Descriptor: "[CHIM.ORGA] Chemical Sciences/Organic chemistry" - Searchworks@Jio Institute Digital Library Search Results

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3,676 results on '"[CHIM.ORGA] Chemical Sciences/Organic chemistry"'

1. Tricyclic SpiroLactams Kill Mycobacteria In Vitro and In Vivo by Inhibiting Type II NADH Dehydrogenases

Author: Sushovan Dam, Salia Tangara, Claire Hamela, Theo Hattabi, Léo Faïon, Paul Carre, Rudy Antoine, Adrien Herledan, Florence Leroux, Catherine Piveteau, Maxime Eveque, Marion Flipo, Benoit Deprez, Laurent Kremer, Nicolas Willand, Baptiste Villemagne, Ruben C. Hartkoorn, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), CHU Lille, Médicaments et molécules pour agir sur les Systèmes Vivants - U 1177 (M2SV), Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille, Institut de Recherche en Infectiologie de Montpellier (IRIM), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), the CPER grants were funded by European Union under the European Regional Development Fund (ERDF) and by the Hauts de Franceregional Council (contract n°20002842 and contract n°18006176), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-19-CE18-0034,NL4TB,Nouvelle génération de composés Lead pour combattre la tuberculose(2019), and Willand, Nicolas
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Antitubercular Agents, Mycobacterium tuberculosis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, NAD, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Drug Discovery, Animals, Molecular Medicine, NADH, NADPH Oxidoreductases, [SDV.MP.BAC] Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Zebrafish
Abstract: International audience; It is critical that novel classes of antituberculosis drugs are developed to combat the increasing burden of infections by multidrug-resistant strains. To identify such a novel class of antibiotics, a chemical library of unique 3-D bioinspired molecules was explored revealing a promising, mycobacterium specific Tricyclic SpiroLactam (TriSLa) hit. Chemical optimization of the TriSLa scaffold delivered potent analogues with nanomolar activity against replicating and nonreplicating Mycobacterium tuberculosis. Characterization of isolated TriSLa-resistant mutants, and biochemical studies, found TriSLas to act as allosteric inhibitors of type II NADH dehydrogenases (Ndh-2 of the electron transport chain), resulting in an increase in bacterial NADH/NAD+ ratios and decreased ATP levels. TriSLas are chemically distinct from other inhibitors of Ndh-2 but share a dependence for fatty acids for activity. Finally, in vivo proof-of-concept studies showed TriSLas to protect zebrafish larvae from Mycobacterium marinum infection, suggesting a vulnerability of Ndh-2 inhibition in mycobacterial infections.
Published: 2022

2. On drug discovery against infectious diseases and academic medicinal chemistry contributions

Author: Yves L Janin, Structure et Instabilité des Génomes (STRING), Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Janin, Yves
Subjects: frequent hitters, [CHIM.ORGA]Chemical Sciences/Organic chemistry, hit to lead chemical library, medicinal chemistry, Organic Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, virtual docking, antibacterials
Abstract: International audience; This perspective is an attempt to document the problems that medicinal chemists are facing in drug discovery. It is also trying to identify relevant/possible, research areas in which academics can have an impact and should thus be the subject of grant calls. Accordingly, it describes how hit discovery happens, how compounds to be screened are selected from available chemicals and the possible reasons for the recurrent paucity of useful/exploitable results reported. This is followed by the successful hit to lead stories leading to recent and original antibacterials which are, or about to be, used in human medicine. Then, illustrated considerations and suggestions are made on the possible inputs of academic medicinal chemists. This starts with the observation that discovering a “good” hit in the course of a screening campaign still rely on a lot of luck – which is within the reach of academics –, that the hit to lead process requires a lot of chemistry and that if public–private partnerships can be important throughout these stages, they are absolute requirements for clinical trials. Concerning suggestions to improve the current hit success rate, one academic input in organic chemistry would be to identify new and pertinent chemical space, design synthetic accesses to reach these and prepare the corresponding chemical libraries. Concerning hit to lead programs on a given target, if no new hits are available, previously reported leads along with new structural data can be pertinent starting points to design, prepare and assay original analogues. In conclusion, this text is an actual plea illustrating that, in many countries, academic research in medicinal chemistry should be more funded, especially in the therapeutic area neglected by the industry. At the least, such funds would provide the intensive to secure series of hopefully relevant chemical entities which appears to often lack when considering the results of academic as well as industrial screening campaigns.
Published: 2022

3. 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

4. Thiol Catalysis of Selenosulfide Bond Cleavage by a Triarylphosphine

Author: Olga Firstova, Oleg Melnyk, Vincent Diemer, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), and Diemer, Vincent
Subjects: Phosphines, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Proteins, [CHIM.CATA] Chemical Sciences/Catalysis, Indicators and Reagents, Sulfhydryl Compounds, [CHIM.CATA]Chemical Sciences/Catalysis, Peptides, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract: International audience; The arylthiol 4-mercaptophenylacetic acid (MPAA) is a powerful catalyst of selenosulfide bond reduction by the triarylphosphine 3,3′,3″-phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS). Both reagents are water-soluble at neutral pH and are particularly adapted for working with unprotected peptidic substrates. Contrary to trialkylphosphines such as tris(2-carboxyethyl)phosphine hydrochloride (TCEP), TPPTS has the advantage of not inducing deselenization reactions. We believe that the work reported here will be of value for those manipulating selenosulfide bonds in peptidic or protein molecules.
Published: 2022

5. Light-Driven Molecular Whirligig

Author: Chuan Gao, Andreas Vargas Jentzsch, Emilie Moulin, Nicolas Giuseppone, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Moulin, Emilie
Subjects: [CHIM.POLY] Chemical Sciences/Polymers, Polymers, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Molecular Motor Proteins, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Catalysis, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, Torque, Humans, Child, Mechanical Phenomena
Abstract: International audience; An unidirectional light-driven rotary motor was looped in a figure-of-eight molecule by linking two polymer chains between its stator and rotor parts. By properly tuning the size of these linkers, clockwise rotation of the motor under UV light was shown to create conformationally strained twists between the polymer chains and, in this tensed conformation, the energy stored in the molecular object was sufficient to trigger the reverse rotation of the motor back to its fully relaxed state. The functioning principle of this motorized molecular device appears very similar to the one of macroscopic whirligig crafts used by children for fun. In addition, we found that in its out-of-equilibrium tensed state, the fluorescence emission of the molecular motor increased by 500% due to the mechanical constraints imposed by the polymer chains on its conjugated core. Finally, by calculating the apparent thermal energies of activation for the backward rotations at different levels of twisting, we quantitatively determined a lower estimate of the work generated by this rotary motor, from which a torque and a force were extracted, thus answering a long-term open question in this field of research.
Published: 2022

6. Imaging and Measuring Vesicular Acidification with a Plasma Membrane-Targeted Ratiometric pH Probe

Author: Sophie Michelis, Lydia Danglot, Romain Vauchelles, Andrey S. Klymchenko, Mayeul Collot, Laboratoire de Bioimagerie et Pathologies (LBP), Université de Strasbourg (UNISTRA)-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), and Collot, Mayeul
Subjects: [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, Cell Membrane, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, Hydrogen-Ion Concentration, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Lysosomes, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, Endocytosis, Fluorescent Dyes, Analytical Chemistry
Abstract: International audience; Tracking the pH variation of intracellular vesicles throughout the endocytosis pathway is of prior importance to better assess the cell trafficking and metabolism of cells. Small molecular fluorescent pH probes are valuable tools in bioimaging but are generally not targeted to intracellular vesicles or are directly targeted to acidic lysosomes, thus not allowing the dynamic observation of the vesicular acidification. Herein, we designed Mem-pH, a fluorogenic ratiometric pH probe based on chromenoquinoline with appealing photophysical properties, which targets the plasma membrane (PM) of cells and further accumulates in the intracellular vesicles by endocytosis. The exposition of Mem-pH toward the vesicle's lumen allowed to monitor the acidification of the vesicles throughout the endocytic pathway and enabled the measurement of their pH via ratiometric imaging.
Published: 2022

7. Blue-Emitting 2-(2′-Hydroxyphenyl)benzazole Fluorophores by Modulation of Excited-State Intramolecular Proton Transfer: Spectroscopic Studies and Theoretical Calculations

Author: Maxime Munch, Erika Colombain, Timothée Stoerkler, Pauline M. Vérité, Denis Jacquemin, Gilles Ulrich, Julien Massue, Massue, Julien, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Ecole européenne de chimie, polymères et matériaux [Strasbourg], Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, and Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)
Subjects: Models, Molecular, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Spectrometry, Fluorescence, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, Hydrogen Bonding, Protons, Physical and Theoretical Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Fluorescent Dyes, Surfaces, Coatings and Films
Abstract: International audience; This article describes the synthesis, spectroscopic studies, and theoretical calculations of nine original fluorophores based on the 2-(2′-hydroxyphenyl)benzazole (HBX) scaffold, functionalized at the 4-position of the phenol ring by ethynyl-extended aniline moieties. HBX dyes are well-known to display an excited-state intramolecular proton transfer (ESIPT) process, owing to a strong six-membered hydrogen bond in their structure that allows for an enol/keto tautomerism after photoexcitation. Appropriate electronic substitution can perturb the ESIPT process, leading to dual fluorescence, both excited tautomers emitting at specific wavelengths. In the examples described herein, it is demonstrated that the proton transfer can be finely frustrated by a modification of the constitutive heteroring, leading to a single emission band from the excited enol or keto tautomer or a dual emission with relative intensities highly dependent on the environment. Moreover, the nature of the functionalization of the N-alkylated aniline moiety also has a significant importance on the relative excited-state stabilities of the two tautomers in solution. To shed more light on these features, quantum chemical calculations by the density functional theory are used to determine the excited-state energies and rationalize the experimental spectroscopic data.
Published: 2022

8. Rapid and Mild Metal-Free Reduction of Epoxides to Primary Alcohols Mediated by HFIP

Author: Marie Vayer, Shaofei Zhang, Joseph Moran, David Lebœuf, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and univOAK, Archive ouverte
Subjects: Brønsted acid, epoxides, hexafluoroisopropanol, [CHIM.ORGA]Chemical Sciences/Organic chemistry, hydrogenolysis, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, (hetero)cycles, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract: The reduction of epoxides is a powerful tool to access anti-Markovnikov alcohols, but reported methods are poorly compatible with strongly electronically deactivated substrates. Here, we describe a general method for the linear-selective reduction of styryl oxides incorporating strong electron-withdrawing groups. The method remains compatible with more traditional epoxide motifs, such as aliphatic and electron-rich styrene oxides. Other (hetero)cycles such as oxetanes, tetrahydrofurans, aziridines, and cyclopropanes can also be reductively opened. This user-friendly reaction relies on the combination of a Brønsted acid catalyst and hexafluoroisopropanol as a solvent, and thus, in contrast to existing epoxide reduction methods, it does not require anhydrous reagents or an inert atmosphere. The generated primary alcohols can be conveniently functionalized in situ by a dehydrative Friedel–Crafts arylation without preactivation
Published: 2022

9. 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

10. Very intense polarized emission in self-assembled room temperature metallomesogens based on Zn(<scp>ii</scp>) coordination complexes: an experimental and computational study

Author: Elisabeta I. Szerb, Emilie Voirin, Otilia Costisor, Bertrand Donnio, Mario Amati, Benoît Heinrich, Massimo La Deda, Valentin Badea, Angela Candreva, Giuseppe Di Maio, Evelyn Popa, Adelina A. Andelescu, Donnio, Bertrand, Università della Calabria [Arcavacata di Rende] (Unical), 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), Romanian Academy, Politehnica University of Timisoara (UPT), and Università degli studi della Basilicata [Potenza] (UNIBAS)
Subjects: [CHIM.INOR] Chemical Sciences/Inorganic chemistry, [PHYS.PHYS.PHYS-OPTICS] Physics [physics]/Physics [physics]/Optics [physics.optics], [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Quenching (fluorescence), Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Transition dipole moment, Quantum yield, Mesophase, General Chemistry, Time-dependent density functional theory, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Crystallography, chemistry.chemical_compound, chemistry, Excited state, [CHIM.CRIS]Chemical Sciences/Cristallography, Materials Chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.CRIS] Chemical Sciences/Cristallography, Terpyridine
Abstract: International audience; Three room-temperature metallomesogens based on Zn(II) cations pentacoordinated by different chelating N^N^N terpyridines and two monodentate gallate co-ligands were designed and synthesized. Depending on the terpyridine ligand's tip functionality, the complexes self-assemble into either a 3D hexagonal mesophase or into a columnar hexagonal mesophase. A systematic study between the structure (molecular architecture, arrangement of the molecules and columns, and chains in both types of mesophases) and photophysical properties (emission maxima and yields, lifetimes of the excited states in the mesophase), correlated with investigations of single molecules in solution, was conducted. Remarkably, one complex exhibited a record quantum yield of 95.0% in solution, while in the mesophase, despite quenching due to the radiative deactivation from the ILCT state, still retained a considerable emission yield of ϕ = 20.2%. The polarized emission of an oriented film, determined for the first time in columnar metallomesogens, shows a dichroic emission ratio (I||/I⊥) of 1.30. DFT and TDDFT computational studies confirmed the origin of the observed fluorescence anisotropy from the transition dipole moment oriented along the C2 symmetry axis of the molecule combined with a high level of order in the 3D mesophase.
Published: 2022

11. Site‐Selective Unnatural Amino Acid Incorporation at Single or Multiple Positions to Control Sugar‐Protein Connectivity in Glycoconjugate Vaccine Candidates

Author: Typhaine Violo, Annie Lambert, Aline Pillot, Mathieu Fanuel, Jessica Mac‐Béar, Cédric Broussard, Cyrille Grandjean, Emilie Camberlein, Unité en Sciences Biologiques et Biotechnologies de Nantes - UMR CNRS 6286 (US2B), Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut Cochin (IC UM3 (UMR 8104 / U1016)), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), The Region Pays de la Loire 'pari scientifique program BioSynProt', Nantes University, the GlycoOuest program, COST Action CA18103: INNOGLY: INNOvation with GLYcans: new frontiers from synthesis to new biological targets and the GDR ChemBio Chémobiologie., and DUPRE, Olivier
Subjects: immunology, Streptococcus pneumoniae, unnatural amino acid, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, synthetic biology, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis, glycoconjugate
Abstract: International audience; Incellulosite-specific unnatural amino acid incorporation based on amber stop codon reassignment is a powerful tool to modify protein at defined positions. This technique is herein applied to the selective functionalization of the Pneumococcal surface adhesin A protein at three distinct positions. N-propargyloxycarbonyl-L-lysine residues were incorporated and their alkyne groups reacted using click-chemistry with a synthetic azido-functionalized tetrasaccharide representative of one repeat unit of the Streptococcus pneumoniaeserotype 14 capsular polysaccharide. Anti-PsaA antibody response induced in mice by the trivalent glycoconjugate was determined in comparison with corresponding monovalent and randomly functionalized conjugates. Our results suggest that controlled was superior to random conjugation for preserving antigenicity. In definitive, the reported strategy offers a unique opportunity to study the impact of carbohydrate antigen-carrier protein connectivity on immunogenicity.
Published: 2023

12. Hierarchical Self-Assembly and Multidynamic Responsiveness of Fluorescent Dynamic Covalent Networks Forming Organogels

Author: Esteban Suárez-Picado, Maëva Coste, Jean-Yves Runser, Mathieu Fossépré, Alain Carvalho, Mathieu Surin, Loïc Jierry, Sébastien Ulrich, ULRICH, Sebastien, 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), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Université de Mons (UMons)
Subjects: gel, Biomaterials, Polymers and Plastics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, Bioengineering, Self-assembly, dynamic covalent chemistry, acyl-hydrazone, fluorescence, Peptides, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Fluorescent Dyes
Abstract: International audience; Smart stimuli-responsive fluorescent materials are of interest in the context of sensing and imaging applications. In this project, we elaborated multidynamic fluorescent materials made of a tetraphenylethene fluorophore displaying aggregation-induced emission and short cysteine-rich C-hydrazide peptides. Specifically, we show that a hierarchical dynamic covalent self-assembly process, combining disulfide and acyl-hydrazone bond formation operating simultaneously in a one-pot reaction, yields cage compounds at low concentration (2 mM), while soluble fluorescent dynamic covalent networks and even chemically cross-linked fluorescent organogels are formed at higher concentrations. The number of cysteine residues in the peptide sequence impacts directly the mechanical properties of the resulting organogels, Young’s moduli varying 2500-fold across the series. These materials underpinned by a nanofibrillar network display multidynamic responsiveness following concentration changes, chemical triggers, as well as light irradiation, all of which enable their controlled degradation with concomitant changes in spectroscopic outputs─self-assembly enhances fluorescence emission by ca. 100-fold and disassembly quenches fluorescence emission.
Published: 2021

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

Author: Kossi Efouako Soklou, Hamid Marzag, Karen Plé, Sylvain Routier, Béatrice Vallée, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PLE, Karen, Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nitrogen heterocycles, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Molecular Diversity, Gold catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Synthetic methods, Organic chemistry, Spiro Compounds
Abstract: International audience; Gold-(I) catalysis was used for the intramolecular cyclization of tertiary alcohols with terminal alkynes to form diverse aza-spirocycles. The reaction was carried out with low catalyst loading under microwave irradiation to give both sulfonylated and acylated spirocyclic nitrogen derivatives. Gram scale spirocyclization was carried out and demonstrates the robustness of the reaction. An intramolecular Mizoroki-Heck reaction was performed to give several tetracyclic spirocycles. Double bond reduction and selective protecting group manipulation gave spiropiperazine and spiromorpholine derivatives. These compounds were incorporated into biologically relevant scaffolds to give the first selective spirocyclic inhibitors of LIMK.
Published: 2021

14. Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Author: Andrei Golushko, Florent Noël, Shaofei Zhang, Marie Vayer, Nazanin Rezajooei, Christopher N. Rowley, Vuk D. Vuković, Joseph Moran, David Lebœuf, Institut de Science et d'ingénierie supramoléculaires (ISIS), 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)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Department of Chemistry, Memorial University of Newfoundland, St. John's, Canada, Memorial University of Newfoundland [St. John's], Carleton University, univOAK, Archive ouverte, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemical Engineering, Biochemistry (medical), [CHIM.CATA] Chemical Sciences/Catalysis, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Alkylation, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Electrophile, Materials Chemistry, Nucleophilic substitution, Environmental Chemistry, Organic chemistry, SN2 reaction, Brønsted–Lowry acid–base theory, Friedel–Crafts reaction
Abstract: International audience; Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they are widely available, require no pre-activation, and produce no stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal epoxides are compatible with existing intermolecular Friedel-Crafts methodologies, and sequential Friedel-Crafts reactions starting from epoxides consequently remain underexplored. Here, we report that these limitations are easily overcome using Brønsted acid catalysis in hexafluoroisopropanol (HFIP) as a solvent. Electron-poor aromatic epoxides and aliphatic epoxides undergo stereospecific arylation to give an alcohol which, depending on the reaction conditions, can partake in a second nucleophilic substitution with a different arene in one pot. Phenyl ethanols react through a phenonium intermediate, whereas simple aliphatic alcohols participate in a rare intermolecular SN2 Friedel-Crafts process, delivering linear products exclusively. This work provides an alternative to metal-catalyzed cross-couplings for accessing important scaffolds, widening the range of applications of the Friedel-Crafts reaction
Published: 2021

15. Autonomous Non‐Equilibrium Self‐Assembly and Molecular Movements Powered by Electrical Energy**

Author: Giulio Ragazzon, Marco Malferrari, Arturo Arduini, Andrea Secchi, Stefania Rapino, Serena Silvi, Alberto Credi, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), University of Bologna/Università di Bologna, Università degli studi di Parma = University of Parma (UNIPR), Consiglio Nazionale delle Ricerche [Bologna] (CNR), ANR-10-IDEX-0002,UNISTRA,Par-delà les frontières, l'Université de Strasbourg(2010), European Project: 692981,LEAPS, and univOAK, Archive ouverte
Subjects: Molecular Machines, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Calixarene, Electrochemistry, General Chemistry, General Medicine, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Non-Equilibrium Processes, SECM, Catalysis
Abstract: The ability to exploit energy autonomously is one of the hallmarks of Life. Mastering such processes in artificial nanosystems can open unforeseen technological opportunities. In the last decades, light- and chemically-driven autonomous systems have been developed in relation to conformational motion and self-assembly, mostly in relation to molecular motors. On the contrary, despite electrical energy is an attractive energy source to power nanosystems, its autonomous exploitation remains essentially unexplored. Herein we demonstrate the autonomous exploitation of electrical energy by a self-assembling system. Threading and dethreading motions of a pseudorotaxane take place autonomously in solution, between the electrodes of a scanning electrochemical microscope. This innovative actuation mode allows operating a molecular machine with an energy efficiency of 9%, unprecedented in autonomous systems. The strategy is general and can be applied to any redox-driven system. Ultimately, our study brings molecular nanoscience one step closer to everyday technology.
Published: 2022

16. Quantification of the hydride donor abilities of NADH, NADPH, and BH 3 CN − in water

Author: Joseph Moran, Robert Mayer, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and univOAK, Archive ouverte
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Physical and Theoretical Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry
Abstract: The nucleophilic reactivities of the hydride donors NADH, NADPH, and BH3CN- in water were quantified using kinetic measurements with benzhydrylium ions as reference electrophiles. All three hydride donors were found to possess almost identical nucleophilic reactivities, providing a potential explanation for why they are involved in similar transformations in biochemistry and organic synthesis, respectively.
Published: 2022

17. Optimization of G‐Quadruplex Ligands through a SAR Study Combining Parallel Synthesis and Screening of Cationic Bis(acylhydrazones)

Author: Oksana Reznichenko, Denis Leclercq, Jaime Franco Pinto, Liliane Mouawad, Valérie Gabelica, Anton Granzhan, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Acides Nucléiques : Régulations Naturelle et Artificielle (ARNA), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Européen de Chimie et Biologie (IECB), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), French Ministry of Higher Education, Research and Innovation (PhD fellowship, to OR), European Union's Horizon 2020 Framework Programme(Marie Skłodowska-Curie Grant Agreement No. 666003 through an IC-3i international PhD programme, to JFP), and benefited from access to Plateforme de BioPhysico-Chimie Structurale of the IECB (Univ. Bordeaux, CNRS UMS3033, Inserm US001) for native mass spectrometry., ANR-17-CE07-0004,DYCONAS,Chimie dynamique constitutionnelle pour les structures d'acides nucléiques(2017), GRANZHAN, Anton, and Chimie dynamique constitutionnelle pour les structures d'acides nucléiques - - DYCONAS2017 - ANR-17-CE07-0004 - AAPG2017 - VALID
Subjects: G4 ligands, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Nitrogen heterocycles, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, Combinatorial chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, G-quadruplexes, N-acylhydrazones, Catalysis
Abstract: International audience; G-quadruplexes (G4s), secondary structures adopted by guanine-rich DNA and RNA sequences, are implicated in numerous biological processes and have been suggested as potential drug targets. Accordingly, there is an increasing interest in developing high-throughput methods allowing the generation of congeneric series of G4-targeting molecules (“ligands”) and investigation of their interaction with the targets. Here, we developed an operationally simple method of parallel synthesis to generate “ready-to-screen” libraries of cationic acylhydrazones, a motif that we have previously identified as a promising scaffold for potent, biologically active G4 ligands. Combined with well-established screening techniques, such as fluorescence melting, this method enables rapid synthesis and screening of combinatorial libraries of potential G4 ligands. Following this protocol, we synthesized a combinatorial library of 90 bis(acylhydrazones) and screened it against five different nucleic acid structures. This way, we were able to analyze the structure-activity relationships within this series of G4 ligands, and identified three novel promising ligands whose interaction with G4-DNA of different topologies was carefully studied by a combination of several biophysical techniques, including native mass spectrometry, and molecular modeling.
Published: 2022

18. Catalytic methoxylation of aryl halides using $^{13}$C- and $^{14}$C-labeled CO$_2$

Author: Alexia Ohleier, Antoine Sallustrau, Bouchaib Mouhsine, Fabien Caillé, Davide Audisio, Thibault Cantat, Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Laboratoire d'Imagerie Biomédicale [Paris] (LIB), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), European Project: ERC CoG n°818260 ,ReNewHydrides, European Project: ERC-2019-COG-864576,FASTLABEx, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), LaBoratoire d'Imagerie biOmédicale MultimodAle Paris-Saclay (BIOMAPS), Service Hospitalier Frédéric Joliot (SHFJ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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 la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), CEA (DRF Impulsion 2017), ANR-19-CE07-0046,Thio-Fun,Thio-fonctionnalisation et radiomarquage au 35S de peptides et protéines(2019), Palacin, Serge, Thio-fonctionnalisation et radiomarquage au 35S de peptides et protéines - - Thio-Fun2019 - ANR-19-CE07-0046 - AAPG2019 - VALID, Renewable Hydride Donors and Their Utilization in Catalytic Reduction and Deoxygenation Reactions - ReNewHydrides - ERC CoG n°818260 - INCOMING, and Fast Radio-Labeling and Isotope Exchange - FASTLABEx - ERC-2019-COG-864576 - INCOMING
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM]Chemical Sciences, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; The functionalization of carbon dioxide (CO$_2$) into high-value building blocks is a relevant topic in carbon isotope labeling, where CO$_2$ is the primary carbon source. A catalytic methoxylation of aryl halides directly from [$^{13}$C] and [$^{14}$C]CO$_2$ is reported. Relying on the intermediacy of the methoxyborane BBN-OCH$_3$, as a new secondary nucleophilic labeled source, this strategy allowed labeling of a series of substrates, including challenging pharmaceuticals containing tertiary alkyl amine substituents.
Published: 2022
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19. Direct capture, inhibition and crystal structure of HsaD (Rv3569c) from M. tuberculosis

Author: Sarah Barelier, Romain Avellan, Giri Raj Gnawali, Patrick Fourquet, Véronique Roig‐Zamboni, Isabelle Poncin, Vanessa Point, Yves Bourne, Stéphane Audebert, Luc Camoin, Christopher D. Spilling, Stéphane Canaan, Jean‐François Cavalier, Gerlind Sulzenbacher, Architecture et fonction des macromolécules biologiques (AFMB), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Laboratoire d'ingénierie des systèmes macromoléculaires (LISM), Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), University of Missouri [St. Louis], University of Missouri System, Centre de Recherche en Cancérologie de Marseille (CRCM), Aix Marseille Université (AMU)-Institut Paoli-Calmettes, Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Fédération nationale des Centres de lutte contre le Cancer (FNCLCC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), ANR-19-CE44-0011,LipInTB,Utilisation de nouveaux inhibiteurs sélectifs pour décrypter le métabolisme lipidique et de la virulence chez M. tb(2019), Cavalier, Jean-François, and Utilisation de nouveaux inhibiteurs sélectifs pour décrypter le métabolisme lipidique et de la virulence chez M. tb - - LipInTB2019 - ANR-19-CE44-0011 - AAPG2019 - VALID
Subjects: [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV.BBM.BS] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], [CHIM.THER] Chemical Sciences/Medicinal Chemistry, click chemistry activity-based protein profiling, Cell Biology, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Antituberculous molecules, Cholesterol metabolism, Inhibition mechanism, Cyclipostins and Cyclophostin, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Molecular Biology, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM]
Abstract: International audience; A hallmark of Mycobacterium tuberculosis (M. tb), the etiologic agent of tuberculosis, is its ability to metabolize host-derived lipids. However, the enzymes and mechanisms underlying such metabolism are still largely unknown. We previously reported that the Cyclophostin & Cyclipostins (CyC) analogs, a new family of potent antimycobacterial molecules, react specifically and covalently with (Ser/Cys)-based enzymes mostly involved in bacterial lipid metabolism. Here, we report the synthesis of new CyC alkyne-containing inhibitors (CyCyne) and their use for the direct fishing of target proteins in M. tb culture via bio-orthogonal click-chemistry activity-based protein profiling (CC-ABPP). This approach led to the capture and identification of a variety of enzymes, many of them involved in lipid or steroid metabolisms. One of the captured enzymes, HsaD (Rv3569c), is required for the survival of M. tb within macrophages and is thus a potential therapeutic target. This prompted us to further explore and validate, through a combination of biochemical and structural approaches, the specificity of HsaD inhibition by the CyC analogs. We confirmed that the CyC bind covalently to the catalytic Ser114 residue, leading to a total loss of enzyme activity. These data were supported by the X-ray structures of four HsaD-CyC complexes, obtained at resolutions between 1.6-2.6 Å. The identification of mycobacterial enzymes directly captured by the CyCyne probes through CC-ABPP paves the way to better understand and potentially target key players at crucial stages of the bacilli life-cycle.
Published: 2022

20. A fragment-based drug discovery strategy applied to the identification of NDM-1 β-lactamase inhibitors

Author: Jérémy Caburet, Benjamin Boucherle, Sofiane Bourdillon, Giorgia Simoncelli, Federica Verdirosa, Jean-Denis Docquier, Yohann Moreau, Isabelle Krimm, Serge Crouzy, Marine Peuchmaur, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département de pharmacochimie moléculaire (DPM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Università degli Studi di Siena = University of Siena (UNISI), Université de Liège, Centre de Recherche en Cancérologie de Lyon (UNICANCER/CRCL), Centre Léon Bérard [Lyon]-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Krimm, Isabelle, and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Pharmacology, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, High throughput virtual screening, [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], metallo-β-lactamase, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, General Medicine, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, NDM-1, [CHIM.ORGA] Chemical Sciences/Organic chemistry, beta-Lactams, beta-Lactamases, Anti-Bacterial Agents, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM] Chemical Sciences, Drug Discovery, [CHIM]Chemical Sciences, beta-Lactamase Inhibitors, STD NMR screening, Fragment-Based Drug Discovery
Abstract: International audience; Hydrolysis of β-lactam drugs, a major class of antibiotics, by serine or metallo-β-lactamases (SBL or MBL) is one of the main mechanisms for antibiotic resistance. New Delhi Metallo-β-lactamase-1 (NDM-1), an acquired metallo-carbapenemase first reported in 2009, is currently considered one of the most clinically relevant targets for the development of β-lactam-β-lactamase inhibitor combinations active on NDM-producing clinical isolates. Identification of scaffolds that could be further rationally pharmacomodulated to design new and efficient NDM-1 inhibitors is thus urgently needed. Fragment-based drug discovery (FBDD) has become of great interest for the development of new drugs for the past few years and combination of several FBDD strategies, such as virtual and NMR screening, can reduce the drawbacks of each of them independently. Our methodology starting from a high throughput virtual screening on NDM-1 of a large library (more than 700,000 compounds) allowed, after slicing the hit molecules into fragments, to build a targeted library. These hit fragments were included in an in-house untargeted library fragments that was screened by Saturation Transfer Difference (STD) Nuclear Magnetic Resonance (NMR). 37 fragments were finally identified and used to establish a pharmacophore. 10 molecules based on these hit fragments were synthesized to validate our strategy. Indenone 89 that combined two identified fragments shows an inhibitory activity on NDM-1 with a K i value of 4 µM.
Published: 2022

21. Tunable Approach to C-Linked Analogs of Glycosamines

Author: Tuniyazi Abuduaini, Sizhe Li, Vincent Roy, Luigi A. Agrofoglio, Olivier R. Martin, Cyril Nicolas, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and NICOLAS, Cyril
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Cyclization, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, Deoxy Sugars, Benzene, Stereoisomerism, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Palladium
Abstract: International audience; The synthesis of (1R)-2-amino-2-deoxy-β-L-gulopyranosyl benzene, and the α and β form of 2-amino-2-deoxy-Lidopyranosyl benzene derivatives was accomplished through stereospecific addition of tributylstannyllithium to readily available (SR)-or (SS)-N-tert-butanesulfinyl-arabinofuranosylamine building blocks, followed by stereoretentive Pd-catalyzed Migita-Kosugi-Stille cross-coupling, stereoselective reduction and an activation-cyclization strategy. Application of this methodology paves the way to new three-dimensional chemical space and preparation of unknown (non-natural) and complex 2-amino-2-deoxy sugars of biological interest.
Published: 2022

22. Photoactivatable Small‐Molecule Inhibitors for Light‐Controlled TAM Kinase Activity

Author: Sandrine Piguel, Liliane Mouawad, Sophie Bombard, Thomas Boddaert, Julie Le Bescont, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), 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)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and bombard, sophie
Subjects: protein kinases, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Hardware_PERFORMANCEANDRELIABILITY, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, small molecule inhibitors, 01 natural sciences, Small molecule, imidazopyridines, 0104 chemical sciences, 3. Good health, Analytical Chemistry, Biochemistry, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Hardware_INTEGRATEDCIRCUITS, photopharmacology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, photocaging, Physical and Theoretical Chemistry, Kinase activity
Abstract: International audience; Supporting information for this article is given via a link at the end of the document.
Published: 2021

23. Dual‐State Emissive π‐Extended Salicylaldehyde Fluorophores: Synthesis, Photophysical Properties and First‐Principle Calculations

Author: Denis Frath, Timothée Stoerkler, Julien Massue, Denis Jacquemin, Gilles Ulrich, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Frath, Denis
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Doping, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, Ring (chemistry), Photochemistry, 01 natural sciences, Fluorescence, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, Salicylaldehyde, Ab initio quantum chemistry methods, Intramolecular force, First principle, Moiety, Physical and Theoretical Chemistry
Abstract: International audience; The search for simple, low-cost, versatile, easily accessible, stimuli-responsive, highly emissive molecular fluorophores emitting both in solution and in the solid-state has prompted us to investigate the optical properties of a series of synthetically accessible salicyladehyde derivatives possessing a π-conjugated moiety at their 4-position. These dyes are mainly known as synthetic intermediates but can also display sizeable Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence owing to the presence of a 6-membered H-bonded ring in their structure. The photophysical properties of these compounds have been studied in solution (multiple solvents) and in the solid-state, as doped in PMMA films, leading to the observation of a pronounced fluorosolvatochromism. Modification of the spacer (ethynyl, vinyl or direct connection) involved the π-delocalization triggers major differences in terms of maximum emission wavelength and fluorescence quantum yields in the various media studied. All photophysical observations are rationalized by first-principle calculations.
Published: 2021

24. Modulation of Cellular Fate of Vinyl Triarylamines through Structural Fine Tuning: To Stay or Not To Stay in the Mitochondria?

Author: Marie-Paule Teulade-Fichou, Delphine Naud-Martin, Rahima Chennoufi, Sounderya Nagarajan, Eric Deprez, Aude Sourdon, Florence Mahuteau-Betzer, Florent Poyer, Laura Fourmois, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de biologie et pharmacologie appliquée (LBPA), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), and Mahuteau-Betzer, Florence
Subjects: Mitochondrial DNA, Chemical biology, Context (language use), Mitochondrion, 01 natural sciences, Biochemistry, 03 medical and health sciences, chemistry.chemical_compound, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Inner mitochondrial membrane, Molecular Biology, 030304 developmental biology, 0303 health sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Depolarization, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Mitochondria, 0104 chemical sciences, Nuclear DNA, Biophysics, Molecular Medicine, DNA
Abstract: International audience; Mitochondria is involved in many cellular pathways and dysfunctional mitochondria are linked to various diseases. Hence efforts have been driven to design mitochondria-targeted fluorophores for monitoring the mitochondria status. However, the factors that govern the mitochondria-targeted potential of dyes are not well-understood. In this context, we synthesized analogues of the TP-2Bzim probe belonging to the vinyltriphenylamine (TPA) class and already described for its capacity to bind nuclear DNA in fixed cells and mitochondria in live cells. These analogues (TP-1Bzim, TP n-2Bzim, TP 1+-2Bzim, TN-2Bzim) differ by the cationic charge, the number of vinylbenzimidazolium branches and the nature of the triaryl core. Using microscopy, we demonstrated that the cationic derivatives accumulate in mitochondria but do not reach mtDNA. Under depolarisation of the mitochondrial membrane, TP-2Bzim and TP 1+-2Bzim translocate to the nucleus in direct correlation with their strong DNA affinity. This reversible phenomenon emphasizes that these probes can be used to monitor ΔΨm variations.
Published: 2021

25. Quantifying Reductive Amination in Nonenzymatic Amino Acid Synthesis

Author: Robert J. Mayer, Joseph Moran, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and univOAK, Archive ouverte
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Reductive Amination, Glutamic Acid, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Keto Acids, Catalysis, Kinetics, Metabolism, Hydride Transfer, Ammonia, Ketoglutaric Acids, Amino Acids, Amines, Amination
Abstract: Amino acid biosynthesis initiates with the reductive amination of α-ketoglutarate with ammonia to produce glutamate. However, the other α-keto acids derived from the glyoxylate and Krebs cycles are converted into amino acids by transamination, rather than by reductive amination. Why is only one amino acid synthesized by reductive amination and not the others? To explore this question, we quantified the inherent reactivities of keto acids in nonenzymatic reduction and reductive amination by using BH3 CN- as a model nucleophile. Biological α-keto acids were found to show pronounced nonenzymatic reactivity differences for the formation of amino acids (α-ketoglutarate
Published: 2022

26. Study of Carbamoyl Fluoride: Synthesis, Properties and Applications

Author: Clémence Bonnefoy, Emmanuel Chefdeville, Christian Tourvieille, Armen Panossian, Gilles Hanquet, Frédéric Leroux, Fabien Toulgoat, Thierry Billard, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'Etude et de Recherche Multimodal Et Pluridisciplinaire en imagerie du vivant (CERMEP - imagerie du vivant), Université de Lyon-Université de Lyon-CHU Grenoble-Hospices Civils de Lyon (HCL)-CHU Saint-Etienne-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-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), and Billard, Thierry
Subjects: Fluorides, Fluorine Radioisotopes, Radiochemistry, Halogenation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract: International audience; Carbamoyl fluoride is a fluorinated group which, to this date, remains underexplored, probably due to the lack of data concerning their properties. In this paper, a study of carbamoyl fluoride is proposed. Stability studies, in particular under physiological conditions, and lipophilicity measurement have been performed. A new easy, safe, inexpensive and metal-free synthesis method has also been described. Finally, a potential use in radiochemistry through a 18 F/ 19 F isotopic exchange has been demonstrated.
Published: 2022

27. Prebiotic Isomaltooligosaccharide Provides an Advantageous Fitness to the Probiotic Bacillus subtilis CU1

Author: Romain Villéger, Emilie Pinault, Karine Vuillier-Devillers, Karine Grenier, Cornelia Landolt, David Ropartz, Vincent Sol, Maria C. Urdaci, Philippe Bressollier, Tan-Sothéa Ouk, Ecologie et biologie des interactions (EBI), Université de Poitiers-Centre National de la Recherche Scientifique (CNRS), Biologie Intégrative Santé Chimie Environnement (BISCEm), Institut Génomique, Environnement, Immunité, Santé, Thérapeutique (GEIST), Université de Limoges (UNILIM)-Université de Limoges (UNILIM), Unité de Génétique Moléculaire Animale (UMR GMA), Université de Limoges (UNILIM)-Institut National de la Recherche Agronomique (INRA), OmégaHealth (ΩHealth), PEIRENE (PEIRENE), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Bordeaux Sciences Agro [Gradignan], Ecole Nationale Supérieure des Sciences Agronomiques de Bordeaux-Aquitaine (Bordeaux Sciences Agro), Université de Limoges (UNILIM), The Région Limousin (Fr)., GIBOT LECLERC, Léa, Microbes, Intestin, Inflammation et Susceptibilité de l'Hôte (M2iSH), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre de Recherche en Nutrition Humaine d'Auvergne (CRNH d'Auvergne)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Clermont Auvergne (UCA), 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 PEIRENE (EA 7500)
Subjects: Fluid Flow and Transfer Processes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, General Engineering, [SDV.CAN]Life Sciences [q-bio]/Cancer, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, bile tolerance, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Computer Science Applications, [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, proteomics, probiotics, [SDV.CAN] Life Sciences [q-bio]/Cancer, General Materials Science, prebiotics, Instrumentation, Bacillus subtilis
Abstract: Bacillus subtilis CU1 is a probiotic strain with beneficial effects on immune health in elderly subjects and diarrhea. Commercialized under spore form, new strategies to improve the germination, fitness and beneficial effects of the probiotic once in the gut have to be explored. For this purpose, functional food ingredients, such as isomaltooligosaccharides (IMOSs), could improve the fitness of Bacillus probiotics. IMOSs are composed of α(1 → 6)- and α(1 → 4)-linked oligosaccharides and are partially indigestible. Dietary IMOSs stimulate beneficial members of intestinal microbiota, but the effect of a combination of IMOSs with probiotics, such as B. subtilis CU1, is unknown. In this study, we evaluate the potential effect of IMOSs in B. subtilis CU1 and identify the metabolic pathways involved. The biochemical analysis of the commercial IMOSs highlights a degree of polymerization (DP) comprised between 1 and 29. The metabolism of IMOSs in CU1 was attributed to an α-glucosidase, secreted in the extracellular compartment one hundred times more than with glucose, and which seems to hydrolyze high DP IMOSs into shorter oligosaccharides (DP1, DP2 and DP3) in the culture medium. Proteomic analysis of CU1 after growth on IMOSs showed a reshaping of B. subtilis CU1 metabolism and functions, associated with a decreased production of lactic acid and acetic acid by two times. Moreover, we show for the first time that IMOSs could improve the germination of a Bacillus probiotic in the presence of bile salts in vitro, with an 8 h reduced lag-time when compared to a glucose substrate. Moreover, bacterial concentration (CFU/mL) was increased by about 1 log in IMOS liquid cultures after 48 h when compared to glucose. In conclusion, the use of IMOSs in association with probiotic B. subtilis CU1 in a synbiotic product could improve the fitness and benefits of the probiotic.
Published: 2022
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28. Synthesis of carboxymethyl cyclodextrins coated zirconium based metal organic framework as original hybrid materials

Author: Rousseau, Jolanta, Hoyez, Guillaume, Rousseau, Cyril, Ponchel, Anne, Monflier, Eric, UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Maes, Luc
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry
Abstract: International audience
Published: 2022

29. Dissection of the anti-Candida albicans mannan immune response using synthetic oligomannosides reveals unique properties of β-1,2 mannotriose protective epitopes

Author: Sébastien Damiens, Faustine Dubar, Samir Jawhara, Boualem Sendid, Mayeul Collot, Karine Lecointe, Jean-Maurice Mallet, Anne-Sophie Drucbert, Daniel Poulain, Chantal Fradin, Pierre-Marie Danzé, Jean-Pierre Vilcot, Jérôme de Ruyck, Frédéric Grenouillet, Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-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), Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Facteurs de Risque et Déterminants Moléculaires des Maladies liées au Vieillissement - U 1167 (RID-AGE), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), 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), Optoélectronique - IEMN (OPTO - IEMN), INSA Institut National des Sciences Appliquées Hauts-de-France (INSA Hauts-De-France), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Centre Hospitalier Régional Universitaire de Besançon (CHRU Besançon), We thank the European Union for funding through the INTERREG V France—Wallonie—Vlaanderen program—SmartBioControl-BIOSENS project and the Programme Hospitalier de Recherche Clinique, CandiGene, 2011–1918., Unité de Glycobiologie Structurale et Fonctionnelle (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre National de la Recherche Scientifique (CNRS)-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)-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), Laboratoire des biomolécules [LBM UMR 7203], Institut de Pathologie [CHU Lille], Laboratoire de Bioimagerie et Pathologies [LBP], Médicaments et biomatériaux à libération contrôlée: mécanismes et optimisation - Advanced Drug Delivery Systems - U 1008 [MBLC - ADDS], Lille Inflammation Research International Center - U 995 [LIRIC], Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN], Laboratoire Chrono-environnement (UMR 6249) [LCE], Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 [UGSF], and Collot, Mayeul
Subjects: Antigens, Fungal, medicine.drug_class, [SDV]Life Sciences [q-bio], Science, Immunology, Oligosaccharides, Monoclonal antibody, Biochemistry, Microbiology, Article, Epitope, Mannans, 03 medical and health sciences, Antigen, Antibody Specificity, Candida albicans, medicine, 030304 developmental biology, Mannan, 0303 health sciences, Multidisciplinary, biology, 030306 microbiology, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Candidiasis, Antibodies, Monoclonal, Surface Plasmon Resonance, [CHIM.ORGA] Chemical Sciences/Organic chemistry, biology.organism_classification, Chemical biology, Corpus albicans, 3. Good health, [SDV] Life Sciences [q-bio], Polyclonal antibodies, biology.protein, Medicine, Antibody, Trisaccharides, Epitope Mapping
Abstract: Candida albicans mannan consists of a large repertoire of oligomannosides with different types of mannose linkages and chain lengths, which act as individual epitopes with more or less overlapping antibody specificities. Although anti-C. albicans mannan antibody levels are monitored for diagnostic purposes nothing is known about the qualitative distribution of these antibodies in terms of epitope specificity. We addressed this question using a bank of previously synthesized biotin sulfone tagged oligomannosides (BSTOs) of α and β anomery complemented with a synthetic β-mannotriose described as a protective epitope. The reactivity of these BSTOs was analyzed with IgM isotype monoclonal antibodies (MAbs) of known specificity, polyclonal sera from patients colonized or infected with C. albicans, and mannose binding lectin (MBL). Surface plasmon resonance (SPR) and multiple analyte profiling (MAP) were used. Both methods confirmed the usual reactivity of MAbs against either α or β linkages, excepted for MAb B6.1 (protective epitope) reacting with β-Man whereas the corresponding BSTO reacted with anti-α-Man. These results were confirmed in western blots with native C. albicans antigens. Using patients’ sera in MAP, a significant correlation was observed between the detection of anti-mannan antibodies recognizing β- and α-Man epitopes and detection of antibodies against β-linked mannotriose suggesting that this epitope also reacts with human polyclonal antibodies of both specificities. By contrast, the reactivity of human sera with other α- and β-linked BSTOs clearly differed according to their colonized or infected status. In these cases, the establishment of an α/β ratio was extremely discriminant. Finally SPR with MBL, an important lectin of innate immunity to C. albicans, classically known to interact with α-mannose, also interacted in an unexpected way with the protective epitope. These cumulative data suggest that structure/activity investigations of the finely tuned C. albicans anti-mannose immune response are worthwhile to increase our basic knowledge and for translation in medicine.
Published: 2021

30. Electrochemical TEMPO-Catalyzed Oxidative Ugi-Type Reaction

Author: Na Pan, Maegan Xinen Lee, Maxime R. Vitale, Laurence Grimaud, Louis Bunel, 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), East China Normal University [Shangaï] (ECNU), and VITALE, Maxime R.
Subjects: Cultural Studies, History, Literature and Literary Theory, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Isocyanide, Organic chemistry, Oxidative phosphorylation, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Electrosynthesis, Electrochemistry, Combinatorial chemistry, Indirect anodic oxidation, Catalysis, chemistry.chemical_compound, QD241-441, Oxidative Ugi reaction, TEMPO, human activities, Inorganic chemistry, Muticomponent reaction, QD146-197
Abstract: International audience; Oxidative isocyanide-based multicomponent reactions (oxidative IMCRs) are very useful tools for the rapid construction of molecular diversity starting from readily available and stable substrates. Despite all their benefits, such multicomponent reactions are underdeveloped and strictly limited to 3component processes. Indeed, in the presence of several reaction partners, the oxidation event needs to be rigorously chemoselective, which becomes incredibly more intricate as the number of reactive components increases. Nonetheless, we could overcome this significant pitfall and reach the first oxidative Ugi-type 4-IMCR by capitalizing on a very mild and green TEMPO-catalyzed electro-oxidation process. Employing alcohols as aldehyde surrogates and in the notable absence of any supporting electrolyte, this transformation proved to be extremely chemoselective in the presence of an amine and was compatible with a wide range of alcohols, amines, isocyanides, and carboxylic acids.
Published: 2021

31. Butterfly‐like Shape Liquid Crystals Based Fused‐Thiophene as Unidimensional Ambipolar Organic Semiconductors with High Mobility

Author: Bi-Qin Wang, Hirosato Monobe, Tao Ma, Yu-Jie Zhong, Bertrand Donnio, Ke-Qing Zhao, Ping Hu, Hai-Feng Wang, Sichuan Normal University (SNU), National Institute of Advanced Industrial Science and Technology [Tokyo] (AIST), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), National Institute of Advanced Industrial Science and Technology (AIST), 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), and Donnio, Bertrand
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, business.industry, Ambipolar diffusion, Chemistry, Mesogen, Organic Chemistry, Mesophase, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Organic semiconductor, Crystallography, Semiconductor, Liquid crystal, Charge carrier, business, Luminescence
Abstract: Mesomorphous butterfly-like shape molecules based on benzodithiophene, benzodithiophene-4,8-dione and cyclopentadithiophen-4-one core moieties were efficiently synthesized by the Suzuki-Miyaura coupling and Scholl oxidative cyclo-dehydrogenation reactions' tandem. Most of the butterfly molecules spontaneously self-organize into columnar hexagonal mesophase. The electron-deficient systems possess strong solvent-gelling ability but are not luminescent, whereas the electron-rich terms do not form gels but strongly emit light between 400 and 600 nm. The charge carrier mobility was also measured by time-of-flight transient photocurrent technique in the mesophases for some of the compounds. They display hole-transport performances with positive charge mobility in the 10 -3 cm -2 V -1 s -1 range, consistent with the high degree of ordering and stability of the columnar superstructures. One mesogen in particular with benzodithiophen-4,8-dione core shows outstanding ambipolar charge carrier transport with both high electron (μe = 6.6×10 -3 cm -2 V -1 s -1 ) and hole (μh = 4.5×10 -3 cm -2 V -1 s -1 ) mobility values.
Published: 2021

32. Synthesis and Properties of Higher Nuclearity Polyazanes

Author: Maurice Médebielle, Emmanuel Lacôte, Thomas Criton, Debora Vilona, Lionel Joucla, Elise Dumont, Guy Jacob, Lacôte, Emmanuel, Laboratoire Hydrazines et Composés Energetiques Polyazotés (LHCEP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-HERAKLES - SAFRAN-Centre National d'Études Spatiales [Toulouse] (CNES)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, ArianeGroup, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon), Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), and École normale supérieure - Lyon (ENS Lyon)
Subjects: Molecular model, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Reducing agent, Organic Chemistry, chemistry.chemical_element, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Nitrogen, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Reagent, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Diazo, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Polyazanes (that is, higher nuclearity homologues of hydrazines) with increasing numbers of bound nitrogen atoms (from 3 to 5) were prepared via additions of lower order polyazanes to diazo reagents, including the first pentazane ever described. A structure was obtained. It was shown that the polynitrogen chains adopt a helical conformation. DFT modeling shows that the arrangement subsists in solution. While the polyazanes are all reducing agents, they become less so with the increasing number of nitrogens.
Published: 2021

33. How research in green chemistry could be redefined to meet the challenges identified in the IPCC’s climate models, a personal interrogation from a young researcher

Author: Pietraru, Marie-Hélène, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Palacin, Serge
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [SDE.ES] Environmental Sciences/Environmental and Society, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, [SDE.ES]Environmental Sciences/Environmental and Society, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; From the 1960s, rising awareness on the impact of chemistry on the environment and human health led to the emergence of the concept of green chemistry, defined by Paul Anastas and John Warner in 1998 according to 12 principles. Green chemistry aimed mostly at addressing pollution-related issues, and promotes the development of chemical procedures, which are atom-economical, catalytic, energy-efficient, based on renewable feedstocks, while use and release of toxic or hazardous compounds are to be reduced.
Published: 2022

34. Photocatalytic deoxygenation of nitrogen oxide compounds

Author: Kjellberg, M., Nicolas, E., Anthore-Dalion, L., Ohleier, A., Quaranta, A., Cantat, T., Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Palacin, Serge, Laboratoire des Mécanismes fondamentaux de la Bioénergétique (LMB), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The accumulation of nitrogen oxides in the environment calls for new pathways to interconvert the various oxidation states of nitrogen, and especially their reduction. However, the large spectrum of reduction potentials covered by nitrogen oxides makes it difficult to find general systems capable of efficiently reducing various N-oxides. Commonly known as 'laughing gas', nitrous oxide N$_2$O is an ozone-depleting substance 298 times more powerful a greenhouse gas than CO$_2$. It accumulates in the atmosphere due to its kinetic stability (120 years), thus contributing to 6% of anthropogenic greenhouse effect. A solution would be the reduction of N$_2$O back to N$_2$ , which would close the nitrogen cycle; however, few methods have been proposed due to the low reactivity of N$_2$O. Herein we describe a new pathway to reduce N$_2$O back to nitrogen at room temperature by means of photocatalysis. N$_2$O being isoelectronic with CO$_2$ , inspiration came from previous work on the photoreduction of CO$_2$ to CO first disclosed by the group of Lehn. Remarkably, [Re(bpy)(CO)$_3$ Cl] and its derivatives proved successful for the reduction of N $_2$O, up to 86% yield. Encouraged by this success, we extended this methodology to the reduction of other N−O bonds, leading to a selective and synthetically applicable photocatalytic version of the deoxygenation of pyridine N-oxides. The mechanism of the NO bond deoxygenation was studied on this substrate using laser flash photolysis and spectroelectrochemistry. These mechanistic insights enabled to optimize the system by shortening the reaction time from 34 h to 2 h. This unlocked the path to the deoxygenation of a broader scope of organic, N-oxide compounds.
Published: 2022

35. Fast protein modification in the nanomolar concentration range using an oxalyl amide as latent thioester

Author: Benoît Snella, Benjamin Grain, Jérôme Vicogne, Frédéric Capet, Birgit Wiltschi, Oleg Melnyk, Vangelis Agouridas, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), CHU Lille, 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), University of Natural Resources and Life Sciences Vienna, Partenaires IRSTEA, Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA), Centrale Lille, ANR, ANR-21-CE44-0031,MISTER,Incorporation métabolique de thioesters latents hautement réactifs : une solution intégrée pour la production de protéines étiquetées et de biopolymères(2021), Universität für Bodenkultur Wien = University of Natural Resources and Life [Vienne, Autriche] (BOKU), and VICOGNE, Jérôme
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Proteins, General Medicine, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Amides, Catalysis, Thioester, Latency, S-Acyl Shift Systems, Peptides, Protein Processing, Post-Translational, Non-Native Ligation, Protein Modification
Abstract: International audience; We show that latent oxalyl thioester surrogates are a powerful means to modify peptides and proteins in highly dilute conditions in purified aqueous media or in mixtures as complex as cell lysates. Designed to be shelf-stable reagents, they can be activated on-demand for enabling ligation reactions down to peptide concentrations as low as a few hundreds nM at rates approaching 30 M-1 s-1 .
Published: 2022

36. Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling

Author: Fen Zhao, Mehdi Abdellaoui, Wided Hagui, Maria Ballarin-Marion, Jérôme Berthet, Vincent Corcé, Stéphanie Delbaere, Héloïse Dossmann, Agathe Espagne, Jérémy Forté, Ludovic Jullien, Thomas Le Saux, Virginie Mouriès-Mansuy, Cyril Ollivier, Louis Fensterbank, 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), Lille Neurosciences & Cognition - U 1172 (LilNCog), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Pigeon, Pascal, CHU Lille, Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), 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)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ESPAGNE, Agathe, ANR-17-CE07-0018,HyperSiLight,Utilisation de dérivés hypervalents du silicium en catalyse photoredox et duale(2017), and ANR-20-CE07-0038,LuxOr,Catalyse à l'or sous lumière visible(2020)
Subjects: Multidisciplinary, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, General Physics and Astronomy, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, General Biochemistry, Genetics and Molecular Biology
Abstract: Photosensitization of organogold intermediates is an emerging field in catalysis. In this context, an access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process is observed. Of note, 2-iodo-ynamides can be used as electrophiles in this cross-coupling reaction. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converge on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.
Published: 2022

37. Catalyseurs moléculaires et matériaux à base de graphène pour le développement de processus multicatalytiques 'one pot' bio-inspirés et durables

Author: Yagoub, Ikram, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Université Grenoble Alpes [2020-....], Geneviève Blondin, and STAR, ABES
Subjects: Grafting, [CHIM.ORGA]Chemical Sciences/Organic chemistry, N-Alkylation d'amines, N-Alkylation of amines, Iron complexes, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Complexes de Fer, One-Pot, Greffage
Abstract: N-alkylation of amines with alcohols is a method of choice for accessing compounds of pharmaceutical interest in a more sustainable way. This field of catalysis is now largely dominated by the use of molecular complexes in homogeneous phase. The proposed mechanism is based on hydrogen auto-transfer (HAT). Among the two main families of iron-based catalysts that have been developed, we have chosen to focus more particularly on iron(cyclopentadienone) type catalysts. These catalysts have several advantages: air stability and easy synthesis in few steps, as well as the possibility of modulating catalytic activity via ligand modification. Iron(cyclopentadienone) complexes have been shown to be effective catalysts but several challenges remain. The main problem in terms of substrates concerns the use of primary alcohols bearing electron-withdrawing groups but also secondary alcohols. In addition, they often require the use of high temperatures and/or unwanted additives. Reactions are most often carried out at solvent reflux or in closed vials for reaction times of up to days for some. This highlights the presence of a high-energy barrier within at least one stage of the catalytic cycle, severely limiting the application of these molecular catalysts to develop new reactivities. In addition, these molecular catalysts operate under homogeneous conditions making their recycling difficult and reducing the atom economy of the process as a whole. The development of efficient catalysts that can be recycled and can operate in milder conditions remains a challenge.As a first step, an in-depth mechanistic study on the functioning of known molecular complexes of iron (cyclopentadienone)carbonyl is conducted. It has led to a better understanding of the chemical activation step of the catalyst by shedding light on the formation of new iron species.In a second step, this same strategy was applied in the development of a new multi-catalytic process with the aim of synthesizing fluorinated pharmaceutical compounds. The results suggest that neither the mode of activation – i.e. chemical and/or thermal – nor the type of complex [LFe(CO)3] or [LFe(CO)2(NCPh)], has any influence on yields.Finally, the grafting of these catalysts on a graphene surface was studied. Two types of grafting were considered: covalent grafting and supramolecular grafting. Our choice finally fell on supramolecular grafting. For this purpose, a synthetic pathway to access functionalized complexes with a perylene-type anchor has been developed. This strategy was established with the aim of developing a heterogeneous and therefore recyclable version of the catalyst., La N-alkylation d’amines avec des alcools constitue une méthode de choix pour accéder à des composés d’intérêt pharmaceutique de manière plus durable. Ce domaine de catalyse est désormais largement dominé par l’emploi de complexes moléculaires en phase homogène. Le mécanisme proposé se base sur l’auto-transfert de dihydrogène (HAT). Parmi les deux grandes familles de catalyseurs à base de fer qui ont été développées, nous avons choisi de nous intéresser plus particulièrement aux catalyseurs de type fer(cyclopentadiénone). Ces catalyseurs présentent plusieurs avantages : stabilité à l’air et synthèse aisée en peu d’étapes ainsi que la possibilité de moduler l’activité catalytique via la modification des ligands. Ces catalyseurs se sont montrés efficaces mais plusieurs défis restent à relever. Le principal problème en terme de substrats concerne l’utilisation d’alcools primaires portant des groupements électroattracteurs mais aussi les alcools secondaires. Par ailleurs, ils nécessitent souvent l’usage de températures élevées et/ou d’additifs non désirés. Les réactions sont le plus souvent effectuées à reflux du solvant ou dans des vials clos pour des temps de réaction pouvant atteindre des jours pour certaines. Ceci met en évidence la présence d’une barrière énergétique élevée au sein d’au moins une étape du cycle catalytique, limitant fortement l’application de ces catalyseurs moléculaires pour développer de nouvelles réactivités. De plus, ces catalyseurs moléculaires opèrent en conditions homogènes rendant leur recyclage difficile et diminuant l’économie d’atomes du procédé dans son ensemble. Le développement de catalyseurs efficaces pouvant être recyclés et pouvant opérer en conditions plus douces reste un défi à relever.Dans un premier temps, une étude mécanistique approfondie sur le fonctionnement des complexes moléculaires connus de fer(cyclopentadiénone)carbonyle est menée. Elle a permis de mieux comprendre l'étape d'activation par voie chimique du catalyseur en mettant en lumière la formation de nouvelles espèces de fer.Dans un second temps, cette même stratégie a été appliquée dans le développement d’un nouveau procédé multi-catalytique dans le but de synthétiser des composés pharmaceutiques fluorés. Les résultats suggèrent que ni le mode d’activation – à savoir chimique et/ou thermique – ni le type de complexe [LFe(CO)3] or [LFe(CO)2(NCPh)], n’a d’influence sur les rendements.Enfin, le greffage de ces catalyseurs sur une surface de graphène a été étudié. Deux types de greffage ont été envisagés : le greffage covalent et le greffage supramoléculaire. Notre choix s’est finalement porté sur le greffage supramoléculaire. Dans ce but, une voie de synthèse permettant d’accéder aux complexes fonctionnalisés avec une ancre de type pérylène a été développée. Cette stratégie a été établie dans le but de développer une version hétérogène et donc recyclable du catalyseur.
Published: 2022

38. Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets

Author: Bappaditya Gole, Brice Kauffmann, Arnaud Tron, Victor Maurizot, Nathan McClenaghan, Ivan Huc, Yann Ferrand, 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), Soutien à la Recherche de l'Institut Européen de Chimie Biologique, Université Sciences et Technologies - Bordeaux 1 (UB)-Institut Européen de Chimie et de Biologie-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ludwig-Maximilians-Universität München (LMU), and Ferrand, Yann
Subjects: photochemistry, Magnetic Resonance Spectroscopy, [CHIM.ORGA]Chemical Sciences/Organic chemistry, cooperativity, structure elucidation, Molecular Conformation, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Amides, Catalysis, Foldamer, aromatic sheet, Colloid and Surface Chemistry, X-ray crystallography
Abstract: International audience; A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. NMR and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations. Sequences composed of an even number of turn units were found to fold in a canonical symmetrical conformation with two helices of identical handedness stacked above and below the sheet segment. Sequences composed of an odd number of turns revealed a coexistence between a canonical fold with helices of opposite handedness, and an alternate fold with a twist within the sheet and two helices of identical handedness. The proportions between these species could be manipulated, in some cases quantitatively, being dependent on solvent, temperature and absolute control of helix handedness. Diazaanthracene units were shown to display distinct reactivity towards 4+4 photocycloadditions according to the substituent in the 9 position. Their organization within the sequences was programmed to allow photoreactions to take place in a specific order. Reaction pathways and kinetics were deciphered and products characterized, demonstrating the possibility to orchestrate successive photoreactions so as to avoid orphan units, or to deliberately produce orphan units at precise locations. Strong cooperative effects were observed in which the photoreaction rate was influenced by the presence (or absence) of photoadducts in the structure. Multiple photoreactions within the aromatic sheet eventually lead to the structure lengthening and stiffening, locking conformational equilibria. Photoproducts could be thermally reverted.
Published: 2022

39. SOD mimics: From the tool box of the chemists to cellular studies

Author: Clotilde Policar, Jean Bouvet, Hélène C. Bertrand, Nicolas Delsuc, 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), 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 Policar, Clotilde
Subjects: [CHIM.INOR] Chemical Sciences/Inorganic chemistry, Superoxide Dismutase, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Catalysis, Analytical Chemistry, Cellular studies, Design of metallodrugs, Biomimetic Materials, Coordination Complexes, Superoxides, [CHIM.OTHE] Chemical Sciences/Other, Metalloproteins, SOD mimics or mimetics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, X-fluorescence imaging or X-fluorescence microscopy XFM, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Superoxide dismutases (SODs) are metalloproteins that protect cells against oxidative stress by controlling the concentration of superoxide (O2-) through catalysis of its dismutation. The activity of superoxide dismutases can be mimicked by low-molecular-weight complexes having potential therapeutic applications. This review presents recent strategies for designing efficient SOD mimics, from molecular metal complexes to nanomaterials. Studies of these systems in cells reveal that some SOD mimics, designed to react directly with superoxide, may also indirectly enhance the cellular antioxidant arsenal. Finally, a good understanding of the bioactivity requires information on the cell-penetration, speciation, and subcellular location of the SOD mimics: we will describe recent studies and new techniques that open opportunities for characterizing SOD mimics in biological environments.
Published: 2022

40. Diazine-based thermally activated delayed fluorescence chromophores

Author: Sylvain Achelle, Maxime Hodée, Julien Massue, Arnaud Fihey, Claudine Katan, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and KATAN, Claudine
Subjects: Pyrimidine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, General Chemical Engineering, Push-Pull, TD-DFT, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Pyrazine, Thermally Activated Delayed Fluorescence, Diazine
Abstract: International audience; Diazines are electron deficient six-membered aromatic rings heterocycles which have successfully been employed in the design of a wide range of push-pull chromophores for various applications in the field of organic electronics and optoelectronics. For instance, some have been specifically designed to be inserted in the electroluminescent emission layer of organic light emitting diodes (OLED). OLED technology has continuously evolved and is currently used in industry for display and lighting purposes, offering many advantages including low turn-on voltage and power consumption. In the prospect to further reduce energy waste, a third generation of OLED based on thermally activated delayed fluorescence (TADF), which allows harvesting both triplet and singlet excitons, attracts increasing attention from the scientific community. In this review, we provide a comprehensive overview of the present status of diazine-based dyes developed for TADF. The pyrimidine core is by far the most used and has demonstrated deep blue, blue or sky-blue and green emission when combined with carbazole, acridan and phenoxazine fragments, respectively. Further design of TADF emitters is desirable to afford red OLED and both the pyrazine and pyridazine cores have been scarcely explored.
Published: 2022

41. Arènes et Hétéroarènes Sulfurés, Oxygénés et Azotés sous Forme d'Astérisques: Synthèse, Structures, Photophysique, Chimie Covalente Dynamique et Supramolécuaire

Author: Gahlot, Sapna, Aix Marseille Université (AMU), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Aix-Marseille Université, Marc Gingras, and GAHLOT, Sapna
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, Aromatic compounds, Chimie aromatique, Matériaux -- Propriétés optiques, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Soufre compose organique, Aromatique persubstitué, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Sulfur Compoounds
Abstract: The content of this thesis focusses on functionalized and branched polysulfurated, polyoxygenated or polycyanated molecular asterisks incorporating either a benzene, a pyridine or a pyrene core. The main objectives are to report the synthesis and the structural, photophysical, supramolecular and covalent dynamic properties of the newly created molecular architectures, in order to develop further uses and applications of them in a near future, toward molecular electronics, imaging, materials and life sciences in general. This work also tackles the relation between topology and optoelectronic properties for opening a new direction and future perspectives in materials science and polyaromatic chemistry. It also questions some fundamental principles and mechanisms in organic chemistry, notably the reversibility of a main and historical mechanism in organic chemistry: the nucleophilic aromatic substitution, which is known since 1854. At first, the thesis covers new synthetic approaches to functionalize pyrene in its K-region, which has been neglected in spite of the historical importance of pyrenes in optoelectronic sensing, materials and biological sciences. It is followed by the synthesis of various sulfurated, oxygenated and cyanated molecular asterisks with a benzene or pyridine core, in search for a new field in dynamic covalent chemistry (DCC) with arenes and heteroarenes, by implementing and promoting reversible nucleophilic aromatic substitutions in DCC, while at the same time developing all-organic highly phosphorescent smart materials via a rigidity-induced phosphorescence (RIP) phenomena. Thus, we report the "Sulfur Dance" around arenes and heteroarenes from a reversible exchange of sulfur components around an aromatic template, a new process in aromatic chemistry. In order to study reversible SNAr reactions, several reaction conditions, substituent effects, analytical and separative methods were necessary in DCC for anayzing the created library of compounds. In that direction, we also analyzed the importance of π-extended sulfurated and oxygenated asterisks with a benzene core, incorporting phenyl, biphenyl, naphthyl or heteroaromatic arms, in search for some exalted photohysical properties or metal cations bindings of uses in supramolecular chemistry. Thereofore, this thesis covers broad areas of aromatic chemistry, basic reaction mechanisms, photophysics and dynamic covalent and supramolecular chemistry, towards materials and life sciences., Le contenu de cette thèse porte sur les astérisques moléculaires fonctionnalisés, ramifiés et polysulfurés, polyoxygénés ou polycyanés incorporant soit un noyau benzénique, un noyau pyridine, ou un noyau pyrène. Les principaux objectifs sont de rapporter la synthèse et les propriétés structurales, photophysiques, supramoléculaires et covalentes dynamiques des architectures moléculaires nouvellement créées, afin de développer d'autres utilisations et applications de celles-ci dans un futur proche, vers l'électronique moléculaire, l'imagerie, les sciences des matériaux et de la vie, en général. Ce travail aborde également la relation entre la topologie (chaines, rubans, torsades, etc.) et les propriétés optoélectroniques afin d'ouvrir une nouvelle direction et des perspectives futures en science des matériaux et en chimie polyaromatique. Elle interroge également certains principes et mécanismes fondamentaux en chimie organique, notamment la réversibilité d'un mécanisme principal et historique en chimie organique : la substitution nucléophile aromatique, connue depuis 1854. Dans un premier temps, la thèse porte sur de nouvelles approches synthétiques pour fonctionnaliser le pyrène dans sa région K, ce qui a été négligé malgré l'importance historique des pyrènes dans les capteurs optoélectroniques, les matériaux et les sciences biologiques. Elle se poursuit par la synthèse de divers astérisques moléculaires soufrés, oxygénés et cyanés à noyau benzénique ou pyridinique, à la recherche d'un nouveau domaine de la chimie covalente dynamique (DCC) avec les arènes et les hétéroarènes, en mettant en œuvre et en promouvant des substitutions nucléophiles aromatiques réversibles pour la DCC, tout en développant des matériaux intelligents entièrement organiques hautement phosphorescents via un phénomène de phosphorescence induite par la rigidité (RIP). Ainsi, nous rapportons la « danse du soufre » autour des arènes et des hétéroarènes à partir d'un échange réversible de composants soufrés autour d'un template aromatique, un nouveau processus en chimie aromatique. Afin d'étudier les réactions SNAr réversibles, plusieurs conditions de réaction, effets de substituants, méthodes analytiques et séparatives étaient nécessaires pour analyser la bibliothèque de composés créés par DCC. Dans cette direction, nous avons également analysé l'importance des astérisques sulfurés et oxygénés avec un système π étendus autour d'un noyau benzénique, en incorporant des bras phényle, biphényle, naphtyle ou hétéroaromatiques, à la recherche de propriétés photophysiques exaltées ou de coordination de cations métalliques vers des applications en chimie supramoléculaire. Cette thèse couvre donc des larges domaines de la chimie aromatique, mécanismes réactionnels de base, photohysique et chimie covalente dynamique et supramoléculaire, vers les sciences de matériaux et de la vie.
Published: 2022

42. Catalysis of Hydrazone and Oxime Peptide Ligation by Arginine

Author: Rémi Desmet, Hervé Drobecq, Oleg Melnyk, Nathalie Ollivier, Benoît Snella, Vangelis Agouridas, Jérôme Vicogne, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology of Flatworms [Lille] (CBF), Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS)-Institut Pasteur de Lille, Mécanismes de la Tumorigénèse et Thérapies Ciblées (M3T) - UMR 8161 (M3T), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie de Lille - IBL (IBLI), Université de Lille, Sciences et Technologies-Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Droit et Santé, Centre National de la Recherche Scientifique (CNRS)-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Université de Lille-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP), Melnyk, Oleg, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Université de Lille, Droit et Santé-Centre National de la Recherche Scientifique (CNRS)
Subjects: Arginine, [SDV]Life Sciences [q-bio], Bicarbonate, Hydrazone, Peptide, Protein aggregation, Hydrazide, Biochemistry, Catalysis, chemistry.chemical_compound, Nucleophile, Oximes, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Organic Chemistry, Hydrazones, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, Hydrogen-Ion Concentration, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Oxime, Combinatorial chemistry, Peptides, Ligation
Abstract: Hydrazone and oxime peptide ligations are catalyzed by arginine. The catalysis is assisted intramolecularly by the side-chain guanidinium group. Hydrazone ligation in the presence of arginine proceeds efficiently in phosphate buffer at neutral pH but is particularly powerful in bicarbonate/CO2 buffer. In addition to acting as a catalyst, arginine prevents the aggregation of proteins during ligation. With its dual properties as nucleophilic catalyst and protein aggregation inhibitor, arginine hydrochloride is a useful addition to the hydrazone/oxime ligation toolbox.
Published: 2020

43. Aza‐Piancatelli Cyclization as a Platform for the Preparation of Scaffolds of Natural Compounds: Application to the Total Synthesis of Bruceolline D

Author: David Lebœuf, Lucile Marin, Guillaume Force, Emmanuelle Schulz, Vincent Gandon, 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 Science et d'ingénierie supramoléculaires (ISIS), 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)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Leboeuf, David
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, Total synthesis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Organic chemistry, Lewis acids and bases, Physical and Theoretical Chemistry, Bruceolline D
Abstract: International audience; The aza‐Piancatelli cyclization provides an expedient synthesis of 4‐aminocyclopentenone building blocks that may be converted into aminocyclopentitols, which are heavily represented motifs among natural products. However, its use as a key step in total synthesis was still unprecedented. Here, we disclose our in‐depth investigations regarding this reaction in order to access highly complex structures representing the core of some natural molecules. The applicability of the cyclization was highlighted by the 3‐step total synthesis of bruceolline D. Thus, we anticipate that this work will lay the ground for further applications in total synthesis
Published: 2020

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

Author: Sylvain Routier, Kossi Efouako Soklou, Karen Plé, Mathieu Marchivie, Jean-Philippe Bouillon, Hamid Marzag, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank the Région Centre Val de Loire (Ph.D. funding SKE), the Labex programs SYNORG (ANR-11-LABX-0029) and IRON (ANR-11-LABX-0018-01), the Ligue contre le Cancer du Grand Ouest (comités des Deux Sèvres, du Finistère, de l’Ile et Villaine, du Loir et Cher, de Loire Atlantique, du Loiret, de la Vienne), and the Canceropole Grand Ouest for their financial support., ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), PLE, Karen, Synthèse Organique : des molécules au vivant - - SYNORG2011 - ANR-11-LABX-0029 - LABX - VALID, and Radiopharmaceutiques Innovants en Oncologie et Neurologie - - IRON2011 - ANR-11-LABX-0018 - LABX - VALID
Subjects: Annulation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, education, Organic Chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, humanities, 0104 chemical sciences, Catalysis, Cascade reaction, Intramolecular force, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Hydroamination, Physical and Theoretical Chemistry, Tertiary alcohols, Hydroalkoxylation
Abstract: International audience; We report here a simple and robust gold-catalyzed annulation reaction, giving N- and O-spirocycles in good to excellent yields. We have prepared a library of protected amines and tertiary alcohols that give, upon cyclization with alkynes, a representative set of heterospirocycles and illustrate reaction compatibility with diverse functional groups. A change in catalytic activity is possible by modifying the solvent, and two original tricyclic spirocycles were synthesized in a tandem reaction.
Published: 2020

45. Exploiting hexafluoroisopropanol (HFIP) in Lewis and Brønsted acid-catalyzed reactions

Author: David Lebœuf, Vincent Gandon, Valentyn Pozhydaiev, Joseph Moran, Martin Power, Université de Strasbourg (UNISTRA), Institut de Science et d'ingénierie supramoléculaires (ISIS), 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)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université Paris-Saclay, 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), Leboeuf, David, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Metals and Alloys, Cationic polymerization, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Chemical reaction, Combinatorial chemistry, Catalysis, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Solvent, Acid catalysis, Nucleophile, Materials Chemistry, Ceramics and Composites, Brønsted–Lowry acid–base theory
Abstract: International audience; Hexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting a wide range of challenging chemical reactions. It was initially believed that HFIP was almost exclusively involved in the stabilization of cationic intermediates, owing to its high polarity and low nucleophilicity. However, in many cases, the mechanism of action of HFIP appears to be more complex. Recent findings reveal that many Lewis and Brønsted acid-catalyzed transformations conducted in HFIP additionally involve cooperation between catalyst and HFIP hydrogen-bond clusters, akin to Lewis-or Brønsted acid-assisted-Brønsted acid catalysis. This feature article showcases the remarkable versatility of HFIP in Lewis and Brønsted acid-catalyzed reactions, with an emphasis on examples yielding mechanistic insight.
Published: 2020

46. Multimodal optical contrast agents as new tools for monitoring and tuning nanoemulsion internalisation into cancer cells. From live cell imaging to in vivo imaging of tumours

Author: Coralie Genevois, Isabelle Sasaki, Geoffrey Prévot, Jonathan Daniel, Sébastien Marais, Talia Bsaibess, Sylvie Crauste-Manciet, Franck Couillaud, Mireille Blanchard-Desce, Guillaume Clermont, Acides Nucléiques : Régulations Naturelle et Artificielle (ARNA), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Centre National de la Recherche Scientifique (CNRS), Imagerie moléculaire et thérapies innovantes en oncologie (IMOTION), Université de Bordeaux (UB), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Bordeaux Imaging Center (BIC), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut François Magendie-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Imagerie moléculaire et fonctionnelle: de la physiologie à la thérapie, Université Bordeaux Segalen - Bordeaux 2-IFR8-Centre National de la Recherche Scientifique (CNRS), Résonance magnétique des systèmes biologiques (RMSB), Université Bordeaux Segalen - Bordeaux 2-Centre National de la Recherche Scientifique (CNRS), Synthèse et électrosynthèse organiques (SESO), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-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 Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de résonance magnétique des systèmes biologiques (CRMSB), Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB), SASAKI, Isabelle, Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Institut François Magendie-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux, Conseil Régional d'Aquitaine, and Blanchard-Desce, Mireille
Subjects: [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, [SDV]Life Sciences [q-bio], Kinetics, [SDV.CAN]Life Sciences [q-bio]/Cancer, Bioengineering, 02 engineering and technology, 010402 general chemistry, Endocytosis, 01 natural sciences, [SDV.CAN] Life Sciences [q-bio]/Cancer, Live cell imaging, In vivo, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, [SCCO.NEUR]Cognitive science/Neuroscience, General Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 021001 nanoscience & nanotechnology, Fluorescence, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [SDV] Life Sciences [q-bio], [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, Cancer cell, Biophysics, Surface modification, 0210 nano-technology, Preclinical imaging
Abstract: International audience; Tailor-made NIR emitting dyes were designed as multimodal optical probes. These asymmetric amphiphilic compounds combine intense absorption in the visible region, NIR fluorescence emission, high two-photon absorption in the NIR (with maximum located around 1000 nm) as well as large Stokes’ shift values and second-harmonic generation ability. Thanks to their structure, high loading into nanoemulsions (NEs) could be achieved leading to giant one- and two-photon brightness’. These dyes were demonstrated to act as multimodal contrast agents able to generate different optical modalities of interest for bioimaging. Indeed, the uptake and carrier behaviour of the dye-loaded NEs into cancer cells could be monitored by simultaneous Two-Photon Fluorescence and Second-Harmonic Generation optical imaging. Multimodal imaging provided deep insight into the mechanism and kinetics of the dyes internalisation. Quite interestingly, the nature of the dye was also found to influence both the kinetics of endocytosis and the internalisation pathways into glioblastoma cancer cells. By modulating the charge distribution within the dyes, the NEs can be tuned to escape lysosome and enter the mitochondria. Moreover, surface functionalization with PEG macromolecules was realized to yield stealth NIRF-NEs which could be used for in vivo NIRF imaging of subcutaneous tumours in mice.
Published: 2020

47. Liquid crystal ionic self-assembly and anion-selective photoluminescence in discotic azatriphenylenes

Author: Ping Hu, Benoît Heinrich, Ke-Qing Zhao, Dai Jia, Bi-Qin Wang, Bertrand Donnio, Sichuan Normal University (SNU), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Donnio, Bertrand, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Photoluminescence, Materials science, Ionic bonding, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, symbols.namesake, Liquid crystal, [CHIM.CRIS]Chemical Sciences/Cristallography, Materials Chemistry, Hexagonal lattice, [CHIM.CRIS] Chemical Sciences/Cristallography, ComputingMilieux_MISCELLANEOUS, [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Discotic liquid crystal, Mesophase, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Crystallography, symbols, van der Waals force, 0210 nano-technology, Trifluoromethanesulfonate
Abstract: We report on the straightforward synthesis of a new series of ionic discotic liquid crystals based on positively charged azatriphenylene. In our design, the quaternized azatriphenylene core is surrounded by four to six flexible aliphatic chains and various types of anions, including small inorganic anions (i.e. Br−, I−, NO3−, BF4−, PF6−), and organic ones such as triflate, bis(trifluoromethylsulfonyl)imide, tosylate, saccharinate, D and L camphorsulfate, alkylsulfonates, and alkylsulfates. The mesophases and thermal behaviour of the salts were characterized by polarizing optical microscopy, differential scanning calorimetry, thermal gravimetry and small-angle X-ray scattering. A classical hexagonal columnar mesophase, i.e. p6mm-Colhex, was observed for most salts. Two exotic new phases were however identified for four compounds, namely a mesophase with a hexagonal lattice of p3m1 symmetry (Hex), and another mesophase with a rectangular lattice of pseudo-hexagonal geometry (i.e. a/b = √3) of p2mg symmetry (Recphex). The former results from the bulkiness of the triflimide anion and the arrangement of columns into a honeycomb lattice, whereas the latter is induced by the clustering of three columns, disposed according to a low-symmetry rectangular lattice. Their temperature ranges and stabilities strongly depend as expected on the anion type and the number (and length) of the alkyl side-chains (O- and N-alkyl, respectively), highlighting the delicate balance and interplay between van der Waals, electrostatic and π–π core interactions. The UV/Vis absorption and fluorescent emission spectra were measured, and a strong yellow light photoluminescence was observed depending on the anion type, whereas anion-selective luminescence was observed in thin films. The neutral azatriphenylene precursor, 6,7,10,11-tetrakis(hexyloxy)dibenzo[f,h]isoquinoline, is also an interesting luminophore, showing an absolute emission quantum yield of 75%, while the corresponding salts exhibit anion-selective emission quantum yields as high as 20%.
Published: 2020

48. On the Road Toward More Efficient Biocompatible Two‐Photon Excitable Fluorophores

Author: Marie Auvray, Frédéric Bolze, Delphine Naud‐Martin, Matthieu Poulain, Margaux Bossuat, Gilles Clavier, Florence Mahuteau‐Betzer, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Conception et application de molécules bioactives (CAMB), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), and Mahuteau-Betzer, Florence
Subjects: Diagnostic Imaging, Photons, Ionophores, molecular modeling, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, live-cell imaging, Catalysis, quadrupolar structures, fluorescent probes, two-photon absorption, Fluorescent Dyes
Abstract: International audience; Red to NIR absorption and emission wavelengths are key requirements for intravital bioimaging. One of the way to reach such excitation wavelengths is to use two-photon excitation. Unfortunately, there is still a lack of two-photon excitable fluorophores that are both efficient and biocompatible. Thus, we design a series of biocompatible quadrupolar dyes in order to study their ability to be used for live-cell imaging, and in particular for two-photon microscopy. Hence, we report the synthesis of 5 probes based on different donor cores (phenoxazine, acridane, phenazasiline and phenothiazine) and the study of their linear and non-linear photophysical properties. TD-DFT calculations were performed and were able to highlight the structure-property relationship of this series. All these studies highlight the great potential of three of these biocompatible dyes for two-Photon microscopy, as they both exhibit high two-photon cross-sections (up to 3 650 GM) and emit orange to red light. This potential was confirmed through live-cell two-photon microscopy experiments, leading to images with very high brightness and contrast.
Published: 2022

49. Dynamic Amino Acid Side-Chains Grafting on Folded Peptide Backbone

Author: Benjamin Zagiel, Taleen Peker, Rodrigue Marquant, Guillaume Cazals, Gabrielle Webb, Emeric Miclet, Claudia Bich, Emmanuelle Sachon, Roba Moumné, 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), Université de Montpellier (UM), 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), and Moumné, Roba
Subjects: Peptide Library, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Combinatorial Chemistry Techniques, Proteins, General Chemistry, Amino Acids, Peptides, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract: International audience; An efficient strategy for the synthesis of large libraries of conformationally defined peptides is reported, using dynamic combinatorial chemistry as a tool to graft amino acid side chains on a well-ordered 3D (3-dimension) peptide backbone. Combining rationally designed scaffolds with combinatorial side chains selection represents an alternative method to access peptide libraries for structures that are not genetically encodable. This method would allow a breakthrough for the discovery of protein mimetic for unconventional targets for which little is known.
Published: 2022

50. Nanoarchitectonics of Electrically Activable Phosphonium Self-Assembled Monolayers to Efficiently Kill and Tackle Bacterial Infections on Demand

Author: Serena Carrara, Florent Rouvier, Sanjana Auditto, Frédéric Brunel, Charlotte Jeanneau, Michel Camplo, Michelle Sergent, Imad About, Jean-Michel Bolla, Jean-Manuel Raimundo, Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), University of Kinshasa (UNIKIN), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Acides Nucléiques : Régulations Naturelle et Artificielle (ARNA), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences du Mouvement Etienne Jules Marey (ISM), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU), Service de Santé des Armées, Institut de Recherche Biomédicale des Armées (IRBA), Membranes et cibles thérapeutiques (MCT), Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Biomédicale des Armées (IRBA), Raimundo, Jean-Manuel, Institut de Recherche Biomédicale des Armées [Brétigny-sur-Orge] (IRBA), and Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Biomédicale des Armées [Brétigny-sur-Orge] (IRBA)
Subjects: Staphylococcus aureus, Surface Properties, biocidal effect, Catalysis, Inorganic Chemistry, responsive surfaces, Gram-Negative Bacteria, Humans, electroactivation, Physical and Theoretical Chemistry, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Molecular Biology, Spectroscopy, Titanium, [CHIM.MATE] Chemical Sciences/Material chemistry, Bacteria, [CHIM.ORGA]Chemical Sciences/Organic chemistry, phosphoniums, self-assembled monolayers, Organic Chemistry, General Medicine, Bacterial Infections, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Computer Science Applications, Anti-Bacterial Agents, [SDV.IB.BIO] Life Sciences [q-bio]/Bioengineering/Biomaterials
Abstract: International audience; Prosthetic implants are widely used in dentistry and orthopedics and, as a result, infections can occur which cause their removal. Therefore, it is essential to propose methods of eradicating the bacteria that remain on the prosthesis during treatment. For this purpose, it is necessary to develop surfaces whose antibacterial activity can be controlled. Herein, we designed innovative and smart phosphonium self-assembled monolayer (SAM) interfaces that can be electrically activated on demand for controlling bacterial contaminations on solid surfaces. Upon electroactivation with a low potential (0.2 V for 60 min., conditions determined through a DOE), a successful stamping out of Gram-positive and Gram-negative bacterial strains was obtained with SAM-modified titanium surfaces, effectively killing 95% of Staphylococcus aureus and 90% Klebsiellapneumoniae. More importantly, no toxicity towards eukaryotic cells was observed which further enhances the biocompatible character of these novel surfaces for further implementation.
Published: 2022

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