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1. Fabrication and optical properties of transparent fine-grained Zn1.1Ga1.8Ge0.1O4 and Ni2+ (or Cr3+)-doped Zn1.1Ga1.8Ge0.1O4 spinel ceramics

Author: Julie Carreaud, Jean-René Duclere, Yann Launay, Nicolas Tessier-Doyen, David S. Smith, Mathieu Allix, Vincent Couderc, Gaëlle Delaizir, Sébastien Chenu, Institut de Recherche sur les CERamiques (IRCER), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Matériaux Procédés Environnement Ouvrages (IMPEO), Université de Limoges (UNILIM)-Université de Limoges (UNILIM), 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), XLIM (XLIM), Université de Limoges (UNILIM)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-10-LABX-0074-01, European Commission, EC, European Regional Development Fund, ERDF: AAPR2021-2020-11934110, and ANR-10-LABX-0074,Sigma-LIM,From specific ceramic materials and components to integrated, secured and intelligent communication systems(2010)
Subjects: Zinc gallate (ZnGa2O4), Optical properties, Persistent luminescence, Spark Plasma Sintering (SPS), Materials Chemistry, Ceramics and Composites, [CHIM.MATE]Chemical Sciences/Material chemistry, Transparent spinel ceramics
Abstract: International audience; For the first time, a Zn1.1Ga1.8Ge0.1O4 transparent spinel ceramic has been fully densified by spark plasma sintering. XRD measurements show that this ceramic is composed of a pure cubic spinel phase. SEM analysis revealed a homogeneous and dense microstructure with the average grain size being 200 ± 100 nm. The transmittance of these fine-grained ceramics reached 70 % in the visible range and is very close to 80 % at 2 µm, thus close to the Tmax value deduced from the measurement of the refractive index. The ceramics exhibit excellent mechanical properties with a Young modulus of 222 GPa, a Vickers hardness of 14.25 GPa and a thermal conductivity of 7.3 W.m−1. K−1. By doping with Cr3+ ions, transparent Zn1.1Ga1.8Ge0.1O4 ceramics present both a red luminescence and a long-lasting afterglow during several minutes. Moreover, a near infrared broadband emission at 1.3 µm is also achieved with Ni2+ ions.
Published: 2023
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2. Robotic Instruments Inside the MRI Bore: Key Concepts and Evolving Paradigms in Imaging-enhanced Cranial Neurosurgery

Author: Manjila, Sunil, Rosa, Benoit, Price, Karl, Manjila, Rehan, Mencattelli, Margherita, Dupont, Pierre E., Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [INFO.INFO-RB]Computer Science [cs]/Robotics [cs.RO], Surgery, Neurology (clinical)
Published: 2023
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3. Deactivation of Pd/C catalysts by irreversible loss of hydrogen spillover ability of the carbon support

Author: Laurent Vanoye, Boris Guicheret, Camila Rivera-Cárcamo, Jérémy Audevard, Javier Navarro-Ruiz, Iker del Rosal, Iann C. Gerber, Cristian H. Campos, Bruno Fernandes Machado, Jérôme Volkman, Régis Philippe, Philippe Serp, Alain Favre-Réguillon, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Universidad de Concepción - University of Concepcion [Chile], Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia (LSRE-LCM), Universidade do Porto = University of Porto, Conservatoire National des Arts et Métiers [CNAM] (CNAM), HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM), and ANR-19-CE07-0030,COMET,Catalyse Coopérative Entre Atomes Et Nanoparticules Métalliques(2019)
Subjects: [CHIM]Chemical Sciences, [CHIM.CATA]Chemical Sciences/Catalysis, Physical and Theoretical Chemistry, Catalysis
Abstract: International audience; General interest in solvent-free catalytic processes is driven by the development of environmentally and economically acceptable procedures. Such processes require the use of highly active and stable catalysts. This study reports on the synthesis, characterization, and kinetic evaluation of two highly active Pd catalysts supported on different carbons support, i.e., multi-walled carbon nanotubes (CNT) and few-layer graphene (FLG). These catalysts, with similar Pd loading (∼2 wt%) and containing both Pd single atoms (PdSA) and nanoparticles (PdNP), were systematically tested for solvent-free total hydrogenation of squalene (SQE) to obtain high-purity squalane (SQA). Thanks to the unique cooperative catalysis between PdSA and PdNP involving H-spillover, the activities of both catalysts were high compared to catalysts described in the literature. Solvent-free total hydrogenation of SQE could be performed under mild conditions (120 °C, 20 bar H2, 4 h) using ultralow Pd loading (60 ppm). However, since this reduction reaction is highly exothermic (ΔHR= − 765 kJ.mol−1), heat management during the reactor operation with these highly active catalysts is crucial to avoid deactivation and thermal runaway. Under these conditions, Pd/FLG was highly active but deactivated, unlike Pd/CNT, which still has high activity, but does not deactivate. Characterizations (ICP, XPS, Raman, TPD-MS, HAADF-STEM) of the Pd/FLG catalyst before and after reaction, supported by calculations based on density functional theory, allowed us to propose a new mechanism of catalyst deactivation involving the chemical reduction of specific surface oxygen groups of the carbon support induced by H-spillover.
Published: 2023
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4. A silicone-based slippery polymer coating with humidity–dependent nanoscale topography

Author: Callau, M., Fajolles, C., Leroy, J., Verneuil, E., Guenoun, P., Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Sciences et Ingénierie de la Matière Molle (UMR 7615) (SIMM), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Biomaterials, Colloid and Surface Chemistry, [CHIM]Chemical Sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; Hypothesis: Slippery Omniphobic Covalently Attached Liquids (SOCAL) have been proposed for making omnirepellent thin films of self-assembled dimethylsiloxane polymerbrushes grafted from silica surfaces. Smooth and flat at very small scale, these fluid surfaces could exhibit a more complex multiscale structure though showing very weak contact angle hysteresis (less than 5°).Experiment: In this work, coatings were deposited on glass surfaces from an acidic dimethoxydimethylsilane solution under carefully controlled relative humidity. Ellipsometry mapping was used to analyze the surface structuration with nanometric thickness sensitivity. The sliding properties were determined using a drop shape analyzer with a tilting device, and chemical analyses of the coatings were performed using on-surface techniques (XPS, ATR-FTIR spectroscopy).Findings: Coated materials possessed an unexpected surface structure with multiscale semispherical-like features, which surprisingly, did not increase the contact angle hysteresis. A careful study of some parameters of the coating process and the related evolution of the surface properties allowed us to propose a new model of the chemical organization of the polymer to support this remarkable liquid-like behavior. These structures are made of endgrafted strongly adsorbed Guiselin brushes with humidity-dependent thickness: the higher the humidity, the thinner and the more slippery the coating.
Published: 2023
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5. Anti-Cancer and Radio-Sensitizing Properties of New Bimetallic (N-Heterocyclic Carbene)-Amine-Pt(II) Complexes

Author: Tao Jia, Oumar Diane, Deepanjan Ghosh, Myriem Skander, Gaelle Fontaine, Pascal Retailleau, Joël Poupon, Jérôme Bignon, Ytabelle Maga Moulai Siasia, Vincent Servajean, Nathalie Hue, Jean-François Betzer, Angela Marinetti, Sophie Bombard, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Toxicologie Biologique, Hôpital Lariboisière, Hôpital Lariboisière-Fernand-Widal [APHP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP), and European Project: 666003,H2020,H2020-MSCA-COFUND-2014,IC-3i-PhD(2016)
Subjects: Drug Discovery, [CHIM]Chemical Sciences, Molecular Medicine
Abstract: International audience; Bioactive NHC-transition metal complexes have shown promise as anti-cancer agents, but their potential use as radiosensitizers has been neglected so far. We disclose here a new series of bimetallic platinum(II) complexes displaying NHC-type bridging ligands, (bis-NHC)[trans-Pt(RNH2)I2]2 that have been synthesized via a simple, two-step procedure. They display cytotoxicity in the micromolar range on cancerous cell lines, accumulate in cells and bind to genomic DNA, by inducing DNA damages. Notably, these bimetallic complexes demonstrate significant radiosensitizing effects on both ovarian cells A2780 and non-small lung carcinoma cells H1299. Further investigations revealed that bimetallic species make irradiation-induced DNA damages more persistent by inhibiting repair mechanisms. Indeed, a higher and persistent accumulation of both -H2AX and 53BP1 foci post-irradiation was detected, in the presence of the NHC-Pt complexes. Overall, we provide the first in vitro evidence for the radiosensitizing properties of NHC-platinum complexes, that suggests their potential use in combined chemo-radio therapy protocols.
Published: 2023
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6. Influence of Sintering Conditions on the Structure and Redox Speciation of Homogeneous (U,Ce)O2+δ Ceramics: A Synchrotron Study

Author: Malvina Massonnet, Laurent Claparede, Julien Martinez, Philippe M. Martin, Myrtille O.J.Y. Hunault, Damien Prieur, Adel Mesbah, Nicolas Dacheux, Nicolas Clavier, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), European Synchroton Radiation Facility [Grenoble] (ESRF), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, XAS, O/M ratio, nuclear fuel, structure, uranium oxide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract: International audience; Although uranium–cerium dioxides are frequently used as a surrogate material for (U,Pu)O2−δ nuclear fuels, there is currently no reliable data regarding the oxygen stoichiometry and redox speciation of the cations in such samples. In order to fill this gap, this manuscript details a synchrotron study of highly homogeneous (U,Ce)O2±δ sintered samples prepared by a wet-chemistry route. HERFD-XANES spectroscopy led to determining accurately the O/M ratios (with M = U + Ce). Under a reducing atmosphere (pO2 ≈ 6 × 10–29 atm at 650 °C), the oxides were found to be close to O/M = 2.00, while the O/M ratio varied with the sintering conditions under argon (pO2 ≈ 3 × 10–6 atm at 650 °C). They globally appeared to be hyperstoichiometric (i.e., O/M > 2.00) with the departure from the dioxide stoichiometry decreasing with both the cerium content in the sample and the sintering temperature. Nevertheless, such a deviation from the ideal O/M = 2.00 ratio was found to generate only moderate structural disorder from EXAFS data at the U-L3 edge as all the samples retained the fluorite-type structure of the UO2 and CeO2 parent compounds. The determination of accurate lattice parameters owing to S-PXRD measurements led to complementing the data reported in the literature by various authors. These data were consistent with an empirical relation linking the unit cell parameter, the chemical composition, and the O/M stoichiometry, showing that the latter can be evaluated simply within a ± 0.02 uncertainty
Published: 2023
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7. Visualizing Water Reduction with Diazonium Grafting on a Glassy Carbon Electrode Surface in a Water-in-Salt Electrolyte

Author: Yachao Zhu, Lea Droguet, Jie Deng, Xuanze Wang, Luming Li, Yannick Dufil, Mathieu Deschannels, Rossukon Jommongkol, Chayaporn Pareseecharoen, Alexis Grimaud, Jean-Marie Tarascon, Olivier Fontaine, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chongqing University [Chongqing], Universitat Ramon Llull [Barcelona] (URL), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: water-in-salt electrolyte, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, artificial SEI layer, glassy carbon, hydrophobic grafting layer, passivation layer, solid-electrolyte interphase, diazonium grafting, aqueous batteries
Abstract: International audience; Aqueous batteries are regaining interest, thanks to the extended working stability voltage window in a highly concentrated electrolyte, namely the water-in-salt electrolyte. A solid-electrolyte interphase (SEI) forms on the negative electrode to prevent water access to the electrode surface. However, we further reported that the formed SEI layer was not uniform on the surface of the glassy carbon electrode. The SEI after passivation will also show degradation during the remaining time of open-circuit voltage (OCV); hence, it calls for a more stable passivation layer to cover the electrode surface. Here, a surface modification was successfully achieved via artificial diazonium grafting using monomers, such as poly(ethylene glycol), α-methoxy, ω-allyloxy (PEG), and allyl glycidyl cyclocarbonate (AGC), on glassy carbon. Physical and electrochemical measurements indicated that the hydrophobic layer composed of PEG or AGC species was well grafted on the electrode surface. The grafted hydrophobic coatings could protect the electrode surface from the water molecules in the bulk electrolyte and then suppress the free water decomposition (from LSV) but still migrating lithium ions. Furthermore, multiple cycles of CV with one-hour resting OCV identified the good stability of the hydrophobic grafting layer, which is a highlight compared with our precious work. These findings relying on the diazonium grafting design may offer a new strategy to construct a stable artificial SEI layer that can well protect the electrode surface from the free water molecule.
Published: 2023
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8. Impact of Hard Carbon Properties on Their Performance in Potassium-Ion Batteries

Author: Louiza Larbi, Badre Larhrib, Adrian Beda, Lénaïc Madec, Laure Monconduit, Camelia Matei Ghimbeu, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and ANR-19-CE05-0026,TROPIC,Vers des batteries innovantes K-ion(2019)
Subjects: Energy storage, Hard carbon, Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, Energy Engineering and Power Technology, Chemical Engineering (miscellaneous), Graphite, Potassium-ion batteries, Electrical and Electronic Engineering, Anodes
Abstract: International audience; This work reports on the synthesis of hard carbon spheres (HCS) and the impact of the pyrolysis temperature (1500 to 1900 °C) on the properties of HC and its relationship with the electrochemical performance in potassium-ion batteries (KIBs). Comparison with commercial graphite performance is provided as well. Spherical morphology, disordered structure, and low surface area were obtained for the HCSs. Most properties (interlayer space, active surface area, and oxygen-based functional groups) were found to decrease with increasing pyrolysis temperature, except for the helium density and closed porosity, which increase. However, graphite presents a flake-like morphology with a larger particle size, a higher helium density, an ordered structure with a smaller interlayer distance, and no closed pores. Electrochemical tests in a half-cell vs K+/K showed that HCSs perform better than graphite with higher initial Coulombic efficiency (ICE) and better specific capacities. The HCSs pyrolyzed at 1500 and 1700 °C exhibit the best initial Coulombic efficiency, ICEs of 54 and 62%, and specific capacities of 254 and 247 mAh g–1 (C/20, 11.5 mA g–1), respectively. The ICE is affected by multiple surface and bulk parameters but also by electrolyte formulation (67% for 0.8 M KFSI vs 62% for 0.8 M KPF6). The capacity is governed by diffusive phenomena, and a larger interlayer graphitic spacing and defects favor a better insertion of K ions. Closed pores did not lead to an improvement in capacity. Furthermore, HCSs exhibit significantly better capacity retention (97%) than graphite (84%), especially when cycled at high current rates (up to 10C depotassiation rate).
Published: 2023
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9. On the Effect of Symmetry Requirement for Rendezvous on the Complete Graph

Author: Marthe Bonamy, Michał Pilipczuk, Jean-Sébastien Sereni, Richard Weber, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Mathematics, Management Science and Operations Research, [INFO.INFO-AI]Computer Science [cs]/Artificial Intelligence [cs.AI], Computer Science Applications
Abstract: We consider a classic rendezvous game in which two players try to meet each other on a set of n locations. In each round, every player visits one of the locations, and the game finishes when the players meet at the same location. The goal is to devise strategies for both players that minimize the expected waiting time till the rendezvous. In the asymmetric case, when the strategies of the players may differ, it is known that the optimum expected waiting time of [Formula: see text] is achieved by the wait-for-mommy pair of strategies, in which one of the players stays at one location for n rounds, while the other player searches through all the n locations in a random order. However, if we insist that the players are symmetric—they are expected to follow the same strategy—then the best known strategy, proposed by Anderson and Weber [Anderson EJ, Weber RR (1990) The rendezvous problem on discrete locations. J. Appl. Probab. 27(4):839–851], achieves an asymptotic expected waiting time of [Formula: see text]. We show that the symmetry requirement indeed implies that the expected waiting time needs to be asymptotically larger than in the asymmetric case. Precisely, we prove that for every [Formula: see text], if the players need to employ the same strategy, then the expected waiting time is at least [Formula: see text], where [Formula: see text]. We propose in addition a different proof for one our key lemmas, which relies on a result by Ahlswede and Katona [Ahlswede R, Katona GOH (1978) Graphs with maximal number of adjacent pairs of edges. Acta Mathematica Academiae Scientiarum Hungaricae 32(1–2):97–120]: the argument is slightly shorter and provides a constant larger than [Formula: see text], namely, [Formula: see text]. However, it requires that n be at least 16. Both approaches seem conceptually interesting to us. Funding: This work is a part of project TOTAL (Mi. Pilipczuk) that has received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation program [Grant 677651]. It is also partially funded by French ANR projects [Grant ANR-16-CE40-0023] (DESCARTES) and [Grant ANR-17-CE40-0015] (DISTANCIA).
Published: 2023
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10. First La2O2S infrared transparent ceramics

Author: Alexandre Le Coz, Guillaume R. Durand, Louis Cornet, Nathalie Herbert, Francis Gouttefangeas, Loïc Joanny, Fabrice Célarié, François Cheviré, Odile Merdrignac-Conanec, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse Caractérisation Analyse de la Matière (ScanMAT), Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and French Direction Générale de l’Armement (DGA) and the Ministère des armées - Agence de l’Innovation de Défence (AID)
Subjects: Hot-pressing, Materials Chemistry, Ceramics and Composites, Young modulus, [CHIM]Chemical Sciences, La2O2S, [CHIM.MATE]Chemical Sciences/Material chemistry, Vickers hardness, Infrared transmission
Abstract: International audience; Lanthanum oxysulfide (La2O2S) was investigated as infrared transparent ceramic to benefit from stronger chemical bonds and superior mechanical performances to that of non-oxide benchmark infrared materials. La2O2S ceramics were processed by hot-pressing powders prepared by combustion synthesis followed by a sulfurization treatment. Powders and ceramics were characterised through various techniques (XRD, UV-Vis-IR spectroscopy, particle size analysis, SEM, Impulse Excitation Technique, microhardness and fracture toughness tests) to assess their purity, study their microstructure and determine their optical and mechanical properties. The study reports the first IR transmission spectra, Poisson’s ratio, Young’s and shear moduli and fracture toughness values of La2O2S polycrystalline ceramics. The ceramics showed transparency in the 2-11 μm range and their mechanical performances were all superior to that of commercial infrared ceramics. The best transmission (89% of the theoretical transmission) was measured at 7.3 µm for 1 mm-thick ceramics hot-pressed at 1200-1250°C.
Published: 2023
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11. Ultraviolet exposure regulates skin metabolome based on the microbiome

Author: Vijaykumar Patra, Natalie Bordag, Yohann Clement, Harald Köfeler, Jean-Francois Nicolas, Marc Vocanson, Sophie Ayciriex, Peter Wolf, Medical University Graz, Centre International de Recherche en Infectiologie (CIRI), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Medical University of Graz, CheMod, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANABIO-MS - Analyse biomoléculaire par spectrométrie de masse - Biological Analysis by Mass Spectrometry, BioTechMed-Graz, Graz University of Technology [Graz] (TU Graz)-Karl-Franzens-Universität Graz-Medical University Graz, and Austrian Science Fund (FWF, W1241)
Subjects: [STAT]Statistics [stat], Multidisciplinary, [SDV]Life Sciences [q-bio]
Abstract: Skin metabolites (
Published: 2023
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12. Highly Robust and Efficient Blechert-Type Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Olefin Metathesis

Author: Antonio Del Vecchio, Jakub Talcik, Sophie Colombel-Rouen, Jan Lorkowski, Melinda R. Serrato, Thierry Roisnel, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), University of California [San Diego] (UC San Diego), University of California (UC)-University of California (UC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of California (UC), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Prematuration Program of CNRS, Agence Nationale de la Recherche [ANR-19-CE07-0017 ChiCAAC], France Relance, U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program [DE-SC0009376], Rennes Metropole [Eco-SFC], and ANR-19-CE07-0017,ChiCAAC,Carbènes alkyl amino cycliques chiraux en catalyse asymétrique(2019)
Subjects: ruthenium complex, Olefin metathesis, asymmetric catalysis, [CHIM]Chemical Sciences, cyclic(alkyl)(amino)carbene, General Chemistry, Catalysis
Abstract: International audience; New Blechert-type ruthenium complexes containing cyclic(alkyl)(amino)carbene (CAAC) ligands are reported. These catalysts demonstrate remarkable thermal stability in solution and excellent catalytic performances at low catalytic loading (up to 0.005 mol %) in ring-closing metathesis (RCM), macro-RCM, ring-closing enyne metathesis (RCEYM), cross-metathesis (CM), ethenolysis and ring-opening cross metathesis (ROCM). Moreover, up to 95% enantiomeric excess (ee) was obtained in asymmetric ring-opening cross metathesis (AROCM) and 57% ee was obtained in asymmetric cross-metathesis (ACM).
Published: 2023
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13. Hexagonal Tungsten Bronze H0.25Cs0.25Nb2.5W2.5O14 as a Negative Electrode Material for Li-Ion Batteries

Author: Etienne Le Calvez, Julio César Espinosa-Angeles, Éric Gautron, Éric Quarez, Olivier Crosnier, Thierry Brousse, Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), ANR-16-IDEX-0007,NExT (I-SITE),NExT (I-SITE)(2016), and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
Subjects: General Chemical Engineering, Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Oxides derived from the ReO3 structure, such as bronzes or Wadsley-Roth phases, have re-emerged from the past as they offer very attractive properties as negative electrodes for high-power Li-ion batteries. Here, we revisit the hexagonal bronze Cs0.5Nb2.5W2.5O14 and its protonated H0.25Cs0.25Nb2.5W2.5O14 derivative, which was newly obtained after ion exchange. A panel of characterization techniques (HAADF-STEM imaging, EDX mapping, and XRD) revealed a specific cation ordering in the material and a preferential ion exchange in the heptagonal tunnels of this oxide. When used as Li-ion battery electrodes, H0.25Cs0.25Nb2.5W2.5O14 exhibits higher specific capacities as well as better capacity retention at high currents than Cs0.5Nb2.5W2.5O14. The protonated phase provides specific capacities of 132 and 111 mAh center dot g-1 at, respectively, 0.02 and 0.2 A center dot g-1. Kinetic analysis reveals that the good capacity at a high rate is due to favorable diffusion of lithium ions into the tunnels of H0.25Cs0.25Nb2.5W2.5O14. In addition, using in situ XRD, a solid solution mechanism occurring during lithium insertion was proposed, as well as the different lithiation sites of the material.
Published: 2023
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14. Enhanced Performance of KVPO4F0.5O0.5 in Potassium Batteries by Carbon Coating Interfaces

Author: Louiza Larbi, Romain Wernert, Philippe Fioux, Laurence Croguennec, Laure Monconduit, Camelia Matei Ghimbeu, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), 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), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The Algerian Ministry of High Education and Scientific Research and Agence Nationale de la Recherche. The authors acknowledge financial support of the Agence Nationale de la Recherche (ANR) under Grants ANR-19-CE05-0026 (TROPIC project) and ANR-10-LABX-76-01 (RS2E (French research network on electrochemical energy storage), STORE-EX Labex Project), as well as Région Nouvelle Aquitaine for sustaining this work., ANR-19-CE05-0026,TROPIC,Vers des batteries innovantes K-ion(2019), and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
Subjects: Positive electrode material, Chemical vapor deposition, Carbon coating, Chitosan biopolymer, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Potassium-ion batteries, Vanadium oxyfluoride phosphate, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Potassium vanadium oxyfluoride phosphate of composition KVPO4F0.5O0.5 was modified by a carbon coating to enhance its electrochemical performance. Two distinct methods were used, first, chemical vapor deposition (CVD) using acetylene gas as a carbon precursor and second, an aqueous route using an abundant, cheap, and green precursor (chitosan) followed by a pyrolysis step. The formation of a 5 to 7 nm-thick carbon coating was confirmed by transmission electron microscopy and it was found to be more homogeneous in the case of CVD using acetylene gas. Indeed, an increase of the specific surface area of one order of magnitude, low content of C sp2, and residual oxygen surface functionalities were observed when the coating was obtained using chitosan. Pristine and carbon-coated materials were compared as positive electrode materials in potassium half-cells cycled at a C/5 (C = 26.5 mA g–1) rate within a potential window of 3 to 5 V vs K+/K. The formation by CVD of a uniform carbon coating with the limited presence of surface functions was shown to improve the initial coulombic efficiency up to 87% for KVPFO4F0.5O0.5-C2H2 and to mitigate electrolyte decomposition. Thus, performance at high C-rates such as 10 C was significantly improved, with ∼50% of the initial capacity maintained after 10 cycles, whereas a fast capacity loss is observed for the pristine material.
Published: 2023
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15. When Ions Defy Electrostatics: The Case of Superchaotropic Nanoion Adsorption

Author: Max Hohenschutz, Jean-François Dufrêche, Olivier Diat, Pierre Bauduin, Ions aux Interfaces Actives (L2IA), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Modélisation Mésoscopique et Chimie Théorique (LMCT)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Materials Science, Physical and Theoretical Chemistry
Abstract: International audience; Nanometer-sized anions, like polyoxometalates and borate clusters, bind to nonionic hydrated matter driven by the chaotropic effect, which arises from the favorable dehydration of the ions. Herein, we evaluate the adsorption and activity coefficient of the superchaotropic Keggin polyoxometalate SiW12O404– (SiW) on nonionic surfactant (C8E4) micelles by modeling small-angle X-ray and neutron-scattering spectra. Neither hard sphere nor electrostatic repulsion models reproduce the experimental activity coefficient of adsorbed SiW ions on the micelles. However, the activity and binding of SiW on the micelles is well-described by a Langmuir adsorption isotherm. These results imply that adsorbed SiW ions are non-interacting and “create” around themselves adsorption sites on the micelle. The temperature dependence of the adsorption constant showed that the SiW adsorption is enthalpically driven and entropically unfavorable, in line with the typical chaotropic thermochemical signature. The adsorption enthalpy can be split into an electrostatic term and a water-recovery term to evaluate and qualitatively predict the superchaotropicity of a nanoion.
Published: 2023
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16. Intentional overdose of glargine insulin: Determination of the parent compound in postmortem blood by <scp>LC‐HRMS</scp>

Author: Arbouche, Nadia, Walch, Alexis, Raul, Jean-Sébastien, Kintz, Pascal, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de pharmacologie et de toxicologie neurocardiovasculaire (LPTNC), and Université de Strasbourg (UNISTRA)
Subjects: [SDV.OT]Life Sciences [q-bio]/Other [q-bio.OT], Sciences du Vivant [q-bio]/Autre [q-bio.OT], Genetics, Pathology and Forensic Medicine
Published: 2023
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17. Understanding the Electronic Structure Basis for N2 Binding to FeMoco: A Systematic Quantum Mechanics/Molecular Mechanics Investigation

Author: Yunjie Pang, Ragnar Bjornsson, Beijing Normal University (BNU), Max Planck Institute for Chemical Energy Conversion, Max-Planck-Gesellschaft, Chimie computationnelle, modélisation et rayons X (COMX), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation
Abstract: International audience; The FeMo cofactor (FeMoco) of Mo nitrogenase is responsible for reducing dinitrogen to ammonia, but it requires the addition of 3-4 e-/H+ pairs before N2 even binds. A binding site at the Fe2/Fe3/Fe6/Fe7 face of the cofactor has long been suggested based on mutation studies, with Fe2 or Fe6 nowadays being primarily discussed as possibilities. However, the nature of N2 binding to the cofactor is enigmatic as the metal ions are coordinatively saturated in the resting state with no obvious binding site. Furthermore, the cofactor consists of high-spin Fe(II)/Fe(III) ions (antiferromagnetically coupled but also mixed-valence delocalized), which are not known to bind N2. This suggests that an Fe binding site with a different molecular and electronic structure than the resting state must be responsible for the experimentally known N2 binding in the E4 state of FeMoco. We have systematically studied N2 binding to Fe2 and Fe6 sites of FeMoco at the broken-symmetry QM/MM level as a function of the redox-, spin-, and protonation state of the cofactor. The local and global electronic structure changes to the cofactor taking place during redox events, protonation, Fe-S cleavage, hydride formation, and N2 coordination are systematically analyzed. Localized orbital and quasi-restricted orbital analysis via diamagnetic substitution is used to get insights into the local single Fe ion electronic structure in various states of FeMoco. A few factors emerge as essential to N2 binding in the calculations: spin-pairing of dxz and dyz orbitals of the N2-binding Fe ion, a coordination change at the N2-binding Fe ion aided by a hemilabile protonated sulfur, and finally hydride ligation. The results show that N2 binding to E0, E1, and E2 models is generally unfavorable, likely due to the high-energy cost of stabilizing the necessary spin paired electronic structure of the N2-binding Fe ion in a ligand environment that clearly favors high-spin states. The results for models of E4, however, suggest a feasible model for why N2 binding occurs experimentally in the E4 state. E4 models with two bridging hydrides between Fe2 and Fe6 show much more favorable N2 binding than other models. When two hydrides coordinate to the same Fe ion, an increased ligand-field splitting due to octahedral coordination at either Fe2 or Fe6 is found. This altered ligand field makes it easier for the Fe ion to acquire a spin-paired electronic structure with doubly occupied dxz and dyz orbitals that backbond to a terminal N2 ligand. Within this model for N2 binding, both Fe2 and Fe6 emerge as possible binding site scenarios. Due to steric effects involving the His195 residue, affecting both the N2 ligand and the terminal SH- group, distinguishing between Fe2 and Fe6 is difficult; furthermore, the binding depends on the protonation state of His195.
Published: 2023
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18. Large-Scale Colloidal Synthesis of Chalcogenides for Thermoelectric Applications

Author: Viviana Sousa, Arka Sarkar, Oleg I. Lebedev, Christophe Candolfi, Bertrand Lenoir, Rodrigo Coelho, António P. Gonçalves, Eliana M. F. Vieira, Pedro Alpuim, Kirill Kovnir, Yury V. Kolen’ko, Centre of Physics of the University of Minho (CFUM), Iowa State University (ISU), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-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)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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 Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Instituto Superior Técnico, Technical University of Lisbon, Universidade do Minho = University of Minho [Guimarães], and International Iberian Nanotechnology Laboratory (INL)
Subjects: Tin selenide, Spark plasma sintering, Transport properties, Lead tellurides, Seebeck coefficient, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Lead selenides, Microstructure
Abstract: International audience; A simple and effective preparation of solution-processed chalcogenide thermoelectric materials is described. First, PbTe, PbSe, and SnSe were prepared by gram-scale colloidal synthesis relying on the reaction between metal acetates and diphenyl dichalcogenides in hexadecylamine solvent. The resultant phase-pure chalcogenides consist of highly crystalline and defect- free particles with distinct cubic-, tetrapod-, and rod-like morphologies. The powdered PbTe, PbSe, and SnSe products were subjected to densification by spark plasma sintering (SPS), affording dense pellets of the respective chalcogenides. Scanning electron microscopy shows that the SPS-derived pellets exhibit fine nano-/micro-structures dictated by the original morphology of the key constituting particles, while the powder X-ray diffraction and electron microscopy analyses confirm that the SPS-derived pellets are phase-pure materials, preserving the structure of the colloidal synthesis products. The resultant solution-processed PbTe, PbSe, and SnSe exhibit low thermal conductivity, which might be due to the enhanced phonon scattering developed over fine microstructures. For undoped n-type PbTe and p-type SnSe samples, an expected moderate thermoelectric performance is achieved. In contrast, an outstanding figure-of-merit of 0.73 at 673 K was achieved for undoped n-type PbSe outperforming, the majority of the optimized PbSe-based thermoelectric materials. Overall, our findings facilitate the design of efficient solution-processed chalcogenide thermoelectrics.
Published: 2023
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19. Effect of Solvent on Convectively Driven Silica Particle Assembly: Decoupling Surface Tension, Viscosity, and Evaporation Rate

Author: Lucien Roach, David Gonzalez-Rodriguez, Jie Gao, Eric Laurichesse, Alexander Castro-Grijalba, Reiko Oda, Véronique Schmitt, Emilie Pouget, Mona Tréguer-Delapierre, Glenna L. Drisko, 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), Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Funding for this work from the European Research Council (ERC) under European Union′s Horizon 2020 Research and Innovation Program (Grant No. 948319). L.R., G.L.D., and M.T.-D. received financial support from the Conseil Régional d′Aquitaine and the LabEx AMADEus (Grant No. ANR-10-LABX-42) in the framework of IdEx Bordeaux (Grant No. ANR-10-IDEX-03-02) managed by the National Agency for Research., ANR-10-IDEX-0302,ANR-10-IDEX-03-02,Investments for the Future Programme IdEx Bordeaux-LAPHIA, and European Project: 948319-ERC-2020-STG,SCATTER
Subjects: Landau‑Levich flow, evaporative rate, stick‑slip, viscosity, Electrochemistry, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, Convective flux, Condensed Matter Physics, Spectroscopy
Abstract: International audience; The process of convectively self-assembling particles in films suffers from low reproducibility due to its high dependency on particle concentration, as well as a variety of interactions and physical parameters. Inhomogeneities in flow rates and instabilities at the air–liquid interface are mostly responsible for reproducibility issues. These problems are aggravated by adding multiple components to the dispersion, such as binary solvent mixtures or surfactant/polymer additives, both common approaches to control stick-slip behavior. When an additive is used, not only does it change the surface tension, but also the viscosity and the evaporation rate. Worse yet, gradients in these three properties can form, which then lead to Marangoni currents. Here, we use a series of alcohols to study the role of viscosity independently of other solvent properties, to show its impact on stick-slip behavior and interband distances. We show that mixtures of glycerol and alcohol or poly(acrylic acid) and alcohol lead to more complex patterning. Marangoni currents are not always observed in co-solvent systems, being dependent on the rate of solvent evaporation. To produce homogeneous particle assemblies and control stick-slip behavior, gradients must be avoided, and the surface tension and viscosity need both be carefully controlled.
Published: 2023
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20. Eremoxylarins D–J, Antibacterial Eremophilane Sesquiterpenes Discovered from an Endolichenic Strain of Xylaria hypoxylon

Author: Alice Miral, Solenn Ferron, Isabelle Rouaud, Dinmukhammed Slyambayev, Latifa Bousarghin, Charline Camuzet, Sandrine Belouzard, Karin Séron, Pierre Le Pogam, Sylvain Tranchimand, Sophie Tomasi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nutrition, Métabolismes et Cancer (NuMeCan), Université de Rennes (UR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), 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)-Centre National de la Recherche Scientifique (CNRS), Biomolécules : Conception, Isolement, Synthèse (BioCIS), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY)
Subjects: Specialized metabolites, Pharmacology, Complementary and alternative medicine, Fungal compounds, Organic Chemistry, Drug Discovery, Pharmaceutical Science, Molecular Medicine, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Bioactive compounds, [SDV.MP.MYC]Life Sciences [q-bio]/Microbiology and Parasitology/Mycology, Structural identification, Analytical Chemistry
Abstract: International audience; An endolichenic strain of the Ascomycetaceous Xylaria hypoxylon, cultivated alone or in coculture with another endolichenic fungus Dendrothyrium variisporum, produced seven new bioactive eremophilane sesquiterpenes eremoxylarins D−J (1−7). The isolated compounds disclosed a high similarity with the eremophilane core of the bioactive integric acid, and structures were elucidated by 1D and 2D NMR spectra and electronic circular dichroism (ECD) analyses. Eremoxylarins D, F, G, and I showed a selective activity against Gram-positive bacteria such as methicillin-resistant Staphylococcus aureus with minimum inhibitory concentration (MIC) values between 0.39 and 12.5 μg/mL. Eremoxylarin I, the most antibacterial active sesquiterpene, was also active against HCoV-229E at a concentration nontoxic to the hepatoma Huh-7 cell line with an 50% inhibitory concentration (IC 50) of 18.1 μM and a 50% cytotoxic concentration (CC 50) of 46.6 μM.
Published: 2023
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21. Ambivalent Role of Rotamers in Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Enantioselective Ring-Opening Cross-Metathesis

Author: Jennifer Morvan, François Vermersch, Ziyun Zhang, Thomas Vives, Thierry Roisnel, Christophe Crévisy, Laura Falivene, Luigi Cavallo, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), University of California [San Diego] (UC San Diego), University of California (UC)-University of California (UC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of California (UC), King Abdullah University of Science and Technology (KAUST), Università degli Studi di Salerno = University of Salerno (UNISA), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Region Bretagne (ARED 2018 'Biometa') [ANR-19-CE07-0017 ChiCAAC], Agence Nationale de la Recherche [DE-SC0009376], U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, King Abdu l l a h University of Science and Technology (KAUST), 601, and ANR-19-CE07-0017,ChiCAAC,Carbènes alkyl amino cycliques chiraux en catalyse asymétrique(2019)
Subjects: Inorganic Chemistry, Organic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; The development of highly efficient enantioselective olefin metathesis catalysts is a significant challenge. Using optically pure chiral cyclic (alkyl)(amino)carbene (ChiCAAC) ligands combined with preliminary mechanistic insights and density functional theory (DFT) computations, we show that catalytic performances in this field can be impaired by the formation of rotamers before the enantio-determining step. Using DFT, we also demonstrate that these results can help accelerate the process of ligand discovery by providing faster methods to discriminate potential candidates.
Published: 2023
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22. Impact of additive manufacturing on reaction to fire

Author: Thomas Nazé, Franck Poutch, Fanny Bonnet, Maude Jimenez, Serge Bourbigot, Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Mechanics of Materials, Mechanical Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, Safety, Risk, Reliability and Quality
Abstract: International audience; Additive manufacturing, including fused deposition modelling, is a growing technology opening up wide perspectives in material sciences. However, the ability to produce suitable fire-retarded materials via this process has never been studied extensively. This work focuses on understanding the relation between reaction to fire and numerous additive manufacturing parameters. The goal was to determine the impact of those parameters on standard fire tests such as flame propagation test (UL94V) and cone calorimetry. The results were compared with material samples formulated via usual processes. On one hand, flame propagation results are impacted by many additive manufacturing parameters, such as the design of the part and the material flow. On the other hand, cone calorimeter results are only influenced by parameters having an impact on the sample mass.
Published: 2023
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23. Critical assessment of the sulfo-phospho-vanillin method to quantify lipids in freeze-dried microalgae

Author: Farinacci, Julie, Laurent, Julien, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, Plant Science, Aquatic Science
Published: 2023
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24. Advances on Microsupercapacitors: Real Fast Miniaturized Devices toward Technological Dreams for Powering Embedded Electronics?

Author: Pascal Roussel, Christophe Lethien, Khac Huy Dinh, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Circuits Systèmes Applications des Micro-ondes - IEMN (CSAM - IEMN ), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement no. 847568. The authors thank the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01). The French RENATECH network and the University of Lille are greatly acknowledged for supporting the Center of MicroNanoFabrication (CMNF) facility from IEMN., Renatech Network, ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), and European Project: 847568,H2020,H2020-MSCA-COFUND-2018,PEARL(2019)
Subjects: General Chemical Engineering, General Chemistry, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics
Abstract: International audience; Electrochemical lithium (de)intercalation in an atomic layer deposited (ALD) TiO2 anatase thin film deposited on a planar Si /Al2O3/Pt substrate is investigated by Raman spectroscopy. An initial discharge capacity of 63 µAh cm−2 µm−1 (0.5 Li+ mole−1) is reached at C/10 rate, which increases up to 77 µAh cm−2 µm−1 upon further cycles. An excellent capacity retention is achieved over at least 100 cycles, showing the good adherence of the ALD thin film. Raman spectra of LixTiO2 (0 ≤ x ≤ 0.5) thin film electrodes point to the nucleation of the orthorhombic lithiated titanate (LT) Li0.5TiO2 phase from x = 0.1. This LT phase coexists with tetragonal TiO2 in the 0.1 ≤ x ≤ 0.4 composition domain to be pure for x = 0.5. A fully reversible transformation from orthorhombic LT to tetragonal TiO2 is observed upon the charge. The high quality of the Raman spectra allows identifying for the first time 12 modes in the 100–800 cm−1 region for the electrochemically formed LT phase. Furthermore, an appropriate Raman spectra analysis allows a reliable and quantitative determination of the thin film composition during discharge and charge. These results illustrate Raman spectroscopy is a powerful probe to scrutinize the Li insertion/extraction mechanism in TiO2 thin films.
Published: 2023
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25. Flexible Aliphatic Diammonioacetates as Zwitterionic Ligands in UO22+ Complexes: Diverse Topologies and Interpenetrated Structures

Author: Sotaro Kusumoto, Youssef Atoini, Shunya Masuda, Yoshihiro Koide, Jee Young Kim, Shinya Hayami, Yang Kim, Jack Harrowfield, Pierre Thuéry, Kanagawa University, Technische Universität München = Technical University of Munich (TUM), kosin university (Kosin), Kumamoto University, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; N,N,N′,N′-Tetramethylethane-1,2-diammonioacetate (L1) and N,N,N′,N′-tetramethylpropane-1,3-diammonioacetate (L2) are two flexible zwitterionic dicarboxylates which have been used as ligands for the uranyl ion, 12 complexes having been obtained from their coupling to diverse anions, mostly anionic polycarboxylates, or oxo, hydroxo and chlorido donors. The protonated zwitterion is a simple counterion in [H2L1][UO2(2,6-pydc)2] (1), where 2,6-pydc2– is 2,6-pyridinedicarboxylate, but it is deprotonated and coordinated in all the other complexes. [(UO2)2(L2)(2,4-pydcH)4] (2), where 2,4-pydc2– is 2,4-pyridinedicarboxylate, is a discrete, binuclear complex due to the terminal nature of the partially deprotonated anionic ligands. [(UO2)2(L1)(ipht)2]·4H2O (3) and [(UO2)2(L1)(pda)2] (4), where ipht2– and pda2– are isophthalate and 1,4-phenylenediacetate, are monoperiodic coordination polymers in which central L1 bridges connect two lateral strands. Oxalate anions (ox2–) generated in situ give [(UO2)2(L1)(ox)2] (5) a diperiodic network with the hcb topology. [(UO2)2(L2)(ipht)2]·H2O (6) differs from 3 in being a diperiodic network with the V2O5 topological type. [(UO2)2(L1)(2,5-pydc)2]·4H2O (7), where 2,5-pydc2– is 2,5-pyridinedicarboxylate, is a hcb network with a square-wave profile, while [(UO2)2(L1)(dnhpa)2] (8), where dnhpa2– is 3,5-dinitro-2-hydroxyphenoxyacetate, formed in situ from 1,2-phenylenedioxydiacetic acid, has the same topology but a strongly corrugated shape leading to interdigitation of layers. (2R,3R,4S,5S)-Tetrahydrofurantetracarboxylic acid (thftcH4) is only partially deprotonated in [(UO2)3(L1)(thftcH)2(H2O)] (9), which crystallizes as a diperiodic polymer with the fes topology. [(UO2)2Cl2(L1)3][(UO2Cl3)2(L1)] (10) is an ionic compound in which discrete, binuclear anions cross the cells of the cationic hcb network. 2,5-Thiophenediacetate (tdc2–) is peculiar in promoting self-sorting of the ligands in the ionic complex [(UO2)5(L1)7(tdc)(H2O)][(UO2)2(tdc)3]4·CH3CN·12H2O (11), which is the first example of heterointerpenetration in uranyl chemistry, involving a triperiodic, cationic framework and diperiodic, anionic hcb networks. Finally, [(UO2)7(O)3(OH)4.3Cl2.7(L2)2]Cl·7H2O (12) crystallizes as a 2-fold interpenetrated, triperiodic framework in which chlorouranate undulating monoperiodic subunits are bridged by the L2 ligands. Complexes 1, 2, 3, and 7 are emissive with photoluminescence quantum yields in the range of 8–24%, and their solid-state emission spectra show the usual dependence on number and nature of donor atoms.
Published: 2023
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26. Bismuth Nanoparticles Supported on Biobased Chitosan as Sustainable Catalysts for the Selective Hydrogenation of Nitroarenes

Author: Mustapha El kadiri, Taha El Assimi, Pascal Thébault, Abdellatif El Meziane, Sébastien Royer, Abdelkrim El Kadib, Géraldine Gouhier, Mohammed Lahcini, Université Cadi Ayyad [Marrakech] (UCA), Polymères Biopolymères Surfaces (PBS), 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)-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), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université Euro Méditerranéenne de Fès (UEMF), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), and 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)
Subjects: heterogeneous catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, bismuth, nanocomposites, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis, chitosan, hydrogenation
Abstract: International audience; The use of chitosan as a support in the field of catalysis has gained tremendous interest because of its abundance and sustainability. We herein disclose a straightforward strategy to trap and stabilize bismuth nanoparticles (BiNPs) on chitosan biopolymer Bi@CS and their use for catalytic applications. Bi@CS was configured as micrometer-thick films, porous beads, and native powders analyzed and next used for the controlled and selective reduction of nitroaromatic compounds to their corresponding anilines and azoarenes, respectively, by varying the concentration medium in reducing NaBH 4. A regioselective mechanism has been suggested. Powder nanocomposites CSp-BiNPs exhibited high catalytic capacity, and 10 corresponding anilines and 15 azoarenes were obtained with very high yields. The reductions were achieved under mild and sustainable reaction conditions (water solvent and room temperature) with easy processing and 12 recovery cycles. Shaped catalysts were easily recovered by simple filtration. This catalyst, derived from nontoxic and affordable bismuth metal supported on chitosan ocean waste, presents significant improvements in the realm of sustainable chemistry and could open a new channel of possibilities for green catalysis.
Published: 2023
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27. A new tire-sensor-pavement coupling chain for investigating asphalt mixture responses under rolling tire loads

Author: Haitao Ge, Juan Carlos Quezada, Vincent Le Houerou, Cyrille Chazallon, Pierre Hornych, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SPI.GCIV]Engineering Sciences [physics]/Civil Engineering, Civil and Structural Engineering
Published: 2023
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28. Bio-Based Poly(hydroxy urethane)s for Efficient Organic High-Power Energy Storage

Author: Florian Le Goupil, Victor Salvado, Valère Rothan, Thomas Vidil, Guillaume Fleury, Henri Cramail, Etienne Grau, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 4 : Deciphering organ immune regulation in inflammation and transplantation (DORI-t) (U1064 Inserm - CR2TI), Centre de Recherche en Transplantation et Immunologie - Center for Research in Transplantation and Translational Immunology (U1064 Inserm - CR2TI), Institut National de la Santé et de la Recherche Médicale (INSERM)-Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Caractérisation Physique Off-line (LCPO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, and ANR-10-EQPX-0028,ELORPrinttec,'Plate-forme de l'Université de Bordeaux pour l'organique électronique imprimable : de la molécule aux dispositifs et systèmes intégrés - valorisation et commercialisation'(2010)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Biochemistry, Catalysis
Abstract: International audience; Fast, low-cost and efficient energy storage technologies are urgently needed to balance the intermittence of sustainable energy sources. High-power capacitors using organic polymers offer a green and scalable answer. They require dielectrics with high permittivity ($\epsilon _r$) and breakdown strength ($E_B$), which bio-based poly(hydroxy urethane)s (PHUs) can provide. PHUs combine high concentrations of hydroxyl and carbamate groups, thus enhancing their $\epsilon _r$, and a highly tuneable glass transition ($T_g$), which dictates the regions of low dielectric losses. By reacting erythritol dicarbonate with bio-based diamines, fully bio-based PHUs were synthesised with $T_g$ ~ 50 °C, $\epsilon _r$ > 8, $E_B$ > 400 MV•m$^{-1}$ and low losses (tan δ < 0.03). This results in energy storage performance comparable with the flagship petrochemical materials (discharge energy density, $U_e$ > 6 J•cm$^{-3}$) combined with a remarkably high discharge efficiency, with η = 85% at $E_B$ and up to 91% at 0.5 $E_B$. These bio-based PHUs thus represent a highly promising route to green and sustainable energy-storage.
Published: 2023
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29. Chitosan-Modified Polyethyleneimine Nanoparticles for Enhancing the Carboxylation Reaction and Plants’ CO2 Uptake

Author: Cyril Routier, Lorenzo Vallan, Yohann Daguerre, Marta Juvany, Emin Istif, Daniele Mantione, Cyril Brochon, Georges Hadziioannou, Åsa Strand, Torgny Näsholm, Eric Cloutet, Eleni Pavlopoulou, Eleni Stavrinidou, Laboratory of Organic Electronics [Norrköping, Sweden] (Department of Science and Technology), Linköping University (LIU), Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Umea Plant Science Center (UPSC), Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences (SLU)-Swedish University of Agricultural Sciences (SLU), Institute of Electronic Structure and Laser (FORTH-IESL), Foundation for Research and Technology - Hellas (FORTH), and European Project: 800926,HyPhOE
Subjects: photosynthesis, [SDE.IE]Environmental Sciences/Environmental Engineering, Botany, Biochemistry and Molecular Biology, General Engineering, nanoparticles CO2 capture polyethyleneimine chitosan photosynthesis, General Physics and Astronomy, Botanik, CO2 capture, [CHIM.POLY]Chemical Sciences/Polymers, Nano Technology, nanoparticles, General Materials Science, chitosan, polyethyleneimine, Biokemi och molekylärbiologi
Abstract: Increasing plants photosynthetic efficienc y is a major challenge that must be addressed in order to cover the food demands of the growing population in the changing climate. Photosynthes i s is greatly limited at the initial carboxylation reaction, where CO2 is converted to the organic acid 3-PGA, catalyzed by the RuBisCO enzyme. RuBisCO has poor affinity for CO2, but also the CO2 concentration at the RuBisCO site is limited by the diffusion of atmospheric CO2 through the various leaf compartments to the reaction site. Beyond genetic engineer-ing, nanotechnology can offer a materials-based approach for enhancing photosynthesis, and yet, it has mostly been explored for the light-dependent reactions. In this work, we developed polyethyleneimine-based nanoparticl e s for enhancing the carbox-ylation reaction. We demonstrate that the nanoparticles can capture CO2 in the form of bicarbonate and increase the CO2 that reacts with the RuBisCO enzyme, enhancing the 3-PGA production in in vitro assays by 20%. The nanoparticles can be introduced to the plant via leaf infiltration and, because of the functionalization with chitosan oligomers, they do not induce any toxic effect to the plant. In the leaves, the nanoparticles localize in the apoplastic space but also spontaneously reach the chloroplasts where photosynthetic activity takes place. Their CO2 loading-dependent fluorescence verifies that, in vivo, they maintain their abi l i t y to capture CO2 and can be therefore reloaded with atmospheric CO2 while in planta. Our results contribute to the development of a nanomaterials-based CO2-concentrating mechanism in plants t h a t can potentially increase photosynthetic efficiency and overall plants CO2 storage. Funding Agencies|European Union [800926, 101042148]; Swedish Research Council [VR-2017-04910]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; MCIN/AEI [Ayuda RYC2021-031668-I]
Published: 2023
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30. Data-Driven Quantitative Intrinsic Hazard Criteria for Nanoproduct Development in a Safe-by-Design Paradigm: A Case Study of Silver Nanoforms

Author: Furxhi, Irini, Bengalli, Rossella, Motta, Giulia, Mantecca, Paride, Kose, Ozge, Carriere, Marie, Haq, Ehtsham Ul, O’Mahony, Charlie, Blosi, Magda, Gardini, Davide, Costa, Anna, University of Limerick (UL), Università degli Studi di Milano-Bicocca = University of Milano-Bicocca (UNIMIB), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), CNR Istituto di Scienza e Tecnologia dei Materiali Ceramici [Faenza] (CNR | ISTEC), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Furxhi, I, Bengalli, R, Motta, G, Mantecca, P, Kose, O, Carriere, M, Haq, E, O'Mahony, C, Blosi, M, Gardini, D, and Costa, A
Subjects: Bayes rules, nanoforms, nanoparticle, quantitative structure−activity relationship, [SDV]Life Sciences [q-bio], Bayes rule, nanoform, safe and sustainable by design, machine learning, Metrics & More Article Recommendations safe and sustainable by design nanoforms nanoparticles quantitative structure−activity relationship machine learning Bayes rules intrinsic hazard criteria, Metrics & More Article Recommendations safe and sustainable by design, nanoparticles, General Materials Science, intrinsic hazard criteria
Abstract: International audience; The current European (EU) policies, that is, the Green Deal, envisage safe and sustainable practices for chemicals, which include nanoforms (NFs), at the earliest stages of innovation. A theoretically safe and sustainable by design (SSbD) framework has been established from EU collaborative efforts toward the definition of quantitative criteria in each SSbD dimension, namely, the human and environmental safety dimension and the environmental, social, and economic sustainability dimensions. In this study, we target the safety dimension, and we demonstrate the journey toward quantitative intrinsic hazard criteria derived from findable, accessible, interoperable, and reusable data. Data were curated and merged for the development of new approach methodologies, that is, quantitative structure−activity relationship models based on regression and classification machine learning algorithms, with the intent to predict a hazard class. The models utilize system (i.e., hydrodynamic size and polydispersity index) and non-system (i.e., elemental composition and core size)-dependent nanoscale features in combination with biological in vitro attributes and experimental conditions for various silver NFs, functional antimicrobial textiles, and cosmetics applications. In a second step, interpretable rules (criteria) followed by a certainty factor were obtained by exploiting a Bayesian network structure crafted by expert reasoning. The probabilistic model shows a predictive capability of ≈78% (average accuracy across all hazard classes). In this work, we show how we shifted from the conceptualization of the SSbD framework toward the realistic implementation with pragmatic instances. This study reveals (i) quantitative intrinsic hazard criteria to be considered in the safety aspects during synthesis stage, (ii) the challenges within, and (iii) the future directions for the generation and distillation of such criteria that can feed SSbD paradigms. Specifically, the criteria can guide material engineers to synthesize NFs that are inherently safer from alternative nanoformulations, at the earliest stages of innovation, while the models enable a fast and cost-efficient in silico toxicological screening of previously synthesized and hypothetical scenarios of yet-to-be synthesized NFs.
Published: 2023
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31. Assessing the Extent of Potential Inversion by Cyclic Voltammetry: Theory, Pitfalls, and Application to a Nickel Complex with Redox-Active Iminosemiquinone Ligands

Author: Cheriehan Hessin, Jules Schleinitz, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Vincent Fourmond, Marine Desage-El Murr, Christophe Léger, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), 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)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Bioénergétique et Ingénierie des Protéines (BIP ), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Potential inversion refers to the situation where a protein cofactor or a synthetic molecule can be oxidized or reduced twice in a cooperative manner, that is the second electron transfer (ET) is easier than the first. This property is very important regarding the catalytic mechanism of enzymes that bifurcate electrons and the properties of bidirectional redox molecular catalysts that function in either direction of the reaction with no overpotential. Cyclic voltammetry is the most common technique for characterizing the thermodynamics and kinetics of ET to or from these molecules. However, a gap in the literature is the absence of analytical predictions to help interpret the values of the voltammetric peak potentials when potential inversion occurs ; the cyclic voltammograms are therefore often analyzed by simulating the data, with no discussion of the possibility of overfitting and often no estimation of the error on the determined parameters. Here we formulate the theory for the voltammetry of freely-diffusing or surface-confined two-electron redox species in the experimentally relevant irreversible limit where the peak separation depends on scan rate. We explain why the model is intrinsically underdetermined, and we illustrate this conclusion by the analysis of the voltammetry of a Ni complex with redox-active iminosemiquinone ligands. Being able to characterize the thermodynamics of two-electron transfer reactions will be crucial for designing more efficient catalysts.
Published: 2023
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32. Detecting and quantifying spatial misalignment between longitudinal kilovoltage computed tomography (kVCT) scans of the head and neck by using convolutional neural networks (CNNs)

Author: Lallement, Alex, Noblet, Vincent, Antoni, Delphine, Meyer, Philippe, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire Hubert Curien (IPHC), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Biomaterials, [INFO.INFO-TI]Computer Science [cs]/Image Processing [eess.IV], Biomedical Engineering, Biophysics, Health Informatics, Bioengineering, Information Systems
Abstract: BACKGROUND: Adaptive radiotherapy (ART) aims to address anatomical modifications appearing during the treatment of patients by modifying the planning treatment according to the daily positioning image. Clinical implementation of ART relies on the quality of the deformable image registration (DIR) algorithms included in the ART workflow. To translate ART into clinical practice, automatic DIR assessment is needed. OBJECTIVE: This article aims to estimate spatial misalignment between two head and neck kilovoltage computed tomography (kVCT) images by using two convolutional neural networks (CNNs). METHODS: The first CNN quantifies misalignments between 0 mm and 15 mm and the second CNN detects and classifies misalignments into two classes (poor alignment and good alignment). Both networks take pairs of patches of 33x33x33 mm3 as inputs and use only the image intensity information. The training dataset was built by deforming kVCT images with basis splines (B-splines) to simulate DIR error maps. The test dataset was built using 2500 landmarks, consisting of hard and soft landmark tissues annotated by 6 clinicians at 10 locations. RESULTS: The quantification CNN reaches a mean error of 1.26 mm (± 1.75 mm) on the landmark set which, depending on the location, has annotation errors between 1 mm and 2 mm. The errors obtained for the quantification network fit the computed interoperator error. The classification network achieves an overall accuracy of 79.32%, and although the classification network overdetects poor alignments, it performs well (i.e., it achieves a rate of 90.4%) in detecting poor alignments when given one. CONCLUSION: The performances of the networks indicate the feasibility of using CNNs for an agnostic and generic approach to misalignment quantification and detection.
Published: 2023
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33. The role of the gold-platinum interface in AuPt/TiO 2-catalyzed plasmon-induced reduction of CO 2 with water

Author: Leila Hammoud, Claire Strebler, Joumana Toufaily, Tayssir Hamieh, Valérie Keller, Valérie Caps, Maastricht Science Programme, RS: FSE MSP, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Matériaux, Catalyse, Environnement et Méthodes Analytiques (MCEMA), Université Libanaise, Lebanese University [Beirut] (LU), Maastricht University [Maastricht], and CAPS, Valérie
Subjects: [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, Physical and Theoretical Chemistry
Abstract: International audience; Bimetallic gold–platinum nanoparticles have been widely studied in the fields of nanoalloys, catalysis and plasmonics. Many preparation methods can lead to the formation of these bimetallic nanoparticles (NPs), and the structure and related properties of the nanoalloy often depend on the preparation method used. Here we investigate the ability of thermal dimethylformamide (DMF) reduction to prepare bimetallic gold–platinum sub-nm clusters supported on titania. We find that deposition of Pt preferentially occurs on gold. Formation of sub-nm clusters (vs. NPs) appears to be dependent on the metal concentration used: clusters can be obtained for metal loadings up to 4 wt% but 7–8 nm NPs are formed for metal loadings above 8 wt%, as shown using high resolution transmission electron microscopy (HRTEM). X-ray photoelectron spectroscopy (XPS) shows electron-rich Au and Pt components in a pure metallic form and significant platinum enrichment of the surface, which increases with increasing Pt/Au ratio and suggests the presence of Au@Pt core–shell type structures. By contrast, titania-supported bimetallic particles (typically >7 nm) obtained by sodium borohydride (NaBH4) reduction in DMF, contain Au/Pt Janus-type objects in addition to oxidized forms of Pt as evidenced by HRTEM, which is in agreement with the lower Pt surface enrichment found by XPS. Both types of supported nanostructures contain a gold–platinum interface, as shown by the chemical interface damping, i.e. gold plasmon damping by Pt, found using UV-visible spectroscopy. Evaluation of the materials for plasmon-induced continuous flow CO2 reduction with water, shows that: (1) subnanometer metallic clusters are not suitable for CO2 reduction with water, producing hydrogen from the competing water reduction instead, thereby highlighting the plasmonic nature of the reaction; (2) the highest methane production rates are obtained for the highest Pt enrichments of the surface, i.e. the core–shell-like structures achieved by the thermal DMF reduction method; (3) selectivity towards CO2 reduction vs. the competing water reduction is enhanced by loading of the plasmonic NPs, i.e. coverage of the titania semi-conductor by plasmonic NPs. Full selectivity is achieved for loadings above 6 wt%, regardless of the NPs composition and alloy structure.
Published: 2023
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34. Efficient Hydrogen Production at pH 7 in Water with a Heterogeneous Electrocatalyst Based on a Neutral Dimeric Cobalt-Dithiolene Complex

Author: Chanjuan Zhang, Erwan Prignot, Olivier Jeannin, Antoine Vacher, Diana Dragoe, Franck Camerel, Zakaria Halime, Rafael Gramage-Doria, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: hydrogen, multi-wall carbon nanotubes, modified-electrode, electrocatalysis, [CHIM]Chemical Sciences, General Chemistry, cobalt-dithiolene, Catalysis, hydrogen electrocatalysis cobalt-dithiolene multi-wall carbon nanotubes modified-electrode
Abstract: International audience; The development of efficient hydrogen production technologies is fundamental for replacing fossil fuel-based energies. As such, electrocatalysts derived from earth abundant metal complexes are appealing, and interesting performances have typically been disclosed under acidic conditions in organic solvents. However, their applicability under relevant pH neutral conditions is underexplored. Herein, we demonstrate that non-ionic, dimeric cobalt-dithiolene complexes supported on multi-wall carbon nanotubes (MWCNTs)/carbon paper (CP) electrode are powerful electrocatalysts for hydrogen production in aqueous media at pH 7. The high turnover numbers encountered (TON up to 50980) after long reaction times (up to 16 hours) are reasoned by the increased electro-active cobalt concentration on the modified electrode, which is ca. 4 times higher than that of a state-of-the-art cobalt porphyrin electrocatalyst. These findings point out that immobilizing well-defined, multinuclear low cost metal complexes on carbon material is a promising strategy to design highly electroactive electrodes enabling production of green energies.
Published: 2023
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35. Revealing the Elusive Structure and Reactivity of Iron Boride α-FeB

Author: Fernando Igoa Saldaña, Emile Defoy, Daniel Janisch, Gwenaëlle Rousse, Pierre-Olivier Autran, Anissa Ghoridi, Amandine Séné, Marzena Baron, Leopoldo Suescun, Yann Le Godec, David Portehault, Novel Advanced Nano-Objects (LCMCP-NANO), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Design et étude de nouveaux matériaux à propriété remarquables [IMPMC] (IMPMC_DEMARE), 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)-Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), European Synchroton Radiation Facility [Grenoble] (ESRF), Laboratorio de Cristalografıa, Estado Solido y Materiales [UCUR] (Cryssmat-Lab), Universidad de la República [Montevideo] (UDELAR), and Doctoral School ED397ESRF proposal MA-5188
Subjects: Inorganic Chemistry, crystal structure, borides, intergrowth, in situ XRD, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, FAULTS
Abstract: International audience; Crystal structures can strongly deviate from bulk states when confined into nanodomains. These deviations may deeply affect properties and reactivity and then call for a close examination. In this work, we address the case where extended crystal defects spread through a whole solid and then yield an aperiodic structure and specific reactivity. We focus on iron boride, α-FeB, whose structure has not been elucidated yet, thus hindering the understanding of its properties. We synthesize the two known phases, α-FeB and β-FeB, in molten salts at 600 and 1100 °C, respectively. The experimental X-ray diffraction (XRD) data cannot be satisfactorily accounted for by a periodic crystal structure. We then model the compound as a stochastic assembly of layers of two structure types. Refinement of the powder XRD pattern by considering the explicit scattering interference of the different layers allows quantitative evaluation of the size of these domains and of the stacking faults between them. We, therefore, demonstrate that α-FeB is an intergrowth of nanometer-thick slabs of two structure types, β-FeB and CrB-type structures, in similar proportions. We finally discuss the implications of this novel structure on the reactivity of the material and its ability to perform insertion reactions by comparing the reactivities of α-FeB and β-FeB as reagents in the synthesis of a model layered material: Fe2AlB2. Using synchrotron-based in situ X-ray diffraction, we elucidate the mechanisms of the formation of Fe2AlB2. We highlight the higher reactivity of the intergrowth α-FeB in agreement with structural relationships.
Published: 2023
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36. Detailed Catalyst Layer Structure of Proton Exchange Membrane Fuel Cells from Contrast Variation Small-Angle Neutron Scattering

Author: Florian Chabot, Jongmin Lee, Florent Vandenberghe, Laure Guétaz, Gérard Gebel, Sandrine Lyonnard, Lionel Porcar, Sebastien Rosini, Arnaud Morin, Département de l'électricité et de l'hydrogène dans les transports (DEHT), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut Laue-Langevin (ILL), European Project: 875025,FURTHER-FC, and European Project: 654000,H2020,H2020-INFRADEV-1-2014-1,SINE2020(2015)
Subjects: Materials Chemistry, Electrochemistry, Energy Engineering and Power Technology, Chemical Engineering (miscellaneous), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Electrical and Electronic Engineering
Abstract: International audience; Despite significant decrease in past decades, the cost of Proton Exchange Membrane Fuel Cell (PEMFC), largely due to the rare and expensive electro-catalyst made of platinum, restrains its massive deployment. Therefore, reducing the platinum content in the electrode is the keystone of intense research efforts to increase catalyst activity or utilisation. Catalyst layer structure, and especially the water and ionomer distributions, rule the active sites availability for electrochemical reactions, and thus catalyst utilisation, because of their influence on the transport of protons and oxygen. However, the rational design of more efficient electrodes faces the lack of accurate knowledge of its complex nanoporous structure. Specifically, ionomer and water distribution are very difficult to probe with conventional electron microscopy or X-Ray techniques. This work provides quantitative and new information on electrode structure, regarding ionomer and water distributions thanks to an extensive analysis of Small Angle Neutron Scattering (SANS) profiles at different relative humidity (RH) and contrast. A 2 to 3 nm thin ionomer film spreads around the Pt/C catalyst particles while a condensed water layer appears at the catalyst/ionomer interface depending on the type of carbon support.
Published: 2023
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37. Catalytic Enantioselective Allylboration and Related Reactions of Isatins Promoted by Chiral BINOLs: Scope and Mechanistic Studies

Author: Julien Braire, Aurélie Macé, Rania Zaier, Marie Cordier, Joëlle Vidal, Claudia Lalli, Arnaud Martel, François Carreaux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by the University of Rennes 1 and the Centre National de la Recherche Scientifique (CNRS). One of us (J.B.) thanks 'Ecole doctorale 3M' and University of Rennes 1 for a research fellowship.
Subjects: Organic Chemistry, [CHIM]Chemical Sciences
Abstract: International audience; An improvement in the catalytic enantioselective allylboration of isatins with 2-allyl-1,3,2-dioxaborolane in the presence of chiral BINOL derivatives is reported, offering an efficient one-step access to enantioenriched N-unprotected 3-allyl-3-hydroxy-2-oxindoles. This catalytic process is also effective for the crotylboration reaction with enantiomeric ratios (er) up to 97:3, as well as for the asymmetric synthesis of homopropargylic alcohols via an allenyl addition to indoline-2,3-diones. Origins of the high enantioselectivity in chiral BINOL-catalyzed allylboration of isatins were examined by DFT calculations. A hypothetical scenario suggested a crucial internal hydrogen bonding between the amide group (C═O···H-O) and the ethylene hydroxyl of the transient chiral mixed boronate ester, generating a rigid and stabilized system that favors the addition of the allylboron species to the Re face of the ketone function. The key role of the alcohol additive (t-BuOH or t-AmOH) in the enantioselective allylboration reaction of isatins has also been shown on the basis of a kinetics study and computational calculations by favoring the transesterification of the 2-allyl-1,3,2-dioxaborolane with BINOL via proton transfer processes.
Published: 2023
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38. Ytterbium(III) Complex with Photochromic Ruthenium(II) Acetylide Ligand: All Visible Light Photoswitching of NIR Luminescence

Author: Pramila Selvanathan, Elsa Tufenkjian, Olivier Galangau, Thierry Roisnel, François Riobé, Olivier Maury, Lucie Norel, Stéphane Rigaut, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors thank the Université de Rennes 1, the CNRS, the ANR (RuOxLux─ANR-12-BS07-0010-01), and MESR for support. This work was performed using HPC/AI resources from GENCI-[CINES/TGCC] (Grant 2020-AP010811752 and 2021-AP0090811914)., and ANR-12-BS07-0010,RuOxLux,Modulation redox de la luminescence à l'aide de complexes organométalliques du ruthénium associés à une unité luminescente(2012)
Subjects: Inorganic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry
Abstract: International audience; We report a ruthenium(II) bisacetylide complex bearing a photochromic dithienylethene (DTE) acetylide arm and a coordinating bipyridyl on the trans acetylide unit. Its coordination with Yb(TTA)(3) centers (TTA = 2-thenoyltrifluoroacetonate) produces a bimetallic complex in which the dithienylethene isomerization is triggered by both ultraviolet (UV) light absorbed by the DTE unit and 450 nm excitation in a transition of the organometallic moiety. The redox behavior arising from the ruthenium(II) bisacetylide system is fully investigated by cyclic voltammetry and spectroelectrochemistry, revealing a lack of stability of the DTE-closed oxidized state preventing effective redox luminescence switching. On the other hand, the photoswitching of ytterbium(III) near-infrared (NIR) emission triggered by the photochromic reaction is fully operational. The electronic structure of this complex in its different states characterized by strong electronic coupling between the DTE and the ruthenium(II)-based moieties leading to metal-assisted photochromic behavior were rationalized with the help of time-dependent density functional theory (TD-DFT) calculations.
Published: 2023
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39. Fast and Bioorthogonal Release of Isocyanates in Living Cells from Iminosydnones and Cycloalkynes

Author: Maxime Ribéraud, Karine Porte, Arnaud Chevalier, Léa Madegard, Aurélie Rachet, Agnès Delaunay-Moisan, Florian Vinchon, Pierre Thuéry, Giovanni Chiappetta, Pier Alexandre Champagne, Grégory Pieters, Davide Audisio, Frédéric Taran, CEA- Saclay (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL), New Jersey Institute of Technology [Newark] (NJIT), ANR-11-EQPX-0029,MORPHOSCOPE 2,Imagerie et reconstruction multiéchelles de la morphogenèse. (Plateforme d'innovation technologique et méthodologique pour l'imagerie in vivo et la reconstruction des dynamiques multiéchelles de la morphogenèse)(2011), ANR-10-INBS-0004,France-BioImaging,Développment d'une infrastructure française distribuée coordonnée(2010), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), and ANR-19-CE06-0006,NanoClick,Micelles clivables par chimie bioorthogonale(2019)
Subjects: Colloid and Surface Chemistry, [SDV]Life Sciences [q-bio], General Chemistry, Biochemistry, Catalysis
Abstract: International audience; Bioorthogonal click and release reactions are powerful tools for chemical biology allowing, for example, the selective release of drugs in biological media, including inside animals. Here we developed two new families of iminosydnone mesoionic reactants that allow a bioorthogonal release of electrophilic species under physiological conditions. Their synthesis and reactivities as dipoles in cycloaddition reactions with strained alkynes have been studied in detail. Whereas the impact of the pH on the reaction kinetics was demonstrated experimentally, theoretical calculations suggest that the newly designed dipoles display reduced resonance stabilization energies compared to previously described iminosydnones explaining their higher reactivity. These mesoionic compounds react smoothly with cycloalkynes under physiological, copper-free reaction conditions to form a click pyrazole product together with a released alkyl-or aryl-isocyanate. With kinetic constants up to 1000 M-1 s-1 , this click and release reaction is among the fastest described to date, and represents the first bioorthogonal process allowing the release of isocyanate electrophiles inside living cells offering interesting perspectives in chemical biology.
Published: 2023
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40. Bystander signals from low- and high-dose irradiated human primary fibroblasts and keratinocytes modulate the inflammatory response of peripheral blood mononuclear cells

Author: Isabelle Testard, Elizabeth Garcia-Chartier, Amani Issa, Véronique Collin-Faure, Catherine Aude-Garcia, Serge M Candéias, Protéomique pour la Microbiologie, l'Immunologie et la Toxicologie (PROMIT), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), This work was supported by financing from Electricité de France (EDF) through the Comité de Programme Protection de l’Homme et de l’Environnement (CPPHE), ANR-11-LABX-0063,PRIMES,Physique, Radiobiologie, Imagerie Médicale et Simulation(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Radiation, bystander effects (BEs), [SDV]Life Sciences [q-bio], Health, Toxicology and Mutagenesis, gene expressioncytokines, low-dose radiation, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, [SDV.IB.MN]Life Sciences [q-bio]/Bioengineering/Nuclear medicine, cytokines, inflammation, high-dose radiationgene, [SDV.BBM.GTP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Genomics [q-bio.GN], [SDV.IMM]Life Sciences [q-bio]/Immunology, Radiology, Nuclear Medicine and imaging
Abstract: Irradiated cells can propagate signals to neighboring cells. Manifestations of these so-called bystander effects (BEs) are thought to be relatively more important after exposure to low- vs high-dose radiation and can be mediated via the release of secreted molecules, including inflammatory cytokines, from irradiated cells. Thus, BEs can potentially modify the inflammatory environment of irradiated cells. To determine whether these modifications could affect the functionality of bystander immune cells and their inflammatory response, we analyzed and compared the in vitro response of primary human fibroblasts and keratinocytes to low and high doses of radiation and assessed their ability to modulate the inflammatory activation of peripheral blood mononuclear cells (PBMCs). Only high-dose exposure resulted in either up- or down-regulation of selected inflammatory genes. In conditioned culture media transfer experiments, radiation-induced bystander signals elicited from irradiated fibroblasts and keratinocytes were found to modulate the transcription of inflammatory mediator genes in resting PBMCs, and after activation of PBMCs stimulated with lipopolysaccharide (LPS), a strong inflammatory agent. Radiation-induced BEs induced from skin cells can therefore act as a modifier of the inflammatory response of bystander immune cells and affect their functionality.
Published: 2023
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41. Impact of sulfonated poly(ether ether ketone) membranes pretreatments on their physicochemical properties and fuel cell performances

Author: Meriem Daoudi, Evelise Ferri, Claire Tougne, Assma El Kaddouri, Jean‐Christophe Perrin, Jérôme Dillet, Laurent Gonon, Vincent Mareau, Hakima Mendil‐Jakani, Veronique Dufaud, Eliane Espuche, Olivier Lottin, Laboratoire Énergies et Mécanique Théorique et Appliquée (LEMTA ), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), and ANR-18-CE05-0027,MULTISTABLE,Membranes hybrides multi-stabilisées pour pile à combustible et électrolyseur(2018)
Subjects: [SPI]Engineering Sciences [physics], Polymers and Plastics, Materials Chemistry, PEMFC, pretreatment, Physical and Theoretical Chemistry, sulfonated poly(ether ether ketone) membrane, PEMFC sulfonated poly(ether ether ketone) membrane pretreatment performance, performance
Abstract: International audience; This work focuses on the impact of sulfonated Poly(Ether Ether Ketone) (sPEEK) membrane pretreatments on fuel cell performance, starting from two different batches of Fumapem E730 from Fumatech, acquired in 2019 and in 2020. sPEEK membranes are possible lower cost alternatives to PerFluoroSulfonic Acid (PFSA) membranes for Proton Exchange Membrane Fuel Cells (PEMFC) applications. Before use, they must be pretreated to ensure a complete protonic substitution and removal of residual reagents/solvent: the simplest protocol consists in soaking the membrane in an acid solution followed by a rinsing step in water. In addition to this acidification step, hydrothermal (HT) treatments in water at high temperature for a few hours to a few days were also considered herein, as well as a hydro-alcoholic (HA) step, because of their expected effects on membrane nanostructure. Overall, four different protocols were used. The membrane water uptake, water self-diffusion, proton conductivity, and fuel cell performance-under H2/O2-were measured. It was found that in the best case-membranes from the 2020 batch subjected to HA followed by 72 hours HT pretreatments-the fuel cell performances exceeded those obtained with a PFSA membrane (Nafion XL). This is explained by a higher protonic conductivity, probably resulting from a better sPEEK nano-structuration.
Published: 2023
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42. Stability of the In-Plane Room Temperature van der Waals Ferromagnet Chromium Ditelluride and Its Conversion to Chromium-Interleaved CrTe2 Compounds

Author: Anike Purbawati, Suman Sarkar, Sébastien Pairis, Marek Kostka, Abdellali Hadj-Azzem, Didier Dufeu, Priyank Singh, Daniel Bourgault, Manuel Nuñez-Regueiro, Jan Vogel, Julien Renard, Laëtitia Marty, Florentin Fabre, Aurore Finco, Vincent Jacques, Lei Ren, Vivekanand Tiwari, Cedric Robert, Xavier Marie, Nedjma Bendiab, Nicolas Rougemaille, Johann Coraux, Micro et NanoMagnétisme (NEEL - MNM), Institut Néel (NEEL), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Systèmes hybrides de basse dimensionnalité (NEEL - HYBRID), Croissance Cristalline et MicroAnalyse (NEEL - C2MA), Brno University of Technology [Brno] (BUT), Ingénierie Expérimentale (NEEL - ExpE), Thermodynamique et biophysique des petits systèmes (NEEL - TPS), Magnétisme et Supraconductivité (NEEL - MagSup), Laboratoire Charles Coulomb (L2C), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Condensed Matter - Materials Science, Materials Chemistry, Electrochemistry, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Electronic, Optical and Magnetic Materials
Abstract: Van der Waals magnetic materials are building blocks for novel kinds of spintronic devices and playgrounds for exploring collective magnetic phenomena down to the two-dimensional limit. Chromium-tellurium compounds are relevant in this perspective. In particular, the 1$T$ phase of CrTe$_2$ has been argued to have a Curie temperature above 300~K, a rare and desirable property in the class of lamellar materials, making it a candidate for practical applications. However, recent literature reveals a strong variability in the reported properties, including magnetic ones. Using electron microscopy, diffraction and spectroscopy techniques, together with local and macroscopic magnetometry approaches, our work sheds new light on the structural, chemical and magnetic properties of bulk 1$T$-CrTe$_2$ exfoliated in the form of flakes having a thickness ranging from few to several tens of nanometers. We unambiguously establish that 1$T$-CrTe$_2$ flakes are ferromagnetic above room temperature, have an in-plane easy axis of magnetization, low coercivity, and we confirm that their Raman spectroscopy signatures are two modes, $E_{2\text{g}}$ (103.5~cm$^{-1}$) and $A_{1\text{g}}$ (136.5~cm$^{-1}$). We also prove that thermal annealing causes a phase transformation to monoclinic Cr$_5$Te$_8$ and, to a lesser extent, to trigonal Cr$_5$Te$_8$. In sharp contrast with 1$T$-CrTe$_2$, none of these compounds have a Curie temperature above room temperature, and they both have perpendicular magnetic anisotropy. Our findings reconcile the apparently conflicting reports in the literature and open opportunities for phase-engineered magnetic properties.
Published: 2023
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43. Nickel‐Catalyzed Cyanoalkylation of Ketone Derivatives

Author: Anaïs Coffinet, Vincent Levacher, Isabelle Gillaizeau, Jean‐François Brière, Sylvain Oudeyer, 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 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 University of RouenNormandy, INSA Rouen Normandy, the Centre National de laRecherche Scientifique (CNRS), European Regional DevelopmentFund (ERDF), Labex SynOrg (ANR-11-LABX-0029), Carnot InstituteI2C, the graduate school for research XL-Chem (ANR-18-EURE-0020 XL CHEM) and by Region Normandie.
Subjects: Pincer ligand, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Cyanoalkylation, Organometallic catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Ketone, Nickel complexes
Abstract: International audience; Although the metal-based catalyzed cyanomethylation of aldehydes is well-developed, a similar approach to ketones with acetonitrile derivatives remains a challenge. Thanks to Tolman type complexes, NiIIcomplexes with a pyridine(dicarboxamide) pincer ligand, analternative metal-catalyzed (1-5 mol% catalyst) cyanomethylation of an array of isatins and activated ketones is reported at room temperature. High isolated yields (up to 99%) were obtained not only with the poorly acidic acetonitrile but also with more challenging substituted alkyl cyanide nucleophiles. The in situ generated putative ion paired catalysts [NiCR2CN]-Cat+ likely benefit from the cation part (Cs+ or n-Bu4N+) to facilitate their formation and catalytic activity
Published: 2023
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44. The conformation of glutenin polymers in wheat grain: some genetic and environmental factors associated with this important characteristic

Author: Gérard Branlard, Angelina d’Orlando, Ayesha Tahir, Marc Schmutz, Larbi Rhazi, Annie Faye, Thierry Aussenac, Génétique Diversité et Ecophysiologie des Céréales (GDEC), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Clermont Auvergne (UCA), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), BioInformatique et BioStatistiques (BIBS), Centre International de Recherche en Infectiologie (CIRI), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), COMSATS University Islamabad (CUI), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Transformations et Agro-ressources (UT&A), and UniLaSalle
Subjects: Physiology, [SDV]Life Sciences [q-bio], Plant Science
Abstract: In a previous study we used asymmetric-flow field-flow fractionation to determine the polymer mass (Mw), gyration radius (Rw) and the polydispersity index of glutenin polymers (GPs) in wheat (Triticum aestivum). Here, using the same multi-location trials (4 years, 11 locations, and 192 cultivars), we report the factors that are associated with the conformation (Conf) of the polymers, which is the slope of Log(Rw) versus a function of Log(Mw). We found that Conf varied between 0.285 and 0.740, it had low broad-sense heritability (H2=16.8), and it was significantly influenced by the temperature occurring over the last month of grain filling. Higher temperatures were found to increase Rw and the compactness and sphericity of GPs. Alleles for both high- and low-molecular-weight glutenin subunits had a significant influence on the Conf value. Assuming a Gaussian distribution for Mw, the number of polymers present in wheat grains was computed for different kernel weights and protein concentrations, and it was found to exceed 1012 GPs per grain. Using atomic force microscopy and cryo-TEM, images of GPs were obtained for the first time. Under higher average temperature, GPs became larger and more spherical and consequently less prone to rapid hydrolysis. We propose some orientations that could be aimed at potentially reducing the impact of numerous GPs on people suffering from non-celiac gluten sensitivity.
Published: 2023
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45. Self-Powered Dynamic Glazing Based on Nematic Liquid Crystals and Organic Photovoltaic Layers for Smart Window Applications

Author: Sadiara Fall, Jing Wang, Thomas Regrettier, Nicolas Brouckaert, Olzhas A. Ibraikulov, Nicolas Leclerc, Yaochen Lin, Mohammed Ibn Elhaj, Lachezar Komitov, Patrick Lévêque, Yuhan Zhong, Martin Brinkmann, Malgosia Kaczmarek, Thomas Heiser, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Sadron (ICS), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique
Subjects: General Materials Science, [SPI.MAT]Engineering Sciences [physics]/Materials
Published: 2023
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46. Improved Electrochemical Performance for High-Voltage Spinel LiNi0.5Mn1.5O4 Modified by Supercritical Fluid Chemical Deposition

Author: Gwenaëlle Courbaron, Emmanuel Petit, Jon Serrano-Sevillano, Christine Labrugère-Sarroste, Jacob Olchowka, Dany Carlier, Nathalie Delpuech, Cyril Aymonier, Laurence Croguennec, 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), Technocentre, Renault SAS, Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CIC ENERGIGUNE - Parque Tecnol Alava, Plateforme Aquitaine de Caractérisation des Matériaux (PLACAMAT), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors acknowledge ANRT, Renault SAS, and Région Nouvelle-Aquitaine for the funding of this project, ANRT and Renault SAS for the funding (CIFRE grant) of G.C.′s Ph.D. thesis, as well as the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01) for financial support for their research on the electrochemical energy storage. The authors would also like to acknowledge Nano One Materials Corp. for providing the LNMO material used for the project., and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
Subjects: Supercritical fluid chemical deposition, Lithium-ion batteries, Surface modification, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, High-voltage positive electrode material, Spinel oxide LiNi0.5Mn1.5O4
Abstract: International audience; Among candidates at the positive electrode of the next generation of Li-ion technology and even beyond post Li-ion technology as all-solid-state batteries, spinel LiNi0.5Mn1.5O4 (LNMO) is one of the favorites. Nevertheless, before its integration into commercial systems, challenges still remain to be tackled, especially the stabilization of interfaces with the electrolyte (liquid or solid) at high voltage. In this work, a simple, fast, and cheap process is used to prepare a homogeneous coating of Al2O3 type to modify the surface of the spinel LNMO: the supercritical fluid chemical deposition (SFCD) route. This process is, to the best of our knowledge, used for the first time in the battery field. Significantly improved performance was demonstrated vs those of bare LNMO, especially at high rates and for highly loaded electrodes.
Published: 2023
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47. Homochiral SCM Built of Tetrahedral and Pentagonal Bipyramidal Fe(II) Units Bridged by Chlorine

Author: Valentin Jubault, Barthélémy Pradines, Céline Pichon, Nicolas Suaud, Carine Duhayon, Nathalie Guihéry, Jean-Pascal Sutter, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Systèmes étendus et magnétisme (LCPQ) (SEM), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE07-0007,AnisoChirMag,Anisotropie Optique au sein d'Aimants Moléculaires Chiraux: Vers une Lecture Optique de l'Orientation du Spin(2017)
Subjects: [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, General Chemistry, Condensed Matter Physics
Abstract: International audience; Each enantiomer of a chiral pentagonal bipyramidal (PBP) FeII complex ([FeLN5R,RCl(MeOH)]Cl·H2O, 1R, or [FeLN5S,SCl(MeOH)]Cl·H2O, 1S) has been obtained using either the R or the S stereoisomer of the macrocyclic pentadentate ligand formed in a template-condensation reaction of the tetraamine N,N′-Bis-{(1R,2R)-[2-(amino)]cyclohexyl}-1,2-diaminoethane, or its (1S,2S) enantiomer, and 2,5-diacetylpyridine, respectively LN5R,R and LN5S,S. Subsequently, the 1-D coordination polymers [FeLN5R,R{FeCl4}], 2R, and [FeLN5S,S{FeCl4}], 2S, were formed by reacting respectively 1R or 1S with 1 equiv of FeCl2(H2O)4. These chain compounds consist of an alternation of PBP and tetrahedral FeII units sharing a Cl atom. Theoretical calculations reveal large magnetic anisotropy for each Fe center but of different type with axial zero-field splitting parameter D of respectively −30 cm–1 and 15 cm–1. The magnetic behavior for the 1-D compound revealed canted antiferromagnetic Fe–Fe interactions (J = −6 cm–1) and SCM behavior characterized by Δ/kB = 42 K with pre-exponential factor τ0 = 2.17 × 10–10 s. It was noted that this SCM behavior was accompanied by a magnetic order leading to a weak ferromagnet (i.e., canted antiferromagnet). The preparations, crystal structures (CCDC references 2214580–2214583), spectroscopic data, magnetic behaviors, and theoretical investigations are reported.
Published: 2023
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48. Direct Evidence of the Role of Co or Pt, Co Single-Atom Promoters on the Performance of MoS2 Nanoclusters for the Hydrogen Evolution Reaction

Author: Luz A. Zavala, Kavita Kumar, Vincent Martin, Frédéric Maillard, Françoise Maugé, Xavier Portier, Laetitia Oliviero, Laetitia Dubau, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-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), Electrochimie Interfaciale et Procédés (EIP), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Nanomatériaux, Ions et Métamatériaux pour la Photonique (NIMPH), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), and ANR Carnot Energie et Systèmes de Propulsion (ESP)ANR Carnot Energies du futur (EF)
Subjects: Non-noble electrocatalyst, Hydrogen Evolution Reaction (HER), Single Atom Promoted Molybdenum Sulfides, Proton Exchange Membrane Water Electrolyzer (PEMWE), [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Durability, Catalysis
Abstract: International audience; Developing alternatives to platinum (Pt) and iridium (Ir) in proton exchange membrane water electrolyzers is crucial on the way to viable energy provision schemes. However, although it seems difficult to substitute Ir, alternatives exist for Pt at the PEMWE cathode. Here, we report on the synthesis and the characterization of efficient and durable hydrogen evolution reaction (HER) nanocatalysts based on MoS2 supported on high surface area carbon. Citric acid was used as a chelating agent to control the size of the crystallites (1.4 nm) and thus the density of active sites (slab edges). Inspired by successful approaches in catalysis for hydrodesulfurization reactions, conventional 2H MoS2 was sequentially doped with cobalt (Co) then 1 wt. % of Pt. Overpotentials of 188 mV, 140 and 118 mV at 10 mA cm-2 are reported for MoS2/C, Co-MoS2/C and Pt1%-CoMoS2/C, respectively. This result is attributed to the weakening of Hads binding energy of the promoted MoS2 edge active sites (because the promoting atoms are mostly located at the edges). Associated with small metal dissolution rates (monitored in situ, during HER), our findingsdemonstrate that metal promotion (doping) is a promising route to replace platinum by earth-abundant elements in acidic water electrolyzers.
Published: 2023
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49. Optimized Local Synthetic Conditions Induce Size Reduction and Phase Purification in {[Fe(Htrz)2(trz)](BF4)}n Spin Crossover Particles

Author: Tristan Castel, Anaïs Marchetti, Félix Houard, Nathalie Daro, Mathieu Marchivie, Guillaume Chastanet, Kevin Bernot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), This work was supported by the University of Bordeaux, the CNRS, the ANR FlowSwitch (2019-CE07-0022-01), and the Region Nouvelle Aquitaine. The Region Bretagne (Boost’ERC RECoord No. 1122), the Institut Universitaire de France (IUF), and the INSA Rennes PPI program., and ANR-19-CE07-0022,FlowSwith,Chimie en flux continu pour la synthèse de particules commutables à température ambiante(2019)
Subjects: Granular materials, Mixtures, Nanoparticles, General Materials Science, Chemical synthesis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Condensed Matter Physics, Transmission electron microscopy
Abstract: International audience; The well-known synthesis of the two polymorphs of the {[Fe(Htrz)2(trz)](BF4)}n spin crossover coordination polymer is explored with new template-free methods that allow a control over the local synthetic conditions. A “one-pot” synthesis approach is developed, in which the solid reactants are mixed together before the addition of the solvent, which is expected to generate instantaneous supersaturation conditions favoring the nucleation of particles over their growth. In a second method, the addition of ultrasound pulses promotes the appearance of local “hot spots” that affect the local temperature and allow exploring a different region of the concentration–temperature phase diagram, leading to an increase in the phase purity of the product. These two syntheses are compared to the classical method in which the reactants are first dissolved in separate solutions before being mixed. The use of a one-pot synthesis, with or without ultrasound pulses, induces a downsizing of the particle size by a factor of 500 on their volume. The addition of ultrasound pulses allows moving from a mixture of polymorphs I and II of this compound to the pure phase I. These approaches open the way to more studies on the control over the size or phase purity in such molecular compounds, without the use of any surfactant.
Published: 2023
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50. Origin of Vanadium Site Sequential Oxidation in KxVPO4F1–yOy

Author: Romain Wernert, Antonella Iadecola, Lorenzo Stievano, Dany Carlier, Laurence Croguennec, 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was part of the TROPIC project supported by Agence Nationale de la Recherche (ANR) under the grant ANR-19-CE05-0026. ANR is also acknowledged for funding the RS2E network through the STORE-EX Labex Project ANR-10-LABX-76-01. Synchrotron Soleil (France) is acknowledged for providing beamtime (proposal #20191774) at the beamline ROCK which also benefits from ANR grant as part of the 'Investissements d’Avenir' program ANR-10-EQPX-45., ANR-19-CE05-0026,TROPIC,Vers des batteries innovantes K-ion(2019), and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
Subjects: General Chemical Engineering, Oxidation, Materials Chemistry, Vanadium, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Redox reactions, Electrodes, Materials
Abstract: International audience; M-ion batteries (M = Li, Na, K ...) positive electrode materials most often operate through the reversible oxidation of transition-metal ions. In complex materials involving many transition metals or many redox centers, understanding the sequence in which they participate to the reaction is not trivial but is often necessary to explain the electrochemical properties. Mixed anion vanadium phosphates, such as KVPO4F0.5O0.5, are known to contain two different redox entities that are V3+O4F2 and V3+O5F “ionic” entities on the one hand and {V4+═O}O5 and {V4+═O}O4F “covalent” vanadyl-type units on the other hand. However, their participation to the redox mechanism occurring during the charge of this material has never been studied. Here, we use V K-edge X-ray absorption spectroscopy to unveil the redox mechanism of KVPO4F1–yOy (y = 0, 0.5, 1), performing data analysis via a chemometric approach. With XAS being very sensitive to the oxidation state and bond length, it was found that the ionic V3+–F units oxidize at a lower potential than the covalent {V4+═O} ones, which is surprising considering the high electronegativity of fluoride anions but is consistent with the redox potential observed for KVPO4F and KVOPO4. Further, ab initio calculations and ex situ X-ray diffraction analyses allowed an atomistic description of the redox mechanism with the sequential oxidation of the cis V site before the trans V site in KVPO4F upon charge. Finally, the complete atomically resolved redox mechanism of KVPO4F0.5O0.5 is proposed.
Published: 2023
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