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26,401 results on '"Physique"'

1. Multiarm cyclam-grafted mesoporous silica: a strategy to improve the chemical stability of silica materials functionalized with amine ligands.

Author

Etienne M, Goubert-Renaudin S, Rousselin Y, Marichal C, Denat F, Lebeau B, and Walcarius A

Subjects
Adsorption, Copper chemistry, Gels chemistry, Hydrogen-Ion Concentration, Kinetics, Magnetic Resonance Spectroscopy methods, Models, Chemical, Nitrogen chemistry, Porosity, Silicon chemistry, Time Factors, Amines chemistry, Chemistry methods, Ligands, Silicon Dioxide chemistry
Abstract

We have explored in this work the stability and the reactivity of multiarm cyclam-grafted mesoporous silica samples in aqueous solution. A series of hybrid materials have been prepared by grafting silylated cyclam molecules bearing one, two, or four silyl groups onto both amorphous silica gel (K60) and ordered mesoporous silica (SBA15). Under these conditions, cyclam moieties are attached to the silica walls via one, two, or four arms. Various physicochemical techniques have been applied to characterize the functionalized solids (elemental analysis, 1H-29Si and 1H-13C CPMAS NMR, and N2 adsorption-desorption isotherms). The interest in two and four arms for improving the chemical stability in solution, by comparison with the system displaying only one arm, has been demonstrated by using a set of complementary experiments involving pH measurements and silicon determination with ICP-AES. Then, the investigation of their protonation and binding properties toward copper(II) has revealed a significant decrease in the reactivity of these hybrids as a consequence of multiarm tethering. A comparison of amorphous and ordered materials has permitted us to point out the influence of mesostructuration on the reactivity of these functionalized solids, especially from a kinetic point of view.

Published
2009
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2. Spatio-temporal behaviors of a clock reaction in an open gel reactor.

Author

Benyaich K, Erneux T, Métens S, Villain S, and Borckmans P

Subjects
Arsenites chemistry, Diffusion, Iodates chemistry, Mathematics, Models, Chemical, Models, Statistical, Models, Theoretical, Nonlinear Dynamics, Oscillometry, Systems Theory, Time, Time Factors, Chemistry methods, Gels
Abstract

The concentration profiles along the feeding direction of a one side fed gel reactor are analyzed for the iodate-arsenous acid reaction. Multiplicity of inhomogeneous stationary solutions is derived. It is also shown that such profiles may undergo oscillatory bifurcations under long range activation conditions. The bifurcation diagram is analyzed using a Galerkin approximation, the asymptotic validity of which is discussed.

Published
2006
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3. Exactly solvable model of monomer-monomer reactions on a two-dimensional random catalytic substrate.

Author

Oshanin G, Popescu MN, and Dietrich S

Subjects
Carbon Monoxide, Catalytic Domain, Models, Chemical, Models, Statistical, Oxygen chemistry, Substrate Specificity, Catalysis, Chemistry methods
Abstract

We study the equilibrium properties of a monomer-monomer A+B--> reaction on a two-dimensional substrate containing randomly placed catalytic bonds. Interacting A and B species undergo continuous exchanges with particle reservoirs and react as soon as a pair of unlike particles appears on sites connected by a catalytic bond. For annealed disorder in the placement of catalytic bonds the model is mapped onto a general spin S=1 model and solved exactly for the pressure in a particular case. At equal activities of the two species a second order phase transition is revealed.

Published
2004
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4. Conformational analysis and molecular design of anthranilic acid derivatives as partial agonists of the Farnesoid X Receptor (FXR) with favorable predicted pharmacokinetic profiles

Author

Guy Müller Banquet Okra, Affiba Florance Kouassi, Dali Brice, Hermann N'Guessan, Kre N’Guessan Raymond, and Laboratoire de Physique Fondamentale et Appliquée , Abidjan , Côte d’Ivoire

Subjects
chemistry.chemical_compound, chemistry, Molecular model, Pharmacokinetics, Stereochemistry, Anthranilic acid, Farnesoid X receptor, Pharmacophore, Partial agonist
Abstract

We report here virtual design of new anthranilic acid derivatives (AAD) identified as potent partial Farnesoid X recep-tor (FXR) agonists with favorable predicted pharmacokinetic profiles. By in situ modification of the crystal structure (PDB ID: 3OLF) of FXR complex with a benzimidazole-based partial agonistic ligand, 3D models of 17 FXR:AADx complexes with known observed activity (EC50exp) were prepared to establish a quantitative structure–activity (QSAR) model and linear correla-tion between relative Gibbs free energy (GFE) of receptor-ligand complex formation (Gcom) and EC50exp: pEC50exp = -0,1146 Gcom + 8,175 (#); R2 = 0.98. A 3D QSAR pharmacophore model (PH4) derived from the QSAR directed our effort to design novel AAD analogs. During the design, an initial virtual library of 94501 AAD was focused down to 33134 drug-like compounds and finally, PH4 screened to identify 100 promising compounds. Theoretical EC50 (EC50pre) values of all analogs compounds were predicted by means of equation (#) and their pharmacokinetics (ADME) profiles were computed. More than 12 putative AADs display EC50pre 300 times superior to that of the reported most active training set inhibitor AAD1.

Published
2021

5. Effects of extractable protein hydrolysates, lipids, and polyphenolic compounds from pearl millet (Pennisetum glaucum (L.) R. Br.) whole grain flours on starch digestibility

Author

Mohamed Lemgharbi, Djaffar Djabali, Boubekeur Nadjemi, Ladjel Terbag, Rachid Souilah, Badreddine Belhadi, and Dpt physique, E.N.S, Taleb Abderrahmane, Laghouat, Algeria

Subjects
biology, Chemistry, Starch, food and beverages, engineering.material, biology.organism_classification, Whole grains, chemistry.chemical_compound, Polyphenol, engineering, Protein hydrolysates, Food science, Pearl, Pennisetum
Abstract

Pearl millet and other minor cereal production is marginalized in the Sahara of Algeria (Tidikelt and Hoggar regions). Their productions in these areas depend on traditional harvesting and processing. Pearl millet seeds are used as animal feed and rarely for human consumption. This work was to assess the starch digestion of pearl millet cultivated in the arid areas of Algeria.The seeds from this cereal could provide broad potential benefits to human health. However, their digestion properties have not been reported. Therefore, in this study, the in-vitro starch digestibility of pearl millet flour and the effect of processing on the expected glycemic index (eGI) were investigated. Grains from six pearl millet samples were chosen from two regions: Tidikelt and Hoggar. Five flours were prepared by dry milling (MF) and different treatments after dry milling such as extraction of phenolic compounds (MF-PP), lipid extraction (MF-L), protein hydrolysate extraction (MF-P) or lipid plus protein hydrolysate extraction (MF-L-P). The flours were then subjected to digestion, and the effects of grain treatments on the in vitro starch digestion were investigated. For all pearl millet samples, the kinetics of in vitrostarch digestion displayed first-order model as substrates were digested to different extents; k(kinetic constant), C∞(percentage of starch hydrolyzed at infinite time), HI (hydrolysis index) and eGI (expected glycemic index) of the samples were also calculated. Significant increases in C∞, HI and eGI (P69), with values ranging between 77.50 and 121.44.This study confirmed that some of the processed pearl millet seed flours have acceptable nutritional values suitable for human health and nutrition due to the low glycemic index values.

Published
2020

7. Scavenger Receptor Cysteine-Rich domains of Lysyl Oxidase-Like2 regulate endothelial ECM and angiogenesis through non-catalytic scaffolding mechanisms

Author

Marion Marchand, Jérémie Teillon, Stéphane Germain, Claudia Umana-Diaz, Florence Ruggiero, Corinne Ardidie-Robouant, Marilyne Malbouyres, Christophe Guilluy, A. Barret, Catherine Monnot, Laurent Muller, Romain Salza, Sylvie Ricard-Blum, Yoann Atlas, Cathy Pichol-Thievend, Philippe Girard, Pathologie et virologie moléculaire (PVM (UMR_7151)), Université Paris Diderot - Paris 7 (UPD7)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre interdisciplinaire de recherche en biologie (CIRB), Labex MemoLife, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-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), Pathologie vasculaire et endocrinologie rénale - Chaire de médecine expérimentale (INSERM U36), Collège de France (CdF (institution))-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Assemblages Supramoléculaires Péricellulaires et Extracellulaires (ASPE), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Institut de Génomique Fonctionnelle de Lyon (IGFL), École normale supérieure de Lyon (ENS de Lyon)-Institut National de la Recherche Agronomique (INRA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Inflammasome NLRP3 – NLRP3 Inflammasome, 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), Collège de France (CdF (institution)), Institut Mutualiste de Montsouris (IMM), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), and Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
Collagen Type IV, 0301 basic medicine, Angiogenesis, [SDV]Life Sciences [q-bio], Neovascularization, Physiologic, Lysyl oxidase, Cell Line, Extracellular matrix, 03 medical and health sciences, 0302 clinical medicine, Protein Domains, Human Umbilical Vein Endothelial Cells, medicine, Animals, Humans, Scavenger receptor, Molecular Biology, Zebrafish, Basement membrane, Binding Sites, LOXL2, biology, Chemistry, Dermis, Fibroblasts, Zebrafish Proteins, Extracellular Matrix, Fibronectins, Cell biology, Fibronectin, Surface coating, 030104 developmental biology, medicine.anatomical_structure, 030220 oncology & carcinogenesis, Mutagenesis, Site-Directed, biology.protein, Amino Acid Oxidoreductases
Abstract

International audience; Lysyl oxidases are major actors of microenvironment and extracellular matrix (ECM) remodeling. These cross-linking enzymes are thus involved in many aspects of physiopathology, including tumor progression, fibrosis and cardiovascular diseases. We have already shown that Lysyl Oxidase-Like 2 (LOXL2) regulates collagen IV deposition by endothelial cells and angiogenesis. We here provide evidence that LOXL2 also affects deposition of other ECM components, including fibronectin, thus altering structural and mechanical properties of the matrix generated by endothelial cells. LOXL2 interacts intracellularly and directly with collagen IV and fibronectin before incorporation into ECM fibrillar structures upon exocytosis, as demonstrated by TIRF time-lapse microscopy. Furthermore, surface plasmon resonance experiments using recombinant scavenger receptor cysteine-rich (SRCR) domains truncated for the catalytic domain demonstrated their direct binding to collagen IV. We thus used directed mutagenesis to investigate the role of LOXL2 catalytic domain. Neither enzyme activity nor catalytic domain were necessary for collagen IV deposition and angiogenesis, whereas the SRCR domains were effective for these processes. Finally, surface coating with recombinant SRCR domains restored deposition of collagen IV by LOXL2-depleted cells. We thus propose that LOXL2 SRCR domains orchestrate scaffolding of the vascular basement membrane and angiogenesis through interactions with collagen IV and fibronectin, independently of the enzymatic crosslinking activity.

Published
2023

8. Processes and temperatures of FGR formation in chondrites

Author

C. Le Guillou, Brigitte Zanda, G. Bellino, Roger H. Hewins, Hugues Leroux, P-M. Zanetta, 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), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Institut de Mécanique Céleste et de Calcul des Ephémérides (IMCCE), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Institut National de la Recherche Agronomique (INRA)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Université de Lille, CNRS, INRA, ENSCL, Unité Matériaux et Transformations - UMR 8207 [UMET], Institut de minéralogie et de physique des milieux condensés [IMPMC], Institut de Mécanique Céleste et de Calcul des Ephémérides [IMCCE], and Institut de minéralogie, de physique des matériaux et de cosmochimie [IMPMC]

Subjects
Materials science, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Mineralogy, [PHYS.PHYS.PHYS-GEO-PH]Physics [physics]/Physics [physics]/Geophysics [physics.geo-ph], engineering.material, Primitive chondrites, 010502 geochemistry & geophysics, 01 natural sciences, chemistry.chemical_compound, Geochemistry and Petrology, Chondrite, Chondrule formation episode, 0103 physical sciences, Texture (crystalline), Fine-grained rims, Matrix, Amorphous silicate, Modal abundances, ACADEMY, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Olivine, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Chondrule, [CHIM.MATE]Chemical Sciences/Material chemistry, Grain size, Silicate, Amorphous solid, Meteorite, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], engineering, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph]
Abstract

International audience; In order to understand the nature of the dust that accreted onto chondrules in the nebula and to unravel the conditions of formation of fine grained rims (FGRs), we studied three of the least altered chondrites from different chondrite groups (LL3.00 Semarkona, CO3.0 DOM 08006, CR2.8 QUE 99177) and compared the results with our previous work on the Paris CM chondrite (Zanetta et al., 2021). For each sample, we selected representative rimmed chondrules showing minimal traces of aqueous alteration. We performed high-resolution SEM X-ray chemical mapping to obtain relevant phase abundances and grain size distributions. Four FIB sections were then extracted from each meteorite, two in the rims and two in their adjacent matrix for quantitative TEM analysis. At the microscale, texture, modal abundances and grain size differ depending on the chondrite but also between FGRs and their adjacent matrix. At the nanoscale (i.e. TEM observations), matrices of the four chondrites consist mostly of domains of amorphous silicate associated with Fe-sulfides, Fe-Ni metal, Mg-rich anhydrous silicates and an abundant porosity. The related FGRs in Semarkona (LL) and DOM 08006 (CO) exhibit more compact textures with a lower porosity while FGRs in QUE99177 (CR) are similar to the matrix in terms of porosity. In the three chondrites, FGRs are made of smooth and chemically homogeneous amorphous (or nanocrystalline) silicate with no porosity that encloses domains of porous amorphous silicate bearing Mg-rich anhydrous silicates, Fe-sulfides, Fe-oxides and sometimes metal and Fe-rich olivines. The average compositions in major elements of the amorphous regions are similar for the FGRs and the matrix within a given chondrite (but differ between chondrites). The texture and the chemical homogeneity of the smooth silicate and the fact that it encloses domains of porous amorphous silicate bearing other mineral phases similar to matrix-like material suggests a formation by condensation. Areas that are enclosed in this smooth silicate exhibit Fe-rich olivine formed through Fe interdiffusion that also suggest a thermal modification of the dust accreted to form FGRs. These characteristics indicate a transformation process for the modification of the FGR material similar to the one proposed in our previous work on Paris. We conclude that matrix and FGRs accreted a similar type of dust but FGR material was affected by thermal modification and compaction contemporary with their accretion. For each chondrite, dust accreted onto chondrules under different conditions (dust density, temperature) which led to diverse degrees of compaction/thermal modification of the sub-domains and explain the textural differences observed in FGRs. They accreted on chondrules in a warm environment related to the chondrule formation episode, whereas matrix accreted later in a cooler environment.

Published
2022

9. Insights into tropical cloud chemistry in Réunion (Indian Ocean): results from the BIO-MAÏDO campaign

Author

P. A. Dominutti, P. Renard, M. Vaïtilingom, A. Bianco, J.-L. Baray, A. Borbon, T. Bourianne, F. Burnet, A. Colomb, A.-M. Delort, V. Duflot, S. Houdier, J.-L. Jaffrezo, M. Joly, M. Leremboure, J.-M. Metzger, J.-M. Pichon, M. Ribeiro, M. Rocco, P. Tulet, A. Vella, M. Leriche, L. Deguillaume, Laboratoire de Météorologie Physique (LaMP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA), Wolfson Atmospheric Chemistry Laboratories (WACL), University of York [York, UK], Laboratoire de Recherche en Géosciences et Energies [UR2_1] (LARGE), Université des Antilles (UA), Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Centre national de recherches météorologiques (CNRM), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA)-Institut national polytechnique Clermont Auvergne (INP Clermont Auvergne), Université Clermont Auvergne (UCA)-Université Clermont Auvergne (UCA), Laboratoire de l'Atmosphère et des Cyclones (LACy), Institut national des sciences de l'Univers (INSU - CNRS)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Météo-France, Institut des Géosciences de l’Environnement (IGE), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-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), and ANR-17-MPGA-0013,MOBIDIC,Modeling biologically-driven processes in clouds(2017)

Subjects
Chemistry, Atmospheric Science, [SDE.IE]Environmental Sciences/Environmental Engineering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Physics, QC1-999, [SDE.MCG]Environmental Sciences/Global Changes, QD1-999, [SDE.ES]Environmental Sciences/Environmental and Society
Abstract

We present here the results obtained during an intensive field campaign conducted in the framework of the French “BIO-MAÏDO” (Bio-physico-chemistry of tropical clouds at Maïdo (Réunion Island): processes and impacts on secondary organic aerosols' formation) project. This study integrates an exhaustive chemical and microphysical characterization of cloud water obtained in March–April 2019 in Réunion (Indian Ocean). Fourteen cloud samples have been collected along the slope of this mountainous island. Comprehensive chemical characterization of these samples is performed, including inorganic ions, metals, oxidants, and organic matter (organic acids, sugars, amino acids, carbonyls, and low-solubility volatile organic compounds, VOCs). Cloud water presents high molecular complexity with elevated water-soluble organic matter content partly modulated by microphysical cloud properties. As expected, our findings show the presence of compounds of marine origin in cloud water samples (e.g. chloride, sodium) demonstrating ocean–cloud exchanges. Indeed, Na+ and Cl− dominate the inorganic composition contributing to 30 % and 27 %, respectively, to the average total ion content. The strong correlations between these species (r2 = 0.87, p value: < 0.0001) suggest similar air mass origins. However, the average molar Cl-/Na+ ratio (0.85) is lower than the sea-salt one, reflecting a chloride depletion possibly associated with strong acids such as HNO3 and H2SO4. Additionally, the non-sea-salt fraction of sulfate varies between 38 % and 91 %, indicating the presence of other sources. Also, the presence of amino acids and for the first time in cloud waters of sugars clearly indicates that biological activities contribute to the cloud water chemical composition. A significant variability between events is observed in the dissolved organic content (25.5 ± 18.4 mg C L−1), with levels reaching up to 62 mg C L−1. This variability was not similar for all the measured compounds, suggesting the presence of dissimilar emission sources or production mechanisms. For that, a statistical analysis is performed based on back-trajectory calculations using the CAT (Computing Atmospheric Trajectory Tool) model associated with the land cover registry. These investigations reveal that air mass origins and microphysical variables do not fully explain the variability observed in cloud chemical composition, highlighting the complexity of emission sources, multiphasic transfer, and chemical processing in clouds. Even though a minor contribution of VOCs (oxygenated and low-solubility VOCs) to the total dissolved organic carbon (DOC) (0.62 % and 0.06 %, respectively) has been observed, significant levels of biogenic VOC (20 to 180 nmol L−1) were detected in the aqueous phase, indicating the cloud-terrestrial vegetation exchange. Cloud scavenging of VOCs is assessed by measurements obtained in both the gas and aqueous phases and deduced experimental gas-/aqueous-phase partitioning was compared with Henry's law equilibrium to evaluate potential supersaturation or unsaturation conditions. The evaluation reveals the supersaturation of low-solubility VOCs from both natural and anthropogenic sources. Our results depict even higher supersaturation of terpenoids, evidencing a deviation from thermodynamically expected partitioning in the aqueous-phase chemistry in this highly impacted tropical area.

Published
2022

10. Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet‐Oxygen Production and Storage

Author

Christian Philouze, Guy Royal, Martial Boggio-Pasqua, Elise Lognon, Frédérique Loiseau, Saioa Cobo, Zakaria Ziani, Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), 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 (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), and ANR-18-CE29-0012,Photochromics,Architectures Moléculaires Multi-Photochromes Innovantes pour la Production de NO et 1O2(2018)

Subjects
010405 organic chemistry, Singlet oxygen, Organic Chemistry, Quantum yield, General Chemistry, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, 7. Clean energy, Acceptor, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Photochromism, chemistry.chemical_compound, chemistry, Cyclic voltammetry, Methylpyridinium, Absorption (electromagnetic radiation)
Abstract

International audience; A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methyl-pyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry and its properties were rationalized by theoretical calculations. The incorporation of both electron donor and withdrawing groups on the photochromic center allows i) an efficient photo-isomerization of the system when illuminated at low energy (quantum yield: Фc-o = 13.3% at λex.= 660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature and iii) the storage and production of singlet oxygen. The photo-isomerization mechanism was also investigated by spin-flip TD-DFT (SF-TD-DFT) calculations.

Published
2021

11. Block Copolymers Based on Ethylene and Methacrylates Using a Combination of Catalytic Chain Transfer Polymerisation (CCTP) and Radical Polymerisation

Author

David M. Haddleton, Franck D'Agosto, Florian Baffie, Georgios Patias, Vincent Monteil, Fabrice Brunel, Lionel Perrin, Ataulla Shegiwal, Ludmilla Verrieux, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, 010405 organic chemistry, food and beverages, Chain transfer, General Medicine, General Chemistry, 010402 general chemistry, Methacrylate, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Methacrylic acid, chemistry, Polymerization, Catalytic chain transfer, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, Methyl methacrylate
Abstract

International audience; Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. w-Unsaturated methacrylic oligomers (MMA n) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 8C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA n is involved in a degradative chain transfer process resulting in the formation of (MMA) n-b-PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA n molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.

Published
2021

12. Impact of the Difluoromethylene Group in the Organocatalyzed Acylative Kinetic Resolution of α,α‐Difluorohydrins

Author

Adrien Quintard, Daniela Andrei, Jean-Marc Pons, Jérémy Merad, Maurice Médebielle, Cyril Bressy, Titouan Desrues, Jean-Luc Parrain, 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), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), ANR-18-CE07-0036,AMPLI,Amplification d'Enantiosélectivité en Organocatalyse: Criblage Rapide de Catalyseurs, Développements & Applications Synthétiques(2018), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Enantioselective, Kinetic Resolution, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organcatalysis, Enantioselective synthesis, chemistry.chemical_element, Context (language use), General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Adduct, Kinetic resolution, Acylation, chemistry, Alcohols, fluorine, Organocatalysis, Fluorine, Moiety
Abstract

International audience; Due to the omnipresence of chiral organofluorine compounds in pharmaceutical, agrochemical, and material chemistry, the development of enantioselective methods for their preparation is highly desirable. In the present study, the enantioselective organocatalyzed acylation of a,a-difluorohydrins using a commercially available chiral isothiourea is reported through a kinetic resolution (KR) process. It reveals that the difluoromethylene moiety (C(sp 3)F 2) can serve as a directing group through electrostatic fluorine-cation interactions, greatly improving the enantioselectivity of the KR. In this context, a broad range of fluorinated alcohols such as valuable 4,4-difluoro-1,3-diols could be synthesized with exquisite enantiocontrol (typically > 99:1 er). Turning to 2,2difluoro-1,3-diols, we also demonstrated that aromatic and fluorinated groups were mutually compatible to provide the expected enantioenriched adducts with > 99:1 er.

Published
2021

13. Magnetic Hysteresis in a Monolayer of Oriented 6 nm CsNiCr Prussian Blue Analogue Nanocrystals

Author

Christophe Cartier dit Moulin, M.-A. Arrio, Laurent Lisnard, Edwige Otero, Weibin Li, Sandra Mazerat, Philippe Ohresser, Laure Catala, Luqiong Zhang, Philippe Sainctavit, Talal Mallah, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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 de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), and Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Prussian blue, Coordination sphere, Magnetic circular dichroism, 02 engineering and technology, Coercivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, Linear dichroism, Magnetic hysteresis, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Condensed Matter::Materials Science, Magnetization, chemistry.chemical_compound, Crystallography, chemistry, Monolayer, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Prussian blue analogue nanocrystals of the CsINiII[CrIII(CN)6] cubic network with 6 nm size were assembled as a single monolayer on highly organized pyrolytic graphite (HOPG). X-ray magnetic circular dichroism (XMCD) studies, at the Ni and Cr L2,3 edges, reveal the presence of an easy plane of magnetization evidenced by an opening of the magnetic hysteresis loop (coercive field of ≈200 Oe) when the magnetic field, B, is at 60° relative to the normal to the substrate. The angular dependence of the X-ray natural linear dichroism (XNLD) reveals both an orientation of the nanocrystals on the substrate and an anisotropy of the electronic cloud of the NiII and CrIII coordination sphere species belonging to the nanocrystals' surface. Ligand field multiplet (LFM) calculations that reproduce the experimental data are consistent with an elongated tetragonal distortion of surface NiII coordination sphere responsible for the magnetic behavior of monolayer.

Published
2021

14. Trinuclear Cyanido‐Bridged [Cr 2 Fe] Complexes: To Be or not to Be a Single‐Molecule Magnet, a Matter of Straightness

Author

Jean-Pascal Sutter, Céline Pichon, Carine Duhayon, Nathalie Guihéry, Valentin Jubault, Nicolas Suaud, 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), ANR-17-CE07-0007,AnisoChirMag,Anisotropie Optique au sein d'Aimants Moléculaires Chiraux: Vers une Lecture Optique de l'Orientation du Spin(2017), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Steric effects, 010405 organic chemistry, Chemistry, Magnetism, Organic Chemistry, Relaxation (NMR), General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Magnetization, Crystallography, Magnetic anisotropy, Pentagonal bipyramidal molecular geometry, Single-molecule magnets, Anisotropy, Moiety, Single-molecule magnet, Ab initio calculations, Pentagonal bipyramid
Abstract

International audience; Trinuclear systems of formula [{Cr(LN3O2Ph)(CN)2}2M(H2LN3O2R)] (M=MnII and FeII, LN3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M−N≡C linkages on the magnetic anisotropy of the FeII derivatives and in turn on their Single-Molecule Magnet (SMM) behaviors. The cyanido-bridged [Cr2M] derivatives were obtained by assembling trans-dicyanido CrIII complex [Cr(LN3O2Ph)(CN)2]− and divalent pentagonal bipyramid complexes [MII(H2LN3O2R)]2+ with various R substituents (R=NH2, cyclohexyl, S,S-mandelic) imparting different steric demand to the central moiety of the complexes. A comparative examination of the structural and magnetic properties showed an obvious effect of the deviation from straightness of the M−N≡C alignment on the slow relaxation of the magnetization exhibited by the [Cr2Fe] complexes. Theoretical calculations have highlighted important effects of the bending of the apical C−N−Fe linkages on both the magnetic anisotropy of the FeII center and the exchange interactions with the CrIII units.

Published
2021

15. Diffusion Behavior of Methane in 3D Kerogen Models

Author

Narasimhan Loganathan, Geoffrey M. Bowers, Andrey G. Kalinichev, Kai Bin Yu, A. Ozgur Yazaydin, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
[PHYS]Physics [physics], Materials science, General Chemical Engineering, Energy Engineering and Power Technology, Thermodynamics, 02 engineering and technology, 021001 nanoscience & nanotechnology, Methane, chemistry.chemical_compound, Fuel Technology, 020401 chemical engineering, chemistry, Kerogen, 0204 chemical engineering, Diffusion (business), 0210 nano-technology
Abstract

International audience; As global energy demand increases, natural gas recovery from source rocks is attracting considerable attention since recent development in shale extraction techniques has made the recovery process economically viable. Kerogens are thought to play an important role in gas recovery; however, the interactions between trapped shale gas and kerogens remain poorly understood due to the complex, heterogeneous microporous structure of kerogens. This study examines the diffusive behavior of methane molecules in kerogen matrices of different types (Type I, II, and II) and maturity levels (A to D for Type II kerogens) on a molecular scale. Models of each kerogen type were developed using simulated annealing. We employed grand canonical Monte Carlo simulations to predict the methane loadings of the kerogen models and then used equilibrium molecular dynamics simulations to compute the mean square displacement of methane molecules within the kerogen matrices under reservoir-relevant conditions, that is, 365 K and 275 bar. Our results show that methane self-diffusivity exhibits some degree of anisotropy in all kerogen types examined here except for Type I-A kerogens, where diffusion is the fastest and isotropic diffusion is observed. Self-diffusivity appears to correlate positively with pore volume for Type II kerogens, where an increase in diffusivity is observed with increasing maturity. Swelling of the kerogen matrix up to a 3% volume change is also observed upon methane adsorption. The findings contribute to a better understanding of hydrocarbon transport mechanisms in shale and may lead to further development of extraction techniques, fracturing fluids, and recovery predictions

Published
2021

16. Is muscle and protein loss relevant in long‐term fasting in healthy men? A prospective trial on physiological adaptations

Author

Audrey Bergouignan, Claire Laurens, Yvon Le Maho, Françoise Wilhelmi de Toledo, Stéphane Blanc, Guillemette Gauquelin-Koch, Chantal Simon, Anthony Damiot, Anne-Laure Le Maho, Franziska Grundler, Isabelle Chery, Alexandre Zahariev, Centre National d’Études Spatiales [Paris] (CNES), Département Ecologie, Physiologie et Ethologie (DEPE-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Buchinger Wilhelmi Clinic [Überlingen, Germany] (BWC), Charité - UniversitätsMedizin = Charité - University Hospital [Berlin], Clinique Générale Annecy (CGA), Centre Scientifique de Monaco (CSM), University of Colorado Anschutz [Aurora], Cardiovasculaire, métabolisme, diabétologie et nutrition (CarMeN), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Hospices Civils de Lyon (HCL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Hospices Civils de Lyon (HCL), and CarMeN, laboratoire

Subjects
Adult, Male, medicine.medical_specialty, [SDV]Life Sciences [q-bio], Blood lipids, Diseases of the musculoskeletal system, Body composition, chemistry.chemical_compound, Long-term fasting, Weight loss, Physiology (medical), Internal medicine, Ketogenesis, medicine, Humans, Orthopedics and Sports Medicine, Prospective Studies, Protein sparing, Exercise, Glycogen, business.industry, Muscles, QM1-695, Original Articles, Energy metabolism, Fasting, Middle Aged, Lipids, Adaptation, Physiological, [SDV] Life Sciences [q-bio], Protein catabolism, Blood pressure, Endocrinology, RC925-935, chemistry, Muscle function, Human anatomy, Basal metabolic rate, Apelin, Original Article, Long‐term fasting, medicine.symptom, business
Abstract

International audience; BACKGROUND: Fasting is attracting an increasing interest as a potential strategy for managing diseases, including metabolic disorders and complementary cancer therapy. Despite concerns of clinicians regarding protein catabolism and muscle loss, evidence-based clinical data in response to long-term fasting in healthy humans are scarce. The objective of this study was to measure clinical constants, metabolic, and muscular response in healthy men during and after a 10 day fast combined with a physical activity programme. METHODS: Sixteen men (44 ± 14 years; 26.2 ± 0.9 kg/m(2) ) fasted with a supplement of 200-250 kcal/day and up to 3 h daily low-intensity physical activity according to the peer-reviewed Buchinger Wilhelmi protocol. Changes in body weight (BW) and composition, basal metabolic rate (BMR), physical activity, muscle strength and function, protein utilization, inflammatory, and metabolic status were assessed during the 10 day fast, the 4 days of food reintroduction, and at 3 month follow-up. RESULTS: The 10 day fast decreased BW by 7% (-5.9 ± 0.2 kg, P \textless 0.001) and BMR by 12% (P \textless 0.01). Fat mass and lean soft tissues (LST) accounted for about 40% and 60% of weight loss, respectively, -2.3 ± 0.18 kg and -3.53 ± 0.13 kg, P \textless 0.001. LST loss was explained by the reduction in extracellular water (44%), muscle and liver glycogen and associated water (14%), and metabolic active lean tissue (42%). Plasma 3-methyl-histidine increased until Day 5 of fasting and then decreased, suggesting that protein sparing might follow early proteolysis. Daily steps count increased by 60% (P \textless 0.001) during the fasting period. Strength was maintained in non-weight-bearing muscles and increased in weight-bearing muscles (+33%, P \textless 0.001). Glycaemia, insulinemia, blood lipids, and blood pressure dropped during the fast (P \textless 0.05 for all), while non-esterified fatty acids and urinary beta-hydroxybutyrate increased (P \textless 0.01 for both). After a transient reduction, inflammatory cytokines returned to baseline at Day 10 of fasting, and LST were still lower than baseline values (-2.3% and -3.2%, respectively; P \textless 0.05 for both). CONCLUSIONS: A 10 day fast appears safe in healthy humans. Protein loss occurs in early fast but decreases as ketogenesis increases. Fasting combined with physical activity does not negatively impact muscle function. Future studies will need to confirm these first findings.

Published
2021

17. Long-Term Stable Near-Infrared–Short-Wave-Infrared Photodetector Driven by the Photothermal Effect of Polypyrrole Nanostructures

Author

Lionel Aigouy, Zhuoying Chen, Chenghao Xin, Hengyang Xiang, Xiaojiao Yuan, Zhelu Hu, Laboratoire de Physique et d'Etude des Matériaux (UMR 8213) (LPEM), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, solution-process, Photodetector, Nanoparticle, 02 engineering and technology, 010402 general chemistry, Polypyrrole, 7. Clean energy, 01 natural sciences, broadband photodetection, [SPI.MAT]Engineering Sciences [physics]/Materials, chemistry.chemical_compound, polypyrrole nanostructures, General Materials Science, photothermal effect, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Solution process, ComputingMilieux_MISCELLANEOUS, Conductive polymer, business.industry, Near-infrared spectroscopy, Photothermal effect, long-term stability, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Rise time, [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, Optoelectronics, 0210 nano-technology, business
Abstract

Polypyrrole (PPy) is a conductive polymer and widely applied in different applications owing to its broadband absorption in the UV-visible, near-infrared (NIR), and short-wave-infrared (SWIR) spectrum, excellent conductivity, and strong photothermal effect. In this work, we explored for the first time the photothermal effect of PPy nanoparticles (PPy-NPs) in a photothermal-induced detector structure and developed a new type of air-stable hybrid PPy-NPs/Pt photodetector (PD) with NIR/SWIR sensitivity. By combining PPy-NPs with a platinum (Pt)-resistive pattern, we fabricated PPy-NPs/Pt PDs that are sensitive to illumination in the wavelength range from 800 to 2000 nm. Under the illumination of λ = 1.5 μm, the maximum photoresponsivity was measured to be ∼1.3 A/W with a 131 μs photoresponse rise time. Owing to the excellent material stability from both PPy-NPs and the Pt pattern, the current photodetectors show long-term stable photoresponsivity when they were stored in air without encapsulation. The results suggest that the PPy-NPs/Pt hybrid PDs are promising candidates for a new type of low-cost and broadband due to their multiple advantages such as free of toxic heavy metals, air stability, and solution processing.

Published
2021

18. Characterization of a functional V1B vasopressin receptor in the male rat kidney: evidence for cross talk between V1B and V2 receptor signaling pathways

Author

Claudine Serradeil-Le Gal, Maithé Corbani, Catherine Llorens-Cortes, Nadine Bouby, Annette Hus-Citharel, Csaba Tömböly, Christiane Mendre, Miguel Trueba, Gilles Guillon, Judit Darusi, Julie Mion, Neuropeptides centraux et régulations hydrique et cardiovasculaire, Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre interdisciplinaire de recherche en biologie (CIRB), Labex MemoLife, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Labex MemoLife, Université Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Centre de Recherche des Cordeliers (CRC (UMR_S_1138 / U1138)), École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Université de Paris (UP), Institut de Génomique Fonctionnelle (IGF), Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS), Biological Research Center [Hungarian Academy of Sciences], University of the Basque Country [Bizkaia] (UPV/EHU), VibioSphen, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Labex MemoLife, Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Hungarian Academy of Sciences (MTA), and University of the Basque Country/Euskal Herriko Unibertsitatea (UPV/EHU)

Subjects
0301 basic medicine, Physiology, [SDV]Life Sciences [q-bio], 030232 urology & nephrology, Rat kidney, Diuresis, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, [SDV.MHEP.UN]Life Sciences [q-bio]/Human health and pathology/Urology and Nephrology, Vasopressin V1B and V2 receptor, 03 medical and health sciences, 0302 clinical medicine, Arginine vasopressin receptor 2, medicine, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Receptor, receptor heterodimerization, Arginine vasopressin receptor 1B, Messenger RNA, Kidney, Chemistry, vasopressin V1B and V2 receptors, inner medullary collecting duct, calcium and cAMP signaling, Cell biology, diuresis, 030104 developmental biology, medicine.anatomical_structure, Signal transduction
Abstract

International audience; Although vasopressin V1B receptor (V1BR) mRNA has been detected in the kidney, the precise renal localization as well as pharmacological and physiological properties of this receptor remain unknown. Using the selective V1B agonist d[Leu4, Lys8]VP, either fluorescent or radioactive, we showed that V1BR is mainly present in principal cells of the inner medullary collecting duct (IMCD) in the male rat kidney. Protein and mRNA expression of V1BR were very low compared with the V2 receptor (V2R). On the microdissected IMCD, d[Leu4, Lys8]VP had no effect on cAMP production but induced a dose-dependent and saturable intracellular Ca2+ concentration increase mobilization with an EC50 value in the nanomolar range. This effect involved both intracellular Ca2+ mobilization and extracellular Ca2+ influx. The selective V1B antagonist SSR149415 strongly reduced the ability of vasopressin to increase intracellular Ca2+ concentration but also cAMP, suggesting a cooperation between V1BR and V2R in IMCD cells expressing both receptors. This cooperation arises from a cross talk between second messenger cascade involving PKC rather than receptor heterodimerization, as supported by potentiation of arginine vasopressin-stimulated cAMP production in human embryonic kidney-293 cells coexpressing the two receptor isoforms and negative results obtained by bioluminescence resonance energy transfer experiments. In vivo, only acute administration of high doses of V1B agonist triggered significant diuretic effects, in contrast with injection of selective V2 agonist. This study brings new data on the localization and signaling pathways of V1BR in the kidney, highlights a cross talk between V1BR and V2R in the IMCD, and suggests that V1BR may counterbalance in some pathophysiological conditions the antidiuretic effect triggered by V2R activation.NEW & NOTEWORTHY Although V1BR mRNA has been detected in the kidney, the precise renal localization as well as pharmacological and physiological properties of this receptor remain unknown. Using original pharmaceutical tools, this study brings new data on the localization and signaling pathways of V1BR, highlights a cross talk between V1BR and V2 receptor (V2R) in the inner medullary collecting duct, and suggests that V1BR may counterbalance in some pathophysiological conditions the antidiuretic effect triggered by V2R activation.

Published
2021

19. Development of radioactive beams at ALTO: Part 1. Physicochemical comparison of different types of UCx targets using a multivariate statistical approach

Author

Julien Guillot, B. Roussière, Sylvain Denis, Sandrine Tusseau-Nenez, François Brisset, Nicole Barré-Boscher, Institut de Physique Nucléaire d'Orsay (IPNO), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique de la matière condensée (LPMC), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), and Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nuclear and High Energy Physics, Materials science, Physics - Instrumentation and Detectors, FOS: Physical sciences, chemistry.chemical_element, Sintering, 02 engineering and technology, Carbon nanotube, 01 natural sciences, law.invention, chemistry.chemical_compound, law, 0103 physical sciences, [PHYS.PHYS.PHYS-INS-DET]Physics [physics]/Physics [physics]/Instrumentation and Detectors [physics.ins-det], [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Porosity, Instrumentation, 010302 applied physics, Fission products, Condensed Matter - Materials Science, Aggregate (composite), Materials Science (cond-mat.mtrl-sci), Instrumentation and Detectors (physics.ins-det), 021001 nanoscience & nanotechnology, Microstructure, chemistry, Uranium carbide, 0210 nano-technology, Biological system, Carbon
Abstract

International audience; The optimization of the microstructure of the UCx target is a key point since many years in the field of ISOL method. The ultimate goal is to facilitate the release of the fission products, especially those with short half-lives. Fourteen UCx samples were synthetized from different uranium and carbon sources using three mixing protocols. All carburized samples were systematically characterized in terms of nature and proportion phases, grain and aggregate size, open and close porosity proportion and open pore size distribution. Our results were analysed using a multivariate statistical approach in order to remove any subjective bias. Strong correlations between the physicochemical characteristics of the samples as well as the impact of the synthesis process have been highlighted. In particular, using carbon nanotubes as carbon source combined with a new method of mixing is the key parameter to limit the sintering and to obtain samples with small grains and a high porosity well distributed over small pores. Moreover the microstructure obtained proved to be stable at high temperature.

Published
2022

20. High-Resolution IMS–MS to Assign Additional Disulfide Bridge Pairing in Complementarity-Determining Regions of an IgG4 Monoclonal Antibody

Author

Elsa Wagner-Rousset, Olivier Colas, Kevin Giles, Sarah Cianférani, Thomas Botzanowski, Evolène Deslignière, Oscar Hernandez-Alba, Alain Beck, Dale Cooper-Shepherd, Hélène Diemer, Guillaume Béchade, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Infrastructure Nationale de Protéomique, FR2048 ProFI, Waters Corporation, Centre d'Immunologie Pierre Fabre (CIPF), and PIERRE FABRE

Subjects
medicine.drug_class, Complementarity determining region, Monoclonal antibody, Immunoglobulin light chain, 01 natural sciences, Mass Spectrometry, 03 medical and health sciences, chemistry.chemical_compound, Structural Biology, Ion Mobility Spectrometry, medicine, Humans, [CHIM]Chemical Sciences, Disulfides, Spectroscopy, 030304 developmental biology, 0303 health sciences, Dipeptide, biology, Chemistry, Immunogenicity, 010401 analytical chemistry, Antibodies, Monoclonal, Complementarity Determining Regions, 0104 chemical sciences, Biochemistry, Immunoglobulin G, biology.protein, Antibody, Critical quality attributes, Cysteine
Abstract

International audience; Monoclonal antibodies (mAbs) have taken on an increasing importance for the treatment of various diseases, including cancers and immunological disorders. Disulfide bonds play a pivotal role in therapeutic antibody structure and activity relationships. Disulfide connectivity and cysteine-related variants are considered as critical quality attributes (CQAs) that must be monitored during mAb manufacturing and storage, as non-native disulfide bridges and aggregates might be responsible for loss of biological function and immunogenicity. The presence of cysteine residues in the Complementarity-Determining Regions (CDRs) is rare in human antibodies but may be critical for the antigen-binding or deleterious for therapeutic antibody development. Consequently, in-depth characterization of their disulfide network is a prerequisite for mAb developability assessment. Mass spectrometry (MS) techniques represent powerful tools for accurate identification of disulfide connectivity. We report here on the MS-based characterization of an IgG4 comprising two additional cysteine residues in the CDR of its light chain. Classical bottom-up approaches after trypsin digestion first allowed identification of a dipeptide containing two disulfide bridges. To further investigate the conformational heterogeneity of the disulfide-bridged dipeptide, we performed ion mobility spectrometry-mass spectrometry (IMS-MS) experiments. Our results highlight benefits of high resolution IMS-MS to tackle the conformational landscape of disulfide peptides generated after trypsin digestion of a humanized IgG4 mAb under development. By comparing arrival time distributions of the mAb collected peptide and synthetic peptides, cyclic IMS afforded unambiguous assessment of disulfide bonds. In addition to classical peptide mapping, qualitative high-resolution IMS-MS can be of great interest to identify disulfide bonds within therapeutic mAbs.

Published
2021

21. Product Detection of the CH(X2Π) Radical Reaction with Cyclopentadiene: A Novel Route to Benzene

Author

David L. Osborn, Sébastien D. Le Picard, Talitha M. Selby, Fabien Goulay, Kacee L. Caster, University of Wisconsin - Milwaukee, Sandia National Laboratories - Corporation, Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), West Virginia University [Morgantown], National Science Foundation (NSF) [CHE-1764178], Washington County Campus Foundation, Agence Nationale de la Recherche French National Research Agency (ANR) European Commission [ANR-11-BS04-024-CRESUSOL-01], French INSU/CNRS Program \'Physique et Chimie du Milieu Interstellaire\' (PCMI), Institut Nationalde Physique (INPCNRS), Region Bretagne Region Bretagne, Universite de Rennes 1, Institut Universitaire de France, Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences, the U.S. Department of EnergyUnited States Department of Energy (DOE), U.S. DOE's National Nuclear Security Administration National Nuclear Security Administration [DE-NA0003525], Office of Science, Office of Basic Energy Sciences, the U.S. Department of Energy at Lawrence Berkeley National Laboratory United States Department of Energy (DOE) [DE-AC02-05CH11231], ANR-11-BS04-0024,CRESUSOL,Cinétique et détermination des rapports de branchements de processus collisionnels à très basses températures(2011), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], Cyclopentadiene, 010304 chemical physics, Radical, Photoionization, 010402 general chemistry, 01 natural sciences, Cycloaddition, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Methylidyne radical, 0103 physical sciences, Potential energy surface, Physical chemistry, Physical and Theoretical Chemistry, Molecular physics, Benzene, Fulvene
Abstract

International audience; The reaction of the methylidyne radical (CH((XII)-I-2)) with cyclopentadiene (c-C5H6) is studied in the gas phase at 4 Ton and 373 K using a multiplexed photoionization mass spectrometer. Under multiple collision conditions, the dominant product channel observed is the formation of C6H6 + H. Fitting the photoionization spectrum using reference spectra allows for isomeric resolution of C6H6 isomers, where benzene is the largest contributor with a relative branching fraction of 90 (+/- 5)%. Several other C6H6 isomers are found to have smaller contributions, including fulvene with a branching fraction of 8 (+/- 5)%. Master Equation calculations for four different entrance channels on the C6H7 potential energy surface are performed to explore the competition between CH cycloaddition to a C=C bond vs CH insertion into C-H bonds of cyclopentadiene. Previous studies on CH addition to unsaturated hydrocarbons show little evidence for the C-H insertion pathway. The present computed branching fractions support benzene as the sole cyclic product from CH cycloaddition, whereas fulvene is the dominant product from two of the three pathways for CH insertion into the C-H bonds of cyclopentadiene. The combination of experiment with Master Equation calculations implies that insertion must account for similar to 10 (+/- 5)% of the overall CH + cyclopentadiene mechanism.

Published
2021

22. Advances in the Chemistry of Astatine and Implications for the Development of Radiopharmaceuticals

Author

Gilles Montavon, François Guérard, Jean-François Gestin, Nicolas Galland, Romain Eychenne, Lu Liu, Clémence Maingueneau, Nuclear Oncology (CRCINA-ÉQUIPE 13), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), GIPARRONAX [Saint-Herblain, France], Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), INCa-DGOSInserm_12558, ANR-11-EQPX-0004,ARRONAXPLUS,Nucléaire pour la Santé(2011), ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011), ANR-16-IDEX-0007,NExT (I-SITE),NExT (I-SITE)(2016), Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), Université de Nantes (UN)-Université de Nantes (UN)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Guérard, François, Nucléaire pour la Santé - - ARRONAXPLUS2011 - ANR-11-EQPX-0004 - EQPX - VALID, Radiopharmaceutiques Innovants en Oncologie et Neurologie - - IRON2011 - ANR-11-LABX-0018 - LABX - VALID, and NExT (I-SITE) - - NExT (I-SITE)2016 - ANR-16-IDEX-0007 - IDEX - VALID

Subjects
Halogen bond, 010405 organic chemistry, [SDV]Life Sciences [q-bio], chemistry.chemical_element, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, [SDV] Life Sciences [q-bio], chemistry, 13. Climate action, Computational chemistry, Electrophile, Halogen, Nucleophilic substitution, Fluorine, Molecule, Earth (chemistry), Astatine, ComputingMilieux_MISCELLANEOUS
Abstract

ConspectusAstatine (At) is the rarest on Earth of all naturally occurring elements, situated below iodine in the periodic table. While only short-lived isotopes (t1/2 ≤ 8.1 h) are known, 211At is the object of growing attention due to its emission of high-energy alpha particles. Such radiation is highly efficient to eradicate disseminated tumors, provided that the radionuclide is attached to a cancer-targeting molecule. The interest in applications of 211At in nuclear medicine translates into the increasing number of cyclotrons able to produce it. Yet, many challenges related to the minute amounts of available astatine are to be overcome in order to characterize its physical and chemical properties. This point is of paramount importance to develop synthetic strategies and solve the labeling instability in current approaches that limits the use of 211At-labeled radiopharmaceuticals. Despite its discovery in the 1940s, only the past decade has seen a significant rise in the understanding of astatine's basic chemical and radiochemical properties, thanks to the development of new analytical and computational tools.In this Account, we give a concise summary of recent advances in the determination of the physicochemical properties of astatine, putting in perspective the duality of this element which exhibits the characteristics both of a halogen and of a metal. Striking features were evidenced in the recent determination of its Pourbaix diagram such as the identification of stable cationic species, At+ and AtO+, contrasting with other halogens. Like metals, these species were shown to form complexes with anionic ligands and to exhibit a particular affinity for organic species bearing soft donor atoms. On the other hand, astatine shares many characteristics with other halogen elements. For instance, the At- species exists in water, but with the least range of EH-pH stability in the halogen series. Astatine can form molecular interactions through halogen bonding, and it was only recently identified as the strongest halogen-bond donor. This ability is nonetheless affected by relativistic effects, which translate to other peculiarities for this heavy element. For instance, the spin-orbit coupling boosts astatine's propensity to form charge-shift bonds, catching up with the behavior of the lightest halogens (fluorine, chlorine).All these new data have an impact on the development of radiolabeling strategies to turn 211At into radiopharmaceuticals. Inspired by the chemistry of iodine, the chemical approaches have sparsely evolved over the past decades and have long been limited to electrophilic halodemetalation reactions to form astatoaryl compounds. Conversely, recent developments have favored the use of the more stable At- species including the aromatic nucleophilic substitution with diaryliodonium salts or the copper-catalyzed halodeboronation of arylboron precursors. However, it is clear that new bonding modalities are necessary to improve the in vivo stability of 211At-labeled aryl compounds. The tools and data gathered over the past decade will contribute to instigate original strategies for overcoming the challenges offered by this enigmatic element. Alternatives to the C-At bond such as the B-At and the metal-At bonds are typical examples of exciting new axes of research.

Published
2021

23. Native Separation and Metallation Analysis of SOD1 Protein from the Human Central Nervous System: a Methodological Workflow

Author

Glenda M. Halliday, Benjamin G. Trist, Asuncion Carmona, Gerald Falkenberg, Stéphane Roudeau, Richard Ortega, Stéphane Claverol, Stijn Van Malderen, Katherine M. Davies, Yann Rufin, Kay L. Double, Centre d'Etudes Nucléaires de Bordeaux Gradignan (CENBG), Université Sciences et Technologies - Bordeaux 1-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Brain and Mind Centre and School of Medical Sciences (Neuroscience), Faculty of Medicine and Health, The University of Sydney, Sydney, New South Wales 2050, Australia, Brain and Mind Centre and Faculty of Medicine and Health, School of Medical Sciences, The University of Sydney, Sydney, New South Wales 2050, Australia, Université de Bordeaux (UB), Plateforme Proteome, Univ. Bordeaux, F- 33076 Bordeaux, France, and Deutsches Elektronen-Synchrotron [Hamburg] (DESY)

Subjects
SOD1, Central nervous system, Context (language use), Substantia nigra, Workflow, Analytical Chemistry, Superoxide dismutase, 03 medical and health sciences, Superoxide Dismutase-1, Superoxide dismutase 1 SOD1, 0302 clinical medicine, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Metalloprotein, medicine, Humans, Amyotrophic lateral sclerosis, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, biology, Superoxide Dismutase, Isoelectric focusing, Chemistry, Amyotrophic Lateral Sclerosis, zinc, Human brain, medicine.disease, central nervous system, Spinal cord, synchrotron X-ray fluorescence, Isoelectric point, medicine.anatomical_structure, Biochemistry, copper, Mutation, ddc:540, biology.protein, Locus coeruleus, 030217 neurology & neurosurgery
Abstract

Analytical chemistry 93(32), 11108 - 11115 (2021). doi:10.1021/acs.analchem.1c01128, Studies of the metal content of metalloproteins in tissues from the human central nervous system (CNS) can be compromised by preparative techniques which alter levels of, or interactions between, metals and the protein of interest within a complex mixture. We developed a methodological workflow combining size exclusion chromatography, native isoelectric focusing, and either proton or synchrotron X-ray fluorescence within electrophoresis gels to analyze the endogenous metal content of copper-zinc superoxide dismutase (SOD1) purified from minimal amounts (, Published by American Chemical Society, Columbus, Ohio

Published
2021

24. Porous functionalized polymers enable generating and transporting hyperpolarized mixtures of metabolites

Author

James G. Kempf, Jonas Milani, Sami Jannin, Morgan Ceillier, Quentin Stern, Basile Vuichoud, Damien Montarnal, Marc Schnell, Dmitry Eshchenko, Samuel F. Cousin, Roberto Melzi, Théo El Daraï, Aurélien Bornet, Olivier Cala, Laurent Gremillard, 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), Centre de RMN à très hauts champs de Lyon (CRMN), 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), Bruker BioSpin [Billerica, MA], Bruker Biospin, Bruker, Bruker BioSpin, Matériaux, ingénierie et science [Villeurbanne] (MATEIS), 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)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Nitroxide mediated radical polymerization, Materials science, Science, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Article, General Biochemistry, Genetics and Molecular Biology, Hyperpolarization (physics), Polarization (electrochemistry), Dissolution, chemistry.chemical_classification, Multidisciplinary, Aqueous solution, Relaxation (NMR), [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Spin diffusion, Polymer synthesis, 0210 nano-technology, Solution-state NMR
Abstract

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. Broad democratization of dDNP could be realized by remote preparation and distribution of hyperpolarized samples from dedicated facilities. Here we show the synthesis of hyperpolarizing polymers (HYPOPs) that can generate radical- and contaminant-free hyperpolarized samples within minutes with lifetimes exceeding hours in the solid state. HYPOPs feature tunable macroporous porosity, with porous volumes up to 80% and concentration of nitroxide radicals grafted in the bulk matrix up to 285 μmol g−1. Analytes can be efficiently impregnated as aqueous/alcoholic solutions and hyperpolarized up to P(13C) = 25% within 8 min, through the combination of 1H spin diffusion and 1H → 13C cross polarization. Solutions of 13C-analytes of biological interest hyperpolarized in HYPOPs display a very long solid-state 13C relaxation times of 5.7 h at 3.8 K, thus prefiguring transportation over long distances., Hyperpolarization by dissolution dynamic nuclear polarization has brought highly sensitive magnetic resonance to reality but there still remains severe limitations. Here the authors show an approach relying on the generation of hyperpolarizing polymers that bear a dual function.

Published
2021

25. Shadow Electrochemiluminescence Microscopy of Single Mitochondria

Author

Neso Sojic, Camille Colin, Julie Descamps, Stéphane Arbault, Yumeng Ma, Université de Bordeaux (UB), Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)

Subjects
endocrine system, medicine.medical_specialty, [SDV.BC.BC]Life Sciences [q-bio]/Cellular Biology/Subcellular Processes [q-bio.SC], Mitochondrion, 010402 general chemistry, 01 natural sciences, Catalysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Microscopy, Organelle, Organometallic Compounds, medicine, Electrochemiluminescence, Fluorescent Dyes, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Propylamines, 010405 organic chemistry, Chemistry, Colocalization, General Medicine, Electrochemical Techniques, General Chemistry, Photobleaching, Fluorescence, 0104 chemical sciences, Mitochondria, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Bioelectrochemistry, Luminescent Measurements, Biophysics, Biomarkers
Abstract

International audience; Mitochondria are the subcellular bioenergetic organelles. The analysis of their morphology and topology is essential to provide useful information on their activity and metabolism. Herein, we report a labelfree shadow electrochemiluminescence (ECL) microscopy based on the spatial confinement of the ECLemitting reactive layer to image single living mitochondria deposited on the electrode surface. The ECL mechanism of the freely-diffusing [Ru(bpy)3] 2+ dye with the sacrificial tri-n-propylamine coreactant restrains the light-emitting region to a micrometric thickness allowing to visualize individual mitochondria with a remarkable sharp negative optical contrast. The imaging approach named "shadow ECL" (SECL) reflects the negative imprint of the local diffusional hindrance of the ECL reagents by each mitochondrion. The statistical analysis of the colocalization of the shadow ECL spots with the functional mitochondria revealed by classical fluorescent biomarkers, MitoTracker Deep Red and the endogenous intramitochondrial NADH, validates the reported methodology. The versatility and extreme sensitivity of the approach are further demonstrated by visualizing single mitochondria, which remain hardly detectable with the usual biomarkers. Finally, by alleviating problems of photobleaching and phototoxicity associated with conventional microscopy methods, SECL microscopy should find promising applications in the imaging of subcellular structures.

Published
2021

26. Impact of Changing the Core in Tetrapyrrolic Dendrimers Designed for Oxygen Sensitization: New Fluorescent Phthalocyanine-Based Dendrimers with High Two-Photon Absorption Cross-sections

Author

Nicolas Richy, Sarra Ben Hassine, Bassem Jamoussi, Olivier Mongin, Seifallah Abid, Franck Camerel, Mireille Blanchard-Desce, Frédéric Paul, Zhipeng Sun, Christine O. Paul-Roth, Université de Carthage - University of Carthage, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Tunis El Manar, King Abdulaziz University, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors acknowledge CNRS for their financial support and 'the Ministère de l’Enseignement Supérieur et de la Recherche Scientifique de Tunisie' for PhD funding (SA and SB) as well as China Scholarship Council (CSC) for PhD funding (ZS). This project was supported by the departmental committees CD35, CD49, and CD28 of the 'Ligue contre le Cancer du Grand-Ouest'. We also thank Guillaume Clermont (ISM) for his help in the two-photon and singlet oxygen measurements. This work was granted access to the high-performance computing resources of CINES (Montpellier, France) under allocation 2020-A0080805032 awarded by GENCI., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Polymers and Plastics, Conjugated system, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Two-photon absorption, Absorption, Inorganic Chemistry, chemistry.chemical_compound, Dendrimer, Materials Chemistry, [CHIM]Chemical Sciences, Molecule, Dendrons, 010405 organic chemistry, Organic Chemistry, Phthalocyanine, Molecules, Fluorescence, Porphyrin, 0104 chemical sciences, Oxygen, chemistry, Macromolecule
Abstract

International audience; In the continuation of our sustained interest for porphyrin-based dendrimers and their use as luminescent photo-sensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the central porphyrin core for a phthalocyanine core in these macromolecular structures. Thus, related phthalocyanine-based dendrimers possessing up to 16 conjugated 9,9-dibutyl-2-fluorenyl endgroups at their periphery were now prepared and studied. As for porphyrin analogues, it was found that an efficient energy transfer occurs from the peripheral fluorenyl units toward the central phthalocyanine unit of these compounds, leading to intense red light emission and photosensitization of oxygen. While the linear optical properties of these new dendrimers are only slightly improved compared to those of their porphyrin-cored analogues for PDT and fluorescence imaging, their two-photon absorption (2PA) cross-sections are much more significantly boosted, evidencing the key role played by the central tetrapyrrolic unit in this respect. The impact of this structural change in relation with the impact resulting from the change in dendrimer generations is then discussed with the help of DFT and molecular dynamic calculations.

Published
2021

27. Conceptual polymorphism of entropy into the history: extensions of the second law of thermodynamics towards statistical physics and chemistry during nineteenth–twentieth centuries

Author

Emilio Marco Pellegrino, Abdelkader Anakkar, Maxime Nagels, Raffaele Pisano, 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), Physique - IEMN (PHYSIQUE - IEMN), and 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)

Subjects
Physics, History, Philosophy of science, Chemistry, Entropy (statistical thermodynamics), media_common.quotation_subject, Second law of thermodynamics, General Chemistry, Biochemistry, Epistemology, [SPI]Engineering Sciences [physics], symbols.namesake, Theory of heat, Boltzmann constant, symbols, Comparative historical research, Carnot cycle, Function (engineering), media_common
Abstract

International audience; After the birth of thermodynamics’ second principle—outlined in Carnot's Réflexions sur la puissance motrice du feu (1824)—several studies provided new arguments in the field. Mainly, they concerned the thermodynamics’ first principle—including energy conceptualisation—, the analytical aspects of the heat propagation, the statistical aspects of the mechanical theory of heat. In other words, the second half of nineteenth century was marked by an intense interdisciplinary research activity between physics and chemistry: new disciplines applied to the heat developed in the form of analytical, mechanical and statistical theories. Inside all these theories, entropy—the brand-new function that Clausius coined in his Mechanical theory of heat—started to play a central epistemic role. In the present paper, we analyse some steps of the historical process of conceptualisation of such function from 1850 to 1902. Particularly, we retrace the historical–foundational path that—starting from Clausius’ Second Law—lead Boltzmann and Gibbs to their distinguished formulations of statistical entropy. As usual, our research has been unrolled through the analyses of primary sources and by leaning on critical readings of the secondary literature. As for the methodological approach, text analysis of historical documents constituted our privileged modus operandi. This paper is the expression of a collaborative historical research program focused on the thermodynamic foundations of physics–chemistry relationship; early results have already been published by the same authors upon the concepts of reversibility––and––thermal equilibrium.

Published
2021

28. Rod-Like Nanoparticles with Striped and Helical Topography

Author

Tina I. Löbling, Johanna Majoinen, Olli Ikkala, André H. Gröschel, Nonappa, Maria Morits, Jani-Markus Malho, Felix H. Schacher, Department of Applied Physics [Aalto], Aalto University, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Lab Organic and Macromolecular Chemistry (IOMC) and Jena Center for Soft Matter (JCSM), Institute of Organic Chemistry and Macromolecular Chemistry and Jena Center for Soft Matter (JCSM), Physical Chemistry and Center for Nanointegration (CENIDE), and Universität Duisburg-Essen [Essen]

Subjects
CELLULOSE NANOCRYSTALS, Materials science, MULTICOMPARTMENT MICELLES, Polymers and Plastics, ta221, PATCHY NANOPARTICLES, SHELL, Shell (structure), Nanoparticle, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Colloid, Materials Chemistry, Copolymer, PARTICLES, MICELLAR INTERPOLYELECTROLYTE COMPLEXES, chemistry.chemical_classification, Organic Chemistry, NANOSTRUCTURED MATERIALS, Polymer, Physik (inkl. Astronomie), 021001 nanoscience & nanotechnology, COLLOIDS, 3d topography, 0104 chemical sciences, BLOCK-COPOLYMERS, Cellulose nanocrystals, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Transmission electron microscopy, POLYMERS, 0210 nano-technology
Abstract

International audience; The behavior of nanoparticles in solution is largely dominated by their shape and interaction potential. Despite considerable progress in the preparation of patchy and compartmentalized particles, access to nanoparticles with complex surface patterns and topographies remains limited. Here, we show that polyanionic brushes tethered to rod-like cellulose nanocrystals (CNCs) spontaneously develop a striped or helical topography through interpolyelectrolyte complexation with polycationic diblock copolymers. Using cryogenic transmission electron microscopy (cryo-TEM) and tomography (cryo-ET), we follow the complexation process and analyze the delicate 3D topography on the CNC surface. The described approach is facile and modular and can be extended to other block chemistries, nanoparticles, and surfaces, thereby providing a versatile platform toward surface-patterned particles with complex topographies and spatially arranged functional groups.

Published
2022

29. Fragmentation of Nickel(II) and Cobalt(II) Bis(acetylacetonate) Complexes Induced by Slow (<10 eV) Electrons

Author

Hassan Abdoul-Carime, Franck Rabilloud, Janina Kopyra, Physico-chimie théorique (THEOCHEM), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Siedlce University of Natural Sciences and Humanities, Institut de Physique des 2 Infinis de Lyon (IP2I Lyon), and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
[PHYS]Physics [physics], 010405 organic chemistry, chemistry.chemical_element, Electron, 010402 general chemistry, 01 natural sciences, Decomposition, 0104 chemical sciences, Inorganic Chemistry, Metal, [SPI]Engineering Sciences [physics], Nickel, chemistry, Fragmentation (mass spectrometry), visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical chemistry, Molecule, Density functional theory, Physical and Theoretical Chemistry, Cobalt
Abstract

International audience; Metal acetylacetonate complexes have high potentiality in nanoscale fabrication processes (e.g., focus electron beam-induced deposition) thanks to the versatile character and ease of preparation compounds. In this work, we study and compare the physics and the physicochemistry induced by the interaction of low-energy (

Published
2021

30. Insight into the Formation and Stability of Solid Electrolyte Interphase for Nanostructured Silicon-Based Anode Electrodes Used in Li-Ion Batteries

Author

Mariam Ezzedine, Lucie Leveau, Fatme Jardali, Eleonor Caristan, Mihai-Robert Zamfir, Ovidiu Ersen, Ileana Florea, Costel Sorin Cojocaru, Laboratoire de physique des interfaces et des couches minces [Palaiseau] (LPICM), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), National Institute for Laser, Plasma and Radiation Physics (INFLPR), RENAULT, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Cojocaru, Costel Sorin, Université de Strasbourg (UNISTRA)-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
Battery (electricity), [CHIM.MATE] Chemical Sciences/Material chemistry, Materials science, Passivation, Silicon, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Electrolyte, Current collector, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, Anode, chemistry, Chemical engineering, Electrode, General Materials Science, 0210 nano-technology, Layer (electronics)
Abstract

International audience; Silicon-based anode fabrication with nanoscale structuration improves the energy density and life cycle of Li-ion batteries. As-synthesized silicon (Si) nanowires (NWs) or nanoparticles (NPs) directly on the current collector represent a credible alternative to conventional graphite anodes. However, the operating potentials of these electrodes are below the electrochemical stability window of all electrolytes used in commercial Li-ion systems. During the first charging phase of the cell, partial decomposition of the electrolyte takes place, which leads to the formation of a layer at the surface of the electrode, called solid electrolyte interphase (SEI). A stable and continuous SEI layer formation is a critical factor to achieve reliable lifetime stability of the battery. Once formed, the SEI acts as a passivation layer that minimizes further degradation of the electrolyte during cycling, while allowing lithium-ion diffusion with their subsequent insertion into the active material and ensuring reversible operation of the electrode. However, one of the major issues requiring deeper investigation is the assessment of the morphological extension of the SEI layer into the active material, which is one of the main parameters affecting the anode performances. In the present study, we use electron tomography with a low electron dose to retrieve three-dimensional information on the SEI layer formation and its stability around SiNWs and SiNPs. The possible mechanisms of SEI evolution could be inferred from the interpretation and analysis of the reconstructed volumes. Significant volume variations in the SiNW and an inhomogeneous distribution of the SEI layer around the NWs are observed during cycling and provide insights into the potential mechanism leading to the generally reported SiNW anode capacity fading. By contrast, analysis of the reconstructed SiNPs’ volume for a sample undergoing one lithiation–delithiation cycle shows that the SEI remains homogeneously distributed around the NPs that retain their spherical morphology and points to the potential benefit of such nanoscale Si anode materials to improve their cycling lifetime.

Published
2021

31. Production of scandium radionuclides for theranostic applications: towards standardization of quality requirements

Author

Piotr Garnuszek, Cyrille Alliot, Sandrine Huclier-Markai, Viktória Forgács, Ferid Haddad, Dezső Szikra, Renata Mikolajczak, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Cyclotron ARRONAX, and GIP

Subjects
Standardization, Computer science, R895-920, chemistry.chemical_element, Review, RM1-950, 010403 inorganic & nuclear chemistry, 01 natural sciences, Medical care, In vivo studies, 030218 nuclear medicine & medical imaging, Analytical Chemistry, 03 medical and health sciences, Medical physics. Medical radiology. Nuclear medicine, 0302 clinical medicine, Pharmacology (medical), Radiology, Nuclear Medicine and imaging, Scandium, [PHYS]Physics [physics], Pharmacology, Accelerator- and nuclear reactor production, Positron emitters, 3. Good health, 0104 chemical sciences, chemistry, Coordination, Quality specifications, Scandium radionuclides, Biochemical engineering, Therapeutics. Pharmacology, Radiolabeling
Abstract

International audience; AbstractIn the frame of “precision medicine”, the scandium radionuclides have recently received considerable interest, providing personalised adjustment of radiation characteristics to optimize the efficiency of medical care or therapeutic benefit for particular groups of patients. Radionuclides of scandium, namely scandium-43 and scandium-44 (43/44Sc) as positron emitters and scandium-47 (47Sc), beta-radiation emitter, seem to fit ideally into the concept of theranostic pair. This paper aims to review the work on scandium isotopes production, coordination chemistry, radiolabeling, preclinical studies and the very first clinical studies. Finally, standardized procedures for scandium-based radiopharmaceuticals have been proposed as a basis to pave the way for elaboration of the Ph.Eur. monographs for perspective scandium radionuclides.

Published
2021

32. Effects of the Chemical and Structural Properties of Silane Monolayers on the Organization of Water Molecules and Ions at Interfaces, from Molecular Dynamics Simulations

Author

Antonin Lavigne, Solène Lecot, Zihua Yang, Magali Phaner-Goutorbe, Christelle Yeromonahos, Yann Chevolot, INL - Chimie et Nanobiotechnologies (INL - C&N), Institut des Nanotechnologies de Lyon (INL), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Centrale de Lyon (ECL), Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)

Subjects
Materials science, [PHYS.PHYS.PHYS-BIO-PH]Physics [physics]/Physics [physics]/Biological Physics [physics.bio-ph], 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Molecular dynamics, chemistry.chemical_compound, Adsorption, Monolayer, Electrochemistry, Molecule, General Materials Science, ComputingMilieux_MISCELLANEOUS, Spectroscopy, Alkyl, chemistry.chemical_classification, Biomolecule, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation, Silane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Chemical engineering, Surface modification, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

Understanding the organization of the hydration layer at functionalized silica surfaces is relevant for a large range of biosensing applications or surface phenomena such as biomolecule adsorption. Silane monolayers are widely used to functionalize silica surfaces. Using molecular dynamics simulations, we have investigated the role of silane molecule head-group charge, alkyl chain length, and surface coverage in the structural organization and dynamic properties of Na+ ions, Cl- ions, and water molecules at the interface. The silane molecules studied are 3-aminopropyldimethylethoxysilane, n-propyldimethylmethoxysilane, octadecyldimethylmethoxysilane, and (dimethylamino)dimethylsilylundecanoate. Our results suggest that the distribution of interfacial ions is sensitive to the 2D dispersion of the silane-charged head groups. Also, while charged silane monolayers show a strong orientation of interfacial water molecules, which leads to a rupture in the hydrogen bond network and disturbs their tetrahedral organization, the arrangement of water molecules at the interface with uncharged silane monolayers seems to be related to the surface roughness and to alkyl chain length. In line with these results, the diffusion of ions and water molecules is higher at the CH3 long monolayer interface than at the CH3 short monolayer interface and at the charged monolayer interfaces. Also, whatever the silane molecules studied, bulk properties are recovered around 0.7 nm above the interface. The interfacial water organization is known to impact biomolecule adsorption. Therefore, these results could further help in optimizing the functionalization layers to capture analytes.

Published
2021

33. Storing the portrait of Antoine de Lavoisier in a single macromolecule

Author

Kevin Launay, Thibault Schutz, Jean-Louis Clément, Alexandre Burel, Laurence Charles, Didier Gigmes, Eline Laurent, Christine Carapito, Jean-Arthur Amalian, Jean-François Lutz, Marc-André Delsuc, 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), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Génétique et de Biologie Moléculaire et Cellulaire (IGBMC), Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and Lutz, Jean-François

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Polymer science, 010405 organic chemistry, Chemistry, Building and Construction, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Portrait, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Electrical and Electronic Engineering, ComputingMilieux_MISCELLANEOUS, Macromolecule
Abstract

International audience

Published
2021

34. Cyclic Poly(α-peptoid)s by Lithium bis(trimethylsilyl)amide (LiHMDS)-Mediated Ring-Expansion Polymerization: Simple Access to Bioactive Backbones

Author

Pierre Verhaeghe, Sébastien Lecommandoux, Antoine Tronnet, Marc Since, Jean-Luc Stigliani, Pedro Salas-Ambrosio, Sandra Bourgeade-Delmas, Bruno Dupuy, Amelie Vax, Colin Bonduelle, Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Pathogénèse des Bactéries Anaérobies / Pathogenesis of Bacterial Anaerobes (PBA (U-Pasteur_6)), Institut Pasteur [Paris]-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Centre d'Etudes et de Recherche sur le Médicament de Normandie (CERMN), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU), Pharmacochimie et Biologie pour le Développement (PHARMA-DEV), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut de Recherche pour le Développement (IRD), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Trimethylsilyl Compounds, Cell Survival, Polymers, Lithium bis(trimethylsilyl)amide, Microbial Sensitivity Tests, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Catalysis, Cell Line, Polymerization, Macrocyclic polypeptoids, Peptoids, chemistry.chemical_compound, Colloid and Surface Chemistry, Biological property, Humans, Density Functional Theory, Ring expansion polymerization (REP), chemistry.chemical_classification, Clostridioides difficile, Peptoid, General Chemistry, Polymer, Combinatorial chemistry, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Cyclization
Abstract

International audience; Cyclic polymers display unique physicochemical and biological properties. However, their development is often limited by their challenging preparation. In this work, we present a simple route to cyclic poly(α-peptoids) from N-alkylated-N-carboxyanhydrides (NNCA) using LiHMDS promoted ring-expansion polymerization (REP) in DMF. This new method allows the unprecedented use of lysine-like monomers in REP to design bioactive macrocycles bearing pharmaceutical potential against Clostridioides difficile, a bacterium responsible for nosocomial infections.

Published
2021

35. Mercury Chalcogenide Quantum Dots: Material Perspective for Device Integration

Author

Clément Livache, Nicolas Goubet, Emmanuel Lhuillier, Sandrine Ithurria, Charlie Gréboval, Audrey Chu, Physico-chimie et dynamique des surfaces (INSP-E6), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Los Alamos National Laboratory (LANL), Laboratoire de Physique et d'Etude des Matériaux (UMR 8213) (LPEM), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-19-CE24-0022,COPIN,Détecteur plasmonique à nanoCristaux colloïdaux: une nouvelle filière pour l'OPtoélectronique INfrarouge(2019), ANR-19-CE09-0017,FRONTAL,Nanocristaux Colloïdaux Dopés Infrarouges(2019), ANR-19-CE09-0026,GRaSkop,Tuning Giant Rashba Spin-Orbit Coupling in Polar Single Layer Transition Metal Dichalcogenides(2019), ANR-20-ASTR-0008,NITquantum,Design et fabrication d'un plan focal dans le proche infrarouge à base de nanocrisrtaux(2020), ANR-18-CE30-0023,IPER-Nano2,Nanocristaux de perovskite inorganique pour la nanophotonique(2018), ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), European Project: 756225,blackQD, and European Project: 853049,ne2dem

Subjects
light detection, optoelectronics, 010405 organic chemistry, Chemistry, Band gap, Infrared, Chalcogenide, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Photodetection, Electronic structure, 010402 general chemistry, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, nanocrystals, Quantum dot, Infrared window, infrared, Light emission, mercury chalcogenides, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat]
Abstract

International audience; Nanocrystals (NCs) are one of the few nanotechnologies to have attained mass market applications with their use as light sources for displays. This success relies on Cd-and In-based wide bandgap materials. NCs are likely to be employed in more applications as they provide a versatile platform for optoelectronics, specifically, infrared optoelectronics. The existing material technologies in this range of wavelengths are generally not cost effective, which limits the spread of technologies beyond a few niche domains, such as defense and astronomy. Among the potential candidates to address the infrared window, mercury chalcogenide (HgX) NCs exhibit the highest potential in terms of performance. In this review, we discuss how material developments have facilitated device enhancements. Because such NCs are primarily used because of their infrared optical features, we first review the strategies for the associated colloidal growth and electronic structure. The review is organized considering three main device-related applications: light emission, electronic transport and infrared photodetection.

Published
2021

36. Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates

Author

Christophe Detrembleur, Philip Scholten, Antoine Debuigne, Henri Cramail, Grégory Cartigny, Bruno Grignard, Michael A. R. Meier, Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Laboratoire de Chimie des Polymères Organiques (LCPO), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Polymers and Plastics, Polymers, Radical polymerization, Carbonates, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Polymerization, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, business.industry, Organic Chemistry, Fossil fuel, Polymer, Polyethylene, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Renewable energy, Molecular Weight, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, 0210 nano-technology, business
Abstract

Partly or fully renewable (co)polymers are gaining interest in both academia and industry. Polyethylene is a widely used polymer, classically derived from fossil fuels, with a high versatility stemming from the introduction of comonomers altering the mechanical properties. The introduction of renewable functionalities into this polymer is highly attractive to obtain functional, tunable, and at least partially renewable polyethylenes. We herein report the introduction of biosourced cyclic carbonates into polyethylene using organometallic-mediated radical polymerization under mild conditions. Molecular weights of up to 14 600 g mol

Published
2021

37. Lipid Droplet Nucleation

Author

Elina Ikonen, Abdou Rachid Thiam, Fédération de recherche du Département de physique de l'Ecole Normale Supérieure - ENS Paris (FRDPENS), Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Sorbonne Université (SU), Laboratoire de physique de l'ENS - ENS Paris (LPENS (UMR_8023)), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), University of Helsinki, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Microfluidique, Émulsion et Biologie, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Université de Paris (UP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Université de Paris (UP)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique de l'ENS - ENS Paris (LPENS), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Sorbonne Université (SU)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Sorbonne Université (SU)-École normale supérieure - Paris (ENS Paris)

Subjects
[SDV]Life Sciences [q-bio], Nucleation, Phospholipid, Biology, Endoplasmic Reticulum, Seipin, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, Lipid droplet, Organelle, Humans, Phospholipids, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Endoplasmic reticulum, Membrane Proteins, Lipid Droplets, Cell Biology, Lipid Metabolism, chemistry, Membrane curvature, Biophysics, 030217 neurology & neurosurgery, Biogenesis
Abstract

All living organisms can make lipid droplets (LDs), intracellular oil-in-water droplets, surrounded by a phospholipid and protein monolayer. LDs are at the nexus of cellular lipid metabolism and function in diverse biological processes. During the past decade, multidisciplinary approaches have shed light on LD assembly steps from the endoplasmic reticulum (ER): nucleation, growth, budding, and formation of a separate organelle. However, the molecular mechanisms underpinning these steps remain elusive. In this review, we focus on the nucleation step, defining where and how LD assembly is initiated. We present how membrane biophysical and physicochemical properties control this step and how proteins act on it to orchestrate LD biogenesis.

Published
2021

38. Optimization of Polyethylene Grade Transitions in Fluidized Bed Reactors with Constraints on the Polymer Sticking Temperature

Author

Nida Sheibat-Othman, Sabrine Kardous, Timothy F. L. McKenna, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire d'automatique, de génie des procédés et de génie pharmaceutique (LAGEPP), Université de Lyon-Université de Lyon-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), and Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Work (thermodynamics), Materials science, General Chemical Engineering, Melting temperature, 02 engineering and technology, General Chemistry, Polymer, Polyethylene, 021001 nanoscience & nanotechnology, Industrial and Manufacturing Engineering, Polyolefin, chemistry.chemical_compound, 020401 chemical engineering, chemistry, Fluidized bed, Particle, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, 0204 chemical engineering, Composite material, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

In gas-phase polyolefin processes, it is important to evaluate the melting temperature of particles since exceeding this temperature may cause particle sticking and aggregation. In this work, a mod...

Published
2021

39. Synthesis and Properties of Higher Nuclearity Polyazanes

Author

Maurice Médebielle, Emmanuel Lacôte, Thomas Criton, Debora Vilona, Lionel Joucla, Elise Dumont, Guy Jacob, Lacôte, Emmanuel, Laboratoire Hydrazines et Composés Energetiques Polyazotés (LHCEP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-HERAKLES - SAFRAN-Centre National d'Études Spatiales [Toulouse] (CNES)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, ArianeGroup, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon), Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), and École normale supérieure - Lyon (ENS Lyon)

Subjects
Molecular model, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Reducing agent, Organic Chemistry, chemistry.chemical_element, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Nitrogen, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Reagent, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Diazo, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Polyazanes (that is, higher nuclearity homologues of hydrazines) with increasing numbers of bound nitrogen atoms (from 3 to 5) were prepared via additions of lower order polyazanes to diazo reagents, including the first pentazane ever described. A structure was obtained. It was shown that the polynitrogen chains adopt a helical conformation. DFT modeling shows that the arrangement subsists in solution. While the polyazanes are all reducing agents, they become less so with the increasing number of nitrogens.

Published
2021

40. Monocationic Bis-Alkyl and Bis-Allyl Yttrium Complexes: Synthesis, 89Y NMR Characterization, Ethylene or Isoprene Polymerization, and Modeling

Author

Pierre-Alain Breuil, Helene Olivier-Bourbigou, Lionel Perrin, Aymane El Bouhali, Alexis D. Oswald, Christophe Boisson, Florent Vaultier, Emmanuel Chefdeville, Aimery De Mallmann, Mostafa Taoufik, Julien Thuilliez, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), IFP Energies nouvelles (IFPEN), and Société Michelin

Subjects
chemistry.chemical_classification, Ethylene polymerization, Ethylene, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Yttrium, Molecules, Ligands, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Polymerization, Metals, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isoprene, Alkyl
Abstract

International audience; Monocationic complexes of yttrium with various bis-alkyl and bis-allyl ligands Y(CH2SiMe2Ph)2(THF)4][B(C6F5)4], [Y(CH2C6H4NMe2)2(THF)2][B(C6F5)4], and [Y[1,3-(SiMe3)2C3H3]2(THF)2][B(C6F5)4] have been prepared by protonolysis of the corresponding homoleptic tris-alkyl or -allyl complexes using the anilinium borate salt [PhNMe2H][B(C6F5)4]. The resulting ion-pair complexes have been isolated and characterized by different techniques such as elemental analysis, 1H, 13C, and 89Y NMR, and EXAFS for the allyl cationic complex [Y[1,3-(SiMe3)2C3H3]2(THF)2][B(C6F5)4]. More specifically, a 1H-coupled 89Y INEPT sequence has been developed in order to quantify the metal/alkyl ligand stoichiometry of both synthesized neutral tris-alkyl and cationic bis-alkyl yttrium complexes. The activity of the cationic complexes toward ethylene and isoprene homopolymerization has been assessed. In presence of TiBA, polyethylene was produced with activities ranging from 6 to 26 kgPE molY–1 h–1 bar–1. The molar mass of the yielded polymers shows a bimodal distribution. Under similar conditions, polyisoprene was produced up to full conversion of the monomer. The microstructure of the yielded polyisoprene displayed mainly cis-1,4-units (ca. 60–70%) and 3,4-units (ca. 20–30%). Only a few percent of trans-1,4 units was revealed.

Published
2021

41. Bio-Based Polyricinoleate and Polyhydroxystearate: Properties and Evaluation as Viscosity Modifiers for Lubricants

Author

Etienne Grau, Jean-François Le Meins, Henri Cramail, Hélène Méheust, Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Team 3 LCPO : Polymer Self-Assembly & Life Sciences

Subjects
Condensation polymer, Polymers and Plastics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, polyhydroxystearate, Viscosity, Rheology, medicine, Thermal stability, Lubricant, Mineral oil, thickeners, Chemistry, Process Chemistry and Technology, Organic Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Polyester, [CHIM.POLY]Chemical Sciences/Polymers, viscosity index, Chemical engineering, viscosity modifiers, lubricant, Viscosity index, 0210 nano-technology, polyricinoleate, medicine.drug
Abstract

International audience; This paper aims to design bio-based polyester as a viscosity modifier for lubricant properties. Bio-based polyricinoleate (PRic) and its saturated homologous polyhydroxystearate (PHS) have been synthesized from fatty acid methyl esters. The polycondensation performed in bulk in a one-step reaction without any purification leads to two series of polyesters within a large range of molecular weights, with Mw between 3 and 130 kg·mol–1. Their thermal properties were investigated. Good thermal stability was observed with degradation temperatures above 300 °C. As expected, PRic appeared to be amorphous with a particularly low glass-transition temperature, while PHS is semicrystalline. A rheological study determined that polyricinoleate entangled when its molecular weight was above 25 kg·mol–1. These two bio-based and biodegradable polymers were then evaluated as viscosity modifiers in both organic and mineral oils. PHS with high molecular weights appeared to be an excellent thickener as well as a good viscosity index improver with a viscosity index (VI) increase above +50 in organic lubricant oil and +64 in mineral oil.

Published
2021

42. SERS characterization of aggregated and isolated bacteria deposited on silver-based substrates

Author

Lea Rosselle, Eric Larquet, Anne Chantal Gouget-Laemmel, Simion Astilean, Cristina-Cassiana Andrei, Anne Moraillon, Sabine Szunerits, Monica Potara, François Ozanam, Endre Jakab, Nadia Skandrani, Rabah Boukherroub, Julie Bouckaert, Laboratoire de physique de la matière condensée, CNRS, École polytechnique,IP Paris, Palaiseau, France, 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), NanoBioInterfaces - IEMN (NBI - IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), European Project: 690836,H2020,H2020-MSCA-RISE-2015,PANG(2016), Laboratoire de Physique de la Matière Condensée (LPMC), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), 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), Université de Lille, CNRS, Laboratoire de physique de la matière condensée [LPMC], Babes-Bolyai University [Cluj-Napoca] [UBB], Unité de Glycobiologie Structurale et Fonctionnelle (UGSF) - UMR 8576, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN], and Institut d'Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520

Subjects
Surface-enhanced Raman scattering (SERS), Silver nanostructures, Escherichia coli, Staphylococcus aureus, Aggregated and single bacteria, Principal component analysis (PCA), Silver, Surface Properties, 02 engineering and technology, Spectrum Analysis, Raman, medicine.disease_cause, 01 natural sciences, Biochemistry, Pilus, Analytical Chemistry, Cell wall, symbols.namesake, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, medicine, Humans, Molecule, Escherichia coli Infections, biology, Chemistry, 010401 analytical chemistry, Substrate (chemistry), [CHIM.MATE]Chemical Sciences/Material chemistry, Staphylococcal Infections, 021001 nanoscience & nanotechnology, biology.organism_classification, 0104 chemical sciences, Biophysics, symbols, 0210 nano-technology, Raman spectroscopy, Bacteria, Raman scattering
Abstract

International audience; Surface-enhanced Raman scattering (SERS), based on the enhancement of the Raman signal of molecules positioned within a few nanometres from a structured metal surface, is ideally suited to provide bacterial-specific molecular fingerprints which can be used for analytical purposes. However, for some complex structures such as bacteria, the generation of reproducible SERS spectra is still a challenging task. Among the various factors influencing the SERS variability (such as the nature of SERS-active substrate, Raman parameters and bacterial specificity), we demonstrate in this study that the environment of Gram-positive and Gram-negative bacteria deposited on ultra-thin silver films also impacts the origin of the SERS spectra. In the case of densely packed bacteria, the obtained SERS signatures were either characteristic of the secretion of adenosine triphosphate for Staphylococcus aureus (S. aureus) or the cell wall and the pili/flagella for Escherichia coli (E. coli), allowing for an easy discrimination between the various strains. In the case of isolated bacteria, SERS mapping together with principal component analysis revealed some variabilities of the spectra as a function of the bacteria environment and the bactericidal effect of the silver. However, the variability does not preclude the SERS signatures of various E. coli strains to be discriminated.

Published
2021

43. Metal–organic framework/graphene oxide composites for CO2 capture by microwave swing adsorption

Author

Christian Serre, Gilles Patriarche, Nicolas Heymans, Damien Aureau, Alexandros Ploumistos, Mégane Muschi, Rudolf Emmerich, Sabine Devautour-Vinot, Saad Sene, Guy De Weireld, Nathalie Steunou, Amine Geneste, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Thermodynamique et Physique Mathématique - Faculté Polytechnique de Mons, Université de Mons-Hainaut, Fraunhofer Institute for Chemical Technology (Fraunhofer ICT), Fraunhofer (Fraunhofer-Gesellschaft), and Université Paris-Saclay

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, Graphene, Composite number, Oxide, 02 engineering and technology, General Chemistry, Microporous material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Adsorption, chemistry, law, Desorption, [CHIM]Chemical Sciences, General Materials Science, Metal-organic framework, Composite material, 0210 nano-technology, Microwave
Abstract

Metal–organic frameworks (MOFs)/graphene oxide (GO) composites are of growing interest due to their properties which can exceed those of the pure components, including post-combustion CO2 capture. Series of composites suitable for CO2 capture under flue gas conditions based on the microporous water stable MIL-91(Ti) have been prepared with different GO contents, following two routes, in situ and post-synthetic. It was observed that the 5 wt% GO in situ composite exhibits a semi-conducting behavior, while the post-synthetic materials are insulating, even with high (20 wt%) GO content. As a consequence, this composite absorbs microwave radiation more efficiently compared to the pure MOF and post-synthetic materials. Finally, we report that CO2 desorption is much faster under microwave irradiation compared to direct electric heating on MOF/GO in situ materials, paving the way for future energy-saving microwave swing adsorption processes.

Published
2021

44. Complexation of europium(<scp>iii</scp>) with exopolysaccharides from a marine bacterium envisaged as luminescent probe in a theranostic approach

Author

Pascal E. Reiller, Cyrille Alliot, Mattia Mazza, Sandrine Huclier-Markai, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), GIP ARRONAX, Université de Nantes (UN), CEA- Saclay (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Université de Nantes (UN)-Université de Nantes (UN)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique)

Subjects
Inorganic chemistry, Ionic bonding, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Theranostic Nanomedicine, Fluorescence spectroscopy, Inorganic Chemistry, Metal, Europium, Coordination Complexes, Polysaccharides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Fluorescent Dyes, Viscosity, 010405 organic chemistry, Fluorescence, Polyelectrolyte, 0104 chemical sciences, Spectrometry, Fluorescence, chemistry, visual_art, Drug delivery, visual_art.visual_art_medium, Alteromonas, Luminescence
Abstract

International audience; Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties in osteosarcoma (bone tumor). These EPSs could be employed as new drug deliverysystems for therapeutic uses. They may represent a new class of ligands to be combined in a theranosticapproach with fluorescent metals, such as Eu(III), to serve as imaging probe. The goal of this work was toinvestigate the feasibility of such coupling by time-resolved laser-induced fluorescence spectroscopy(TRLFS). Since these EPSs are polyelectrolytes their conformation could affect the complexation properties.Thus, viscosimetric measurements were performed as a function of their concentration as well asthe background electrolyte concentration. Polysaccharides conformation exhibited a lower hydrodynamicvolume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexationwith metal for high concentration but no change was evidenced when increasing europiumconcentration. Two sites of complexation of Eu(III) were evidenced by TRLFS in heparin, whereas only onesite was evidenced in two modified EPSs produced from Alteromonas infernus.

Published
2021

45. Control of the single atom/nanoparticle ratio in Pd/C catalysts to optimize the cooperative hydrogenation of alkenes

Author

Camila Rivera‐Cárcamo, Alain Favre-Réguillon, C. de Bellefon, Iann C. Gerber, Boris Guicheret, Régis Philippe, J. Audevard, I. del Rosal, Bruno F. Machado, R. Castro Contreras, Laurent Vanoye, Philippe Serp, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Laboratoire de Génie des Procédés Catalytiques (LGPC), École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Conservatoire National des Arts et Métiers [CNAM] (CNAM), Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM) Departamento de Tecnologia Quimica e Biologica Escola Superior de Tecnologia e Gestao (LSRE-LCM), Instituto Politecnico de Braganca, Fundação para a Ciência e a Tecnologia, CONICYT, Région Auvergne-Rhône-Alpes (contract number 15 021131 01 – CNR006), ANR-19-CE07-0030,COMET,Catalyse Coopérative Entre Atomes Et Nanoparticules Métalliques(2019), 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), 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), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS), and HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)

Subjects
chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Alkene, Inorganic chemistry, Nanoparticle, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, Orders of magnitude (numbers), 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Oxygen, Catalysis, 0104 chemical sciences, Hydrogen spillover, 0210 nano-technology, Dispersion (chemistry), Isomerization
Abstract

International audience; We recently reported (R. Castro Contreras, B. Guicheret, B. F. Machado, C. Rivera-Cárcamo, M. A. Curiel Alvarez, B. Valdez Salas, M. Ruttert, T. Placke, A. Favre Réguillon, L. Vanoye, C. de Bellefon, R. Philippe and P. Serp, J. Catal., 2019, 372, 226–244) that a structure/activity correlation exists in Pd/C catalysts for myrcene hydrogenation, which integrates the Pd dispersion, and the surface concentration of oxygen groups and defects of the support. Here, through a combined experimental–theoretical study, we provide an explanation of the influence of these three structural characteristics of Pd/C catalysts for alkene hydrogenation. Highly dispersed Pd nanoparticles (PdNP) are necessary to activate dihydrogen. A high concentration of surface defects on the support is necessary to stabilize Pd single atoms (PdSA), which coexist with PdNP on Pd/C catalysts. A high concentration of oxygenated surface groups is also necessary on the support to allow hydrogen spillover. We demonstrate that such a combination allows cooperative catalysis to operate between PdNP and PdSA that involves the formation of PdSA–H species, which are much more active than PdNP–H for alkene hydrogenation but also isomerization. Importantly, we also report an efficient method to control the ratio between PdSA and PdNP in Pd/C catalysts of similar loadings and show that the control of this ratio allows the development of a new generation of stable and highly active catalysts integrating the ultra-rational use of precious metals in short supply. Indeed, for myrcene hydrogenation, activity variations of several orders of magnitude were measured as a function of the value of this ratio.

Published
2021

46. Functional nanostructures by NiCCo-PISA of helical poly(aryl isocyanide) copolymers

Author

Andrew P. Dove, Sètuhn Jimaja, Yujie Xie, Rachel K. O'Reilly, Jeffrey C. Foster, Daniel Taton, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), University of Warwick [Coventry], School of Chemistry [Birmingham], and University of Birmingham [Birmingham]

Subjects
Circular dichroism, Materials science, Polymers and Plastics, Aryl, Isocyanide, Organic Chemistry, Bioengineering, Pentafluorophenyl esters, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Micelle, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Amphiphile, Polymer chemistry, Copolymer, 0210 nano-technology, Maleimide
Abstract

International audience; Herein, we present a straightforward and versatile methodology to achieve functional polymeric nano-objects that contain helical cores. Nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers was conducted, affording micelles containing controllable quantities of activated ester groups (i.e. pentafluorophenyl esters) in the core that were subsequently modified using post-polymerisation modification (PPM) with amine nucleophiles. Three amines bearing different functionalities (alcohol, trifluoro and a maleimide dye) were successfully introduced into the nano-object cores as verified via NMR and FT-IR spectroscopy, while the retention of helicity within the resulting diblock copolymers was confirmed by circular dichroism (CD) spectroscopy. Changes in nanostructure morphology following modification were monitored by dynamic light-scattering (DLS), confirming the disassembly of the nano-objects when the core hydrophilicity was increased through the introduction of polar functionalities. These readily-synthesised and modified nanostructures containing helical cores are valuable scaffolds for use in applications such as circularly polarised luminescence, enantioselective chemistry or chiral separation.

Published
2021

47. A chiral thiourea and a phosphazene for fast and stereoselective organocatalytic ring-opening-polymerization of racemic lactide

Author

Mohamed Samir Zaky, Olivier Coulembier, Anne-Laure Wirotius, Daniel Taton, Gilles Guichard, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre d'Innovation et de Recherche en Matériaux Polymères (CIRMAP), Université de Mons (UMons), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lactide, 010405 organic chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Ring-opening polymerization, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Thiourea, Polymerization, Organocatalysis, Tacticity, Materials Chemistry, Ceramics and Composites, Phosphazene
Abstract

International audience; Control of stereoregularity is inherent to precision polymerization chemistry for the development of functional materials. A prototypal example of this strategy is the ring-opening polymerization (ROP) of racemic lactide (rac-LA), a bio-sourced monomer. Despite significant advances in organocatalysis, stereoselective ROP of rac-LA employing chiral organocatalysts remains unexplored. Here we tackle that challenge by resorting to Takemoto's catalyst, a chiral aminothiourea, in the presence of a phosphazene base. This chiral binary organocatalytic system allows for fast, chemo- and stereoselective ROP of rac-LA at room temperature, yielding highly isotactic, semi-crystalline and metal-free polylactide, with a melting temperature as high as 187 °C.

Published
2021

48. Mass-independent and mass-dependent Cr isotopic composition of the Rumuruti (R) chondrites: Implications for their origin and planet formation

Author

Martin Schiller, Jean-Alix Barrat, Frédéric Moynier, Conel M. O'd. Alexander, Martin Bizzarro, Addi Bischoff, Ke Zhu, Institut de Physique du Globe de Paris (IPGP (UMR_7154)), Institut national des sciences de l'Univers (INSU - CNRS)-Université de La Réunion (UR)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Centre for Star and Planet Formation (STARPLAN), Globe Institute, Faculty of Health and Medical Sciences, University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH)-Faculty of Health and Medical Sciences, University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH), Carnegie Institution for Science, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut für Planetologie [Münster], Westfälische Wilhelms-Universität Münster = University of Münster (WWU), F. M. acknowledges funding from the European Research Council under the H2020 framework program/ERC grant agreement (ERC starting grant, #637503-PRISTINE) and financial support of the UnivEarthS Labex program at Université de Paris (#ANR-10-LABX-0023 and #ANR-11-IDEX-0005-02), and the IPGP platform PARI, and the Region Île-de-France Sesame grant no. 12015908. M. S. acknowledges funding from the Villum Fonden (#00025333). M. B. acknowledges funding from the Carlsberg Foundation (#CF18-1105), the Danish National Research Foundation (#DNRF97) and the European Research Council (ERC Advanced Grant Agreement, #833275-DEEPTIME). A. B. thanks the support by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation, #263649064) – TRR 170 (subproject B05). This is TRR170 Publication No. 116. K. Z. thanks the China Scholarship Council (CSC) for the PhD fellowship (#201706340161) and IPGP for the funding support of traveling, 'Aide à la MOBILITE INTERNATIONALE des doctorants de l’IPGP' (2019), to visit Earth and Planetary Laboratory, Carnegie Institution for Science., ANR-10-LABX-0023,UnivEarthS,Earth - Planets - Universe: observation, modeling, transfer(2010), ANR-11-IDEX-0005,USPC,Université Sorbonne Paris Cité(2011), European Project: 637503,H2020,ERC-2014-STG,PRISTINE(2015), Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), University of Copenhagen = Københavns Universitet (KU)-University of Copenhagen = Københavns Universitet (KU)-Faculty of Health and Medical Sciences, University of Copenhagen = Københavns Universitet (KU)-University of Copenhagen = Københavns Universitet (KU), Carnegie Institution for Science [Washington], Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Westfälische Wilhelms-Universität Münster (WWU)

Subjects
chondrules, cr-54, 010504 meteorology & atmospheric sciences, oxygen-isotope, Geochemistry, EARLY SOLAR-SYSTEM, earth, Ureilite, engineering.material, CHEMICAL-COMPOSITION, 010502 geochemistry & geophysics, 01 natural sciences, Cosmochemistry, CR-54, Geochemistry and Petrology, Chondrite, Cr stable isotopes, QUANTITATIVE MODELS, EARTH, fractionation, UBO, 0105 earth and related environmental sciences, Isotope, Chemistry, FRACTIONATION, ACL, METEORITE, Chondrule, Cr-54 nucleosynthetic anomalies, CHONDRULES, Rumuruti Chondrites, meteorite, OXYGEN-ISOTOPE, Mn-53-Cr-53 chronometry, Planetary science, 13. Climate action, DISCOVERY, Enstatite, engineering, Chondritic clast, quantitative models, chemical-composition, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, early solar-system, Planetary differentiation
Abstract

WOS:000600550100030; International audience; Chromium (Cr) isotopes play an important role in cosmochemistry and planetary science because they are powerful tools for dating (Mn-53-Cr-53 short-lived chronometry), tracing (Cr-54 nucleosynthetic anomalies) the origins of the materials, and studying the processes involved in volatile element fractionation and planetary differentiation (Cr stable isotopic fractionation). To use Cr isotopes for these purposes, it is essential to precisely know the compositions of the various chondritic reservoirs. However, the Cr isotope composition of Rumuruti (R) chondrites remains unknown. Here, we report high-precision mass-independent (average 2SE uncertainty of similar to 0.02 and similar to 0.06 for epsilon Cr-53 and epsilon Cr-54, respectively; epsilon indicates 10,000 deviation) and mass-dependent (uncertainty of average 0.03 parts per thousand for delta Cr-53; .delta indicates 1000 deviation) Cr isotope data for 12 bulk R chondrites of petrologic types 3-6 (including R chondrite breccias), and one R chondrite-like clast (MS-CH) in the Almahata Sitta polymict ureilite. All the R chondrites show homogeneous bulk epsilon Cr-54 values, -0.06 +/- 0.08 (2SD), similar only to those of the Earth-Moon system and enstatite chondrites. This first epsilon Cr-54 dataset for R chondrites provides significant addition to the epsilon Cr-54-A, Delta O-17 diagram, and positions them as a potential endmember for planetary precursors. The R chondrites possess a higher Mn-55/Cr-52 of 0.68 +/- 0.04 relative to most of carbonaceous chondrites and higher epsilon Cr-53 values 0.23 +/- 0.05 (2SD) relative to most of chondrite groups. This likely results from the lower chondrule abundance in R chondrites compared to that of ordinary and enstatite chondrites. The stable Cr isotope composition of R chondrites is homogeneous with a delta Cr-53 = -0.12 +/- 0.03%e (2SD). Combined with previous data of other groups of chondrites, we show that the stable Cr isotopic composition of all the chondrites is homogeneous with delta Cr-53 of -0.12 +/- 0.04%e (2SD, N = 42) and is independent of the petrologic type and redox conditions. The lack of mass-dependent fractionation between all groups of chondrites suggests that the average chondrite delta Cr-53 value is also representative for the initial composition of all differentiated planets in the Solar System. Finally, the MS-CH clast in Almahata Sitta has a Cr isotopic composition (epsilon Cr-53 = 0.18 +/- 0.04, epsilon Cr-54 = 0.16 +/- 0.07, and delta Cr-53 = -0.11 +/- 0.05%e) that is consistent (within error) with it being an R chondrite-like clast. (C) 2020 Elsevier Ltd. All rights reserved.

Published
2021

49. An expanded halogen bonding scale using astatine

Author

Nicolas Galland, Jérôme Graton, Rémi Maurice, Cecilia Gomez Pech, Gilles Montavon, Jean-Yves Le Questel, Lu Liu, Julie Champion, Seyfeddine Rahali, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Qassim University [Kingdom of Saudi Arabia], This work was supported in part by grants from the French National Agency for Research called ‘Investissements d'Avenir’, Equipex Arronax-Plus (ANR-11-EQPX-0004), Labex IRON (ANR-11-LABX-18-01) and ISITE NExT (ANR-16-IDEX-0007). The work was carried out using HPC resources from CCIPL (Centre de Calcul Intensif des Pays de la Loire). The authors acknowledge the GIP ARRONAX for the production of At-211., ANR-11-EQPX-0004,ARRONAXPLUS,Nucléaire pour la Santé(2011), ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011), and ANR-16-IDEX-0007,NExT (I-SITE),NExT (I-SITE)(2016)

Subjects
Halogen bond, Scale (ratio), 010405 organic chemistry, Intermolecular force, Astatine monoiodide, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Acceptor, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, chemistry.chemical_compound, chemistry, Computational chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, Astatine, Carbon
Abstract

As a non-covalent interaction, halogen bonding is now acknowledged to be useful in all fields where the control of intermolecular recognition plays a pivotal role. Halogen-bond basicity scales allow quantification of the halogen bonding of referential donors with organic functional groups from a thermodynamic point of view. Herein we present the pKBAtI basicity scale to provide the community an overview of halogen-bond acceptor strength towards astatine, the most potent halogen-bond donor element. This experimental scale is erected on the basis of complexation constants measured between astatine monoiodide (AtI) and sixteen selected Lewis bases. It spans over 6 log units and culminates with a value of 5.69 ± 0.32 for N,N,N′,N′-tetramethylthiourea. On this scale, the carbon π-bases are the weakest acceptors, the oxygen derivatives cover almost two-thirds of the scale, and sulphur bases exhibit the highest AtI basicity. Regarding the applications of 211At in targeted radionuclide therapy, stronger labelling of carrier agents could be envisaged on the basis of the pKBAtI scale., Based on the halogen bonding between astatine monoiodide (AtI) and 16 Lewis bases, the newly established pKBAtI scale indicates that the halogen bond basicity of AtI follows the order C ≤ O ≤ S ≈ Se for the acceptor atomic site.

Published
2021

50. Delocalized relativistic effects, from the viewpoint of halogen bonding

Author

Gilles Montavon, Jérôme Graton, Serigne Sarr, Nicolas Galland, Seyfeddine Rahali, Université de Nantes (UN), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
[PHYS]Physics [physics], inorganic chemicals, Halogen bond, Materials science, 010405 organic chemistry, General Physics and Astronomy, Electron, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Electronegativity, Delocalized electron, Propellane, chemistry.chemical_compound, chemistry, Chemical physics, Halogen, Physics::Atomic and Molecular Clusters, Redistribution (chemistry), Physics::Atomic Physics, Physical and Theoretical Chemistry, Relativistic quantum chemistry
Abstract

International audience; The ability of organic and inorganic compounds bearing both iodine and astatine atoms to form halogen-bond interactions is theoretically investigated. Upon inclusion of the relativistic spin–orbit interaction, the I-mediated halogen bonds are more affected than the At-mediated ones in many cases. This unusual outcome is disconnected from the behavior of iodine's electrons. The significant decrease of astatine electronegativity with the spin–orbit coupling triggers a redistribution of the electron density, which propagates relativistic effects toward the distant iodine atom. This mechanism can be controlled by introducing suitable substituents and, in particular, strengthened by taking advantage of electron-withdrawing inductive and mesomeric effects. Noticeable relativistic effects can actually be transferred to light atoms properties, e.g., the halogen-bond basicity of bridgehead carbon atoms doubled in propellane derivatives.

Published
2021

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