, and its crystal structure was solved in presence or absence of d-xylose product. Modelling of notoginsenoside R1 in DtXyl active site led to the identification of several hydrophobic residues interacting in close contact to the substrate hydrophobic core. Unlike other residues involved in substrate binding, these residues are not conserved among GH39 xylosidase family, and their physico-chemical properties can be correlated to the efficient binding and subsequent hydrolysis of Notoginsenoside R1.

Published
2021

18. Combustion of silane-nitrous oxide-argon mixtures: Analysis of laminar flame propagation and condensed products

Author

Mathieu Allix, Karl P. Chatelain, Yizhuo He, C. Paillard, Rémy Mével, Nabiha Chaumeix, Deanna A. Lacoste, Simon Lapointe, Tsinghua University [Beijing] (THU), King Abdullah University of Science and Technology (KAUST), Lawrence Livermore National Laboratory (LLNL), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS)

Subjects
Materials science, Laminar flame speed, Silicon, silane, 020209 energy, General Chemical Engineering, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, Combustion, 7. Clean energy, chemistry.chemical_compound, Silica particle, Lattice constant, Expanding flame, 0202 electrical engineering, electronic engineering, information engineering, Physical and Theoretical Chemistry, Argon, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, Mechanical Engineering, 021001 nanoscience & nanotechnology, Silane, chemistry, Volume (thermodynamics), 13. Climate action, 0210 nano-technology, Silicon nanowire, Powder diffraction
Abstract

International audience; The laminar burning rate, the explosion peak pressure, and the pressure rise coefficient have been measured for the first time for silane-nitrous oxide-argon mixtures using the spherically expanding flame technique in a constant volume combustion chamber. For these three parameters, the values obtained were higher than for hydrogen-nitrous oxide-argon and typical hydrocarbon-based mixtures. A maximum burning rate of 1800 g/m2 s was measured at 101 kPa, whereas under similar conditions, a maximum burning rate around 950 g/m2 s has been reported for hydrogen-nitrous oxide-argon mixtures. To better understand the chemical dynamics of flames propagating in SiH4–N2O–Ar mixtures, a detailed reaction model from the literature was improved using collision limit violation analysis and updated thermodynamic properties calculated with a high-level ab initio approach. The reaction model predicts the burning rate within 14% on average but demonstrates error close to 50% for the richest mixtures. The chemistry of the H–O–N system is important under all the conditions presently studied. The chemistry of the Si–H–O–N system demonstrates an increasing importance under rich conditions. In particular, the reactions (i) forming SiOx(s); (ii) describing the interaction of Si-species with N2O; and (iii) involving silicon hydrides, have an important role for the heat release dynamics. The condensed combustion products formed in the silane-nitrous oxide-argon flames were sampled and characterized using electron micrograph, electronic diffraction, energy-dispersive spectroscopy, and X-ray powder diffraction. For all equivalence ratios, silica spherical particles with a mean diameter in the range 200–300 nm were observed. In addition, for mixtures with Φ ≥ 2.2, silicon nanowires were formed. X-ray diffraction experiments showed that the silicon nanowires are composed of metal silicon characterized by a cubic structure (lattice parameter: a=5.425Å) with the Fm-3m space group.

Published
2021

19. Stability, relaxometric and computational studies on Mn2+ complexes with ligands containing a cyclobutane scaffold

Author

Oriol Porcar-Tost, Ona Illa, Éva Tóth, Rosa M. Ortuño, David Esteban-Gómez, Agnès Pallier, Carlos Platas-Iglesias, Universitat Autònoma de Barcelona (UAB), 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), Universidade da Coruña, Jakab Toth, Eva, and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, 010405 organic chemistry, Chemistry, Chemical shift, Potentiometric titration, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Cyclobutane, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, Metal, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, Stability constants of complexes, visual_art, visual_art.visual_art_medium, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate
Abstract

International audience; The stability constants of Mn2+ complexes with ligands containing a trans-1,2-cyclobutanediamine spacer functionalized with picolinate and/or carboxylate functions were determined using potentiometric titrations (25 °C, 0.1 M KCl). The stability constant of the complex with a hexadentate ligand containing four acetate groups (L14−, log KMnL = 10.26) is improved upon replacing one (L24−, log KMnL = 14.71) or two (L34−, log KMnL = 15.81) carboxylate groups with picolinates. The [Mn(L1)]2− complex contains a water molecule coordinated to the metal ion in aqueous solutions, as evidenced by 1H NMRD studies and 17O chemical shifts and transverse relaxation rates. The 1H relaxivities determined at 60 MHz (3.3 and 2.4 mM−1 s−1 at 25 and 37 °C, respectively) are comparable to those of monohydrated complexes such as [Mn(edta)]2−. The exchange rate of the inner-sphere water molecule (k298ex = 248 × 106 s−1) is slightly lower than that of the edta4− analogue. DFT calculations (M11/def2-TZVP) suggest that the water exchange reaction follows a dissociatively activated mechanism, providing activation parameters in reasonably good agreement with the experimental data. DFT calculations also show that the 17O hyperfine coupling constant A/ℏ is affected slightly by changes in the Mn–Owater distance and the orientation of the water molecule with respect to the Mn–O vector.

Published
2021

20. Oxidation of di-n-butyl ether: Experimental characterization of low-temperature products in JSR and RCM

Author

Guillaume Dayma, Bruno Moreau, Philippe Dagaut, Nesrine Belhadj, Roland Benoit, Zeynep Serinyel, Maxence Lailliau, Fabrice Foucher, Fethi Khaled, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Laboratoire pluridisciplinaire de recherche en ingénierie des systèmes, mécanique et énergétique (PRISME), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), and ANR-11-LABX-0006,CAPRYSSES,Cinétique chimique et Aérothermodynamique pour des Propulsions et des Systèmes Energétiques Propres(2011)

Subjects
Reaction mechanism, Electrospray, 020209 energy, General Chemical Engineering, Radical, Inorganic chemistry, General Physics and Astronomy, Energy Engineering and Power Technology, Atmospheric-pressure chemical ionization, Ether, 02 engineering and technology, Mass spectrometry, 7. Clean energy, chemistry.chemical_compound, 020401 chemical engineering, 0202 electrical engineering, electronic engineering, information engineering, cool flame, 0204 chemical engineering, Uhplc-Hrms/ms, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, ketohydroperoxides, General Chemistry, Orbitrap mass spectrometry, rapid compression machine, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dibutyl ether, Fuel Technology, chemistry, jet-stirred reactor, 13. Climate action, dibutyl ether, highly oxygenated molecules, Stoichiometry
Abstract

International audience; The oxidation of di-n-butyl-ether (DBE) was performed in a jet-stirred reactor (JSR) at 1 atm, 520 and 530 K, and from 480 to 670 K at 10 atm, at a residence time of 1 s, an equivalence ratio of 0.5, and an initial fuel concentration of 5000 ppm. Ignition experiments on DBE/air mixtures were also performed in a rapid compression machine (RCM) under stoichiometric conditions, 5 bar, and from 550 to 630 K. Low-temperature products formed in JSR and RCM experiments were characterized. To this end, high-resolution mass spectrometry analyses (HRMS) with flow injection analyses or ultra-high pressure liquid chromatography coupling were used to characterize hydroperoxides and diols (C8H18O3), ketohydroperoxides (C8H16O4), carboxylic acids (C2H4O2, C3H6O2, C4H8O2), di-keto ethers (C8H14O3), and highly oxygenated molecules (C8H14O5, C8H16O6, C8H14O6, C8H14O7, C8H16O8, and C8H14O9) resulting from up to five O2 additions on fuel's radicals. Whereas HOMs are of minor importance in combustion, they are considered key species for the formation of secondary organic aerosols. In addition, cyclic ethers and esters (C8H16O2) were observed. Heated electrospray and atmospheric pressure chemical ionizations (HESI and APCI) were used in positive and negative modes for MS analyses. H/D exchange with D2O was used to confirm the presence of –OH or –OOH groups in the products. The present results show that DBE oxidation proceeds similarly under JSR and RCM conditions. Whereas the CH2 groups neighboring the ether group are the most favorable sites for H-atom abstraction reactions, speciation indicated that other sites can react by metathesis forming a large pool of intermediates and products. Our kinetic reaction mechanism needs to be extended for simulating the formation of newly detected species.

Published
2020

21. Eucalyptol as bio-based solvent for Migita–Kosugi–Stille coupling reaction on O,S,N-heterocycle

Author

Sabine Berteina-Raboin, Joana F. Campos, CCSD, Accord Elsevier, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Chemistry, chemistry.chemical_element, Bio based, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Nitrogen, Sulfur, Oxygen, Catalysis, 0104 chemical sciences, Stille reaction, Solvent, chemistry.chemical_compound, Eucalyptol, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Organic chemistry, 0210 nano-technology
Abstract

International audience; We report herein an investigation on the use of eucalyptol as new solvent for organic transformations applied to the Migita-Kosugi-Stille palladium-catalyzed cross-coupling reaction. Heterocycles containing oxygen, sulfur and nitrogen were chosen as starting materials. Eucalyptol turned out to be a viable sustainable alternative to common solvents for this reaction.

Published
2020

22. Preface to Multiscale Simulation in Geochemistry

Author

Carl I. Steefel, Christophe Tournassat, Xiandong Liu, State Key Laboratory for Mineral Deposits Research, Nanjing University (NJU), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), and Lawrence Berkeley National Laboratory [Berkeley] (LBNL)

Subjects
[SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Geochemistry and Petrology, Chemistry, Geochemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience

Published
2020

23. How reproducible are surface areas calculated from the BET equation?

Author

Christian Serre, Peyman Z. Moghadam, Feng P, Rama Oktavian, Lin R, Ting, Telalovic S, Omar M. Yaghi, Mark D. Allendorf, Russell E. Morris, Muhammad Sadiq, Philip L. Llewellyn, Jonathan L. Snider, Stavila, Matthew J. Rosseinsky, Hou B, Pütz A, Daniel W. Siderius, Rowlandson J, Randall Q. Snurr, van der Veen M, Nguyen T, Kaneko K, Linares N, Félix Zamora, Zhou H, Camille Petit, Sebastian T. Emmerling, Aran Lamaire, Cui Y, David G. Madden, Salcedo-Abraira P, Krista S. Walton, Soumya Mukherjee, Karam B. Idrees, Doheny Pw, Timur Islamoglu, Azevedo Dcs, Conchi O. Ania, Bu X, Zang X, Martin Schröder, Vilarrasa-García E, Michael T. Huxley, Ken-ichi Otake, Sanchez E, Rega D, Vanspeybroeck, Georges Mouchaham, Carmen Montoro, Lee Sj, David Danaci, Goncalves Rb, Yamil J. Colón, Patricia Horcajada, David S. Sholl, David Fairen-Jimenez, Shane G. Telfer, Bethany M. Connolly, Christian J. Doonan, Ryan P. Lively, D’Alessandro D, Raffaele Ricco, Paul S. Wheatley, Clowes R, Bettina V. Lotsch, Alexandros P. Katsoulidis, François-Xavier Coudert, Dominic Bara, Garcia-Martinez J, Carlos Martí-Gastaldo, Yavuz C, Chen B, Matthew R. Hill, Ross S. Forgan, Shuhei Furukawa, Ghosha Sk, Johannes W.M. Osterrieth, Jack D. Evans, Jorge A. R. Navarro, Suarez Ja, Zhang B, João Marreiros, Jorge Gascon, Neil R. Champness, Kenvin J, Yang S, Iiyuka T, Nakul Rampal, Daniel Maspoch, falcaro p, Rampersad J, Han X, Jacopo Andreo, Benoit Coasne, Yang H, Angelo K, Stefan Wuttke, Santos Bf, Chenyue Sun, Susumu Kitagawa, Luka Skoric, Moreton Jc, Rob Ameloot, Muñoz N, DeWitt Sja, Uemura T, Sven Rogge, Seda Keskin, Lukas W. Bingel, Raghuram Thyagarajan, Mircea Dincă, Seth M. Cohen, Bunzen H, Kukobat R, Omar K. Farha, Sarah L. Griffin, Chen L, University of St Andrews. EaSTCHEM, University of St Andrews. School of Chemistry, University of St Andrews. Institute of Behavioural and Neural Sciences, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), University of Cambridge [UK] (CAM), Sandia National Laboratories [Livermore], Sandia National Laboratories - Corporation, Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade Federal do Ceará = Federal University of Ceará (UFC), Nankai University (NKU), University of Augsburg (UNIA), University of Nottingham, UK (UON), The University of Texas at San Antonio (UTSA), Laboratoire Interdisciplinaire de Physique [Saint Martin d’Hères] (LIPhy ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), University of California [San Diego] (UC San Diego), University of California (UC), University of Notre Dame [Indiana] (UND), University of Liverpool, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Shanghai Jiaotong University, The University of Sydney, Massachusetts Institute of Technology (MIT), University of Adelaide, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Graz University of Technology [Graz] (TU Graz), Northwestern University [Evanston], University of California [Riverside] (UC Riverside), University of Glasgow, Kyoto University, King Abdullah University of Science and Technology (KAUST), Indian Institute of Science Education and Research Pune (IISER Pune), Monash university, Instituto IMDEA Energy [Madrid], Instituto IMDEA Energía, Shinshu University [Nagano], Koç University, Georgia Institute of Technology [Atlanta], TotalEnergies, Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS), Max Planck Institute for Solid State Research, Max-Planck-Gesellschaft, Ludwig-Maximilians-Universität München (LMU), Universitat de València (UV), Universidad de Alicante, Barcelona Institute of Science and Technology (BIST), University of Sheffield [Sheffield], University of Saint Andrews, Universidad de Granada = University of Granada (UGR), Imperial College London, University of Manchester [Manchester], École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute of Standards and Technology [Gaithersburg] (NIST), Massey University, University of Bristol [Bristol], The University of Tokyo (UTokyo), Delft University of Technology (TU Delft), Universiteit Gent = Ghent University (UGENT), Ikerbasque - Basque Foundation for Science, University of California [Berkeley] (UC Berkeley), Korea Advanced Institute of Science and Technology (KAIST), Universidad Autónoma de Madrid (UAM), Texas A&M University [College Station], Universidad de Alicante. Departamento de Química Inorgánica, Laboratorio de Nanotecnología Molecular (NANOMOL), European Commission, European Research Council, University of Cambridge, Trinity College Cambridge, National Nuclear Security Administration (US), Department of Energy (US), Alexander von Humboldt Foundation, Center for Advancing Electronics Dresden, Science and Engineering Research Board (India), Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Research Foundation - Flanders, Engineering and Physical Sciences Research Council (UK), National Research Foundation of Korea, Indonesia Endowment Fund for Education, National Institute of Standards and Technology (US), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Avcı, Seda Keskin (ORCID 0000-0001-5968-0336 & YÖK ID 40548), Osterrieth, J.W.M., Rampersad, J., Madden, D., Rampal, N., Skoric, L., Connolly, B., Allendorf, M.D., Stavila, V., Snider, J.L., Ameloot, R., Marreiros, J., Ania, C., Azevedo, D., Vilarrasa-Garcia, E., Santos, B.F., Bu, X.H., Chang, Z., Bunzen, H., Champness, N.R., Griffin, S.L., Chen, B., Lin, R.B., Coasne, B., Cohen, S., Moreton, J.C., Colón, Y.J., Chen, L., Clowes, R., Coudert, F.X., Cui, Y., Hou, B., D'Alessandro, D.M., Doheny, P.W., Dinc?, M., Sun, C., Doonan, C., Huxley, M.T., Evans, J.D., Falcaro, P., Ricco, R., Farha, O., Idrees, K.B., Islamoglu, T., Feng, P., Yang, H., Forgan, R.S., Bara, D., Furukawa, S., Sanchez, E., Gascon, J., Telalovi?, S., Ghosh, S.K., Mukherjee, S., Hill, M.R., Sadiq, M.M., Horcajada, P., Salcedo-Abraira, P., Kaneko, K., Kukobat, R., Kenvin, J., Kitagawa, S., Otake, K.I., Lively, R.P., DeWitt, S.J.A., Llewellyn, P., Lotsch, B.V., Emmerling, S.T., Pütz, A.M., Martí-Gastaldo, C., Padial, N.M., García-Martínez, J., Linares, N., Maspoch, D., Suárez Del Pino, J.A., Moghadam, P., Oktavian, R., Morris, R.E., Wheatley, P.S., Navarro, J., Petit, C., Danacı, D., Rosseinsky, M.J., Katsoulidis, A.P., Schröder, M., Han, X., Yan, S., Serre, C., Mouchaham, G., Sholl, D.S., Thyagarajan, R., Siderius, D., Snurr, R.Q., Goncalves, R.B., Telfer, S., Lee, S.J., Ting, V.P., Rowlandson, J.L., Uemura T, Iiyuka, T., van derVeen, Monique A., Rega, Davide, Van Speybroeck, Veronique, Rogge, Sven M. J., Lamaire, Aran, Walton, Krista S., Bingel, Lukas W., Wuttke, Stefan, Andreo, Jacopo, Yaghi, Omar, Zhang, Bing, Yavuz, Cafer T., Nguyen, Thien S., Zamora, Felix, Montoro, Carmen, Zhou, Hongcai, Kirchon, Angelo, Fairen-Jimenez, David, College of Engineering, Department of Chemical and Biological Engineering, UAM. Departamento de Química Inorgánica, Fairen-Jimenez, David [0000-0002-5013-1194], and Apollo - University of Cambridge Repository

Subjects
Surface (mathematics), Technology, Chemistry, Multidisciplinary, Surface area, 02 engineering and technology, 01 natural sciences, GAS-STORAGE, Surface Area Analysis, General Materials Science, Porous materials, QD, BET theory, Chemistry, Physical, Nanoporous, Physics, 1. No poverty, Química, [CHIM.MATE]Chemical Sciences/Material chemistry, 3rd-DAS, Reproducibilities, 021001 nanoscience & nanotechnology, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, Physics, Condensed Matter, Mechanics of Materials, Physical Sciences, Science & Technology - Other Topics, 0210 nano-technology, Porosity, Materials Science, APPLICABILITY, Materials Science, Multidisciplinary, Nanotechnology, 010402 general chemistry, Physics, Applied, METAL-ORGANIC FRAMEWORKS, Adsorption, Porosimetry, [CHIM]Chemical Sciences, ddc:530, Nanoscience & Nanotechnology, MCC, Química Inorgánica, Science & Technology, Mechanical Engineering, Science and technology, Reproducibility of Results, QD Chemistry, 0104 chemical sciences, Physics and Astronomy, Brunauer Emmett Tellers
Abstract

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the TrinityHenry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE-FG02-08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC-2015-StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC-2017-StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (ZEOBIOCHEM -872102) and the Spanish MICINN and AEI/FEDER (RTI2018-099504-B-C21). N.L. thanks the University of Alicante for funding (UATALENTO17-05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education-LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf)., Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of microand mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This roundrobin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., European Research Council (ERC) ERC-2016-COG 726380 ERC-2015-StG 677289 ERC-2017-StG 756489 639233, UK Research & Innovation (UKRI) Innovate UK 104384 UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) IAA/RG85685, Cambridge International Scholarship TrinityHenry Barlow Scholarship, United States Department of Energy (DOE) DE-FG02-08ER15967, National Nuclear Security Administration DE-NA-0003525, United States Department of Energy (DOE), Alexander von Humboldt Foundation, Center for Information Services and High Performance Computing (ZIH) at TU Dresden, Department of Science & Technology (India), Science Engineering Research Board (SERB), India CRG/2019/000906, Active Co. Research Grant, European Commission through the H2020-MSCA-RISE-2019 program ZEOBIOCHEM -872102, Spanish MICINN and AEI/FEDER RTI2018-099504-B-C21, University of Alicante UATALENTO17-05, Spanish Government SEV-2017-0706 FWO 12T3519N 11D2220N, UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/L015978/1, National Research Foundation of Korea NRF-2017M3A7B4042140 NRF-2017M3A7B4042235, United States Department of Energy (DOE) DE-SC0010596, Indonesian Endowment Fund for Education-LPDP 202002220216006

Published
2022

24. Untargeted metabolomic and molecular network approaches to reveal tomato root secondary metabolites

Author

Souhila Messaili, Thomas Michel, Emilie Destandau, Anne-Violette Lavoir, Nicolas Desneux, Laëtitia Fougère, Cyril Colas, Yanyan Qu, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Sophia Agrobiotech (ISA), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Côte d'Azur (UCA), Institut de Chimie de Nice (ICN), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), ARIMNet2 (ERA-NET) 618127European Commission 2699-33931, Region Centre-Val de Loire, ANR-15-IDEX-0001,UCA JEDI,Idex UCA JEDI(2015), European Project: 618127, European Project: DP130102699,ARC::Discovery Projects(2013), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and Université Nice Sophia Antipolis (... - 2019) (UNS)

Subjects
Plant Science, 01 natural sciences, Biochemistry, Analytical Chemistry, Metabolomics, Solanum lycopersicum, Statistical analyses, Drug Discovery, Botany, liquid chromatography, [CHIM]Chemical Sciences, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Cultivar, Chromatography, High Pressure Liquid, mass spectrometry, 2. Zero hunger, molecular networking, biology, Chemistry, fungi, 010401 analytical chemistry, food and beverages, General Medicine, biology.organism_classification, 0104 chemical sciences, Plant Leaves, untargeted metabolomics, 010404 medicinal & biomolecular chemistry, Molecular network, Complementary and alternative medicine, Phytochemical, Molecular networking, Molecular Medicine, Solanum, Solanaceae, Food Science
Abstract

International audience; Introduction The tomato plant, Solanum lycopersicum L. (Solanaceae), is one of the most widely consumed vegetables in the world and plays an important role in human diet. Tomato cultivars are hosts for diverse types of pests, implying diverse chemical defence strategies. Glycoalkaloids are the main specialised metabolites produced by tomato leaves and fruits to protect against pests. However, the roots have received little attention, leading to limited knowledge about their phytochemical content.Objective The main goal of the current study was the development of an untargeted ultra-high-performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS) based metabolomic approach to study phytochemical variations in tomato roots at two different development stages (i.e. 34th and 62nd day after sowing).Methods UHPLC-HRMS was used to establish the fingerprint of 24 batches of tomato roots. Statistical analyses were performed to highlight the compounds that discriminated between young and mature tomato roots. A dereplication strategy using molecular networking and HRMS/MS data was set up to identify the metabolites regulated during early root development.Key findings The main biomarkers were guanidine and adenosine derivatives associated with tryptophan. Secondary metabolites such as glycoalkaloids and steroidal alkaloids were also characterised. Most of the metabolites were up-regulated in young tomato roots (34 days old) while tryptophan was up-regulated in the older roots (62 days old).Conclusion The metabolic changes observed in this work contribute to a deeper understanding of early-stage root development and may help our understanding of the complex processes involved in the tomato root defence arsenal.

Published
2020

25. Influence of elastic-viscoplastic behaviour on the filling efficiency of amorphous thermoplastic polymer during the micro hot embossing process

Author

N. Aït Hocine, G. Cheng, Thierry Barriere, F. Rabhi, Franche-Comté Électronique Mécanique, Thermique et Optique - Sciences et Technologies (UMR 6174) (FEMTO-ST), Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique Gabriel Lamé (LaMé), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours, Mécanique des Matériaux et Procédés (MMP), Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_classification, 0209 industrial biotechnology, Materials science, Viscoplasticity, Computer simulation, Strategy and Management, Constitutive equation, [PHYS.MECA]Physics [physics]/Mechanics [physics], 02 engineering and technology, Polymer, Management Science and Operations Research, 021001 nanoscience & nanotechnology, Methacrylate, Industrial and Manufacturing Engineering, Amorphous solid, 020901 industrial engineering & automation, chemistry, [SPI.MECA.MEMA]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Mechanics of materials [physics.class-ph], [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Composite material, 0210 nano-technology, Displacement (fluid), ComputingMilieux_MISCELLANEOUS, Microscale chemistry
Abstract

International audience; An unsolved issue in simulating the hot embossing of polymers is modelling the unfilled structured mould. This is because the constitutive law of such polymers has not been adequately determined, especially at the microscale or smaller. The present study investigated the influence of the elastic-viscoplastic behaviour on the filling efficiency of an amorphous polymer during the micro hot embossing process. Constitutive equations based on the two-layer viscoplastic model were used to simulate the hot embossing process. The micro-cavity of the mould was completely filled by the polymer, and the elastic, viscous, and plastic behaviours were considered simultaneously in the simulation. Compression tests were performed to identify the model parameter values for poly-methyl methacrylate. A numerical simulation was performed to analyse the contributions of the polymer’s elastic, viscous, and plastic behaviours. The unfilled area in the micro-cavity was evaluated after a displacement of 0.2 mm was applied to the mould. This was used as an indicator to compare the mould filling efficiency with those of the elastoplastic and elastic-viscoplastic constitutive models. The analysis led to the selection of an optimal elastic-viscoplastic model to completely fill the micro-cavity, which was consistent with the experimental results.

Published
2020

26. Photophysical studies on lanthanide(iii) chelates conjugated to Pittsburgh compound B as luminescent probes targeted to Aβ amyloid aggregates

Author

Hugh D. Burrows, Carlos F. G. C. Geraldes, Rui Fausto, Alexandre C. Oliveira, Éva Tóth, Jean-François Morfin, Licínia L. G. Justino, Telma Costa, Universidade de Coimbra [Coimbra], Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Jakab Toth, Eva, and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Coordination sphere, [SDV]Life Sciences [q-bio], Quantum yield, Conjugated system, 010402 general chemistry, Lanthanoid Series Elements, 7. Clean energy, 01 natural sciences, Protein Aggregates, Humans, Molecule, Physical and Theoretical Chemistry, Triplet state, Density Functional Theory, Chelating Agents, Amyloid beta-Peptides, Aniline Compounds, Luminescent Agents, Molecular Structure, 010405 organic chemistry, Chemistry, Optical Imaging, Chromophore, Photochemical Processes, 0104 chemical sciences, [SDV] Life Sciences [q-bio], Thiazoles, Crystallography, Luminescent Measurements, Luminescence
Abstract

International audience; The photophysical properties of Eu3+ and Tb3+ complexes of DOTAGA and DO3A-monoamide conjugates of the Pittsburgh compound B (PiB) chromophore, prepared using linkers of different lengths and flexibilities, and which form stable negatively charged (LnL1), and uncharged (LnL2) complexes, respectively, were studied as potential probes for optical detection of amyloid aggregates. The phenylbenzothiazole (PiB) moiety absorbs light at wavelengths longer than 330 nm with a high molar absorption coefficient in both probes, and acts as an antenna in these systems. The presence of the luminescent Ln3+ ion quenches the excited states of PiB through an energy transfer process from the triplet state of PiB to the metal centre, and structured emission is seen from Eu3+ and Tb3+. The luminescence study indicates the presence of a 5D4 → T1 back transfer process in the Tb3+ complexes. It also provides insights on structural properties of the Eu3+ complexes, such as the high symmetry environment of the Eu3+ ion in a single macrocyclic conformation and the presence of one water molecule in its inner coordination sphere. The overall quantum yield of luminescence of EuL1 is higher than for EuL2. However, their low values reflect the low overall sensitization efficiency of the energy transfer process, which is a consequence of the large distances between the metal center and the antenna, especially in the EuL2 complex. DFT calculations confirmed that the most stable conformation of the Eu3+ complexes involves a combination of a square antiprismatic (SAP) geometry of the chelate and an extended conformation of the linker. The large calculated average distances between the metal center and the antenna point to the predominance of the Förster energy transfer mechanism, especially for EuL2. This study provides insights into the behavior of amyloid-targeted Ln3+ complexes as optical probes, and contributes towards their rational design.

Published
2020

27. Conformationally Restricted Oxazolidin‐2‐one Fused Bicyclic Iminosugars as Potential Glycosidase Inhibitors

Author

Richard Daniellou, J. A. Figueiredo, Arnaud Tatibouët, Justyna Jaszczyk, Maria I. Ismael, Maria Domingues, Marie Schuler, Pierre Lafite, Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Departamento de Química (Universidade da Beira Interior, ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and University of Beira Interior [Portugal] (UBI)

Subjects
Bicyclic molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Iminosugar, Glycosidase inhibitor, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, [CHIM]Chemical Sciences, Glycoside hydrolase, Physical and Theoretical Chemistry
Abstract

International audience; The synthesis of fused bicyclic oxazolidin-2-one (OZO) iminosugars was achieved through a tandem Staudinger reduction/retro-Michael/intramolecular Michael addition from the corresponding OZO azidosugars. Those precursors, based on both aldopentofuranoses and ketofuranohexoses backbones, were obtained following alkylation and oxidation of the related oxazolidine-2-thione (OZT) azidosugars. Eight OZO based iminosugars were isolated in good yields and evaluated for their potency as glycosidases inhibitors, thus extending the family of known 1-Deoxynojirimycin (DNJ) bicyclic analogues.

Published
2020

28. Modulated structure determination and ion transport mechanism of oxide-ion conductor CeNbO4+δ

Author

Fengjuan Pan, Jianhua Lin, Cong Lin, Junliang Sun, Mathieu Allix, Jian Li, Shipeng Geng, Lukáš Palatinus, Xiaojun Kuang, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), and Université d'Orléans (UO)

Subjects
Solid-state chemistry, Materials science, Science, Oxide, General Physics and Astronomy, chemistry.chemical_element, Ionic bonding, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Oxygen, General Biochemistry, Genetics and Molecular Biology, Ion, chemistry.chemical_compound, [CHIM.CRIS]Chemical Sciences/Cristallography, Ionic conductivity, [CHIM]Chemical Sciences, lcsh:Science, Ion transporter, Multidisciplinary, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Electron diffraction, chemistry, Physical chemistry, lcsh:Q, 0210 nano-technology
Abstract

CeNbO4+δ, a family of oxygen hyperstoichiometry materials with varying oxygen content (CeNbO4, CeNbO4.08, CeNbO4.25, CeNbO4.33) that shows mixed electronic and oxide ionic conduction, has been known for four decades. However, the oxide ionic transport mechanism has remained unclear due to the unknown atomic structures of CeNbO4.08 and CeNbO4.33. Here, we report the complex (3 + 1)D incommensurately modulated structure of CeNbO4.08, and the supercell structure of CeNbO4.33 from single nanocrystals by using a three-dimensional electron diffraction technique. Two oxide ion migration events are identified in CeNbO4.08 and CeNbO4.25 by molecular dynamics simulations, which was a synergic-cooperation knock-on mechanism involving continuous breaking and reformation of Nb2O9 units. However, the excess oxygen in CeNbO4.33 hardly migrates because of the high concentration and the ordered distribution of the excess oxide ions. The relationship between the structure and oxide ion migration for the whole series of CeNbO4+δ compounds elucidated here provides a direction for the performance optimization of these compounds.

Published
2020

29. Kinetic and product studies of the reactions of NO3 with a series of unsaturated organic compounds

Author

Max R. McGillen, Ibrahim Ouchen, Yangang Ren, Abdelwahid Mellouki, Véronique Daële, Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), LE STUDIUM Loire Valley Institute for Advanced Studies, Université Mohammed V, ARD PIVOTS program (Ambition Recherche Développement Plateformes d'Innovation, de Valorisation, d'Optimisation, Technologiques environnmentaleS, supported by the centre-Val de Loire regional council), Le Studium, ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), ANR-16-CE01-0013,SEA-M,Impact des échanges air-mer sur la qualité de l'air dans les mégalopoles du littoral(2016), European Project: 730997,EUROCHAMP2020(2020), European Project: 690958,H2020,H2020-MSCA-RISE-2015,MARSU(2016), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS), and Université Mohammed V de Rabat [Agdal] (UM5)

Subjects
Reaction mechanism, Environmental Engineering, 010504 meteorology & atmospheric sciences, Electrophilic addition, Radical, Epoxide, Methacrolein, Volatile organic compounds (VOCs), General Medicine, 010501 environmental sciences, 01 natural sciences, Medicinal chemistry, chemistry.chemical_compound, chemistry, NO3 radical, [SDE]Environmental Sciences, Methyl vinyl ketone, Environmental Chemistry, Products, Rate coefficient, Crotonaldehyde, [CHIM.OTHE]Chemical Sciences/Other, Isoprene, 0105 earth and related environmental sciences, General Environmental Science
Abstract

International audience; Rate coefficients for the reaction of NO3 radicals with 6 unsaturated volatile organic compounds (VOCs) in a 7300 L simulation chamber at ambient temperature and pressure have been determined by the relative rate method. The resulting rate coefficients were determined for isoprene, 2-carene, 3-carene, methyl vinyl ketone (MVK), methacrolein (MACR) and crotonaldehyde (CA), as (6.6 ± 0.8) × 10−13, (1.8 ± 0.6) × 10−11, (8.7 ± 0.5) × 10−12, (1.24 ± 1.04) × 10−16, (3.3 ± 0.9) × 10−15 and (5.7 ± 1.2) × 10−15 cm3/(molecule•sec), respectively. The experiments indicate that NO3 radical reactions with all the studied unsaturated VOCs proceed through addition to the olefinic bond, however, it indicates that the introduction of a carbonyl group into unsaturated VOCs can deactivate the neighboring olefinic bond towards reaction with the NO3 radical, which is to be expected since the presence of these electron-withdrawing substituents will reduce the electron density in the π orbitals of the alkenes, and will therefore reduce the rate coefficient of these electrophilic addition reactions. In addition, we investigated the product formation from the reactions of 2-carene and 3-carene with the NO3 radical. Qualitative identification of an epoxide (C10H16OH+), caronaldehyde (C10H16O2H+) and nitrooxy-ketone (C10H16O4NH+) was achieved using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a reaction mechanism is proposed.

Published
2020

30. A window in the course of alkaline magma differentiation conducive to immiscible REE-rich carbonatites

Author

Giada Iacono-Marziano, Malcolm Massuyeau, Emmanuel Le Trong, Ida Di Carlo, Johann Tuduri, Fabrice Gaillard, Laurent Bailly, Jérémie Melleton, Grégory Rogerie, Zineb Nabyl, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Magma - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), University of Johannesburg [South Africa] (UJ), Institut für Mineralogie, Westfälische Wilhelms-Universität Münster = University of Münster (WWU), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), European Project: 279790,EC:FP7:ERC,ERC-2011-StG_20101014,ELECTROLITH(2011), University of Johannesburg (UJ), and Westfälische Wilhelms-Universität Münster (WWU)

Subjects
Nephelinite, 010504 meteorology & atmospheric sciences, Geochemistry, 010502 geochemistry & geophysics, 01 natural sciences, Silicate, Cape verde, chemistry.chemical_compound, Igneous rock, chemistry, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Geochemistry and Petrology, Magma, Carbonatite, Carbonate, Igneous differentiation, 0105 earth and related environmental sciences
Abstract

International audience; Rare earth element (REE) enrichments in carbonatites are often described as resulting from late magmatic-hydrothermal or supergene processes. However, magmatic pre-enrichment linked to the igneous processes at the origin of carbonatites are likely to contribute to the REE fertilisation. Experimental constraints reveals that immiscibility processes between carbonate and silicate melts can lead to both REE enrichments and depletions in carbonatites making the magmatic processes controlling REE enrichments unclear.We link REE contents of carbonatites to the magmatic stage at which carbonatites are separated from silicate magma in their course of differentiation. We present results of experiments made at pressure and temperature conditions of alkaline magmas and associated carbonatites differentiation (0.2 to 1.5 GPa; 725 to 975 °C; FMQ to FMQ +2.5), simultaneously addressing crystal fractionation of alkaline magmas and immiscibility between carbonate (calcio-carbonate type) and silicate melts (nephelinite to phonolite type). The experimental data shows that the degree of differentiation, controlling the chemical composition of alkaline melts, is a key factor ruling the REE concentration of the coexisting immiscible carbonate melts. In order to predict carbonate melt REE enrichments during alkaline magma differentiation, we performed a parameterisation of experimental data on immiscible silicate and carbonate melts, based exclusively on the silica content, the alumina saturation index and the alkali/alkaline-earth elements ratio of silicate melts. This parameterisation is applied to more than 1600 geochemical data of silicate magmas from various alkaline provinces (East African Rift, Canary and Cape Verde Islands) and show that REE concentrations of their potential coeval carbonatite melts can reach concentration ranges similar to those of highly REE enriched carbonatites (∑REE > 30 000 ppm) by immiscibility with phonolitic/phono-trachytic melt compositions, while more primitive alkaline magmas can only be immiscible with carbonatites that are not significantly enriched in REE.

Published
2020

31. Modeling of the Electromechanical Behavior of Barium Titanate Under Mechanical Stress and Comparison With Experimental Measurements

Author

Michael Lematre, L.P. Tran-Huu-Hue, Remy Ul, Michel Gratton, Marc Lethiecq, GREMAN (matériaux, microélectronique, acoustique et nanotechnologies) (GREMAN - UMR 7347), Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Mécanique des Matériaux et Procédés (MMP), Laboratoire de Mécanique Gabriel Lamé (LaMé), Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)

Subjects
[SPI.ACOU]Engineering Sciences [physics]/Acoustics [physics.class-ph], Materials science, Acoustics and Ultrasonics, chemistry.chemical_element, Order (ring theory), Barium, [SPI.MECA.MSMECA]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Materials and structures in mechanics [physics.class-ph], Lead zirconate titanate, 01 natural sciences, Piezoelectricity, Displacement (vector), [SPI.MAT]Engineering Sciences [physics]/Materials, chemistry.chemical_compound, Transducer, chemistry, 0103 physical sciences, Barium titanate, Electrical and Electronic Engineering, Composite material, 010301 acoustics, Instrumentation, ComputingMilieux_MISCELLANEOUS
Abstract

Barium titanate (BaTiO3) is increasingly studied to replace lead-based piezoelectric materials, such as those which belong to the lead zirconate titanate (PZT) family, due to lead toxicity. In many applications, such as Tonpilz transducers, piezoelectric materials undergo mechanical stress simulation of which is important to control and predict electroacoustic effects. Thus, this article deals with a fully tensorial model that allows to simulate the behaviors of electrical displacements and elastic strains under mechanical stress. Simulated curves are compared with experimental ones obtained for BaTiO3 samples. It can be verified that the hysteretic curves of strains are well predicted for unpoled samples as well as for poled ones. The order of values and global behavior of the theoretical electrical displacement are also verified, even if a less precise agreement is observed. The optimized values of the physical parameters, such as ${d}_{{{33}}}$ , are discussed, and improvements both of the model and the optimization procedure are finally proposed in order to better predict the mechanical behavior of BaTiO3.

Published
2020

32. Activity of the human immortalized endothelial progenitor cell line HEPC-CB.1 supporting in vitro angiogenesis

Author

Karol Charkiewicz, Maria Paprocka, Agnieszka Krawczenko, Aleksandra Bielawska-Pohl, Danuta Duś, Aneta Kantor, Claudine Kieda, Catherine Grillon, Hirszfeld Institute of Immunology and Experimental Therapy, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Medical University of Bialystok, GRILLON, Catherine, Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Medical University of Białystok (MUB)

Subjects
Vascular Endothelial Growth Factor A, 0301 basic medicine, CD31, EPC secretome, Angiogenesis, EPC function, [SDV.BC.BC]Life Sciences [q-bio]/Cellular Biology/Subcellular Processes [q-bio.SC], [SDV.BC.IC] Life Sciences [q-bio]/Cellular Biology/Cell Behavior [q-bio.CB], 0302 clinical medicine, HLA Antigens, [SDV.BC.IC]Life Sciences [q-bio]/Cellular Biology/Cell Behavior [q-bio.CB], Cyclic AMP, Angiogenic Proteins, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Cell Line, Transformed, Endothelial Progenitor Cells, Tube formation, Chemistry, Cell Differentiation, General Medicine, Fetal Blood, Cell Hypoxia, 3. Good health, Cell biology, Endothelial stem cell, 030220 oncology & carcinogenesis, Cytokines, CD146, Original Article, Cell Division, Neovascularization, Physiologic, Tretinoin, [SDV.CAN]Life Sciences [q-bio]/Cancer, Real-Time Polymerase Chain Reaction, Endothelial progenitor cell, Colony-Forming Units Assay, 03 medical and health sciences, [SDV.CAN] Life Sciences [q-bio]/Cancer, Antigens, CD, [SDV.BC.BC] Life Sciences [q-bio]/Cellular Biology/Subcellular Processes [q-bio.SC], Human Umbilical Vein Endothelial Cells, Genetics, Humans, Regeneration, RNA, Messenger, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Progenitor cell, Molecular Biology, Endothelial Cells, [SDV.MHEP.DERM] Life Sciences [q-bio]/Human health and pathology/Dermatology, EPC, Coculture Techniques, Clone Cells, Oxygen, 030104 developmental biology, Cell culture, [SDV.MHEP.DERM]Life Sciences [q-bio]/Human health and pathology/Dermatology
Abstract

The human HEPC-CB.1 cell line with many characteristics of endothelial progenitor cells (EPC) was tested for its proangiogenic properties as a potentially therapeutic compound. HEPC-CB.1 cells’ potential to differentiate into endothelial cells was revealed after treating the cells with a mixture of ATRA, cAMP and VEGF, as shown by the reduced expression levels of CD133, CD271 and CD90 antigens, augmentation of CD146 and CD31, and a decrease in cell clonogenicity. The cooperation of HEPC-CB.1 with the endothelial cell line HSkMEC.2 resulted in the formation of a common network. Tube formation was significantly more effective when resulting from HEPC-CB.1 and HSkMEC.2 cell co-culture as compared to a monoculture of each cell line. The exocrine mechanism of HEPC-CB.1 and HSkMEC.2 cross talk by secreted factors was evidenced using the HEPC-CB.1 supernatant to increase the efficacy of HSkMEC.2 tube formation. The proangiogenic factors produced by HEPC-CB.1 were identified using cytokine antibody array. Out of 120 examined factors, the HEPC-CB.1 cell line produced 63, some with known angiogenic activity. As in vivo the angiogenic process occurs at low oxygen tension, it was observed that in hypoxia, the production of defined factors was augmented. The presented results demonstrate that HEPC-CB.1 cells are able to both cooperate and integrate in a newly formed network and produce factors that help the network formation. The results suggest that HEPC-CB.1 cells are indeed endothelial progenitors and may prove to be an effective tool in regenerative medicine. Electronic supplementary material The online version of this article (10.1007/s11033-020-05662-6) contains supplementary material, which is available to authorized users.

Published
2020

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

Author

Sylvain Routier, Kossi Efouako Soklou, Karen Plé, Mathieu Marchivie, Jean-Philippe Bouillon, Hamid Marzag, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank the Région Centre Val de Loire (Ph.D. funding SKE), the Labex programs SYNORG (ANR-11-LABX-0029) and IRON (ANR-11-LABX-0018-01), the Ligue contre le Cancer du Grand Ouest (comités des Deux Sèvres, du Finistère, de l’Ile et Villaine, du Loir et Cher, de Loire Atlantique, du Loiret, de la Vienne), and the Canceropole Grand Ouest for their financial support., ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), PLE, Karen, Synthèse Organique : des molécules au vivant - - SYNORG2011 - ANR-11-LABX-0029 - LABX - VALID, and Radiopharmaceutiques Innovants en Oncologie et Neurologie - - IRON2011 - ANR-11-LABX-0018 - LABX - VALID

Subjects
Annulation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, education, Organic Chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, humanities, 0104 chemical sciences, Catalysis, Cascade reaction, Intramolecular force, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Hydroamination, Physical and Theoretical Chemistry, Tertiary alcohols, Hydroalkoxylation
Abstract

International audience; We report here a simple and robust gold-catalyzed annulation reaction, giving N- and O-spirocycles in good to excellent yields. We have prepared a library of protected amines and tertiary alcohols that give, upon cyclization with alkynes, a representative set of heterospirocycles and illustrate reaction compatibility with diverse functional groups. A change in catalytic activity is possible by modifying the solvent, and two original tricyclic spirocycles were synthesized in a tandem reaction.

Published
2020

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

Author

Amélie Cavelan, Claude Le Milbeau, Mohammed Boussafir, Fatima Laggoun-Défarge, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Laboratoire Interdisciplinaire des Environnements Continentaux (LIEC), Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Terre et Environnement de Lorraine (OTELo), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and Region Centre-Val de Loire, France.

Subjects
020209 energy, General Chemical Engineering, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, 02 engineering and technology, 010502 geochemistry & geophysics, 01 natural sciences, Article, Methane, chemistry.chemical_compound, 0202 electrical engineering, electronic engineering, information engineering, Sedimentary organic matter, Porosity, QD1-999, 0105 earth and related environmental sciences, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Thermal conductivity detector, General Chemistry, Chemistry, Hydrocarbon, Kimmeridge Clay, Volume (thermodynamics), Source rock, chemistry, Chemical engineering, 13. Climate action
Abstract

International audience; This work investigates the relation between the molecular composition of the organic matter (OM), hydrocarbon generation, and porosity of artificially matured mudstones from the Kimmeridge Clay formation. Anhydrous thermal maturations, geochemical characterization (gas chromatography−mass spec-trometry, gas chromatography with a thermal conductivity detector), scanning electron microscopy observations, and nitrogen adsorption measurements were carried out. The results were compared to the calculated OM porosity after maturation. Our results reveal that samples richer in phytoplanktonic OM generated more abundant oils enriched in alkanes and lighter aromatic hydrocarbons (i.e., biphenyls and naphthalenes) that are more able to fill the adjacent pores of the mineral matrix during maturation. Both the calculated and the observed OM porosity increases during maturation, but the measured rock pore volume shows a non-linear evolution related to the amount of gas generated and the ensuing ability of the rock to preserve the pores. The secondary cracking of highly oil-prone samples generated larger amounts of C 1 −C 5 gases but lower pore volumes, less well preserved. OM composition and its ability to generate oil and gas seem therefore to affect the pore volume. These variations are nevertheless small compared to the effect of thermal maturity, which remains the major process controlling the evolution of porosity. During gas generation, high C 2 −C 5 concentrations are generated compared to methane. The short thermal maturation duration of our experiments may have delayed the conversion of C 2 −C 5 hydrocarbons to methane. In addition, slight differences in the concentrations of saturated and aromatic components and markedly different pore volumes and pore size distributions exist between artificially and naturally matured rocks. The conditions of artificial maturations may thus impact the thermal transformations of OM, emphasizing the necessity to investigate the role of the artificial maturation kinetics on OM and porosity.

Published
2020

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

Author

Alexis Grimaud, Paul E. Pearce, Daniel Alves Dalla Corte, Domitille Giaume, Ronghuang Zhang, Gwenaëlle Rousse, Heifang Li, Artem M. Abakumov, Michaël Deschamps, Vanessa Pimenta, Jordi Cabana, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Chimie du solide et de l'énergie (CSE), and Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemical transformation, Materials science, Hydrogen, Electrolysis of water, business.industry, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, Protonation, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Catalysis, Renewable energy, chemistry, Value (economics), Materials Chemistry, 0210 nano-technology, business
Abstract

International audience; Water electrolysis is considered as a promising way to store and convert excess renewable energies into hydrogen, which is of high value for many chemical transformation processes such as the Haber-Bosch process. However, to allow for the widespread of the polymer electrolyte membrane water electrolysis (PEMWE) technology, the main challenge lies in the design of robust catalysts for oxygen evolution reaction (OER) under acidic conditions since most of transition metal-based oxides undergo structural degradation under these harsh acidic conditions. To broaden the variety of candidate materials as OER catalysts, a cation-exchange synthetic route was recently explored to reach crystalline pronated iridates with unique structural properties and stability. In this work, a new protonated phase H 3.6 IrO 4 •3.7H 2 O, prepared via Sr 2+ /H + cation exchange at room temperature starting from the parent Ruddlesden-Popper Sr 2 IrO 4 phase, is described. This is the first discovery of crystalline protonated iridate forming from a perovskite-like phase, adopting a layered structure with apex-linked IrO 6 octahedra. Furthermore, H 3.6 IrO 4 •3.7H 2 O is found to possess not only an enhanced specific catalytic activity, superior to that of other perovskite-based iridates, but also a mass activity comparable to that of nanosized IrO x particles, while showing an improved catalytic stability owing to its ability to reversibly exchange protons in acid.

Published
2020

36. Self-combustion of Ti-C and Ti-Al Powder Mixture in a Nitrogen Atmosphere: Product Application as Reinforcement in Metal Matrix Composites

Author

Said Seghar, Akram Alhussein, Clémence Fradet, Salem Dehlouz, Florian Lacroix, Said Azem, Laboratoire des Systèmes Mécaniques et d'Ingénierie Simultanée (LASMIS), Institut Charles Delaunay (ICD), Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS)-Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS), Mécanique des Matériaux et Procédés (MMP), Laboratoire de Mécanique Gabriel Lamé (LaMé), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT), Laboratoire de Mécanique et de Rhéologie (LMR), Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Tours (UT)-Polytech'Tours, Université Mouloud Mammeri [Tizi Ouzou] (UMMTO), Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université d'Orléans (UO)-Université de Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Université de Tours-Polytech'Tours-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), and Université d'Orléans (UO)-Université de Tours (UT)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL)

Subjects
Ti2AlN, Materials science, Composite number, Sintering, chemistry.chemical_element, 02 engineering and technology, 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, SHS, chemistry.chemical_compound, 0103 physical sciences, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, General Materials Science, Composite material, ComputingMilieux_MISCELLANEOUS, [PHYS]Physics [physics], 010302 applied physics, Titanium aluminide, Mechanical Engineering, nitrogen atmosphere, metal matrix composites (MMCs), [SPI.MECA]Engineering Sciences [physics]/Mechanics [physics.med-ph], Nanoindentation, Tribology, 021001 nanoscience & nanotechnology, chemistry, Mechanics of Materials, Wetting, 0210 nano-technology, Tin, mechanical and tribological properties, Ti(C N), Solid solution
Abstract

International audience; In this work, two copper metal matrix composites (MMCs) reinforced with 20 wt.% of Ti(C,N) or Ti2AlN particles were studied. The reinforcement particles were synthesized by flash sintering under 2 bar nitrogen atmosphere causing an SHS reaction ignited by electrical current. This reaction led to produce TiC0.7N0.3 solid solution for the MMC1 reinforcement and Ti2AlN, TiN, and Ti3Al titanium aluminide for the MMC2 reinforcement. Both MMCs were densified by liquid phase sintering. The structural characterization was performed by XRD analysis while the morphology and chemical element distribution of both MMCs were analyzed by SEM and EDS. The structure of the two MMCs was relatively dense and showed good wettability. The mechanical and tribological behavior of MMCs evaluated by nanoindentation and wear testing reveals that the addition of 20 wt.% of reinforcement considerably improves the properties of copper matrix. Indeed, the MMC1 proved to be 3 times harder and 10 times more wear-resistant than the MMC2 composite.

Published
2020

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

Author

Aurélien Virgone, Gérard Sarazin, François Guyot, Vincent Milesi, Mathieu Debure, Virgile Rouchon, Edouard Bard, Nicolas C.M. Marty, Manuela Capano, Magali Ader, Carl I. Steefel, Patrick Albéric, Eric C. Gaucher, Didier Jézéquel, Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), IFP Energies nouvelles (IFPEN), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), TOTAL-Scientific and Technical Center Jean Féger (CSTJF), TOTAL FINA ELF, CNRS-INSU : INTERRIVECNRS-INSU : ARTEMIS, ANR-13-BS06-0001,Dziani,Ecalairages sur les océans précambriens par l'étude biogéochimique et microbiologique d'un analogue actuel: le lac Dziani Dzaha, Mayotte.(2013), Centre National de la Recherche Scientifique (CNRS)-Université de La Réunion (UR)-Université Paris Diderot - Paris 7 (UPD7)-IPG PARIS-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Chaire Evolution du climat et de l'océan, Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Physique du Globe de Paris (IPGP (UMR_7154)), Institut national des sciences de l'Univers (INSU - CNRS)-Université de La Réunion (UR)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Collège de France - Chaire Evolution du climat et de l'océan, Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Centre scientifique et Technique Jean Feger (CSTJF)

Subjects
saponite, Atmospheric Science, 010504 meteorology & atmospheric sciences, volcanic crater lake, Geochemistry, engineering.material, 010502 geochemistry & geophysics, 01 natural sciences, chemistry.chemical_compound, Geochemistry and Petrology, Crater lake, Dissolved organic carbon, magmatic CO2, Dziani Dzaha, 14. Life underwater, Hydromagnesite, rift settings, 0105 earth and related environmental sciences, magnesium phyllosilicates, geography, geography.geographical_feature_category, Mg silicates saponite rift settings pre-salt reactive transport modeling magmatic CO2 volcanic crater lake South-Atlantic early Cretaceous lacustrine carbonates paleoenvironment, Aragonite, Sediment, reactive transport modeling, Diagenesis, isotopy, Volcano, chemistry, kinetics, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, engineering, Carbonate, Geology, [SDU.STU.MI]Sciences of the Universe [physics]/Earth Sciences/Mineralogy
Abstract

International audience; Lacustrine carbonates formed in rift settings are increasingly studied not only as archives of Earth chemical and climatic history but also as potential hydrocarbon source rocks and/or reservoirs. The role of magmatic gases in their formation and diagenetic evolution, hence in their reservoir properties, remains unclear. We studied the first meter of carbonate sediment of the Dziani Dzaha volcanic crater lake (Mayotte Island) and developed a reactive-transport model with CrunchFlow software that allows the quantification of diagenetic reactions by considering depth-dependent burial rates and sediment compaction. The model is constrained by the previously documented solid-phase compositions of the lake sediment and new data consisting of 14C dating of plant macroremains to characterize the sediment age model, chemical composition of sediment pore waters, and chemical and isotopic composition of gases dissolved and bubbling through the lake. These new data reveal a massive magmatic CO2 contribution to the dissolved inorganic carbon of the lake, which fuels the primary productivity and carbonate formation. A pH value of 9 in the surface sediment pore waters induces supersaturation relative to aragonite, hydromagnesite, and saponite. At 1 m depth in the sediment, our model predicts that magmatic CO2 inflows and organic matter degradation account for 22 and 2 mol % dissolved inorganic carbon, respectively. The magmatic CO2 inflows result in a pH decrease at depth, leading to the destabilization of hydromagnesite, while saponite and aragonite remain stable. These results demonstrate the role of magmatic CO2 in fueling carbonate production and controlling the diagenetic evolution of sediment mineralogy.

Published
2020

38. Atmospheric Photosensitization: A New Pathway for Sulfate Formation

Author

Xinke Wang, Nathalie Hayeck, Liwu Zhang, Caihong Xu, Sébastien Perrier, Hui Chen, Zhe Wang, Nicolas Charbonnel, Christian George, R. Gemayel, Abdelwahid Mellouki, Lin Wang, Sergey A. Nizkorodov, Xinming Wang, Chao Zhu, Matthieu Riva, Tao Wang, Jianmin Chen, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Catalytic and Atmospheric Reactivity for the Environment (CARE), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Fudan University [Shanghai], Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), JSTI, Nanyang Technological University [Singapour], The Hong Kong Polytechnic University [Hong Kong] (POLYU), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS), Ministry of Science and Technology, China 2016YFC0202700, National Natural Science Foundation of China, 91843301, 91743202, National research program, DQGG0103, DQGG0102, ANR-16-CE01-0013,SEA-M,Impact des échanges air-mer sur la qualité de l'air dans les mégalopoles du littoral(2016), European Project: 690958,H2020,H2020-MSCA-RISE-2015,MARSU(2016), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS)

Subjects
MECHANISM, China, Asia, Ozone, Haze, [SDE.MCG]Environmental Sciences/Global Changes, 010501 environmental sciences, OXIDATION, Hydrogen atom abstraction, Photochemistry, 01 natural sciences, chemistry.chemical_compound, Electron transfer, Humans, PHOTOOXIDANTS, WATER, [CHIM]Chemical Sciences, Environmental Chemistry, Nitrogen dioxide, Photosensitivity Disorders, Sulfate, Hydrogen peroxide, KINETICS, HAZE, 0105 earth and related environmental sciences, Aerosols, DITHIONITE, Air Pollutants, Sulfates, PHOTOCHEMISTRY, General Chemistry, Aerosol, chemistry, 13. Climate action, Particulate Matter
Abstract

International audience; Northern China is regularly subjected to intense wintertime "haze events", with high levels of fine particles that threaten millions of inhabitants. While sulfate is a known major component of these fine haze particles, its formation mechanism remains unclear especially under highly polluted conditions, with state-of-the-art air quality models unable to reproduce or predict field observations. These haze conditions are generally characterized by simultaneous high emissions of SO2 and photosensitizing materials. In this study, we find that the excited triplet states of photosensitizers could induce a direct photosensitized oxidation of hydrated SO2 and bisulfite into sulfate S(VI) through energy transfer, electron transfer, or hydrogen atom abstraction. This photosensitized pathway appears to be a new and ubiquitous chemical route for atmospheric sulfate production. Compared to other aqueous-phase sulfate formation pathways with ozone, hydrogen peroxide, nitrogen dioxide, or transition-metal ions, the results also show that this photosensitized oxidation of S(IV) could make an important contribution to aerosol sulfate formation in Asian countries, particularly in China.

Published
2020

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

Author

Pierre-Simon Bellaye, Olivier Maury, Célia S. Bonnet, Jacques Pliquett, Océane Florès, Bertrand Collin, Franck Denat, Sandra Même, Ewen Bodio, Laura Abad Galán, Robin Lescure, Christine Goze, Agnès Pallier, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER, Même, Sandra, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, 010405 organic chemistry, Singlet oxygen, Quantum yield, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Wavelength, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Surface modification, Physical and Theoretical Chemistry, Absorption (chemistry), Boron, Excitation
Abstract

In this study, an original aza-BODIPY system comprising two Gd3+ complexes has been designed and synthesized for magnetic resonance imaging/optical imaging application, by functionalization of the boron center. This strategy enabled to obtain a positively-charged bimodal probe, which displays an increased water-solubility, optimized photophysical properties in the near-infrared region, and very promising relaxometric properties. The absorption and emission wavelengths are 705 and 741 nm respectively, with a quantum yield of around 10 % in aqueous media. Moreover, the system does not produce singlet oxygen upon excitation, which would be toxic for tissues. The relaxivity obtained is high at intermediate fields (16.1 mM-1.s-1 at 20 MHz and 310 K) and competes with that of bigger or more rigid systems. A full relaxometric and 17O NMR study and fitting of the data using the Lipari-Szabo approach showed that this high relaxivity can be explained by the size of the system and the presence of some small aggregates. These optimized photophysical and relaxometric properties highlight the potential use of such systems for future bimodal imaging studies.

Published
2020

40. Potential of N2/O2atmospheric pressure needle-water DC microplasmas for nitrogen fixation: nitrite-free synthesis of nitrates

Author

Nepal Chandra Roy, David Petitjean, Cedric Pattyn, Nicolas Maira, Sylvain Iseni, François Reniers, Antoine Remy, Faculté des Sciences [Bruxelles] (ULB), Université libre de Bruxelles (ULB), Groupe de recherches sur l'énergétique des milieux ionisés (GREMI), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)

Subjects
Materials science, Absorption spectroscopy, Inorganic chemistry, General Physics and Astronomy, 02 engineering and technology, 7. Clean energy, 01 natural sciences, law.invention, Physico-chimie générale, chemistry.chemical_compound, [CHIM.GENI]Chemical Sciences/Chemical engineering, [PHYS.PHYS.PHYS-PLASM-PH]Physics [physics]/Physics [physics]/Plasma Physics [physics.plasm-ph], law, 0103 physical sciences, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Physical and Theoretical Chemistry, Nitrite, 010302 applied physics, Atmospheric pressure, Physique, Microplasma, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, [SPI.PLASMA]Engineering Sciences [physics]/Plasmas, Aqueous two-phase system, Chimie théorique, Plasma, Astronomie, 021001 nanoscience & nanotechnology, 6. Clean water, Cathode, Anode, chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

A needle-water DC microplasma system working at atmospheric pressure in N2/O2 gas mixtures is used to study the fundamental mechanisms of nitrate/nitrite synthesis in highly complex and yet little-known plasma-water systems. Plasma properties are investigated by means of optical emission spectroscopy while the activated water is analyzed following the treatment using ionic chromatography and UV-Vis absorbance spectroscopy. Experiments highlight that the energy efficiency and selectivity of the process are influenced by the oxygen content and the plasma-induced water heating, with strong differences when the water surface is the anode or the cathode electrode. Nitrates are successfully synthesized without residual nitrites in the solution with a comparatively higher energy efficiency when the water is the cathode. The possible reactions involved in the gas phase and aqueous phase chemistry are presented and future scope for the optimization of the system is discussed., SCOPUS: ar.j, info:eu-repo/semantics/published

Published
2020

41. Synthesis of oligosaccharides of the linkage region of proteoglycans using regioselective glycosylation

Author

Chrystel Lopin-Bon, Sylvie Fournel-Gigleux, Sandrine Gulberti, Benjamin Ayela, Hélène Ledru, Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Ingénierie Moléculaire et Physiopathologie Articulaire (IMoPA), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Glycosylation, [SDV]Life Sciences [q-bio], Molecular Conformation, Disaccharide, Oligosaccharides, 01 natural sciences, Biochemistry, law.invention, Glycosaminoglycan, 03 medical and health sciences, chemistry.chemical_compound, Sulfation, Biosynthesis, law, Chondroitin sulfate, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Stereoisomerism, 0104 chemical sciences, carbohydrates (lipids), chemistry, Recombinant DNA, Proteoglycans, Linker
Abstract

Proteoglycans (PGs) are complex macromolecules that are composed of glycosaminoglycan (GAG) chains covalently attached to a core protein through a tetrasaccharide linker. Biosynthesis of PGs is complex and involves a large number of glycosyltranferases. We report herein for the first time the synthesis of a collection of various sulfoforms of the disaccharide GlcA-1,3-β-d-Gal and trisaccharides GlcNAc-1,4-α-d-GlcA-1,3-β-d-Gal and GalNAc-1,4-β-d-GlcA-1,3-β-d-Gal using a regioselective glycosylation. Preliminary results on the impact of sulfation of these disaccharides upon recombinant chondroitin sulfate N-acetylgalactosaminyltransferase-1 (CSGalNAcT-1) involved in chondroitin sulfate chain initiation is also reported.

Published
2020

42. Preliminary Characterization of a Post-Industrial Soil for Long-Term Remediation by Phytomanagement: Mesocosm Study of Its Phytotoxicity Before Field Application

Author

Manhattan Lebrun, Nour Hattab-Hambli, Sylvain Bourgerie, Florie Miard, Domenico Morabito, Lydie Le Forestier, Laboratoire de Biologie des Ligneux et des Grandes Cultures (LBLGC), Institut National de la Recherche Agronomique (INRA)-Université d'Orléans (UO), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Région Centre Val de Loire (Restor project, and contract number: 2014-00091906).

Subjects
chemistry.chemical_classification, Soil test, Environmental remediation, Phytotoxicity test, Soil pollution, Mesocosm, 010501 environmental sciences, 01 natural sciences, 6. Clean water, Metal(loid)s, Phytoremediation, chemistry, [SDU]Sciences of the Universe [physics], Environmental chemistry, Soil pH, Dissolved organic carbon, Organic matter, Phytotoxicity, 0105 earth and related environmental sciences, General Environmental Science
Abstract

International audience; The present study focused on the characterization of a multi-contaminated former industrial site, followed by an investigation into the suitability of a possible phytoremediation technique. This study area located in Issoudun (France) was contaminated with high concentrations of trace elements such as copper (Cu), lead (Pb), zinc (Zn), and arsenic (As). The site was divided into 18 blocks, and soil samples (46 samples taken from the 18 blocks) were analyzed for pH, total organic matter (TOC), electrical conductivity (EC), total concentrations in Cu, Pb, Zn and As and granulometry. In a mesocosm experiment soil pore waters (SPWs) were collected from potted soil using rhizon samplers, at both the beginning (T0) and the end of the experiment (TF), with pH, EC and dissolved organic carbon (DOC) being determined directly from the SPW solutions. Cu, Pb, Zn and As concentrations in SPW as well as aboveground and belowground organs of Phaseolus vulgaris were also analyzed. The two main results are shown in this study. Firstly, the physico-chemical properties of the soil revealed the heterogeneity of the area, in particular for blocks 1, 2, 17 and 18. Secondly, the mesocosm phytotoxicity test using Phaseolus vulgaris showed that metal(loid)s plant accumulation depended not only on the soil metal(loid) concentrations, but also on soil pH and sand content. Moreover, Phaseolus vulgaris plants presented a homogeneous growth indicating that the area was able to sustain plant growth. These results revealed that a phytoremediation technique could be applied in this contaminated site.

Published
2020

43. A versatile strategy to synthesize N-methyl-anthranilic acid-labelled glycoprobes for fluorescence-based screening assays

Author

Anne Robert, Sandrine Gulberti, Jean-Claude Jacquinet, Jean-Baptiste Vincourt, Chrystel Lopin-Bon, Nick Ramalanjaona, Mohamed Ouzzine, Isabelle Bertin-Jung, Sylvie Fournel-Gigleux, Catherine Bui, Ingénierie Moléculaire et Physiopathologie Articulaire (IMoPA), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Anomer, 010405 organic chemistry, [SDV]Life Sciences [q-bio], Metals and Alloys, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Fluorescence, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Materials Chemistry, Ceramics and Composites, Anthranilic acid, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

Here we propose a general strategy to label carbohydrates with N-methyl-anthranilic acid at the anomeric position. Through two examples, we demonstrate that the generated glycoprobes are suitable for fluorescence-based binding/competition assays. Our approach is expected to readily generate series of glycoprobes dedicated to screening assays for the discovery of drugs targeting carbohydrate–protein interactions.

Published
2020

44. Innovative in situ remediation of mine waters using a layered double hydroxide-biochar composite

Author

Barbora Hudcová, Michael Komárek, Petr Lacina, Delphine Vantelon, Ivo Šafařík, Peter Šottník, Veronika Veselská, Hana Šillerová, Michael Pohořelý, Gildas Ratié, Bronislava Lalinská-Voleková, Ľubomír Jurkovič, Lukáš Trakal, Czech University of Life Sciences Prague (CZU), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC)

Subjects
Environmental Engineering, Materials science, Environmental remediation, Health, Toxicology and Mutagenesis, Composite number, 0207 environmental engineering, 02 engineering and technology, 010501 environmental sciences, engineering.material, 01 natural sciences, Water Purification, chemistry.chemical_compound, Adsorption, Biochar, Hydroxides, Environmental Chemistry, efficient As and Sb removal, 020701 environmental engineering, Waste Management and Disposal, 0105 earth and related environmental sciences, layered double hydroxide modification, Layered double hydroxides, multiscale columns, Pollution, 6. Clean water, Kinetics, chemistry, Chemical engineering, mine water remediation, [SDU]Sciences of the Universe [physics], Charcoal, engineering, Hydroxide, biochar-based composite, Water treatment, Dispersion (chemistry), Water Pollutants, Chemical
Abstract

International audience; The current demand for alternative water sources requires the incorporation of low-cost composites in remediation technologies; these represent a sustainable alternative to more expensive, commercially used adsorbents. The main objective of this comprehensive field-scale study was to incorporate the layered double hydroxides (LDHs) into the hybrid biochar-based composites and apply an innovative material to remediate As/Sb-rich mine waters. The presence of hydrous Fe oxides (HFOs) within the composite enhanced the total adsorption efficiency of the composite for As(V) and Sb(V). The kinetic data fitted to a pseudo-second order model. Equilibrium experiments confirmed that the composite had a stronger interaction with As(V) than with Sb(V). The efficient removal of As(V) from mine water was achieved in both batch and continuous flow column systems, reaching up to 98% and 80%, respectively. Sb(V) showed different behavior to As(V) during mine water treatment, reaching adsorption efficiencies of up to 39% and 26% in batch and column experiments, respectively. The migration of Sb(V) in mine water was mostly attributed to its dispersion before it was able to show affinity to the composite. In general, the proposed column technology is suitable for the field remediation of small volumes of contaminated water, and thus has significant commercial potential.

Published
2022

45. Fluorescence microscopy and photodielectric characterization studies of the composite films of polyvinyl alcohol and tryptophan functionalized silver nanoparticles

Author

Duško Dudić, Vladimir Djoković, D. Tošić, Jelena Pajovic, Dušan K. Božanić, Radovan Dojčilović, Matthieu Réfrégiers, Vinča Institute of Nuclear Sciences, University of Belgrade [Belgrade], Universitat Pompeu Fabra [Barcelona] (UPF), 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), Refregiers, Matthieu, 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
Materials science, Photodielectric, Nanoparticle, 02 engineering and technology, Ag, 010402 general chemistry, 01 natural sciences, Polyvinyl alcohol, Silver nanoparticle, Crystallinity, chemistry.chemical_compound, Colloid and Surface Chemistry, Differential scanning calorimetry, Fluorescent imaging, Nanocomposite, integumentary system, Tryptophan, 021001 nanoscience & nanotechnology, Fluorescence, [PHYS.COND.CM-MS] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0104 chemical sciences, Chemical engineering, chemistry, PVA, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Glass transition
Abstract

Fluorescent nanocomposite films were prepared by solution mixing of polyvinyl alcohol (PVA) and tryptophan functionalized silver (AgTrp) nanoparticles. Synchrotron excitation deep-ultraviolet (DUV) fluorescence imaging was used to follow the distribution of AgTrp nanoparticles within the polymer matrix. Pronounced growth of dendrite-like structures in the presence of AgTrp nanoparticles was confirmed by bright field and fluorescence imaging as well as with atomic force microscopies. Both tryptophan and AgTrp nanoparticles influence thermal properties of the matrix. Differential scanning calorimetry measurements showed that they reduce crystallinity and significantly increase the glass transition temperature of PVA (in the case of PVA-AgTrp film the Tg increases by ~20 °C). Dielectric properties of the films were studied under two different conditions (dark and illumination). The illumination with 250 nm light induces a significant increase in conductance of the PVA-AgTrp nanocomposite. The relative changes, with respect to the conductance measured in the dark, were almost ~200%.

Published
2022

46. A speciation model linking the fate of carbon and hydrogen during coremagma ocean equilibration

Author

Mohamed Ali Bouhifd, Grégory Rogerie, Valérie Malavergne, Fabrice Gaillard, Magma - UMR7327, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Géomatériaux et Environnement (LGE ), Université Gustave Eiffel, 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), ANR-10-LABX-0100,VOLTAIRE,Geofluids and Volatil elements – Earth, Atmosphere, Interfaces – Resources and Environment(2010), and ANR-18-CE31-0021,GASTON,Les constituants volatils dans les processus magmatiques du noyau aux atmosphères(2018)

Subjects
0303 health sciences, 010504 meteorology & atmospheric sciences, Hydrogen, Lead (sea ice), chemistry.chemical_element, 01 natural sciences, Mantle (geology), Silicate, 03 medical and health sciences, chemistry.chemical_compound, Geophysics, chemistry, 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, [SDU]Sciences of the Universe [physics], Magma, Earth and Planetary Sciences (miscellaneous), Lithophile, Saturation (chemistry), Petrology, Carbon, Geology, 030304 developmental biology, 0105 earth and related environmental sciences
Abstract

International audience; The core – mantle differentiation in the magma ocean constitutes a major planetary event that involved two elements that are essential to life: carbon (C) and hydrogen (H). These two elements are conventionally classified as volatiles (ie. atmophile), but they can also evolve into being siderophile and lithophile at the extreme conditions found in planetary magma oceans. We report here a model for H and C species dissolved in silicate melts in equilibrium with iron-rich alloys under variable pressure, temperature and redox conditions. This speciation model is able to reconcile and reproduce a large body of experimental data on metal-silicate partitioning for H and C at carbon-saturation and in C-undersaturated systems. At low pressure, we conclude that the prevailing species in a silicate magma ocean are CO2, CO, H2O, H2, whereas CH4 appears to dominate at high pressure. These speciation changes explain recent experimental observations that (i) C evolves from being strongly siderophile at low pressure to moderately siderophile at high pressure, and (ii) H is not siderophile at low pressure but becomes increasingly so as pressure rises. Moreover, it shows that H becomes increasingly siderophile as the total H content of the silicate melt and C-activity are lowered. Despite it offers a promising reconciliation of a large set of experimental and molecular dynamics observations, this model still suffers from large uncertainties when extrapolated to high pressure. In particular, endmember and mixing properties in both the silicate melt and the molten metal must be independently deciphered.The enhanced CH4 stability in the silicate melt at high pressure couples the fate of C and H in deep magma oceans. In such cases, the solubility of C in the basal ocean depends on the H-content and is higher than C-solubility at low pressure. This implies an increase in C activity as the ascending convective cells of the magma ocean, which may cause C saturation as graphite or diamond unless Fe-metal droplets, having a great C-solubility, are present in the shallow magma ocean. Under certain conditions, enhanced siderophile behaviour for H can lead via a runaway process to the desiccation of the magma ocean.

Published
2022

47. Investigating Mercury's Environment with the Two-Spacecraft BepiColombo Mission

Author

Oleg Korablev, M. Fujimoto, Léa Griton, Cesare Grava, Masafumi Hirahara, Hirotsugu Kojima, S. Barabash, Wolfgang Baumjohann, A. Martindale, Chuanfei Dong, François Leblanc, Chris Carr, S. T. Lindsay, Yasumasa Kasaba, M. Kobayashi, Herbert Lichtenegger, Philippe-A. Bourdin, Karri Muinonen, J. S. Oliveira, Jan-Erik Wahlund, Ferdinand Plaschke, Christina Plainaki, S. M. P. McKenna-Lawlor, Dominique Delcourt, Eric Quémerais, Xianzhe Jia, Dusan Odstrcil, James A. Slavin, V. Mangano, M. G. Pelizzo, Benoit Langlais, Joe Zender, Emma J. Bunce, Ichiro Yoshikawa, Peter Wurz, Stavro Ivanovski, Stefano Massetti, George C. Ho, Y. Saito, Juhani Huovelin, Suzanne M. Imber, Sae Aizawa, Alessandro Mura, Jim M. Raines, Ayako Matsuoka, F. Sahraoui, Karl-Heinz Glassmeier, Pierre Henri, Rami Vainio, Matthew K. James, Rosemary M. Killen, Stefano Orsini, Shahab Fatemi, Tomas Karlsson, Monica Laurenza, Esa Kallio, Christoph Lhotka, Michiko Morooka, Johannes Benkhoff, David A. Rothery, Yasuhito Narita, Michel Moncuquet, Anna Milillo, Alexey A. Berezhnoy, Satoshi Yagitani, Adam Masters, F. Califano, Manuel Grande, Stefano Livi, Daniel Heyner, Emilia Kilpua, G. Murakami, Jan Deca, S. de la Fuente, R. Moissl, Bernard V. Jackson, Kanako Seki, N. André, M. Dósa, Istituto di Astrofisica e Planetologia Spaziali - INAF (IAPS), Istituto Nazionale di Astrofisica (INAF), Institute of Space and Astronautical Science (ISAS), Japan Aerospace Exploration Agency [Sagamihara] (JAXA), European Space Research and Technology Centre (ESTEC), Agence Spatiale Européenne = European Space Agency (ESA), Institut de recherche en astrophysique et planétologie (IRAP), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), Wigner Research Centre for Physics [Budapest], Hungarian Academy of Sciences (MTA), Institut für Geophysik und Extraterrestrische Physik [Braunschweig] (IGEP), Technische Universität Braunschweig = Technical University of Braunschweig [Braunschweig], Johns Hopkins University Applied Physics Laboratory [Laurel, MD] (APL), Department of Atmospheric, Oceanic, and Space Sciences [Ann Arbor] (AOSS), University of Michigan [Ann Arbor], University of Michigan System-University of Michigan System, Space Research Centre [Leicester], University of Leicester, Department of Space and Plasma Physics [Stockholm], KTH School of Electrical Engineering, Royal Institute of Technology [Stockholm] (KTH )-Royal Institute of Technology [Stockholm] (KTH ), NASA Goddard Space Flight Center (GSFC), Space Technology Ireland Limited, Department of Climate and Space Sciences and Engineering (CLaSP), School of Physical Sciences [Milton Keynes], Faculty of Science, Technology, Engineering and Mathematics [Milton Keynes], The Open University [Milton Keynes] (OU)-The Open University [Milton Keynes] (OU), Space Research Institute of Austrian Academy of Sciences (IWF), Austrian Academy of Sciences (OeAW), Sternberg Astronomical Institute [Moscow], Lomonosov Moscow State University (MSU), University of Pisa - Università di Pisa, University of Colorado [Boulder], European Space Astronomy Centre (ESAC), Princeton Plasma Physics Laboratory (PPPL), Princeton University, Department of Astrophysical Sciences [Princeton], Southwest Research Institute [San Antonio] (SwRI), Swedish Institute of Space Physics [Kiruna] (IRF), Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), INAF - Osservatorio Astronomico di Trieste (OAT), University of California [San Diego] (UC San Diego), University of California (UC), Department of Electronics and Nanoengineering [Espoo], School of Electrical Engineering [Aalto Univ], Aalto University-Aalto University, Planetary Plasma and Atmospheric Research Center [Sendai] (PPARC), Tohoku University [Sendai], Department of Physics [Helsinki], Falculty of Science [Helsinki], Helsingin yliopisto = Helsingfors universitet = University of Helsinki-Helsingin yliopisto = Helsingfors universitet = University of Helsinki, Planetary Exploration Research Center [Chiba] (PERC), Chiba Institute of Technology (CIT), Laboratoire de Planétologie et Géodynamique [UMR 6112] (LPG), Université d'Angers (UA)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), HELIOS - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Blackett Laboratory, Imperial College London, Swedish Institute of Space Physics [Uppsala] (IRF), Institute of Physics [Graz], Karl-Franzens-Universität Graz, Centro de Investigação da Terra e do Espaço da UC (CITEUC), Universidade de Coimbra [Coimbra], CNR Institute for Photonics and Nanotechnologies (IFN), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Italian Space Agency, Laboratoire de Physique des Plasmas (LPP), Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École polytechnique (X)-Sorbonne Université (SU)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Department of Earth and Planetary Science [Tokyo], Graduate School of Science [Tokyo], The University of Tokyo (UTokyo)-The University of Tokyo (UTokyo), Space Research Laboratory [Turku] (SRL), Department of Physics and Astronomy [Turku], University of Turku-University of Turku, Physics Institute [Bern], University of Bern, Department of Physics [Imperial College London], Institute of Mathematical and Physical Sciences [Aberystwyth], University of Wales, Institute for Space-Earth Environmental Research [Nagoya] (ISEE), Nagoya University, Space Research Institute of the Russian Academy of Sciences (IKI), Russian Academy of Sciences [Moscow] (RAS), Research Institute for Sustainable Humanosphere (RISH), Kyoto University, Laboratoire d'études spatiales et d'instrumentation en astrophysique = Laboratory of Space Studies and Instrumentation in Astrophysics (LESIA), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Graduate School of the Natural Science and Technology [Kanazawa], Kanazawa University (KU), Department of Complexity Science and Engineering [Tokyo], The University of Tokyo (UTokyo), European Space Agency (ESA), Institut national des sciences de l'Univers (INSU - CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National d’Études Spatiales [Paris] (CNES), University of California, University of Helsinki-University of Helsinki, Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Karl-Franzens-Universität [Graz, Autriche], Consiglio Nazionale delle Ricerche [Roma] (CNR), Kyoto University [Kyoto], Laboratoire d'études spatiales et d'instrumentation en astrophysique (LESIA (UMR_8109)), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), The Royal Society, Science and Technology Facilities Council, INAF National Institute for Astrophysics, JAXA Institute of Space and Astronautical Science, European Space Research and Technology Centre, IRAP, Hungarian Academy of Sciences, Technical University of Braunschweig, Johns Hopkins Applied Physics Laboratory, University of Michigan, Ann Arbor, KTH Royal Institute of Technology, NASA Goddard Space Flight Center, Space Technology Ireland, Open University Milton Keynes, Austrian Academy of Sciences, Lomonosov Moscow State University, University of Pisa, University of Colorado Boulder, European Space Astronomy Centre, Princeton Plasma Physics Laboratory, Southwest Research Institute, Uppsala University, Université d'Orléans, Osservatorio Astronomico di Trieste, University of California San Diego, Department of Electronics and Nanoengineering, Tohoku University, University of Helsinki, Chiba Institute of Technology, Université de Nantes, Sorbonne Université, University of Graz, National Research Council of Italy, Agenzia Spaziale Italiana, The University of Tokyo, University of Turku, Aberystwyth University, Space Research Institute of the Russian Academy of Sciences, Université de Versailles Saint-Quentin-en-Yvelines, Kanazawa University, Aalto-yliopisto, and Aalto University

Subjects
010504 meteorology & atmospheric sciences, Computer science, BepiColombo, chemistry.chemical_element, FOS: Physical sciences, Astronomy & Astrophysics, 01 natural sciences, Mercury’s environment, Fusion, plasma och rymdfysik, Interplanetary dust cloud, Astronomi, astrofysik och kosmologi, 0201 Astronomical and Space Sciences, 0103 physical sciences, Astronomy, Astrophysics and Cosmology, Exosphere, Magnetosphere, Aerospace engineering, 010303 astronomy & astrophysics, Instrumentation and Methods for Astrophysics (astro-ph.IM), 0105 earth and related environmental sciences, Scientific instrument, Earth and Planetary Astrophysics (astro-ph.EP), Spacecraft, business.industry, 520 Astronomy, Astronomy and Astrophysics, 620 Engineering, Fusion, Plasma and Space Physics, Mercury (element), Solar wind, Planetary science, chemistry, Space and Planetary Science, [SDU]Sciences of the Universe [physics], Mercury's environment, Mercury’s environment · Magnetosphere · Exosphere · BepiColombo, Astrophysics - Instrumentation and Methods for Astrophysics, business, Astrophysics - Earth and Planetary Astrophysics
Abstract

The ESA-JAXA BepiColombo mission will provide simultaneous measurements from two spacecraft, offering an unprecedented opportunity to investigate magnetospheric and exospheric dynamics at Mercury as well as their interactions with the solar wind, radiation, and interplanetary dust. Many scientific instruments onboard the two spacecraft will be completely, or partially devoted to study the near-space environment of Mercury as well as the complex processes that govern it. Many issues remain unsolved even after the MESSENGER mission that ended in 2015. The specific orbits of the two spacecraft, MPO and Mio, and the comprehensive scientific payload allow a wider range of scientific questions to be addressed than those that could be achieved by the individual instruments acting alone, or by previous missions. These joint observations are of key importance because many phenomena in Mercury's environment are highly temporally and spatially variable. Examples of possible coordinated observations are described in this article, analysing the required geometrical conditions, pointing, resolutions and operation timing of different BepiColombo instruments sensors., Comment: 78 pages, 14 figures, published

Published
2022
Full Text
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48. Analysis and Comparison of Electromagnetic Microrobotic Platforms for Biomedical Applications

Author

Ruipeng CHEN, David FOLIO, Antoine Ferreira, Laboratoire pluridisciplinaire de recherche en ingénierie des systèmes, mécanique et énergétique (PRISME), Université d'Orléans (UO)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA), Laboratoire Pluridisciplinaire de Recherche en Ingénierie des Systèmes, Mécanique et Energétique (PRISME), Ecole Nationale Supérieure d'Ingénieurs de Bourges (ENSI Bourges)-Université d'Orléans (UO), and Inserm 'Plan Cancer' 2014–2019 program, Project: Microrobots Targeting Glioblastoma (MTG).

Subjects
electromagnetic actuation, Fluid Flow and Transfer Processes, Technology, 0209 industrial biotechnology, QH301-705.5, Physics, QC1-999, Process Chemistry and Technology, General Engineering, 02 engineering and technology, Engineering (General). Civil engineering (General), 021001 nanoscience & nanotechnology, medical magnetic microrobots, Computer Science Applications, [SPI.AUTO]Engineering Sciences [physics]/Automatic, Chemistry, 020901 industrial engineering & automation, General Materials Science, TA1-2040, Biology (General), 0210 nano-technology, QD1-999, Instrumentation, minimally invasive surgery
Abstract

International audience; Magnetic microrobotics is a promising technology for improving minimally invasive surgery (MIS) with the ambition of enhancing patient care and comfort. The potential benefits include limited incisions, less hemorrhaging and postoperative pain, and faster recovery time. To achieve this, a key issue relies on the design of a proper electromagnetic actuation (EMA) setup which is based on the use of magnetic sources. The magnetic field and its gradient generated by the EMA platform is then used to induce magnetic torque and force for microrobot manipulations inside the human body. Like any control systems, the EMA system must be adapted to the given controlled microrobot and customized for the application. With great research efforts on magnetic manipulating of microrobots, the EMA systems are approaching commercial applications, and their configurations are becoming more suitable to be employed in real medical surgeries. However, most of the proposed designs have not followed any specific rule allowing to take into account the biomedical applications constraints. Through reviewing the different proposed EMA systems in the literature, their various specifications and configurations are comprehensively discussed and analyzed. This study focus on EMA platforms that use electromagnets. From this review and based on the biomedical application specifications, the appropriate EMA system can be determined efficiently.

Published
2022

49. An innovative kinetic model allowing insight in the moderate temperature chemical vapor deposition of silicon oxynitride films from tris(dimethylsilyl)amine

Author

Konstantina Christina Topka, Paris Papavasileiou, Babacar Diallo, Tryfon Tsiros, Laura Decosterd, Brigitte Caussat, Marie-Joëlle Menu, Diane Samélor, Constantin Vahlas, Hugues Vergnes, François Senocq, Nadia Pellerin, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE08-0056,HEALTHYGLASS,Surfaces de verre performantes et durables pour la pharmacie(2017), Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Laboratoire de Génie Civil (LGC), and Université Blaise Pascal - Clermont-Ferrand 2 (UBP)

Subjects
Experimental validation, Silicon oxynitride, Materials science, Silicon, General Chemical Engineering, Matériaux, chemistry.chemical_element, 02 engineering and technology, Chemical vapor deposition, Computational fluid dynamics, 01 natural sciences, Chemical reaction, Industrial and Manufacturing Engineering, [SPI.MAT]Engineering Sciences [physics]/Materials, chemistry.chemical_compound, Phase (matter), 0103 physical sciences, Environmental Chemistry, Molecule, Deposition (phase transition), Génie chimique, Thin film, Génie des procédés, ComputingMilieux_MISCELLANEOUS, 010302 applied physics, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Kinetic model, 021001 nanoscience & nanotechnology, Silanamine precursor, chemistry, Chemical engineering, 0210 nano-technology
Abstract

International audience; An apparent kinetic model is developed for a novel chemical vapor deposition (CVD) process of silicon oxynitride (SiO x N y) films from tris(dimethylsilyl)amine (TDMSA) and O 2 , operating at moderate temperature (600-650 • C) and at atmospheric pressure. The definition of reaction pathways and the extraction of kinetic information is based on recently reported results of the gas phase composition, complemented by solid phase characteristics obtained by spectroscopic ellipsometry (SE) and ion beam analyses (IBA). Incorporation of carbon (up to 20 at. %) is considered alongside nitrogen (up to 25 at.%) for variable O 2 flow rates (0.3-1.2 sccm). This combined gasand solid-phase analysis is utilized to identify the main gaseous species and provide insight into the deposition mechanism. A silicon-and a nitrogen-centered radical intermediates are considered as the primary species of the mechanism, based on evidence from gas phase characterizations. A third, fictitious, nitrogen-and carboncontaining molecule is also conceptualized to account for carbon incorporation. Eight chemical reactions are defined alongside their respective kinetic parameters and are implemented in the ANSYS® FLUENT® computational fluid dynamics (CFD) code. Upon validation, the model allows for the successful prediction of local deposition rates and SiO x N y film composition containing non-negligible carbon, marking it as the first kinetic model able to represent the main chemical mechanisms involved in the CVD of a four-component material. The reported combined approach could be applied to other existing or new CVD chemistries forming multicomponent thin films, favoring their implementation in original applications.

Published
2022

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

Author

Samia Aci-Sèche, Pascal Bonnet, A. Braka, Norbert Garnier, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
General Chemical Engineering, Kinetics, Molecular Dynamics Simulation, Library and Information Sciences, Ligands, 01 natural sciences, Molecular dynamics, In vivo, 0103 physical sciences, Binding site, Protein Kinase Inhibitors, Residence time (statistics), 010304 chemical physics, Drug discovery, Chemistry, Ligand, General Chemistry, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation, [SDV.BIBS]Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], 0104 chemical sciences, Computer Science Applications, 010404 medicinal & biomolecular chemistry, Thermodynamics, Probability distribution, Biological system, [CHIM.CHEM]Chemical Sciences/Cheminformatics, Protein Binding
Abstract

International audience; In the early stage of a drug discovery process, the selection and optimization of a ligand is mainly based on equilibrium thermodynamic constants such as KD or IC50 values, which are representatives of the affinity of the compound for its target. However, these criteria are not able to correctly evaluate the efficacy of compounds in vivo and result in many failures of compound development during phase II of clinical trials. Residence time (RT) is an important parameter associated to an in vivo drug’s safety and efficacy. The determination or modulation of kinetic rates correlated to RT may be performed to identify the best drug candidates in the early stages of a drug design project. For this purpose, a number of experimental methodologies were developed but remain costly in both time and money. Herein, we developed a novel protocol based on biased molecular dynamics simulations and transition-state theory in order to predict relative ligand kinetic rates and relative RTs of a series of compounds. First, we have repeatedly simulated the unbinding process of the ligand from its binding site to the outside of the target. Next, we sample the conformational space along the determined unbinding paths to allow relevant statistical distributions of the system. The free energy profiles associated to these distributions are then computed and used to predict the kinetics parameters. The studied set was composed of eight ligands with fast, intermediate, and slow dissociation rates and binding to the active and inactive states of p38α protein kinase. The proposed method provides an excellent correlation between the predicted values and the experimentally measured kinetic rates, in addition to a detailed characterization of the kinetic paths at the atomic level.

Published
2019

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