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1,331 results on '"Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris)"'

1. Solid-state NMR study of structural heterogeneity of the apo WT mouse TSPO reconstituted in liposomes

Author: Luminita Duma, Lucile Senicourt, Baptiste Rigaud, Vassilios Papadopoulos, Jean-Jacques Lacapère, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut des matériaux de Paris-Centre (IMPC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Southern California (USC), and Duma, Luminita
Subjects: proteoliposomes, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, solid-state NMR, membrane protein, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, General Medicine, Biochemistry, TSPO, conformational mobility
Abstract: International audience; In the last decades, ligand binding to human TSPO has been largely used in clinical neuroimaging, but little is known about the interaction mechanism. Protein conformational mobility plays a key role in the ligand recognition and both, ligand-free and ligand-bound structures, are mandatory for characterizing the molecular binding mechanism. In the absence of crystals for mammalian TSPO, we have exploited solid-state nuclear magnetic resonance (ssNMR) spectroscopy under magic-angle spinning (MAS) to study the apo form of recombinant mouse TSPO (mTSPO) reconstituted in lipids. This environment has been previously described to permit binding of its high-affinity drug ligand PK11195 and appears therefore favourable for the study of molecular dynamics. We have optimized the physical conditions to get the best resolution for MAS ssNMR spectra of the ligand-free mTSPO. We have compared and combined various ssNMR spectra to get dynamical information either for the lipids or for the mTSPO. Partial assignment of residue types suggests few agreements with the published solution NMR assignment of the PK11195-bound mTSPO in DPC detergent. Moreover, we were able to observe some lateral chains of aromatic residues that were not assigned in solution. 13C double-quantum NMR spectroscopy shows remarkable dynamics for ligand-free mTSPO in lipids which may have significant implications on the recognition of the ligand and/or other protein partners.
Published: 2022

2. Natural abundance oxygen-17 solid-state NMR of metal organic frameworks enhanced by dynamic nuclear polarization

Author: Diego Carnevale, Geoffrey Bodenhausen, Sujing Wang, Daniel Abergel, Christian Serre, Georges Mouchaham, Mathieu Baudin, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-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)-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)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - 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), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Mouchaham, Georges
Subjects: Materials science, Diego, General Physics and Astronomy, Protonation, 010402 general chemistry, 01 natural sciences, Magic Angle Spinning, chemistry.chemical_compound, Carnevale, Wang, Baudin, [CHIM]Chemical Sciences, Carboxylate, Physical and Theoretical Chemistry, Polarization (electrochemistry), Bodenhausen, Metal-Organic Frameworks, Sujing, Oxygen-17, Dynamic Nuclear Polarization, [CHIM.MATE] Chemical Sciences/Material chemistry, Mathieu, 010405 organic chemistry, Christian, Chemical shift, Serre, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, Zirconium-Oxo Clusters, 0104 chemical sciences, Geoffrey, chemistry, Solid-state nuclear magnetic resonance, Chemical physics, Physical chemistry, Oxygen-17 NMR, Metal-organic framework, Density functional theory, Mouchaham, Georges, Solid-State NMR
Abstract: International audience; The 17 O resonances of Zirconium-oxo clusters that can be found in porous Zr carboxylate metal-organic frameworks (MOFs) have been investigated by magic-angle spinning (MAS) NMR spectroscopy enhanced by dynamic nuclear polarization (DNP). High-resolution 17 O spectra at 0.037 % natural abundance could be obtained in 48 hours, thanks to DNP enhancement of the 1 H polarization by factors   = S with /S without = 28, followed by 1 H 17 O cross-polarization, allowing a saving in experimental time by a factor of ca. 800. The distinct 17 O sites from the oxo-clusters can be resolved at 18.8 T. Their assignment is supported by density functional theory (DFT) calculations of chemical shifts and quadrupolar parameters. Protonation of 17 O sites seems to be leading to large characteristic shifts. Markedly, natural abundance 17 O NMR spectra of diamagnetic MOFs can thus be used to probe and characterize the local environment of different 17 O sites on an atomic scale.
Published: 2021

3. Building responsive materials by assembling {Fe4Co4} switchable molecular cubes

Author: Rodrigue Lescouëzec, Damien Dambournet, Olaf J. Borkiewicz, Yanling Li, Juan-Ramón Jiménez, Alexandrine Flambard, Laurent Lisnard, Laure Catala, Jana Glatz, Antoine Tissot, Rémi Plamont, Lise-Marie Chamoreau, Amina Benchohra, Marie-Laure Boillot, Qui Pham Xuan, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Argonne National Laboratory [Lemont] (ANL), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), 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), and Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Molecular model, 010405 organic chemistry, Ligand, Precipitation (chemistry), General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Scorpionate ligand, 01 natural sciences, 0104 chemical sciences, Electron transfer, Paramagnetism, Chemical engineering, Materials Chemistry, Cube
Abstract: International audience; Responsive materials that can answer to chemical or physical external stimuli offer numerous prospects in material science. Here, we have elaborated a two-step synthetic approach that allows incorporating molecular cubic switches into a polymeric material. Firstly, a preformed half-capped, Cs+-templated {Fe4Co4} cyanido-polymetallic cubic unit (“pro-cube”) is obtained and proven to be stable in solution, as demonstrated by paramagnetic NMR. Secondly, the reaction of the pro-cube with a ditopic scorpionate ligand enables the precipitation of a polymeric network containing the cubic unit. Furthermore, the adequately chosen ditopic ligand that coordinates the Co ions of the pro-cube allows us to preserve the switchable properties of the cubic unit. Indeed, the magnetic properties of the polymeric material compare well with those of the molecular cubic model that is obtained by reacting a non-bridging scorpionate ligand, and that was prepared as a reference. Both the polymeric material and the molecular model cube show a thermally-induced metal–metal electron transfer near room temperature. Interestingly, the magnetic state of the polymeric material is shown to depend on its hydration state, indicating its capability to act as a chemo-sensor.
Published: 2021

4. Evaluation of the compounds commonly known as superoxide dismutase and catalase mimics in cellular models

Author: Marion Thauvin, Clotilde Policar, Ines Batinic-Haberle, Nicolas Delsuc, Emilie Mathieu, Philippe Seksik, Elodie Quévrain, Sarah Layani, Amandine Vincent, Sophie Vriz, Laboratoire des biomolécules (LBM UMR 7203), 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)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Centre interdisciplinaire de recherche en biologie (CIRB), Labex MemoLife, 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), Centre de Recherche Saint-Antoine (CR Saint-Antoine), Sorbonne Université (SU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-CHU Saint-Antoine [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU), Department of Radiation Oncology [Durham, NC, USA], Duke University Medical Center, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), 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), Centre de Recherche Saint-Antoine (CRSA), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU), and delsuc, nicolas
Subjects: Porphyrins, Metalloporphyrins, 010402 general chemistry, medicine.disease_cause, 01 natural sciences, Biochemistry, Antioxidants, Cell Line, Inorganic Chemistry, Superoxide dismutase, chemistry.chemical_compound, Imisopasem Manganese, Superoxides, [CHIM] Chemical Sciences, Organometallic Compounds, medicine, Animals, Humans, [CHIM]Chemical Sciences, Cellular localization, chemistry.chemical_classification, Glutathione Peroxidase, Manganese, Reactive oxygen species, biology, Superoxide Dismutase, 010405 organic chemistry, Superoxide, Glutathione peroxidase, Molecular Mimicry, Hydrogen Peroxide, Catalase, 0104 chemical sciences, Oxidative Stress, chemistry, biology.protein, Reactive Oxygen Species, Oxidation-Reduction, Oxidative stress
Abstract: Oxidative stress that results from an imbalance between the concentrations of reactive species (RS) and antioxidant defenses is associated with many pathologies. Superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase are among the key enzymes that maintain the low nanomolar physiological concentrations of superoxide and hydrogen peroxide. The increase in the levels of these species and their progeny could have deleterious effects. In this context, chemists have developed SOD and CAT mimics to supplement them when cells are overwhelmed with oxidative stress. However, the beneficial activity of such molecules in cells depends not only on their intrinsic catalytic activities but also on their stability in biological context, their cell penetration and their cellular localization. We have employed cellular assays to characterize several compounds that possess SOD and CAT activities and have been frequently used in cellular and animal models. We used cellular assays that address SOD and CAT activities of the compounds. Finally, we determined the effect of compounds on the suppression of the inflammation in HT29-MD2 cells challenged by lipopolysaccharide. When the assay requires penetration inside cells, the SOD mimics Mn(III) meso-tetrakis(N-(2′-n-butoxyethyl)pyridinium-2-yl)porphyrin (MnTnBuOE-2-PyP5+) and Mn(II) dichloro[(4aR,13aR,17aR,21aR)-1,2,3,4,4a,5,6,12,13,13a,14,15,16,17,17a,18,19,20,21,21a-eicosahydro-11,7-nitrilo-7Hdibenzo[b,h] [1,4, 7,10] tetraazacycloheptadecine-κN5,κN13,κN18,κN21,κN22] (Imisopasem manganese, M40403, CG4419) were found efficacious at 10 μM, while Mn(II) chloro N-(phenolato)-N,N′-bis[2-(N-methyl-imidazolyl)methyl]-ethane-1,2-diamine (Mn1) requires an incubation at 100 μM. This study thus demonstrates that MnTnBuOE-2-PyP5+, M40403 and Mn1 were efficacious in suppressing inflammatory response in HT29-MD2 cells and such action appears to be related to their ability to enter the cells and modulate reactive oxygen species (ROS) levels.
Published: 2021

5. Stability and degradation of PEO20PPO70PEO20 triblock copolymers in mesostructured silica

Author: Sandra Casale, Bénédicte Lebeau, Brindusa Dragoi, François Ribot, Guillaume Laurent, Anne Davidson, Mohamed Selmane, David Kreher, Taissire Benamor, Cédric Boissière, Patrick Schmidt, Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Alexandru Ioan Cuza University of Iași [Romania], Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-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)-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), Centre de Biotechnologie de Borj Cédria (Hammam-Lif, Tunisie), Matériaux Hybrides et Procédés (LCMCP-MHP ), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Novel Advanced Nano-Objects (LCMCP-NANO), Institut des matériaux de Paris-Centre (IMPC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Eberhard Karls Universität Tübingen = Eberhard Karls University of Tuebingen, Chimie des polymères (LCP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Paris-Ile-de-France - SESAME program (700 MHz spectrometer), PERFORM-ERA ‘‘Post- doctoral Performance for Integration in the European Research Area’’ (ID-57649), financed by the European Social Fund and the Romanian Government, Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Laurent, Guillaume
Subjects: [CHIM.POLY] Chemical Sciences/Polymers, Materials science, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biomaterials, Hydrolysis, chemistry.chemical_compound, Materials Chemistry, Copolymer, Propylene oxide, ordered, P123, structured, [CHIM.MATE] Chemical Sciences/Material chemistry, Ethylene oxide, Precipitation (chemistry), technology, industry, and agriculture, template, General Chemistry, NIR, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Decomposition, NMR, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Spray drying, Ceramics and Composites, Self-assembly, 0210 nano-technology
Abstract: International audience; Organic−inorganic hybrid mesostructured silicas are prepared, without stirring (at pH = 0.0) and with stirring (at pH = 0.6) to obtain isolated and gyroidal-like attached silica grains with incorporated triblock P123 poly (ethylene oxide)-poly (propylene oxide)–poly (ethylene oxide) copolymers. Selected hybrids are submitted to various thermal and aging treatments for studying hydrolysis and oxidation of PEO and PPO chains. Two complementary spectroscopic techniques are used: near-infrared (NIR) with measurements performed in diffuse reflectance, as well as 1H and 13C liquid- and solid-state nuclear magnetic resonance (NMR) to study the mobility and stability of PEO and PPO chains. With precipitated fresh hybrids, the ratio of PEO over (PEO + PPO) units is lower (30% ± 5%) than in theory. This ratio also decreases depending on temperature when a hydrothermal treatment is applied. An acidic hydrolysis involving both PEO and PPO chains, with generated fragments eliminated by washing with water and/or synthesis liquor, is then demonstrated. For comparison, another hybrid obtained by spray drying via evaporation-induced self assembly mechanism is also studied. Its NMR signals are much more stable than those of the samples prepared by precipitation. Depending on aging time, thermal history, and materials processing, the textural properties and template decomposition inside mesostructured silica are found significantly different. The influence of the hydrolysis and oxidation of the template onto final materials texture is likely to be as important as the processing conditions.
Published: 2019

6. Electric sampling of soot particles in spreading non-premixed flames: methodology and influence of gravity

Author: Li, Yutao, Bordino, Antoine, Guibaud, Augustin, Montero, David, Citerne, Jean-Marie, Consalvi, Jean-Louis, Torero, Jose, Legros, Guillaume, Institut Jean Le Rond d'Alembert (DALEMBERT), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), École polytechnique (X), University College of London [London] (UCL), Institut des matériaux de Paris-Centre (IMPC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut universitaire des systèmes thermiques industriels (IUSTI), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS - CNRS), and GDR 2799 Micropesanteur Fondamentale & Appliquée
Subjects: Soot sampling, Mechanics of Materials, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, Soot morphology, Fire safety, General Materials Science, Flame spread, Microgravity
Abstract: International audience; Finer strategies of spacecraft fire mitigation require more experimental data related to fire detection. Fire detection systems developed on Earth rely massively on the optical detection of soot particles, which are present in the smoke. To detect the fire correctly, it is thus important to know how the optical properties of these particles are affected in reduced gravity. With different transport processes and increased residence time, soot in reduced gravity can be different from those produced at normal gravity. As their optical properties are related to their morphological properties, a better understanding about the evolution of soot particle morphology in flames under microgravity conditions is required. Within this context, a novel technique of soot sampling using electric field is applied to a spreading non-premixed flame at normal and micro-gravity. The soot particles sampled are observed subsequently under Transmission Electron Microscopy (TEM). Density, soot particle projected area, radius of gyration, fractal dimension, and primary particle size are extracted and the influence of gravity is investigated with the evolution of these morphological properties within the flame. Though the present study cannot be conclusive in itself, the similarity between the evolution of the optical density measured throughout the flame just before the electric perturbation required by the sampling technique and the evolution of the amount of soot deposited due to the electric perturbation along the sampling plates supports the future works that need to be devoted to further assess the consistency of the technique.
Published: 2023

7. Myogenic Progenitor Cells Exhibit Type I Interferon-Driven Proangiogenic Properties and Molecular Signature During Juvenile Dermatomyositis

Author: Stéphane Germain, Patrick Nusbaum, Darragh Duffy, Brigitte Bader-Meunier, Cyril Gitiaux, Christine Bodemer, Mathieu P Rodero, Michèle Weiss-Gayet, Guy Mouchiroud, Claire Latroche, Christophe Glorion, Isabelle Desguerre, Bénédicte Chazaud, Jamel Chelly, Institut Cochin (IC UM3 (UMR 8104 / U1016)), Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), CHU Necker - Enfants Malades [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP), Filière Neuromusculaire (FILNEMUS), Institut NeuroMyoGène (INMG), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Imagine - Institut des maladies génétiques (IMAGINE - U1163), Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), Immunobiologie des Cellules dendritiques, Institut Pasteur [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM), Hôpital Cochin [AP-HP], 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))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), This work was funded by INSERM, CNRS, Université Paris Descartes and Université Claude Bernard Lyon 1, by EU FP7 Endostem (#241440) and by Association Française contre les Myopathies (grant #18003). CGi was supported by a Poste d'Accueil APHP/CNRS, European Project: 241440,EC:FP7:HEALTH,FP7-HEALTH-2009-single-stage,ENDOSTEM(2010), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Centre de Référence pour les Maladies Neuromusculaires, Hôpital Raymond Poincaré [AP-HP]-CHU Henri Mondor-CHU Necker - Enfants Malades [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Filière Neuromusculaire (FILNEMUS), Laboratory of neurogenetics and neuroinflammation (Equipe Inserm U1163), Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), 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 Paris sciences et lettres (PSL)-Collège de France (CdF (institution))-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), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Vougny, Marie-Christine, Activation of vasculature associated stem cells and muscle stem cells for the repair and maintenance of muscle tissue - ENDOSTEM - - EC:FP7:HEALTH2010-01-01 - 2014-12-31 - 241440 - VALID, Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut Pasteur [Paris] (IP)-Institut National de la Santé et de la Recherche Médicale (INSERM), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), ANR-16-CE17-0005,GENMSMD,Dissection génétique de la Susceptibilité Mendélienne aux infections mycobactériennes chez l'homme(2016), ANR-16-CE17-0010,IFNX,Investigation des interferonopathies type I humaine(2016), Institut Mondor de Recherche Biomédicale (IMRB), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-IFR10, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut Pasteur [Paris], CHU Cochin [AP-HP], Service d'immuno-hématologie pédiatrique [CHU Necker], and Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-CHU Necker - Enfants Malades [AP-HP]
Subjects: 0301 basic medicine, Male, MESH: Interferon Type I, Angiogenesis, [SDV]Life Sciences [q-bio], Cell Culture Techniques, MESH: Dermatomyositis, MESH: Child, Immunology and Allergy, MESH: Endothelial Cells, Muscular dystrophy, Child, Juvenile dermatomyositis, ComputingMilieux_MISCELLANEOUS, MESH: Muscle, Skeletal, Neovascularization, Pathologic, Stem Cells, Immunohistochemistry, medicine.anatomical_structure, Child, Preschool, Interferon Type I, [SDV.IMM]Life Sciences [q-bio]/Immunology, Female, Stem cell, medicine.symptom, Cell Migration Assays, medicine.drug, [SDV.IMM] Life Sciences [q-bio]/Immunology, Immunology, MESH: Stem Cells, Biology, Dermatomyositis, 03 medical and health sciences, MESH: Gene Expression Profiling, Rheumatology, MESH: Cell Proliferation, medicine, MESH: Muscular Dystrophy, Duchenne, Humans, Progenitor cell, Myopathy, Muscle, Skeletal, Cell Proliferation, MESH: Cell Culture Techniques, MESH: Humans, Gene Expression Profiling, MESH: Child, Preschool, Skeletal muscle, Endothelial Cells, MESH: Immunohistochemistry, medicine.disease, MESH: Male, Muscular Dystrophy, Duchenne, 030104 developmental biology, MESH: Cell Migration Assays, MESH: Neovascularization, Pathologic, MESH: Female, Interferon type I
Abstract: Objective Juvenile dermatomyositis (JDM) is an inflammatory pediatric myopathy characterized by focal capillary loss in muscle, followed by progressive recovery upon adequate treatment with immunomodulating drugs, although some patients remain refractory to treatment. While the underlying mechanism of capillary depletion remains uncertain, recent studies have identified an up-regulation of type I interferon (IFN) expression specific to JDM. Given that myogenic precursor cells (MPCs) exert proangiogenic activity during normal skeletal muscle regeneration, we hypothesized that they may also modulate vascular remodeling/angiogenesis during JDM. The aim of this study was to investigate that hypothesis. Methods Human cell cocultures were used to analyze angiogenic properties in patients with JDM, patients with Duchenne's muscular dystrophy (DMD) (control patients for vascular remodeling), and healthy control subjects. Transcriptome analysis was used to examine muscle-derived MPCs. Histologic analysis of type I IFN in muscle biopsy samples was also performed. Results Using human cell cocultures, we showed highly angiogenic properties of MPCs from JDM patients in association with the expression of an angiogenic molecular signature. Transcriptome analysis of MPCs freshly isolated from muscle samples revealed type I IFN as the master regulator of the most up-regulated genes in JDM-derived MPCs. Functionally, treatment of normal MPCs with type I IFN recapitulated the molecular pattern and the proangiogenic functions of JDM-derived MPCs. In vivo histologic investigation showed that MPCs synthesized type I IFN and major proangiogenic molecules in JDM muscle. Moreover, MPCs derived from JDM muscles that were characterized by strong vasculopathy produced higher levels of type I IFN, confirming MPCs as a cellular source of type I IFN during JDM, and this correlated with the severity of the disease. Conclusion These results demonstrate a new type I IFN pathway in JDM that activates the production of angiogenic effectors by MPCs, triggering their proangiogenic function to promote vessel recovery and muscle reconstruction.
Published: 2018

8. Assessing the Extent of Potential Inversion by Cyclic Voltammetry: Theory, Pitfalls, and Application to a Nickel Complex with Redox-Active Iminosemiquinone Ligands

Author: Cheriehan Hessin, Jules Schleinitz, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Vincent Fourmond, Marine Desage-El Murr, Christophe Léger, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Bioénergétique et Ingénierie des Protéines (BIP ), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Potential inversion refers to the situation where a protein cofactor or a synthetic molecule can be oxidized or reduced twice in a cooperative manner, that is the second electron transfer (ET) is easier than the first. This property is very important regarding the catalytic mechanism of enzymes that bifurcate electrons and the properties of bidirectional redox molecular catalysts that function in either direction of the reaction with no overpotential. Cyclic voltammetry is the most common technique for characterizing the thermodynamics and kinetics of ET to or from these molecules. However, a gap in the literature is the absence of analytical predictions to help interpret the values of the voltammetric peak potentials when potential inversion occurs ; the cyclic voltammograms are therefore often analyzed by simulating the data, with no discussion of the possibility of overfitting and often no estimation of the error on the determined parameters. Here we formulate the theory for the voltammetry of freely-diffusing or surface-confined two-electron redox species in the experimentally relevant irreversible limit where the peak separation depends on scan rate. We explain why the model is intrinsically underdetermined, and we illustrate this conclusion by the analysis of the voltammetry of a Ni complex with redox-active iminosemiquinone ligands. Being able to characterize the thermodynamics of two-electron transfer reactions will be crucial for designing more efficient catalysts.
Published: 2023

9. Hierarchical superparamagnetic metal–organic framework nanovectors as anti-inflammatory nanomedicines

Author: Heng Zhao, Saad Sene, Angelika M. Mielcarek, Sylvain Miraux, Nicolas Menguy, Dris Ihiawakrim, Ovidiu Ersen, Christine Péchoux, Nathalie Guillou, Joseph Scola, Jean-Marc Grenèche, Farid Nouar, Simona Mura, Florent Carn, Florence Gazeau, Eddy Dumas, Christian Serre, Nathalie Steunou, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Centre de résonance magnétique des systèmes biologiques (CRMSB), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), 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, 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), Université Paris-Saclay, Génétique Animale et Biologie Intégrative (GABI), AgroParisTech-Université Paris-Saclay-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Groupe d'Etude de la Matière Condensée (GEMAC), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)
Subjects: Biomedical Engineering, [CHIM]Chemical Sciences, General Materials Science, General Chemistry, General Medicine
Abstract: International audience; Among a plethora of drug nanocarriers, biocompatible nanoscale metal-organic frameworks (nanoMOFs) with a large surface area and an amphiphilic internal microenvironment have emerged as promising drug delivery platforms, mainly for cancer therapy. However, their application in biomedicine still suffers from shortcomings such as a limited chemical and/or colloidal stability and/or toxicity. Here, we report the design of a hierarchically porous nano-object (denoted as USPIO@MIL) combining a benchmark nanoMOF (that is, MIL-100(Fe)) and ultra-small superparamagnetic iron oxide (USPIO) nanoparticles (that is, maghemite) that is synthesized through a one-pot, cost-effective and environmentally friendly protocol. The synergistic coupling of the physico-chemical and functional properties of both nanoparticles confers to these nano-objects valuable features such as high colloidal stability, high biodegradability, low toxicity, high drug loading capacity as well as stimuli-responsive drug release and superparamagnetic properties. This bimodal MIL-100(Fe)/maghemite nanocarrier once loaded with anti-tumoral and anti-inflammatory drugs (doxorubicin and methotrexate) shows high anti-inflammatory and anti-tumoral activities. In addition, the USPIO@MIL nano-object exhibits excellent relaxometric properties and its applicability as an efficient contrast agent for magnetic resonance imaging is herein demonstrated. This highlights the high potential of the maghemite@MOF composite integrating the functions of imaging and therapy as a theranostic anti-inflammatory formulation.
Published: 2023

10. Adsorption and dynamics of linear and mono-branched hexane isomers in MIL-140 metal–organic frameworks

Author: Hengli Zhao, José A. C. Silva, Adriano Henrique, Farid Nouar, Christian Serre, Guillaume Maurin, Aziz Ghoufi, Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Icahn School of Medicine at Mount Sinai [New York] (MSSM), Universidade do Porto = University of Porto, Centro de Investigação de Montanha [Bragança, Portugal] (CIMO), Instituto Politécnico de Bragança, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)
Subjects: [PHYS]Physics [physics], [CHIM]Chemical Sciences, General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract: International audience; Recent breakthrough experiments revealed the iso-reticular Zr-MOFs, MIL-140B and MIL-140C, as promising sorbents for the separation of C6 isomers.
Published: 2023

11. Dual Thermo- and pH-Responsive N-Cyanomethylacrylamide-Based Nano-Objects Prepared by RAFT-Mediated Aqueous Polymerization-Induced Self-Assembly

Author: Nicolas Audureau, Fanny Coumes, Jean-Michel Guigner, Clément Guibert, François Stoffelbach, Jutta Rieger, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), and Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, vesicles, RAFT polymerization, Polymers and Plastics, Organic Chemistry, PISA, Materials Chemistry, [CHIM]Chemical Sciences
Abstract: International audience; We report the straightforward synthesis of dual stimuli-responsive nano-objects using a RAFT-mediated polymerization-induced self-assembly (PISA) process in water. The key to complex and tunable responsiveness was the copolymerization of N-cyanomethylacrylamide, providing UCST-type polymers, with a pH-sensitive monomer (acrylic acid, AA). Not only the core block length, but also the acrylic acid content and slight changes in the degree of ionization of AA (αAA,0) in the polymerization medium had a great impact on the particle morphology. Generally, higher AA contents favored the formation of spherical nano-objects, while low αAA,0 led to higher order morphologies. We demonstrated that the nano-objects exhibited a complex dual responsiveness to changes in the degree of ionization and temperature. Progressively increasing post-polymerization the degree of ionization of the AA units incorporated in the copolymer (αAA) triggered morphological transitions. Remarkably, a single copolymer composition formed well-defined vesicles, worms, and spheres that eventually dissociated into individual chains. Temperature-dependent SAXS analyses evidenced a complex thermo-responsive behavior, which depended on the copolymer composition and αAA. For some compositions, we observed both a cloud and a clearing point, attributed to the formation of secondary aggregates and chain dissolution, respectively.
Published: 2022

12. In Situ Synthesis of a Mesoporous MIL-100(Fe) Bacteria Exoskeleton

Author: Anastasia Permyakova, Alshaba Kakar, Jonathan Bachir, Effrosyni Gkaniatsou, Bernard Haye, Nicolas Menguy, Farid Nouar, Christian Serre, Nathalie Steunou, Thibaud Coradin, Francisco M. Fernandes, Clémence Sicard, 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), Matériaux et Biologie (LCMCP-MATBIO), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-19-CE08-0023,EMERGE,Conception de matériaux bio-hybrides associant entités biologiques et Metal-Organic Frameworks pour des applications environnementales(2019), and ANR-17-CE08-0009,CellsInFoams,Mousses macroporeuses cœur-coquille pour l'encapsulation de bactéries(2017)
Subjects: Synthesised, Two-component, Bacteria, Pseudomonas putida, General Chemical Engineering, Biomedical Engineering, Membrane integrity, Mesoporous, MIL-100, In-situ synthesis, Aqueous media, Exoskeleton (Robotics), Polycarboxylates, [CHIM]Chemical Sciences, General Materials Science, Cytology, Condition
Abstract: International audience; The mesoporous iron polycarboxylate MIL-100(Fe) was synthesized in the presence of Pseudomonas putida bacteria. The synthesis was performed under green conditions, i.e., pure aqueous media at 30 °C that were compatible with the preservation of the cell membrane integrity. Interestingly, the resulting biohybrid exhibited a very different microstructure than a physical mixture of the two components, as it led to the formation of a novel living material featuring an exoskeleton encapsulating individual bacteria cell. Remarkably, TEM and STEM observations on cross sections revealed that this shell was not directly in contact with the cell wall, suggesting the exopolysaccharides network promotes strong interactions with the MOF precursors, leading to high proximity between the two components.
Published: 2022

13. Solvothermal Synthesis, Temperature-Dependent Structural Study, and Magnetic Characterization of a Multipolydentate Oxamate-Based 2D Coordination Network

Author: Ang Li, Lise-Marie Chamoreau, Benoît Baptiste, Ludovic Delbes, Yanling Li, Francesc Lloret, Yves Journaux, Laurent Lisnard, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular (ICMol), and Universitat de València (UV)
Subjects: [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Condensed Matter Physics
Abstract: International audience; A multi-polydentate N-substituted oxamate ligand bearing an additional carboxylato group has been successfully reacted in solvothermal conditions to form the 2D coordination network (TMA) 3 [CuMn(paba) 2 (OAc)]•8H 2 O (1). This coordination network displays a brick-wall type morphology with, thanks to the augmented connectivity of the ligand, a lower than usual metal ion nuclearity for the building sub-unit. Temperature-dependent structural studies indicate that the layered structure undergoes dehydration at 90°C and remain stable up to 200°C. Magnetic characterizations show that 1 behaves as a ferrimagnet, with a Curie temperature of 2.8 K.
Published: 2022

14. Characterization through scanning electron microscopy and μFourier transform infrared spectroscopy of microcalcifications present in fine needle aspiration smears

Author: Henry, Lucas, Bazin, Dominique, Policar, Clotilde, Haymann, Jean-Philippe, Daudon, Michel, Frochot, Vincent, Mathonnet, Muriel, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL), Sorbonne Université (SU), Université Paris-Saclay, Laboratoire de Physique des Solides (LPS), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Service d'Explorations fonctionnelles multidisciplinaires [CHU Tenon], CHU Tenon [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU), Des Maladies Rénales Rares aux Maladies Fréquentes, Remodelage et Réparation, Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Hôpital Dupuytren [CHU Limoges], ENS-PSL (LH's PhD fellowship)Fondation pour la Recherche Biomédicale (project DEI20151234413), and Policar, Clotilde
Subjects: Thyroid, [CHIM.INOR] Chemical Sciences/Inorganic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Microscopie électronique à balayage, Spectroscopie infrarouge, Nodule, Smears, Building and Construction, Ponctions, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Scanning electron microscopy. Mots-clés. Thyroïde, [CHIM.OTHE] Chemical Sciences/Other, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electrical and Electronic Engineering, [CHIM.OTHE]Chemical Sciences/Other, Infrared spectroscopy
Abstract: International audience; In this contribution, we have characterized for the first time (to the best of our knowledge), microcalcifications present in fine needle aspiration (FNA) smears of thyroid nodules. Abnormal deposits were analysed through Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscopy (FE-SEM) in order to obtain their chemical composition as well as their morphology at the micrometer scale. Thirty-one samples coming from 13 patients were investigated comprising five cases of papillary carcinoma, two of Graves’ disease, and six of adenomatous goitre. The smears were also stained for analysis of the cellular characteristics of these lesions for classifying according to the Bethesda classification. Two mineral species, amorphous and nanocrystallised apatite calcium phosphate, have been identified with very different morphologies. Moreover, FE-SEM observations at the micrometer scale underline the presence of different kinds of abnormal deposits.
Published: 2022

15. Efficient 18.8 T MAS-DNP NMR reveals hidden side chains in amyloid fibrils

Author: Lends, Alons, Birlirakis, Nicolas, Cai, Xinyi, Daskalov, Asen, Shenoy, Jayakrishna, Abdul-Shukkoor, Muhammed Bilal, Berbon, Mélanie, Ferrage, Fabien, Liu, Yangping, Loquet, Antoine, Tan, Kong Ooi, Université de Bordeaux (UB), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Tianjin Medical University, ANR-20-ERC9-0008,PulsedDNP,PulsedDNP: faire progresser la sensibilité RMN au-delà du DNP à ondes continues(2020), ANR-21-CE29-0019,HFPulsedDNP,Polarisation Nucléaire Dynamique Pulsée à Haut Champ(2021), and European Project: 639020,H2020,ERC-2014-STG,Weakinteract(2015)
Subjects: Dynamic Nuclear Polarization, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Amyloid Fibrils, Solid-State NMR
Abstract: International audience; Amyloid fibrils are large and insoluble protein assemblies composed of a rigid core associated with a cross-beta arrangement rich in beta-sheet structural elements. It has been widely observed in solid-state NMR experiments that semi-rigid protein segments or side chains do not yield easily observable NMR signals at room temperature. The reasons for the missing peaks may be due to the presence of unfavorable dynamics that interfere with NMR experiments, which result in very weak or unobservable NMR signals. Therefore, for amyloid fibrils, semi-rigid and dynamically disordered segments flanking the amyloid core are very challenging to study. Here, we show that high-field dynamic nuclear polarization (DNP), an NMR hyperpolarization technique typically performed at low temperatures, can circumvent this issue because (i) the low-temperature environment (~ 100 K) slows down the protein dynamics to escape unfavorable detection regime, (ii) DNP improves the overall NMR sensitivity including flexible side chains, and (iii) efficient cross-effect DNP biradicals (SNAPol-1) optimized for high-field DNP ( 18.8 T) are employed to offer high sensitivity and resolution suitable for biomolecular NMR applications. By combining these factors, we have successfully recorded an unprecedented enhancement factor of ε~50 on amyloid fibrils using an 18.8 T/ 800 MHz magnet. We have compared the DNP efficiencies of M-TinyPol, NATriPol-3, and SNAPol-1 biradicals on amyloid fibrils. We found that SNAPol-1 (with ε~50) outperformed the other two radicals. The MAS DNP experiments revealed signals of flexible side chains previously inaccessible at conventional room-temperature experiments. These results demonstrate the potential of MAS-DNP NMR as a valuable tool for structural investigations of amyloid fibrils, particularly for side chains and dynamically disordered segments otherwise hidden at room temperature.
Published: 2023

16. Thermally Switchable Nanogate Based on Polymer Phase Transition

Author: Pauline J. Kolbeck, Dihia Benaoudia, Léa Chazot-Franguiadakis, Gwendoline Delecourt, Jérôme Mathé, Sha Li, Romeo Bonnet, Pascal Martin, Jan Lipfert, Anna Salvetti, Mordjane Boukhet, Véronique Bennevault, Jean-Christophe Lacroix, Philippe Guégan, Fabien Montel, Laboratoire de Physique de l'ENS Lyon (Phys-ENS), École normale supérieure de Lyon (ENS de Lyon)-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Analyse, Modélisation et Matériaux pour la Biologie et l'Environnement (LAMBE - UMR 8587), Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY), Utrecht University [Utrecht], 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), Technische Universität Dresden = Dresden University of Technology (TU Dresden), and CNRS 80 Prime NanoViro
Subjects: biomolecule filtration, [CHIM.POLY]Chemical Sciences/Polymers, [PHYS.PHYS.PHYS-BIO-PH]Physics [physics]/Physics [physics]/Biological Physics [physics.bio-ph], Mechanical Engineering, thermoresponsive polymer, coil−globule transition, General Materials Science, Bioengineering, General Chemistry, nanopore, zero-mode waveguide, Condensed Matter Physics
Abstract: International audience; Mimicking and extending the gating properties of biological pores is of paramount interest for the fabrication of membranes that could be used in filtration or drug processing. Here, we build a selective and switchable nanopore for macromolecular cargo transport. Our approach exploits polymer graftings within artificial nanopores to control the translocation of biomolecules. To measure transport at the scale of individual biomolecules, we use fluorescence microscopy with a zero-mode waveguide set up. We show that grafting polymers that exhibit a lower critical solution temperature creates a toggle switch between an open and closed state of the nanopore depending on the temperature. We demonstrate tight control over the transport of DNA and viral capsids with a sharp transition (∼1 °C) and present a simple physical model that predicts key features of this transition. Our approach provides the potential for controllable and responsive nanopores in a range of applications.
Published: 2023

17. Experimental observation of the role of countercations on the electrical conductance of Preyssler-type polyoxometalate nanodevices

Author: Huez, Cécile, Renaudineau, Séverine, Volatron, Florence, Proust, Anna, Vuillaume, Dominique, Nanostructures, nanoComponents & Molecules - IEMN (NCM - IEMN), 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)-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), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and CNRS (France), project neuroPOM, under a grant of the 80PRIME program.
Subjects: [PHYS]Physics [physics], Condensed Matter - Mesoscale and Nanoscale Physics, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), FOS: Physical sciences, General Materials Science, Applied Physics (physics.app-ph), Physics - Applied Physics
Abstract: Polyoxometalates are nanoscale molecular oxides with promising properties that are currently explored for molecule-based memory devices. In this work, we synthesize a series of Preyssler polyoxometalates (POMs), (Na-P5W30O110)14-,stabilized with four different counterions, H+, K+, NH4+ and tetrabutylammonium (TBA+), and we study the electron transport properties at the nanoscale (conductive atomic force microscopy, C-AFM) of molecular junctions formed by self-assembled monolayers (SAMs) of POMs electrostatically deposited on ultraflat gold surface prefunctionalized with a positively charged SAM of amine-terminated alkylthiol chains. We report that the electron transport properties of P5W30-based molecular junctions depend on the nature of the counterions, the low-bias current (in the voltage range -0.6 V to 0.6 V) gradually increasing by a factor ca. 100 by changing the counterion in the order K+, NH4+, H+ and TBA+. From a statistical study (hundreds of current-voltage traces) using a simple analytical model for charge transport in nanoscale devices, we show that the energy position of the lowest unoccupied molecular orbital (LUMO) of the P5W30 with respect of the Fermi energy of the electrodes increases from ca. 0.4 eV to 0.7 eV and that that electrode coupling energy also increases from ca. 0.05 to 1 meV in the same order from K+, NH4+, H+ to TBA+. We discuss several hypotheses on the possible origin of these features, such as a counterion-dependent dipole at the POM/electrode interface and counterion-modulated molecule/electrode hybridization, with, in both cases, the largest effect in the case of TBA+ counterions., Preprint: full text, figures and supporting information
Published: 2023

18. Cathodic control using cellular automata approach

Author: Mariem Zenkri, Dung di Caprio, Fayçal Raouafi, Damien Féron, Laboratoire de Physicochimie des Matériaux - IPEST(La Marsa, Tunisia), Institut préparatoire aux études scientifiques et techniques [La Marsa] (IPEST), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Faculté des Sciences de Bizerte [Université de Carthage], Université de Carthage - University of Carthage, Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay
Subjects: corrosion, cellular automata, Mechanical Engineering, Metals and Alloys, General Medicine, cathodic control, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Mechanics of Materials, dissolved oxygen, Materials Chemistry, Environmental Chemistry, passivation, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat]
Abstract: International audience; We present a stochastic three dimensional cellular automata model of aqueous corrosion. We consider the cathodic reaction with dissolved oxygen and different concentrations of the oxidizer. We study the role and the stability of the passive layer and its effect on the kinetics, surface morphology and roughness of the metallic surface. The model considers balanced spatially separated anodic and cathodic reactions and is capable of illustrating the cathodic control of the corrosion rate. Besides the electrochemical reactions, we take into account ionic diffusion, acido/basic neutralization. Results are compared to aqueous corrosion of Fe in near neutral solution.
Published: 2022

19. Hydrophobic MOFs for the efficient capture of highly polar volatile organic compound

Author: Maria Inês Severino, Abeer Al Mohtar, Carla Vieira Soares, Oleksii Kolmykov, Cátia Freitas, Iurii Dovgaliuk, Charlotte Martineau, Vanessa Pimenta, Farid Nouar, Guillaume Maurin, Moisés L. Pinto, Christian Serre, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade de Lisboa = University of Lisbon (ULISBOA), Laboratoire de Nanotechnologie et d'Instrumentation Optique (LNIO), Institut Charles Delaunay (ICD), Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS)-Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), and Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Renewable Energy, Sustainability and the Environment, [CHIM]Chemical Sciences, General Materials Science, General Chemistry
Abstract: Effective capture of polar volatile organic compounds under environmental conditions is a challenge owing to the adsorption competition between polar volatile organic compounds and water.
Published: 2023

20. Identification of a human estrogen receptor α tetrapeptidic fragment with dual antiproliferative and anti-nociceptive action

Author: Baptiste Jouffre, Alexandre Acramel, Mathilde Belnou, Maria Francesca Santolla, Marianna Talia, Rosamaria Lappano, Fariba Nemati, Didier Decaudin, Lucie Khemtemourian, Wang-Qing Liu, Marcello Maggiolini, Alain Eschalier, Christophe Mallet, Yves Jacquot, Neuro-Dol (Neuro-Dol), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Clermont Auvergne (UCA), Cibles Thérapeutiques et conception de médicaments (CiTCoM - UMR 8038), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Investigation Pré-clinique (LIP), Institut Curie [Paris], Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Multidisciplinary, [SDV]Life Sciences [q-bio]
Abstract: The synthetic peptide ERα17p (sequence: PLMIKRSKKNSLALSLT), which corresponds to the 295–311 region of the human estrogen receptor α (ERα), induces apoptosis in breast cancer cells. In mice and at low doses, it promotes not only the decrease of the size of xenografted triple-negative human breast tumors, but also anti-inflammatory and anti-nociceptive effects. Recently, we have shown that these effects were due to its interaction with the seven-transmembrane G protein-coupled estrogen receptor GPER. Following modeling studies, the C-terminus of this peptide (sequence: NSLALSLT) remains compacted at the entrance of the GPER ligand-binding pocket, whereas its N-terminus (sequence: PLMI) engulfs in the depth of the same pocket. Thus, we have hypothesized that the PLMI motif could support the pharmacological actions of ERα17p. Here, we show that the PLMI peptide is, indeed, responsible for the GPER-dependent antiproliferative and anti-nociceptive effects of ERα17p. By using different biophysical approaches, we demonstrate that the NSLALSLT part of ERα17p is responsible for aggregation. Overall, the tetrapeptide PLMI, which supports the action of the parent peptide ERα17p, should be considered as a hit for the synthesis of new GPER modulators with dual antiproliferative and anti-nociceptive actions. This study highlights also the interest to modulate GPER for the control of pain.
Published: 2023

21. In Operando Spectroscopic Ellipsometry Investigation of MOF Thin Films for the Selective Capture of Acetic Acid

Author: Sanchari Dasgupta, Subharanjan Biswas, Kevin Dedecker, Eddy Dumas, Nicolas Menguy, Bruno Berini, Bertrand Lavedrine, Christian Serre, Cédric Boissière, Nathalie Steunou, 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), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Groupe d'Etude de la Matière Condensée (GEMAC), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche sur la Conservation (CRC ), Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Matériaux Hybrides et Procédés (LCMCP-MHP ), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by the Ecole Universitaire de recherche PSGS HCH Humanities, Creation, Heritage, Investissement d’Avenir ANR-17-EURE-0021 - Fondation des sciences du patrimoine. This work has been sponsored by the Ile-de-France Region in the framework of Respore, the Île-de-France network of Excellence in Porous Solids. The authors acknowledge Ali Saad for SEM experiments.
Subjects: Ellipsometry, adsorption, Thin films, [SDE]Environmental Sciences, [CHIM]Chemical Sciences, General Materials Science, Volatile organic compounds, MOFs
Abstract: International audience; The emission of polar volatile organic compounds (VOCs) is a major worldwide concern of air quality and equally impacts the preservation of cultural heritage (CH). The challenge is to design highly efficient adsorbents able to selectively capture traces of VOCs such as acetic acid (AA) in the presence of relative humidity (RH) normally found at storage in museums (40-80%). Although the selective capture of VOCs over water is still challenging, Metal-Organic Frameworks (MOFs) possess highly tunable features (Lewis, Bronsted or redox metal sites, functional groups, hydrophobicity…) suitable to selectively capture a large variety of VOCs. In this context, we have explored the adsorption efficiency of a series of MOFs thin films (ZIF-8(Zn), MIL-101(Cr) and UiO-66(Zr)-2CF3) for the selective capture of AA based on a UV/Vis and FT-IR spectroscopic ellip-sometry in operando study (2-6% of relative pressure of AA under 40% of RH), namely conditions close to the realistic envi-ronmental storage conditions of cultural artefacts. For that purpose, optical quality thin films of MOFs were prepared by dip-coating and their AA adsorption capacity and selectivity were evaluated under humid conditions by measuring the variation of the refractive index as a function of the vapor pressures while the chemical nature of the co-adsorbed analytes (water and AA) was identified by FT-IR ellipsometry. While thin films of ZIF-8(Zn) strongly degraded when exposed to AA/water va-pors, films of MIL-101(Cr) and UiO-66(Zr)-2CF3 present a high chemical stability under those conditions. It was shown that MIL-101(Cr) presents a high AA adsorption capacity due to its high pore volume, but exhibits a poor AA adsorption selectivi-ty under humid conditions. In contrast, UiO-66(Zr)-2CF3 was shown to overpass MIL-101(Cr) in terms of AA/ H2O adsorp-tion selectivity and AA adsorption/desorption cycling stability thanks to its high hydrophobic character, suitable pore size for adequate confinement and specific interactions.
Published: 2023

22. Charge-Driven Arrested Phase-Separation of Polyelectrolyte-Gold Nanoparticle Assemblies Leading to Plasmonic Oligomers

Author: Florent Voisin, Gérald Lelong, Jean Michel Guigner, Thomas Bizien, Jean Maurice Mallet, Florent Carn, 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), Beamline SWING, Synchrotron SOLEIL, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), IMPMC_Propriétés des amorphes, liquides et minéraux (IMPMC_PALM), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Lelong, Gerald, Matière et Systèmes Complexes (MSC), Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Propriétés des amorphes, liquides et minéraux [IMPMC] (IMPMC_PALM), ANR-10-LABX-0096,SEAM,Science and Engineering for Advanced Materials and devices(2010), and ANR-18-CE06-0006,COLIGOMERE,Oligomères colloidaux plasmoniques(2018)
Subjects: Ions, Chitosan, [CHIM.MATE] Chemical Sciences/Material chemistry, Metal Nanoparticles, [CHIM.MATE]Chemical Sciences/Material chemistry, Polyelectrolyte, Polyelectrolytes, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Biomaterials, Self-Assembly, Colloid and Surface Chemistry, Nanoparticle, Complexation, Gold, Particle Size
Abstract: International audience; Aggregates of charged metal particles obtained by electrostatic coupling with a compound of opposite charge in the vicinity of the net zero charge ratio are of interest in the field of plasmonics because the inter-particle distance is minimal, which favours plasmonic coupling. However, these structures present a low colloidal stability limiting the development of applications. In this article we show that globally neutral aggregates formed by electrostatic complexation of citrate-stabilized gold particles and a quaternized chitosan (i.e., polycation) around the net zero charge ratio could be stabilized at a nanometric size by the subsequent addition of polyelectrolyte chains. Furthermore, the sign of the charge carried by the stabilizing chains determines the sign of the global charge carried by the stabilized complexes. The stabilization is demonstrated in saline environment on a broad pH range as well as in a cell culture media over periods of several days. Contrarily to stabilization by charged particles, our stabilized complexes are found to retain their initial characteristics (i.e. shape, size, internal structure and optical properties) after stabilization. Hence, the plasmonic coupling allows to maximize the optical absorption around the 800 nm wavelength at which the lasers used for thermoplasmonic and surface enhanced Raman scattering analysis operate.
Published: 2023

23. Effect of amphiphilic environment on the solution structure of mouse TSPO translocator protein

Author: Sophie Combet, Françoise Bonneté, Stéphanie Finet, Alexandre Pozza, Christelle Saade, Anne Martel, Alexandros Koutsioubas, Jean-Jacques Lacapère, Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), LLB - Matière molle et biophysique (MMB), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de biologie physico-chimique des protéines membranaires (LBPC-PM (UMR_7099)), Institut de biologie physico-chimique (IBPC (FR_550)), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique et d'Acoustique [Marseille] (LMA ), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Institut Laue-Langevin (ILL), Jülich Centre for Neutron Science (JCNS), Forschungszentrum Jülich GmbH at Heinz Maier-Leibnitz Zentrum (MLZ), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and CNRS (MITI 2021 and Tremplin@ INP 2021)
Subjects: [SDV]Life Sciences [q-bio], ddc:540, General Medicine, Biochemistry
Abstract: International audience; The translocator protein (TSPO) is a ubiquitous transmembrane protein of great pharmacological interest thanks to its high affinity to many drug ligands. The only high-resolution 3D-structure known for mammalian TSPO was obtained by NMR for the mouse mTSPO in DPC detergent only in presence of the high-affinity PK 11195 ligand. An atomic structure of free-ligand mTSPO is still missing to better understand the interaction of ligands with mTSPO and their effects on the protein conformation.Here, we decipher the solution structures of the recombinant mTSPO without ligand both in (i) SDS, the detergent used to extract and purify the protein from E. coli inclusion bodies, and (ii) DPC, the detergent used to solve the PK 11195-binding mTSPO NMR structure.We report partially refolded and less flexible mTSPO helices in DPC compared to SDS. Besides, DPC stabilizes the tertiary structure of mTSPO, as shown by a higher intrinsic Trp fluorescence and changes in indole environment.We evaluate by SEC-MALLS that ∼135 SDS and ∼100 DPC molecules are bound to mTSPO. SEC-small-angle X-ray (SAXS) and neutron (SANS) scattering confirm a larger mTSPO-detergent complex in SDS than in DPC. Using the contrast-matching technique in SEC-SANS, we demonstrate that mTSPO conformation is more compact and less flexible in DPC than in SDS. Combining ab initio modeling with SANS, we confirm that mTSPO conformation is less elongated in DPC than in SDS. However, the free-ligand mTSPO envelope in DPC is not as compact as the PK 11195-binding protein NMR structure, the ligand stiffening the protein.
Published: 2023

24. Molten Salts‐Driven Discovery of a Polar Mixed‐Anion 3D framework at the nanoscale: Zn4Si2O7Cl2, Charge Transport and Photoelectrocatalytic Water Splitting

Author: Kumar, Ram, Song, Yang, Ghoridi, Anissa, Boullay, Philippe, Rousse, Gwenaelle, Gervais, Christel, Diogo, Cristina Coelho, Kabbour, Houria, Sassoye, Capucine, Beaunier, Patricia, Castaing, Victor, Viana, Bruno, Ruiz Gonzalez, Maria Luisa, Calbet, José Gonzalez, Laberty-Robert, Christel, Portehault, David, Novel Advanced Nano-Objects (LCMCP-NANO), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Fédération de Chimie et Matériaux de Paris-Centre (FCMat), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Université Paris sciences et lettres (PSL), Universidad Complutense de Madrid = Complutense University of Madrid [Madrid] (UCM), Reactive Materials for Electrochemical Systems (LCMCP-RMES ), and CNRS-CEA METSA network, Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357, GENCI-IDRIS (Grant 097535). Région Ile de France - SESAME
Subjects: electron crystallography, mixed anions, photoelectrocatalysis, molten salts, [CHIM.CRIS]Chemical Sciences/Cristallography, oxychloride, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract: International audience; Mixed-anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn4Si2O7Cl2. We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon-based connectors from a non-oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H2 evolution and water oxidation. This work then paves the way to a new family of mixed-anion solids
Published: 2023

25. Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization‐Induced Self‐Assembly

Author: Clément Debrie, Noémie Coudert, Jean‐Michel Guigner, Taco Nicolai, François Stoffelbach, Olivier Colombani, Jutta Rieger, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and ANR-19-CE06-0002,DYNAMIC-PISA,Auto-assemblage induit par la polymérisation: modulation de la dynamique d'échange des unimères pour contrôler la morphologie(2019)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, General Chemistry, General Medicine, Catalysis
Abstract: International audience; Polymerization-Induced Self-Assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that - unexpectedly - unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange.
Published: 2023

26. Enantiopure Cyclometalated Rh(III) and Ir(III) Complexes Displaying Rigid Configuration at Metal Center: Design, Structures, Chiroptical Properties and Role of the Iodide Ligand

Author: Antoine Groué, Jean-Philippe Tranchier, Geoffrey Gontard, Marion Jean, Nicolas Vanthuyne, Hani Amouri, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Circular dichroism. 30, Configurational stability, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Medicine, Enantiopure, chiral resolution, enantiopure, configurational stability, circular dichroism, Chiral resolution
Abstract: International audience; Enantiopure N-heterocyclic carbene half-sandwich metal complexes of the general formula [Cp*M(C^C:)I] (M = Rh, Ir; C^C: = NI-NHC; NI-H = Naphthalimide; NHC = N-heterocyclic carbene) are reported. The rhodium compound was obtained as a single isomer displaying six membered metallacycle and was resolved on chiral column chromatography to the corresponding enantiomers (S)-[Cp*Rh(C^C:)I] (S)-2 and (R)-[Cp*Rh(C^C:)I] (R)-2. The iridium congener, however, furnishes a pair of regioisomers, which were resolved into (S)-[Cp*Ir(C^C:)I] (S)-3 and (R)-[Cp*Ir(C^C:)I] (R)-3 and (S)-[Cp*Ir(C^C:)I] (S)-4 and (R)-[Cp*Ir(C^C:)I] (R)-4. These regioisomers differ from each other, only by the size of the metallacycle; five-membered for 3 and six-membered for 4. The molecular structures of (S)-2 and (S)-4 are reported. Moreover, the chiroptical properties of these compounds are presented and discussed. These compounds display exceptional stable configurations at the metal center in solution with enantiomerization barrier ΔG≠ up to 124 kJ/mol. This is because the nature of the naphthalimide-NHC clamp ligand and the iodide ligand contribute to their configuration’s robustness. In contrast to related complexes reported in the literature, which are often labile in solution.
Published: 2022

27. Visualizing protein breathing motions associated with aromatic ring flipping

Author: Laura Mariño Pérez, Francesco S. Ielasi, Luiza M. Bessa, Damien Maurin, Jaka Kragelj, Martin Blackledge, Nicola Salvi, Guillaume Bouvignies, Andrés Palencia, Malene Ringkjøbing Jensen, Universitat de les Illes Balears (UIB), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), 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 (UGA), Institut de biologie structurale (IBS - UMR 5075), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), University of Texas Southwestern Medical Center [Dallas], Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), HAL-SU, Gestionnaire, and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: src Homology Domains, Motion, Multidisciplinary, Protein Conformation, [CHIM.CRIS]Chemical Sciences/Cristallography, Proteins, Tyrosine, [CHIM.CRIS] Chemical Sciences/Cristallography, Crystallography, X-Ray, Solution-state NMR, Nuclear Magnetic Resonance, Biomolecular, X-ray crystallography
Abstract: Aromatic residues cluster in the core of folded proteins, where they stabilize the structure through multiple interactions. Nuclear magnetic resonance (NMR) studies in the 1970s showed that aromatic side chains can undergo ring flips—that is, 180° rotations—despite their role in maintaining the protein fold1–3. It was suggested that large-scale ‘breathing’ motions of the surrounding protein environment would be necessary to accommodate these ring flipping events1. However, the structural details of these motions have remained unclear. Here we uncover the structural rearrangements that accompany ring flipping of a buried tyrosine residue in an SH3 domain. Using NMR, we show that the tyrosine side chain flips to a low-populated, minor state and, through a proteome-wide sequence analysis, we design mutants that stabilize this state, which allows us to capture its high-resolution structure by X-ray crystallography. A void volume is generated around the tyrosine ring during the structural transition between the major and minor state, and this allows fast flipping to take place. Our results provide structural insights into the protein breathing motions that are associated with ring flipping. More generally, our study has implications for protein design and structure prediction by showing how the local protein environment influences amino acid side chain conformations and vice versa.
Published: 2022

28. CADPS functional mutations in patients with bipolar disorder increase the sensitivity to stress

Author: Jérémy Sitbon, Dennis Nestvogel, Caroline Kappeler, Aude Nicolas, Stephanie Maciuba, Annabelle Henrion, Réjane Troudet, Elisa Courtois, Gaël Grannec, Violaine Latapie, Caroline Barau, Philippe Le Corvoisier, Nicolas Pietrancosta, Chantal Henry, Marion Leboyer, Bruno Etain, Marika Nosten-Bertrand, Thomas F. J. Martin, JeongSeop Rhee, Stéphane Jamain, Institut Mondor de Recherche Biomédicale (IMRB), Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), Fondation FondaMental [Créteil], Max Planck Institute of Experimental Medicine [Göttingen] (MPI), Max-Planck-Gesellschaft, University of Wisconsin-Madison, Institut du Fer à Moulin (IFM - Inserm U1270 - SU), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU), Plateforme de Ressources Biologiques [Henri Mondor AP-HP, Créteil] (PRB), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-CHU Henri Mondor, Centre d'Investigation Clinique Henri Mondor (CIC Henri Mondor), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpital Henri Mondor-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Groupe Henri Mondor-Albert Chenevier, Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpital Henri Mondor-Hôpital Albert Chenevier, Hôpitaux Universitaire Saint-Louis, Lariboisière, Fernand-Widal, Université Sorbonne Paris Cité (USPC), Optimisation thérapeutique en Neuropsychopharmacologie (OPTeN (UMR_S_1144 / U1144)), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Cité (UPCité), IMRB - 'Neuropsychiatrie translationnelle' [Créteil] (U955 Inserm - UPEC), Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), IMRB - 'NeuroPsychologie Interventionnelle' [Créteil] (U955 Inserm - UPEC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Systèmes glutamatergiques normaux et pathologiques = Normal and Pathologic Glutamatergic Neurons (NPS), Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Jamain, Stéphane
Subjects: Bipolar Disorder, Neuronal Plasticity, [SDV.NEU.NB]Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC]/Neurobiology, [SDV.MHEP.PSM] Life Sciences [q-bio]/Human health and pathology/Psychiatrics and mental health, Calcium-Binding Proteins, [SDV.NEU.NB] Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC]/Neurobiology, Vesicular Transport Proteins, Nerve Tissue Proteins, [SDV.GEN.GH] Life Sciences [q-bio]/Genetics/Human genetics, Exocytosis, Mice, Cellular and Molecular Neuroscience, Psychiatry and Mental health, [SDV.GEN.GH]Life Sciences [q-bio]/Genetics/Human genetics, [SDV.MHEP.PSM]Life Sciences [q-bio]/Human health and pathology/Psychiatrics and mental health, Mutation, Animals, Humans, Calcium, Molecular Biology
Abstract: International audience; Bipolar disorder is a severe and chronic psychiatric disease resulting from a combination of genetic and environmental risk factors. Here, we identified a significant higher mutation rate in a gene encoding the calcium-dependent activator protein for secretion (CADPS) in 132 individuals with bipolar disorder, when compared to 184 unaffected controls or to 21,070 non-psychiatric and non-Finnish European subjects from the Exome Aggregation Consortium. We found that most of these variants resulted either in a lower abundance or a partial impairment in one of the basic functions of CADPS in regulating neuronal exocytosis, synaptic plasticity and vesicular transporter-dependent uptake of catecholamines. Heterozygous mutant mice for Cadps+/- revealed that a decreased level of CADPS leads to manic-like behaviours, changes in BDNF level and a hypersensitivity to stress. This was consistent with more childhood trauma reported in families with mutation in CADPS, and more specifically in mutated individuals. Furthermore, hyperactivity observed in mutant animals was rescued by the mood-stabilizing drug lithium. Overall, our results suggest that dysfunction in calcium-dependent vesicular exocytosis may increase the sensitivity to environmental stressors enhancing the risk of developing bipolar disorder.
Published: 2022

29. Identification of bacterial lipo-amino acids: origin of regenerated fatty acid carboxylate from dissociation of lipo-glutamate anion

Author: Amandine Hueber, Yves Gimbert, Geoffrey Langevin, Jean-Marie Galano, Alexandre Guy, Thierry Durand, Nicolas Cenac, Justine Bertrand-Michel, Jean-Claude Tabet, Gestionnaire, HAL Sorbonne Université 5, MetaboHUB-MetaToul, Génopole Toulouse Midi-Pyrénées [Auzeville] (GENOTOUL), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Vétérinaire de Toulouse (ENVT), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Recherche en Santé Digestive (IRSD ), Institut des Maladies Métaboliques et Casdiovasculaires (UPS/Inserm U1297 - I2MC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Inserm, PhD Grant, Région Occitanie, PhD Grant, MetaToul-MetaboHUB, Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Anions, Spectrometry, Mass, Electrospray Ionization, Tandem mass spectrometry, Lipidomic, Ion-dipole Abbreviations ACN Acetonitrile CID Collision-induced dissociation DCM Dichloromethane DFT Density functional theory EcN Escherichia coli ESI Electrospray, Fatty Acids, Organic Chemistry, Clinical Biochemistry, Lipoamino acid, Glutamic Acid, Biochemistry, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Humans, Regeneration, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Amino Acids
Abstract: The identification of bacterial metabolites produced by the microbiota is a key point to understand its role in human health. Among them, lipo-amino acids (LpAA), which are able to cross the epithelial barrier and to act on the host, are poorly identified. Structural elucidation of few of them was performed by high-resolution tandem mass spectrometry based on electrospray combined with selective ion dissociations reach by collision-induced dissociation (CID). The negative ions were used for their advantages of yielding only few fragment ions sufficient to specify each part of LpAA with sensitivity. To find specific processes that help structural assignment, the negative ion dissociations have been scrutinized for an LpAA: the N-palmitoyl acyl group linked to glutamic acid (C16Glu). The singular behavior of [C16Glu-H]¯ towards CID showed tenth product ions, eight were described by expected fragment ions. In contrast, instead of the expected product ions due to CONH-CH bond cleavage, an abundant complementary dehydrated glutamic acid and fatty acid anion pair were observed. Specific to glutamic moiety, they were formed by a stepwise dissociation via molecular isomerization through ion–dipole formation prior to dissociation. This complex dissociated by partner splitting either directly or after inter-partner proton transfer. By this pathway, surprising regeneration of deprotonated fatty acid takes place. Such regeneration is comparable to that occurred from dissociation to peptides containing acid amino-acid. Modeling allow to confirm the proposed mechanisms explaining the unexpected behavior of this glutamate conjugate.
Published: 2022

30. An expanded palette of fluorogenic HaloTag probes with enhanced contrast for targeted cellular imaging

Author: Sylvestre P. J. T. Bachollet, Yuriy Shpinov, Fanny Broch, Hela Benaissa, Arnaud Gautier, Nicolas Pietrancosta, Jean-Maurice Mallet, Blaise Dumat, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Systèmes glutamatergiques normaux et pathologiques = Normal and Pathologic Glutamatergic Neurons (NPS), Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), ANR-18-CE44-0006,DIPimaging,Sondes fluorogéniques à double détection pour l'imagerie biphotonique localisée(2018), Dumat, Blaise, and APPEL À PROJETS GÉNÉRIQUE 2018 - Sondes fluorogéniques à double détection pour l'imagerie biphotonique localisée - - DIPimaging2018 - ANR-18-CE44-0006 - AAPG2018 - VALID
Subjects: Hydrolases, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Proteins, Molecular Dynamics Simulation, HaloTag, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Fluorogenic probes, Biochemistry, Fluorescence imaging, molecular rotors, embryonic structures, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Physical and Theoretical Chemistry, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Fluorescent Dyes
Abstract: International audience; We report the development of HaloTag fluorogens based on dipolar flexible molecular rotor structures. By modulating the electron donating and withdrawing groups, we have tuned the absorption and emission wavelengths to design a palette of fluorogens with emissions spanning the green to red range, opening new possibilities for multicolor imaging. The probes were studied in glycerol and in presence of HaloTag and exhibited good fluorogenic properties thanks to a viscosity-sensitive emission. In live-cell confocal imaging, the fluorogens yielded only a very low non-specific signal that enabled wash-free targeted imaging of intracellular organelles and proteins with good contrast. Combining experimental studies and theoretical investigation of the protein/fluorogen complexes by molecular dynamics, these results offer new insight into the design of molecular rotor-based fluorogenic HaloTag probes in order to improve reaction rates and the imaging contrast.
Published: 2022

31. Mechanism insights in controlling host–guest (de)complexation by thermoresponsive polymer phase transitions

Author: Hui Guo, Gaëlle Le Fer, Thi Nga Tran, Aurélie Malfait, Dominique Hourdet, Alba Marcellan, François Stoffelbach, Joël Lyskawa, Richard Hoogenboom, Patrice Woisel, Université de Lille, CNRS, INRAE, ENSCL, Unité Matériaux et Transformations (UMET) - UMR 8207, Sciences et Ingénierie de la Matière Molle (UMR 7615) (SIMM), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sun Yat-Sen University [Guangzhou] (SYSU), 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 Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Universiteit Gent = Ghent University (UGENT)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract: International audience; The combination of (thermo)responsive polymers with supramolecular chemistry recently allowed the development of adaptative materials based on the reversible regulation of host-guest complexation. The properties of these artificial systems rely on their synthetic design, which requires a perfect understanding of the mechanisms triggering the thermo-induced decomplexation. Despite recent progress, the origins of this phenomenon are still not fully understood. To investigate the effect of phase separation mechanism and thermodynamics on the host-guest (de)complexation behavior, different naphthalene-functionalized (guest) thermoresponsive polymers, including lower critical solution temperature (LCST) and upper critical solution temperature (UCST) polymers, were prepared. The hostguest complexation of the polymers with cyclobis(paraquat-p-phenylene) (Blue Box) was investigated in water at different temperatures. Host-guest complexation was lost upon heating-induced hydrophobic phase separation of complexed guest-functionalized LCST-polymers, while, in contrast, the host-guest complex was retained upon cooling-induced hydrogen bond-driven phase separation of a complexed guest-functionalized UCST polymer. This comparative analysis showed that the mechanism behind the thermoresponsive polymer phase separation is a key factor that dominates the host-guest (de)complexation.
Published: 2022

32. Can we eradicate viral pathogens?

Author: Samuel Alizon, Paul E. Turner, Génétique et évolution des maladies infectieuses (GEMI), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD [France-Sud]), 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), Department of Ecology and Evolutionary Biology, Yale University, Alizon, Samuel, Maladies infectieuses et vecteurs : écologie, génétique, évolution et contrôle (MIVEGEC), 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), and 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)
Subjects: 0106 biological sciences, [SDV.BID.SPT]Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, 010603 evolutionary biology, 01 natural sciences, 03 medical and health sciences, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, [SDV.BID.SPT] Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, [SDV.BID.EVO] Life Sciences [q-bio]/Biodiversity/Populations and Evolution [q-bio.PE], [SDV.EE.ECO] Life Sciences [q-bio]/Ecology, environment/Ecosystems, [SDV.EE.SANT] Life Sciences [q-bio]/Ecology, environment/Health, Ecology, Evolution, Behavior and Systematics, 030304 developmental biology, [SDV.EE.SANT]Life Sciences [q-bio]/Ecology, environment/Health, [SDV.MP.VIR] Life Sciences [q-bio]/Microbiology and Parasitology/Virology, 0303 health sciences, [SDV.GEN.GPO]Life Sciences [q-bio]/Genetics/Populations and Evolution [q-bio.PE], [SDV.BIBS] Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], [SDV.BID.EVO]Life Sciences [q-bio]/Biodiversity/Populations and Evolution [q-bio.PE], [SDV.EE.IEO] Life Sciences [q-bio]/Ecology, environment/Symbiosis, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation, [SDV.BIBS]Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], 3. Good health, [SDE.BE] Environmental Sciences/Biodiversity and Ecology, [SDV.SPEE] Life Sciences [q-bio]/Santé publique et épidémiologie, [SDV.MP.VIR]Life Sciences [q-bio]/Microbiology and Parasitology/Virology, [SDV.GEN.GPO] Life Sciences [q-bio]/Genetics/Populations and Evolution [q-bio.PE], [SDV.SPEE]Life Sciences [q-bio]/Santé publique et épidémiologie, [INFO.INFO-MO] Computer Science [cs]/Modeling and Simulation, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, [SDV.EE.IEO]Life Sciences [q-bio]/Ecology, environment/Symbiosis
Abstract: International audience; The COVID-19 pandemic has led to a resurgence of the debate on whether host-parasite interactions should evolve towards avirulence. In this review, we first show that SARS-CoV-2 virulence is evolving, before explaining why some expect the mortality caused by the epidemic to converge towards that of human seasonal alphacoronaviruses. Leaning on existing theory, we then include viral evolution into the picture and discuss hypotheses explaining why the virulence has increased since the beginning of the pandemic. Finally, we mention some potential scenarios for the future.
Published: 2021

33. Mn-Doped Quinary Ag–In–Ga–Zn–S Quantum Dots for Dual-Modal Imaging

Author: Raphaël Schneider, Bolat Uralbekov, Perizat Galiyeva, Jordane Jasniewski, Halima Alem, Sébastien Leclerc, Sébastien Blanchard, Hervé Rinnert, Ghouti Medjahdi, Sabine Bouguet-Bonnet, Lavinia Balan, Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Laboratoire Énergies et Mécanique Théorique et Appliquée (LEMTA ), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), 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), Laboratoire d'Ingénierie des Biomolécules (LIBio), Université de Lorraine (UL), Al-Farabi Kazakh National University [Almaty] (KazNU), IMPACT Biomolécules, and ANR-15-IDEX-0004,LUE,Isite LUE(2015)
Subjects: Materials science, General Chemical Engineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Article, [SPI.MECA.MEFL]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Fluids mechanics [physics.class-ph], Condensed Matter::Materials Science, Semiconductor quantum dots, Transition metal, Condensed Matter::Superconductivity, Mn doped, QD1-999, business.industry, Doping, Quinary, General Chemistry, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dual (category theory), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, Modal, Quantum dot, Optoelectronics, Condensed Matter::Strongly Correlated Electrons, 0210 nano-technology, business
Abstract: International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.
Published: 2021

34. 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

35. Covalent Hydrogels with Dual Temperature and Time Memory Function Based on Supramolecular Host–Guest Complexation

Author: Lieselot De Smet, Khaled Belal, Aurelien Vebr, Joel Lyskawa, François Stoffelbach, Richard Hoogenboom, Patrice Woisel, 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), Sorbonne Université (SU), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Universiteit Gent = Ghent University (UGENT)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, General Chemical Engineering, Biomedical Engineering, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; Temperature is among the most important measured physical parameters. Despite that numerous polymeric temperature sensors having been reported, none of these systems can record the time that the object was heated to a certain temperature. Here, we report a supramolecular approach for developing a smart polymeric hydrogel capable of measuring the temperature and the duration of the heat exposure. This double memory principle is based on dual kinetic control of the dissociation of cyclobis(paraquat-p-phenylene) tetrachloride (CBPQT4+,4Cl–)-naphthalene host–guest complexes within a thermoresponsive naphthalene functionalized poly(N-isopropylacrylamide) hydrogel. Heating-induced collapse of this LCST polymer hydrogel induces host–guest complex dissociation, followed by the diffusion-controlled release of the free CBPQT4+,4Cl– host into the medium surrounding the hydrogel. This partial host release is governed by the heat exposure time and the heating temperature that controls the extent of dehydration of the hydrogel and, thus, the diffusion rate of the CBPQT4+,4Cl–. Hence, the amount of host released is an indicator for both the heating temperature and the heating time of the hydrogel and can be recorded by determining the reswelling capability of the hydrogel in water. As such, measuring the reswelling capability provides information on how long the hydrogel system was exposed to a certain temperature.
Published: 2022

36. Long-lived states of methylene protons in achiral molecules

Author: Anna Sonnefeld, Aiky Razanahoera, Philippe Pelupessy, Geoffrey Bodenhausen, Kirill Sheberstov, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and European Project: 951459,HISCORE
Subjects: Multidisciplinary, [CHIM]Chemical Sciences
Abstract: In nuclear magnetic resonance (NMR), the lifetimes of long-lived states (LLSs) are exquisitely sensitive to their environment. However, the number of molecules where such states can be excited has hitherto been rather limited. Here, it is shown that LLSs can be readily excited in many common molecules that contain two or more neighboring CH 2 groups. Accessing such LLSs does not require any isotopic enrichment, nor does it require any stereogenic centers to lift the chemical equivalence of CH 2 protons. LLSs were excited in a variety of metabolites, neurotransmitters, vitamins, amino acids, and other molecules. One can excite LLSs in several different molecules simultaneously. In combination with magnetic resonance imaging, LLSs can reveal a contrast upon noncovalent binding of ligands to macromolecules. This suggests new perspectives to achieve high-throughput parallel drug screening by NMR.
Published: 2022

37. The formulation of a CMC binder/silicon composite anode for Li-ion batteries: from molecular effects of ball milling on polymer chains to consequences on electrochemical performances

Author: Mariama Ndour, Jean-Pierre Bonnet, Sébastien Cavalaglio, Tristan Lombard, Matthieu Courty, Luc Aymard, Cédric Przybylski, Véronique Bonnet, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Laboratoire des technologies de la microélectronique (LTM ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)
Subjects: Chemistry (miscellaneous), [CHIM]Chemical Sciences, General Materials Science
Abstract: The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries.
Published: 2022

38. GRID1/ GluD1 homozygous variants linked to intellectual disability and spastic paraplegia impair mGlu1/5 receptor signaling and excitatory synapses

Author: Dévina C. Ung, Ludovic Tricoire, Nicolas Pietrancosta, Andjela Zlatanovic, Ben Pode-Shakked, Annick Raas-Rothschild, Orly Elpeleg, Bassam Abu-Libdeh, Nasrin Hamed, Marie-Amélie Papon, Sylviane Marouillat, Rose-Anne Thépault, Giovanni Stevanin, Bertrand Lambolez, Annick Toutain, Régine Hepp, Frédéric Laumonnier, Imagerie et cerveau (iBrain - Inserm U1253 - UNIV Tours ), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM), Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie du Développement de Marseille (IBDM), Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Centre National de la Recherche Scientifique (CNRS), Systèmes glutamatergiques normaux et pathologiques = Normal and Pathologic Glutamatergic Neurons (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Tel Aviv University (TAU), Chaim Sheba Medical Center, Department of Genetics and Metabolic Diseases and the Monique and Jacques Roboh Department of Genetic Research, Hadassah Hebrew University Medical Center [Jerusalem], Institute of Human Genetics, Universität Regensburg (UR), Service de génétique [Tours], Centre Hospitalier Régional Universitaire de Tours (CHRU Tours)-Hôpital Bretonneau, Institut de Biologie Paris Seine (IBPS), and Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDV]Life Sciences [q-bio]
Abstract: The ionotropic glutamate delta receptor GluD1, encoded by the GRID1 gene, is involved in synapse formation, function, and plasticity. GluD1 does not bind glutamate, but instead cerebellin and D-serine, which allow the formation of trans-synaptic bridges, and trigger transmembrane signaling. Despite wide expression in the nervous system, pathogenic GRID1 variants have not been characterized in humans so far. We report homozygous missense GRID1 variants in five individuals from two unrelated consanguineous families presenting with intellectual disability and spastic paraplegia, without (p.Thr752Met) or with (p.Arg161His) diagnosis of glaucoma, a threefold phenotypic association whose genetic bases had not been elucidated previously. Molecular modeling indicated that Arg161His and Thr752Met mutations alter the hinge between GluD1 cerebellin and D-serine binding domains and the stiffness of this latter domain, respectively. Expression, trafficking, physical interaction with metabotropic glutamate receptor mGlu1, and cerebellin binding of GluD1 mutants were not conspicuously altered. Conversely, we found that both GluD1 mutants hampered signaling of metabotropic glutamate receptor mGlu1/5 via the ERK pathway in neurons of primary cortical culture. Moreover, both mutants impaired dendrite morphology and excitatory synapse density in neurons of primary hippocampal culture. These results show that the clinical phenotypes are distinct entities segregating in the families as an autosomal recessive trait, and caused by pathophysiological effects of GluD1 mutants involving metabotropic glutamate receptor signaling and neuronal connectivity. Our findings unravel the importance of the GluD1 receptor signaling in sensory, cognitive and motor functions of the human nervous system.
Published: 2022

39. Challenges and Methods for the Study of CPP Translocation Mechanisms

Author: Astrid Walrant, Nicolas Rodriguez, Françoise Illien, Sandrine Sagan, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-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)-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)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)
Subjects: chemistry.chemical_classification, 0303 health sciences, Bilayer, [SDV]Life Sciences [q-bio], Peptide, Biological membrane, 02 engineering and technology, 021001 nanoscience & nanotechnology, Fluorescence, Fluorescence spectroscopy, Cell membrane, 03 medical and health sciences, Membrane, medicine.anatomical_structure, chemistry, Biophysics, medicine, 0210 nano-technology, Tropism, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology
Abstract: Fluorescence-based methods are widely used to detect crossing of peptides across model or biological membranes. For membrane-active peptides, i.e., peptides that have strong membrane tropism, fluorescence experiments must be accompanied by relevant controls, otherwise they can lead to inconsistent interpretation and underestimation of their limitations. Here we describe how to prepare samples to study fluorescent peptide crossing droplet interface bilayer (model membrane) or cell membrane (biological membrane) and the pitfalls that can affect observational qualitative and quantitative data.
Published: 2022

40. Convergent vews on disordered protein dynamics from NMR and computational approaches

Author: Nicola, Salvi, Vojtěch, Zapletal, Zuzana, Jaseňáková, Milan, Zachrdla, Petr, Padrta, Subhash, Narasimhan, Thorsten, Marquardsen, Jean-Max, Tyburn, Lukáš, Žídek, Martin, Blackledge, Fabien, Ferrage, Pavel, Kadeřávek, Institut de biologie structurale (IBS - UMR 5075), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Masaryk University [Brno] (MUNI), Central European Institute of Technology [Brno] (CEITEC MU), Brno University of Technology [Brno] (BUT), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Bruker BioSpin MRI GmbH [Ettlingen, Germany], ANR-18-CE29-0003,NANO-DISPRO,Une méthode intégrative pour déterminer les mouvements nanométriques des protéines désordonnées(2018), Ferrage, Fabien, and APPEL À PROJETS GÉNÉRIQUE 2018 - Une méthode intégrative pour déterminer les mouvements nanométriques des protéines désordonnées - - NANO-DISPRO2018 - ANR-18-CE29-0003 - AAPG2018 - VALID
Subjects: Intrinsically Disordered Proteins, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Magnetic Resonance Spectroscopy, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Protein Conformation, [SDV.BBM.BS] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Biophysics, [SDV.BBM.BP] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, DNA-Directed RNA Polymerases, Molecular Dynamics Simulation, Amides
Abstract: International audience; Intrinsically disordered proteins (IDPs) or intrinsically disordered regions (IDRs) is a class of biologically important proteins exhibiting specific biophysical characteristics. They lack a hydrophobic core, and their conformational behavior is strongly influenced by electrostatic interactions. IDPs and IDRs are highly dynamic, and a characterization of the motions of IDPs and IDRs is essential for their physically correct description. NMR together with molecular dynamics simulations are the methods best suited to such a task because they provide information about dynamics of proteins with atomistic resolution. Here, we present a study of motions of a disordered C-terminal domain of the delta subunit of RNA polymerase from Bacillus subtilis. Positively and negatively charged residues in the studied domain form transient electrostatic contacts critical for the biological function. Our study is focused on investigation of ps-ns dynamics of backbone of the delta subunit based on analysis of amide 15N NMR relaxation data and molecular dynamics simulations. In order to extend an informational content of NMR data to lower frequencies, which are more sensitive to slower motions, we combined standard (high-field) NMR relaxation experiments with high-resolution relaxometry. Altogether, we collected data reporting the relaxation at 12 different magnetic fields, resulting in an unprecedented data set. Our results document that the analysis of such data provides a consistent description of dynamics and confirms the validity of so far used protocols of the analysis of dynamics of IDPs also for a partially folded protein. In addition, the potential to access detailed description of motions at the timescale of tens of ns with the help of relaxometry data is discussed. Interestingly, in our case, it appears to be mostly relevant for a region involved in the formation of temporary contacts within the disordered region, which was previously proven to be biologically important.
Published: 2022

41. Rapid structural characterization of human milk oligosaccharides and distinction of their isomers using trapped ion mobility spectrometry time‐of‐flight mass spectrometry

Author: Estelle Rathahao‐Paris, Aurélie Delvaux, Meijie Li, Blanche Guillon, Eric Venot, François Fenaille, Karine Adel‐Patient, Sandra Alves, Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-11-INBS-0010,METABOHUB,Développement d'une infrastructure française distribuée pour la métabolomique dédiée à l'innovation(2011), and ANR-19-CE36-0008,InfaDiet,Influence de l'alimentation infantile sur la croissance et le développement de l'enfant(2019)
Subjects: spectrometry, Milk, Human, Polysaccharides, Tandem Mass Spectrometry, Ion Mobility Spectrometry, Monosaccharides, Humans, Oligosaccharides, [CHIM]Chemical Sciences, time-of-flight, Spectroscopy
Abstract: International audience; Oligosaccharides have multiple functions essential for health. Derived from the condensation of two toseveral monosaccharides, they are structurally diverse with many co-occurring structural isomer families, which makes their characterization difficult. Thanks to its ability to separate small molecules based on their mass, size, shape and charge, ion mobility-mass spectrometry (IM-MS) has emerged as a powerful tool for separating glycan isomers. Here, the potential of such a technique for the rapid characterization of main human milk oligosaccharides (HMOs) was investigated. Our study focused on eighteen HMO standards. The IM-MS analysis enabled to distinguish almost all the HMOs studied, in particular thanks to the single ion mobility monitoring (SIM2) acquisition using the trapped ion mobility spectrometry (TIMS) device, providing high ion mobility resolution and enhanced ion mobility separation. Alternatively, the combination of IM-MS separation with MS/MS experiments has proven to increase performance in identifying HMOs and especially isomers poorly separated by ion mobility alone. Finally, collision cross-section (CCS) values are provided for each species generated from the eighteen HMOs standards, which can serve as an additional identifier to characterize HMOs.
Published: 2022

42. Targeting hIAPP fibrillation: A new paradigm to prevent β-cell death?

Author: Ghislaine Guillemain, Jean-Jacques Lacapere, Lucie Khemtemourian, Institut de Cardiométabolisme et Nutrition = Institute of Cardiometabolism and Nutrition [CHU Pitié Salpêtrière] (IHU ICAN), CHU Pitié-Salpêtrière [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU), Centre de Recherche Saint-Antoine (CRSA), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and khemtemourian, lucie
Subjects: Inflammation, Amyloid, Cell Death, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], [SDV.BBM.BS] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], [SDV]Life Sciences [q-bio], Cross-fibrils, Biophysics, [SDV.BBM.BP] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Type 2 diabetes, Cell Biology, Biochemistry, Islet Amyloid Polypeptide, β-Cells, Amyloid proteins, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, [SDV] Life Sciences [q-bio], Diabetes Mellitus, Type 2, Humans, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Pancreas, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM]
Abstract: International audience; Loss of pancreatic β-cell mass is deleterious for type 2 diabetes patients since it reduces insulin production, critical for glucose homeostasis. The main research axis developed over the last few years was to generate new pancreatic β-cells or to transplant pancreatic islets as occurring for some specific type 1 diabetes patients. We evaluate here a new paradigm consisting in preservation of β-cells by prevention of human islet amyloid polypeptide (hIAPP) oligomers and fibrils formation leading to pancreatic β-cell death. We review the hIAPP physiology and the pathology that contributes to β-cell destruction, deciphering the various cellular steps that could be involved. Recent progress in understanding other amyloidosis such as Aβ, Tau, α-synuclein or prion, involved in neurodegenerative processes linked with inflammation, has opened new research lines of investigations to preserve neuronal cells. We evaluate and estimate their transposition to the pancreatic β-cells preservation. Among them is the control of reactive oxygen species (ROS) production occurring with inflammation and the possible implication of the mitochondrial translocator protein as a diagnostic and therapeutic target. The present review also focuses on other amyloid forming proteins from molecular to physiological and physiopathological points of view that could help to better decipher hIAPP-induced β-cell death mechanisms and to prevent hIAPP fibril formation.
Published: 2022

43. Precise Rate Control of Pseudorotaxane Dethreading by pH-Responsive Selectively Functionalized Cyclodextrins

Author: Matthieu Sollogoub, Sawsen Cherraben, Guillaume Vives, Jérémy Scelle, Bernold Hasenknopf, 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), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Substitution (logic), Rate control, Stimulus (physiology), 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Threading (manufacturing), Physical and Theoretical Chemistry
Abstract: International audience; A family of cyclodextrins functionalized with zero, one, two, or six amines was shown to control the rate of their threading and dethreading on a molecular axle depending on the pH and their substitution pattern. The originality of this system lies in the rate control of the switch by operating the stimulus directly on the macrocycle.
Published: 2021

44. 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

45. Hexaphyrin-cyclodextrin hybrids: Getting larger, getting confused

Author: Bernard Boitrel, François Robert, Stéphane Le Gac, Mickaël Ménand, 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), 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), We are grateful to the Agence Nationale de la Recherche for financial support (ANR research program PRALLOCAT, ANR-16-CE07-0014 and MIXAR, ANR-20-CE07-0026)., ANR-16-CE07-0014,PRALLOCAT,Vers des catalyseurs processifs allostériques pour l'encodage moléculaire(2016), 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), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: conformation, chemistry.chemical_classification, Möbius, Cyclodextrin, 010405 organic chemistry, Chemistry, Stereochemistry, Aromaticity, aromaticity, General Chemistry, 010402 general chemistry, 01 natural sciences, hexaphyrin, 0104 chemical sciences, cyclodextrin, Covalent bond, [CHIM]Chemical Sciences, N-confused, Hybrid
Abstract: The diversity of hexaphyrin-cyclodextrin hybrids (HCD), previously formed from the covalent assembly of regular hexaphyrin and [Formula: see text]-cyclodextrin subunits, has been increased following two main directions: enlarging the confined space provided by the cyclodextrin and tuning the N-core of the hexaphyrin aiming at bimetallic complexes. The larger [Formula: see text]-cyclodextrin unit was selectively functionalized with aldehyde linkers on its primary rim which were further reacted with 2 eq. of pentafluorophenyl tripyrrane in acidic conditions, followed by DDQ oxidation. Doubly-linked HCD hybrids were obtained with structural variations in the hexaphyrin macrocycles depending on the MSA concentration (2 vs. 200 mM) producing either regular ([26] rectangular/[28] Möbius) or doubly N-confused dioxo ([26] rectangular) scaffolds. For the latter, two isomers were isolated featuring mirror transoid skeletons and long-side meso-linking patterns, giving rise to planar chirality at the origin of intense and opposite electronic circular dichroism (ECD) spectra. Zn(II) complexation was then investigated leading to two main findings. (i) The regular [28] Möbius HCD afforded a mixture of monometallic Möbius Zn(II) complexes in the presence of acac ligand. ECD spectroscopy indicated a chirality transfer from the [Formula: see text]-cyclodextrin favoring a [Formula: see text] Möbius twist, but opposite to that arising from the narrower [Formula: see text]-cyclodextrin congener ([Formula: see text] twist favored). (ii) Owing to N3O coordination boxes, dissymmetric bimetallic Zn(II) complexes were readily formed with the doubly N-confused dioxo HCDs through a positive cooperative process. Both metal centers bind a DMAP ligand in axial positions, which is of interest for the
Published: 2021

46. Ligand‐Directed Modification of Active Matrix Metalloproteases: Activity‐based Probes with no Photolabile Group

Author: Marion Doladilhe, Vincent Dive, Olivier Lequin, Pierrick Bruyat, Monika Kaminska, Dimitris Georgiadis, Carole Fruchart Gaillard, Mélissa De Souza, Robert Thai, Evelyne Cassar-Lajeunesse, Carole Malgorn, Laurent Devel, Andrzej Galat, Fabrice Beau, Sarah Bregant, Isabelle Correia, Service d'Ingénierie Moléculaire pour la Santé (ex SIMOPRO) (SIMoS), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), University of Athens, Athens, ANR-18-CE44-0012,ProMaP,Nouvelles sondes pour la détection de Métallo protéases par spectrométrie de masse(2018), and ANR-10-LABX-0033,LERMIT,Research Laboratory on Drugs and Therapeutic Innovation(2010)
Subjects: biology, Proteomic Profiling, Chemistry, Active site, General Chemistry, General Medicine, Matrix metalloproteinase, Ligand (biochemistry), biology.organism_classification, Catalysis, law.invention, Biochemistry, Covalent bond, law, Proteome, biology.protein, Recombinant DNA, [CHIM]Chemical Sciences, Eukaryote
Abstract: International audience; Activity-based probes enable discrimination between the active enzyme and its inactive or inactivated counterparts. Since metalloproteases catalysis is non-covalent, activity-based probes targeting them have been systematically developed by decorating reversible inhibitors with photo-crosslinkers. By exploiting two types of ligand-guided chemistry, we identified novel activity-based probes capable of covalently modifying the active site of matrix metalloproteases (MMPs) without any external trigger. The ability of these probes to label recombinant MMPs was validated in vitro and the identity of the main labelling sites within their S$_3$′ region unambiguously assigned. We also demonstrated that our affinity probes can react with rhMMP12 at nanogram scale (that is, at 0.07 % (w/w)) in complex proteomes. Finally, this ligand-directed chemistry was successfully applied to label active MMP-12 secreted by eukaryote cells. We believe that this approach could be transferred more widely to many other metalloproteases, thus contributing to tackle their unresolved proteomic profiling in vivo.
Published: 2021

47. Redox-controlled conductance of polyoxometalate molecular junctions

Author: Cécile Huez, David Guérin, Stéphane Lenfant, Florence Volatron, Michel Calame, Mickael L. Perrin, Anna Proust, Dominique Vuillaume, Nanostructures, nanoComponents & Molecules - IEMN (NCM - IEMN), 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)-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), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Swiss Federal Laboratories for Materials Science and Technology [Dübendorf] (EMPA), University of Basel (Unibas), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), We acknowledge support of the CNRS, project 'neuroPOM', under a grant of the 80PRIME program. We acknowledge Xavier Wallart (IEMN-CNRS) for his help with the XPS measurements. K. Trinh (IPCM-CNRS) is warmly acknowledged for the synthesis of PMo 12 (0) and PMo 12 (I ), and PCMP PCP
Subjects: Condensed Matter - Materials Science, Condensed Matter - Mesoscale and Nanoscale Physics, molecular electronics, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, conductive AFM, machine learning, redox, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), polyoxometalate, General Materials Science, electron transport, [PHYS.COND.CM-MSQHE]Physics [physics]/Condensed Matter [cond-mat]/Mesoscopic Systems and Quantum Hall Effect [cond-mat.mes-hall]
Abstract: International audience; We demonstrate the reversible in situ photoreduction of molecular junctions of phosphomolybdate [PMo12O40]3- monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4- molecular junction is increased by ∼ 10, this open-shell state is stable in the junction in air at room temperature. The analysis of a large current-voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetric current-voltage curves, controlled by the lowest unoccupied molecular orbital (LUMO) at 0.6-0.7 eV above the Fermi energy with ∼25% of the junctions having a better electronic coupling to the electrodes than the main part of the dataset. This analysis also shows that a small fraction (∼ 18% of the dataset) of the molecules is already reduced. The UV light in situ photoreduced phosphomolybdate junctions are systematically featuring slightly asymmetric current-voltage behaviors, which is ascribed to electron transport mediated by the single occupied molecular orbital (SOMO) nearly at resonance with the Fermi energy of the electrode and by a closely located single unoccupied molecular orbital (SUMO) at ∼0.3 eV above the SOMO with a weak electronic coupling to the electrodes (∼ 50% of the dataset) or at ∼0.4 eV but with a better electrode coupling (∼ 50% of the dataset). These results shed lights to the electronic properties of reversible switchable redox polyoxometalates, a key point for potential applications in nanoelectronic devices.
Published: 2022

48. Benchmarking higher energy collision dissociation (HCD) by investigation of binding energies of gas-phase host-guest complexes of hemicryptophane cages

Author: Parisa Bayat, David Gatineau, Denis Lesage, Alexandre Martinez, Richard B. Cole, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), 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), and Arcane Labex
Subjects: Ions, Benchmarking, [CHIM]Chemical Sciences, Thermodynamics, Spectroscopy, Mass Spectrometry
Abstract: International audience; Synthesis of host molecules that feature well-defined characteristics for molecular recognition of guest molecules is often a major aim of synthetic host–guest (H–G) chemistry. A key consideration in evaluating the selectivity of hosts and the affinities of guests is the measurement of binding energies of obtained H–G complexes. In contrast to nuclear magnetic resonance (NMR) or fluorescence measurements that are capable of measuring binding strengths in solution, mass spectrometry offers the opportunity to measure gas-phase binding energies. Presented in this article is a higher energy collision dissociation (HCD) approach for determining critical energies of dissociation of H–G complexes. Experiments were performed on electrospray ionization (ESI)-generated H–G pairs in an LTQ-XL/Orbitrap hybrid instrument. The presented HCD approach requires preliminary calibration of the internal energy distribution of generated ions that was achieved by the use of activation parameters that were known from previous low-energy collision-induced dissociation (low-energy CID) experiments. Internal energy deposition was modeled based on a truncated Maxwell–Boltzmann distribution and characteristic temperature (Tchar). Using this method, critical energies of dissociation were determined for 10 H–G biologically relevant complexes of the heteroditopic hemicryptophane cage host (Host). Obtained results are compared with those found previously by low-energy CID. The use of this HCD technique is relatively straightforward, although its implementation does require knowledge (or a presumption) about the Arrhenius pre-exponential factor of the complexes to obtain their critical energies of dissociation.
Published: 2022

49. Comprehensive structural assignment of glycosaminoglycan oligo- and polysaccharides by protein nanopore

Author: Parisa Bayat, Charlotte Rambaud, Bernard Priem, Matthieu Bourderioux, Mélanie Bilong, Salomé Poyer, Manuela Pastoriza-Gallego, Abdelghani Oukhaled, Jérôme Mathé, Régis Daniel, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches sur les Macromolécules Végétales (CERMAV), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP), Laboratoire Analyse, Modélisation et Matériaux pour la Biologie et l'Environnement (LAMBE - UMR 8587), and Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY)
Subjects: Multidisciplinary, Sulfates, Chondroitin Sulfates, Dermatan Sulfate, General Physics and Astronomy, Nanopore GAG, General Chemistry, General Biochemistry, Genetics and Molecular Biology, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Nanopores, Polysaccharides, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Glycosaminoglycans
Abstract: Glycosaminoglycans are highly anionic functional polysaccharides with information content in their structure that plays a major role in the communication between the cell and the extracellular environment. The study presented here reports the label-free detection and analysis of glycosaminoglycan molecules at the single molecule level using sensing by biological nanopore, thus addressing the need to decipher structural information in oligo- and polysaccharide sequences, which remains a major challenge for glycoscience. We demonstrate that a wild-type aerolysin nanopore can detect and characterize glycosaminoglycan oligosaccharides with various sulfate patterns, osidic bonds and epimers of uronic acid residues. Size discrimination of tetra- to icosasaccharides from heparin, chondroitin sulfate and dermatan sulfate was investigated and we show that different contents and distributions of sulfate groups can be detected. Remarkably, differences in α/β anomerization and 1,4/1,3 osidic linkages can also be detected in heparosan and hyaluronic acid, as well as the subtle difference between the glucuronic/iduronic epimers in chondroitin and dermatan sulfate. Although, at this stage, discrimination of each of the constituent units of GAGs is not yet achieved at the single-molecule level, the resolution reached in this study is an essential step toward this ultimate goal.
Published: 2022
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50. Nanoscopic distribution of VAChT and VGLUT3 in striatal cholinergic varicosities suggests colocalization and segregation of the two transporters in synaptic vesicles

Author: Paola Cristofari, Mazarine Desplanque, Odile Poirel, Alison Hébert, Sylvie Dumas, Etienne Herzog, Lydia Danglot, David Geny, Jean-François Gilles, Audrey Geeverding, Susanne Bolte, Alexis Canette, Michaël Trichet, Véronique Fabre, Stéphanie Daumas, Nicolas Pietrancosta, Salah El Mestikawy, Véronique Bernard, Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Systèmes glutamatergiques normaux et pathologiques = Normal and Pathologic Glutamatergic Neurons (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Oramacell [Paris, France], Interdisciplinary Institute for Neuroscience (IINS), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut de psychiatrie et neurosciences de Paris (IPNP - U1266 Inserm), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Cité (UPCité), GHU Paris Psychiatrie et Neurosciences, Microscopie Electronique [IBPS] (IBPS-ME), Institut de Biologie Paris Seine (IBPS), Sorbonne Université (SU), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Imagerie Cellulaire et Cytométrie de Flux [IBPS] (IBPS-IP), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), McGill University = Université McGill [Montréal, Canada], and Bernard, Veronique
Subjects: striatal cholinergic interneurons, vesicular acetylcholine transporter, VGLUT3, Type 3 vesicular glutamate transporter, Striatum, STimulated Emission Depletion microscopy (STED), Cellular and Molecular Neuroscience, VAChT, Quantitative Biology - Neurons and Cognition, FOS: Biological sciences, acetylcholine-glutamate cotransmission, [SDV.NEU]Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC], Neurons and Cognition (q-bio.NC), [SDV.NEU] Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC], scanning electron microscopy (SEM), Molecular Biology
Abstract: International audience; Striatal cholinergic interneurons (CINs) use acetylcholine (ACh) and glutamate (Glut) to regulate the striatal network since they express vesicular transporters for ACh (VAChT) and Glut (VGLUT3). However, whether ACh and Glut are released simultaneously and/or independently from cholinergic varicosities is an open question. The answer to that question requires the multichannel detection of vesicular transporters at the level of single synaptic vesicle (SV). Here, we used super-resolution STimulated Emission Depletion microscopy (STED) to characterize and quantify the distribution of VAChT and VGLUT3 in CINs SVs. Nearest-neighbor distances analysis between VAChT and VGLUT3-immunofluorescent spots revealed that 34% of CINs SVs contain both VAChT and VGLUT3. In addition, 40% of SVs expressed only VAChT while 26% of SVs contain only VGLUT3. These results suggest that SVs from CINs have the potential to store simultaneously or independently ACh and/or Glut. Overall, these morphological findings support the notion that CINs varicosities can signal with either ACh or Glut or both with an unexpected level of complexity.
Published: 2022

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