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411 results on '"Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA )"'

1. Supramolecular control of a mononuclear biomimetic copper(II) center: bowl complexes vs funnel complexes

Author

Arnaud Parrot, Jérôme Gout, Olivia Bistri, Aleksandar Višnjevac, Nicolas Le Poul, Stéphanie Rat, Yves Le Mest, Olivia Reinaud, Assia Hessani, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Institut Parisien de Chimie Moléculaire ( IPCM ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Lavoisier de Versailles ( ILV ), Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), and Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS

Subjects
Models, Molecular, Coordination sphere, Stereochemistry, Phenylalanine, Supramolecular chemistry, chemistry.chemical_element, Crystallography, X-Ray, Inorganic Chemistry, Metal, chemistry.chemical_compound, Phenols, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Biomimetics, Coordination Complexes, Imidazole, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Chemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, biomimetic modelling, copper, supramolecular, X-ray, Resorcinarene, Copper, Crystallography, Tripodal ligand, visual_art, visual_art.visual_art_medium, Biocatalysis, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, Calixarenes, Oxidation-Reduction
Abstract

International audience; Modeling the mononuclear site of copper enzymes is important for a better understanding of the factors controlling the reactivity of the metal center. A major difficulty stems from the difficult control of the nuclearity while maintaining free sites open to coordination of exogenous ligands. A supramolecular approach consists in associating a hydrophobic cavity to a tripodal ligand that will define the coordination spheres as well as access to the metal ion. Here, we describe the synthesis of a bowl Cu-II complex based on the resorcinarene scaffold. This study supplements a previous work on Cu-I coordination. It provides a complete picture of the cavity-copper system in its two oxidation states. The first XRD structure of such a bowl complex was obtained, evidencing a 5-coordinate Cu-II ion with the three imidazole donors bound to the metal (two in the base of the pyramid, one in the apical position) and with an acetate anion, completing the base of the pyramid, and deeply included in the bowl. Solution studies conducted by EPR and UV-vis absorption spectroscopies as well as cyclic voltammetry highlighted interaction with coordinating solvents, various carboxylates that can sit either in the endo or in the exo position depending on their size as well as possible stabilization of hydroxo species in a mononuclear state. A comparison of the binding and redox properties of the bowl complex with funnel complexes based on the calix[6]arene core further highlights the importance of supramolecular features defining the first, second, and third coordination sphere for control of the metal ion.

Published
2014

2. Insights into water coordination associated with the Cu(II)/Cu(I) electron transfer at a biomimetic Cu centre

Author

Ana Gabriela Porras Gutiérrez, Françoise Conan, Olivia Reinaud, Nicolas Le Poul, Nathalie Cosquer, Yves Le Mest, Joceline Zeitouny, Corinne Lagrost, Antoine Gomila, Philippe Hapiot, Bénédicte Douziech, Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Coordination sphere, Inorganic chemistry, Molecular Conformation, Ionic Liquids, Biocompatible Materials, Electrons, Crystallography, X-Ray, Electron Transport, Inorganic Chemistry, Electron transfer, chemistry.chemical_compound, [ SDV.BBM.BC ] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], Coordination Complexes, Molecule, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Coordination geometry, Ligand, Water, Electrochemical Techniques, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], Kinetics, Trigonal bipyramidal molecular geometry, chemistry, Ionic liquid, Thermodynamics, Oxidation-Reduction, Trifluoromethanesulfonate, Copper
Abstract

International audience; The coordination properties of the biomimetic complex [Cu(TMPA)(H2O)](CF3SO3)2 (TMPA = tris(2-pyridylmethyl)amine) have been investigated by electrochemistry combined with UV-Vis and EPR spectroscopy in different non-coordinating media including imidazolium-based room-temperature ionic liquids, for different water contents. The solid-state X-ray diffraction analysis of the complex shows that the cupric centre lies in a N4O coordination environment with a nearly perfect trigonal bipyramidal geometry (TBP), the water ligand being axially coordinated to Cu(II). In solution, the coordination geometry of the complex remains TBP in all media. Neither the triflate ion nor the anions of the ionic liquids were found to coordinate the copper centre. Cyclic voltammetry in all media shows that the decoordination of the water molecule occurs upon monoelectronic reduction of the Cu(II) complex. Back-coordination of the water ligand at the cuprous state can be detected by increasing the water content and/or decreasing the timescale of the experiment. Numerical simulations of the voltammograms allow the determination of kinetics and thermodynamics for the water association-dissociation mechanism. The resulting data suggest that (i) the binding/unbinding of water at the Cu(I) redox state is relatively slow and equilibrated in all media, and (ii) the binding of water at Cu(I) is somewhat faster in the ionic liquids than in the non-coordinating solvents, while the decoordination process is weakly sensitive to the nature of the solvents. These results suggest that ionic liquids favour water exchange without interfering with the coordination sphere of the metal centre. This makes them promising media for studying host-guest reactions with biomimetic complexes.

Published
2014

3. Bowl versus Funnel Supramolecular Concept for Cu-I Complexes within the Biomimetic Tris(imidazole) Core

Author

Olivia Reinaud, Nicolas Le Poul, Stéphanie Rat, Olivia Bistri, Aleksandar Višnjevac, Jérôme Gout, Yves Le Mest, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), and Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS

Subjects
Tris, 010405 organic chemistry, Stereochemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, Supramolecular chemistry, Resorcinarene, 010402 general chemistry, 01 natural sciences, copper coordination, resorcinarenes, biomimetic model, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Biomimetic synthesis, Calixarene, Polymer chemistry, Imidazole, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cyclic voltammetry, Pi backbonding
Abstract

International audience; The coordination of Cu-I to a poly(imidazole) core is of the most importance in biology as it is present in most enzymes as well as in peptides involved in pathological processes. Here, we report a detailed study of the binding of Cu-I to a tris(imidazole) core constructed on a resorcinarene scaffold. NMR and IR spectroscopy as well as cyclic voltammetry have been used to characterize the different species obtained in solution as a function of the presence or absence of exogenous ligands, mainly CO and MeCN, but also Cl-. Within the resorcinarene scaffold, the metal ion can switch from a dynamic two-coordinate to a four-coordinate environment upon binding to a acceptor. A comparison with previously reported calix[6]arene-based tris(imidazole) Cu complexes highlights several key points: (1) the importance of the shape and size of the macrocycle that forms the pocket in which the metal center is partly embedded, (2) the importance of the flexibility of the system as it undergoes induced-fit processes (calixarene) or not (resorcinarene), (3) the consequences on the affinity of the metal center for CO and MeCN in relation to its -backbonding capabilities, and finally (4), the redox behavior of the system.

Published
2013

4. Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

Author

Noémie Lalaoui, Lucía Álvarez-Miguel, Carlos Garcia Bellido, Nolwenn Cabon, Frédéric Gloaguen, Daniel Miguel, Nicolas Le Poul, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Universidad de Valladolid [Valladolid] (UVa), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Nicolas Le Poul is grateful to Gaël Le Roux (UBO) for his participation to the building of the IR spectroelectrochemical cell. Financial support was provided by UBO for a PhD grant (Carlos Garcia Bellido), by FEDER UE Interreg Atlantic Area (HYLANTIC, EAPA204/2016) for a post-doctoral fellowship (Lucía Álvarez Miguel) and by ANR (CATHOMIX, 19-CE43-0013-02). ). This project is co-financed by the Interreg Atlantic Area Programme through the European Regional Development Fund., ANR-19-CE43-0013,CATHOMIX,Biofilms Microbiens Mixtes et Cathodiques Fixant l'Azote Moléculaire par la Valorisation Directe du Dihydrogène(2019), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Ligand, carbon dioxide, electrochemical, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, spectroelectrochemical, Catalysis, 0104 chemical sciences, Reduction (complexity), Mo‐diimine tetracarbonyl complexes, Bipyridine, chemistry.chemical_compound, 13. Climate action, Carbon dioxide, Co release, Inert gas, Diimine
Abstract

International audience; The activation of carbon dioxide by three different Mo‐diimine complexes [Mo(CO) 4 (L)] (L = bipyridine (bpy), 1,10‐phenantroline (phen) or pyridylindoziline (py‐indz)) has been investigated by electrochemistry and spectroelectrochemistry. Under inert atmosphere, monoreduction of the complexes is ligand‐centred and leads to tetracarbonyl [Mo(CO) 4 (L)] •− species, whereas double reduction induces CO release. Under CO 2 , [Mo(CO) 4 (L)] complexes undergo unexpected coupled chemical‐electrochemical reactions at the first reduction step, leading to the formation of reduced CO 2 derivatives. The experimental results obtained from IR, NIR and UV‐Vis spectroelectrochemistry, as well as DFT calculations, demonstrate an electron‐transfer reaction whose rate is ligand‐dependent.

Published
2021

5. Synthesis and Studies of a Water-Soluble and Air-Stable Cu-I/Cu-II Open-Shell Funnel Complex

Author

Michael Carboni, Andrea Brugnara, Nicolas Le Poul, Yves Le Mest, Olivia Reinaud, Benoit Colasson, Grégory Thiabaud, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
Tris, Magnetic Resonance Spectroscopy, Pyridines, Inorganic chemistry, chemistry.chemical_element, Ligands, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Calixarene, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Derivatization, Open shell, Aqueous solution, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, Water, Copper, 0104 chemical sciences, Solubility, Amine gas treating, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, Calixarenes
Abstract

International audience; The derivatization of the large rim of a TMPA-capped calix[6]arene (TMPA = tris(2-pyridylmethyl)amine) with three trimethylammonium groups enables the water-solubilization of two air-stable Cu(I)/Cu(II) complexes. These two complexes present a vacant coordination site shielded from the aqueous environment by the calixarene core. The spectroscopic and electrochemical data recorded in pure water indicate that the host guest properties of the funnel complex are retained in both oxidation states of the copper cation.

Published
2012

6. Dioxygen activation at a mononuclear Cu(I) center Embedded in the calix [6]arene-Tren core

Author

Stéphane Ménage, Ivan Jabin, Yves Le Mest, Yves Frapart, Bénédicte Douziech, Guillaume Izzet, Joceline Zeitouny, Olivia Reinaud, Huriye Akdas-Killig, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), 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 [2016-2019] (UGA [2016-2019]), Service de Chimie Organique Université libre de Bruxelles, Université libre de Bruxelles (ULB), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Libre de Bruxelles [Bruxelles] (ULB), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, Laboratoire de Chimie et Biologie des Métaux ( LCBM - UMR 5249 ), Université Joseph Fourier - Grenoble 1 ( UJF ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Grenoble Alpes ( UGA ), and Université Libre de Bruxelles [Bruxelles] ( ULB )

Subjects
Models, Molecular, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, Adduct, chemistry.chemical_compound, [ CHIM.CATA ] Chemical Sciences/Catalysis, Colloid and Surface Chemistry, Phenols, Oxidizing agent, Polymer chemistry, Calixarene, Spectroscopy, Fourier Transform Infrared, Electrochemistry, Organometallic Compounds, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, Ligand, Superoxide, Electron Spin Resonance Spectroscopy, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Oxygen, Intramolecular force, Calixarenes, Copper
Abstract

The reaction of a cuprous center coordinated to a calix[6]arene-based aza-cryptand with dioxygen has been studied. In this system, Cu(I) is bound to a tren unit that caps the calixarene core at the level of the small rim. As a result, although protected from the reaction medium by the macrocycle, the metal center presents a labile site accessible to small guest ligands. Indeed, in the presence of O2, it reacts in a very fast and irreversible redox process, leading, ultimately, to Cu(II) species. In the coordinating solvent MeCN, a one electron exchange occurs, yielding the corresponding [CalixtrenCu-MeCN](2+) complex with concomitant release of superoxide in the reaction medium. In a noncoordinating solvent such as CH2Cl2, the dioxygen reaction leads to oxygen insertions into the ligand itself. Both reactions are proposed to proceed through the formation of a superoxide-Cu(II) intermediate that is unstable in the Calixtren environment due to second sphere effects. The transiently formed superoxide ligand either undergoes fast substitution for a guest ligand (in MeCN) or intramolecular redox evolutions toward oxygenation of Calixtren. Interestingly, the latter process was shown to occur twice on the same ligand, thus demonstrating a possible catalytic activation of O2 at a single cuprous center. Altogether, this study illustrates the oxidizing power of a [CuO2](+) adduct and substantiates a mechanism by which copper mono-oxygenases such as DbetaH and PHM activate O2 at the Cu(M) center to produce such an intermediate capable of C-H breaking before the electron input provided by the noncoupled Cu(H) center.

Published
2008

7. Investigation of second-order nonlinear optical responses in a series of V-shaped binuclear platinum(<scp>ii</scp>) complexes

Author

Sébastien Gauthier, Denis Jacquemin, Françoise Robin-le Guen, Elsa Caytan, Sylvain Achelle, Raphaël J. Durand, Alberto Barsella, Nicolas Le Poul, Patricia Guevara Level, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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), 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), Ministère de l'Enseignement supérieur, de la Recherche et de l'Innovation, Centre National de la Recherche Scientifique, 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), 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 Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Series (mathematics), Pyrimidine, Ligand, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM]Chemical Sciences, Order (group theory), Density functional theory, 0210 nano-technology, Platinum, Malononitrile
Abstract

International audience; A series of four D-(π-Pt-π-A)2 new V-shaped binuclear platinum(ii) complexes bearing a diphenylpyranylidene ligand as a pro-aromatic donor group (D) and various electron-attracting groups (A) separated by platinum bis-acetylide fragments have been synthesized, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. The nonlinear optical properties of these complexes have been determined by using the Electric-Field-Induced Second Harmonic (EFISH) generation technique, and their optical properties have been rationalized by Time-Dependent Density Functional Theory (TD-DFT) calculations relying on a range-separated hybrid. All complexes display positive μβ0 values. In addition, the second-order NLO responses of the complexes could be easily modulated by incorporating various end-capped electron-attracting groups, namely malononitrile, indane-1,3-dione, pyrimidine and pyrimidinium. Remarkably, complex 7 bearing a pyrimidinium fragment displays the highest μβ0 value among all the complexes of this series. Its NLO response is twice as high as that of the mononuclear analogue complex RD2, which has been confirmed both experimentally and theoretically.

Published
2021

8. Design of polyazamacrocyclic Gd3+ theranostic agents combining magnetic resonance imaging and two-photon photodynamic therapy

Author

Gyula Tircsó, Nadège Hamon, Gyoergy Trencseny, Kamel Hadj-Kaddour, Mélanie Onofre, Christophe Nguyen, Eniko Molnar, Raphaël Tripier, Olivier Maury, Cyrille Monnereau, Laura Abad Galán, János Kiss, Jonathan Mendy, Maryline Beyler, Magali Gary-Bobo, 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, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Debrecen Egyetem [Debrecen], 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), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
Gd(III) complexes, Gadolinium, medicine.medical_treatment, chemistry.chemical_element, Photodynamic therapy, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, picolinate, PDT, Two-photon excitation microscopy, medicine, [CHIM]Chemical Sciences, Solubility, Oxygen singlet, Aqueous solution, medicine.diagnostic_test, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Singlet oxygen, Magnetic resonance imaging, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Solvent, chemistry, Pyclen, Relaxivity, MRI
Abstract

International audience; New “all-in-one” theranostic systems, combining a magnetic resonance imaging (MRI) contrast agent with a biphotonic photodynamic therapy (2P-PDT) photosensitiser generating cytotoxic singlet oxygen, were envisaged and synthesised. They are based on azamacrocycles, regiospecifically functionalised by two-photon PDT π-conjugated dibromobenzene–picolinate photosensitisers and acetate, able to complex gadolinium(III) and allow an MRI signal. Our approach was to use two different macrocyclic platforms, tacn and pyclen, for modulating simultaneously the structures, properties and solubility of the complexes. Photophysical properties of the ligands and their gadolinium(III) complexes were fully investigated. The Gd3+–pyclen derivative showed the best water solubility and the greatest value of singlet oxygen generation of the series with ΦΔ = 0.53 enabling in vitro studies. The biological PDT activity under mono and biphotonic excitation was evaluated in human breast cancer cells (MCF-7). While a very low dark toxicity was observed, an almost total cell death was induced after only 3 successive irradiations of 1.57 s. Finally, its relaxivity was measured in a DMSO/H2O solvent mixture with r1p = 11.21 and r2p = 24.60 mM−1 s−1 at 3.0 T and T1- and T2-weighted phantom MR images were obtained highlighting a first generation of “all-in-one” PDT/MRI theranostic agents.

Published
2021

9. Carbonylmolybdenum complexes with di(imino)pyridine and related ligands: Reduction of a di(imino)pyridine to an aminoiminopyridine system under mild conditions

Author

Jean Sala-Pala, Jean-Michel Kerbaol, Nathalie Cosquer, Benoît Le Gall, Marek M. Kubicki, Françoise Conan, Estelle Vigier, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Synthèse et Electrosynthèse Organométalliques (LSEO), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Synthèse et Electrosynthèse Organométalliques ( LSEO ), and Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS )

Subjects
chemistry.chemical_classification, Ketone, Denticity, 010405 organic chemistry, Stereochemistry, Ligand, Imine, Crystal structure, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, [ CHIM ] Chemical Sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Pyridine, Materials Chemistry, Proton NMR, [CHIM]Chemical Sciences, Amine gas treating, Physical and Theoretical Chemistry
Abstract

The reactions of [Mo(CO) 6 ] towards a 2,6-di(imino)pyridine L 1 and related ligands were studied. The reaction with L 1 afforded two new complexes, [Mo(CO) 4 L 1 ] ( 1 ) and [Mo(CO) 4 L 2 ] ( 2 ), where L 2 is the 2-amino-6-iminopyridine ligand arising from the hydrogenation of one imine function of L 1 ; similar reaction with a 2-acetyl-6-iminopyridine ligand L 3 afforded [Mo(CO) 4 L 3 ] ( 3 ). Compounds 1 , 2 and 3 have been fully characterised by IR, 1 H NMR and X-ray crystallography; they present a metal ion in a pseudo-octahedral environment, the three organic ligands acting with bidentate N 2 coordination modes. One of the imine functions in 1 , the amine function in 2 , and the ketone function in 3 are uncoordinated.

Published
2006

10. Reaction of polyamines with diethyloxalate: a convenient route for the synthesis of tetraazacycloalkanes

Author

Raphaël Tripier, Enrique Espinosa, Franck Denat, Roger Guilard, Frederic Boschetti, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Cristallographie et modélisation des matériaux minéraux et biologiques ( CMMMB ), Université Henri Poincaré - Nancy 1 ( UHP ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire d'Ingénierie Moléculaire pour la Séparation et les Applications des Gaz (LIMSAG), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Cristallographie et modélisation des matériaux minéraux et biologiques (LCM3B), Université Henri Poincaré - Nancy 1 (UHP)-Centre National de la Recherche Scientifique (CNRS), and Clausse, Anne

Subjects
synthesis, Reducing agent, 010402 general chemistry, 01 natural sciences, Adduct, lcsh:QD241-441, chemistry.chemical_compound, lcsh:Organic chemistry, [PHYS.COND.CM-GEN] Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Amide, Cyclam, Organic chemistry, Reactivity (chemistry), ComputingMilieux_MISCELLANEOUS, Primary (chemistry), 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, tetraamines, Organic Chemistry, Combinatorial chemistry, 0104 chemical sciences, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Aminal, Amine gas treating
Abstract

International audience; The reactivity of various polyamines with diethyloxalate has been investigated. It appears that, in similar experimental conditions, primary diamines give predominantly [2+2] adducts while the use of secondary benzylated polyamines results in [1+1] condensation. Although the intermediate tetraamides formed in the first case are extremely poorly soluble and show very slow reactivity towards reducing agents, cyclam has been obtained by using ultrasounds during the reaction of the corresponding tetraoxomacrocycle with BH 3 /THF. The [1+1] cyclization reaction of diversely N-benzylated linear tetraamines, whose selective syntheses have been devised herein, gives access to various N-benzylated cyclens and cyclams. New macrocyclic ligands containing both amine and amide type nitrogen atoms have been formed as intermediates in these syntheses. Two compounds containing an aminal function exhibit an unexpected reactivity, leading to the formation of new bisaminal products whose structures have been established by X-ray diffraction.Discover the world's research

Published
2006

11. Controlled nucleophilic activation of different sites in [Mo 2Cp2L2(μ-SMe)2(μ-L′)] + cations (L = ButNC, xylNC, CO; L′ = SMe or PPh2)

Author

Philippe Schollhammer, Nolwenn Cabon, François Y. Pétillon, Jean Talarmin, Pierre-Yves Orain, Kenneth W. Muir, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, 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), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Cyclopentadiene, Stereochemistry, X ray diffraction, chemistry.chemical_element, Molybdenum compounds, Crystal structure, 010402 general chemistry, Spectroscopic analysis, 01 natural sciences, Biochemistry, Medicinal chemistry, [ CHIM ] Chemical Sciences, Negative ions, Inorganic Chemistry, chemistry.chemical_compound, Cyclopentadienyl complex, Nucleophile, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cyclopentadienyl, Isocyanide liagand, Reaction kinetics, Electronic properties, 010405 organic chemistry, Chemistry, Activation analysis, Nucleophilic activation, Organic Chemistry, Organometallics, 0104 chemical sciences, 3. Good health, Dimolybdenum complexes, Boron compounds, Molybdenum, Reagent, Complexation, Formyl ligand, Carbonyl ligand, Thiolato-bridged complexes
Abstract

The thiolato-bridged binuclear molybdenum complexes [Mo 2 Cp 2 L 2 (μ-SMe) 2 (μ-L′)]Y (Cp = η 5 -C 5 H 5 ; L′ = SMe, L = Bu t NC ( 1a ), xylNC ( 1b ) or CO ( 3 ); L′ = PPh 2 , L = Bu t NC ( 16 ); Y = BF 4 , Cl) react with the anionic reagents NaBH 4 , NaBD 4 , LiR (R = Me, Bu n ), R′MgCl (R′ = Me, Pr i , Bu n or Ph). The products are unsubstituted ( 5 , 7 ) or substituted ( 8 – 12 ) η 4 -cyclopentadiene derivatives, [Mo 2 (η 5 -C 5 H 5 )(η 4 -C 5 H 5 R)L 2 (μ-SMe) 3 ] (L = xylNC, CO), or μ-formimidoyl dinuclear products, [Mo 2 Cp 2 L 2 (μ-SMe) 2 (μ-L′)(μ-CHNR)] (L′ = SMe, L = Bu t NC ( 4 ) or xylNC ( 6 ); L′ = PPh 2 , L = Bu t NC ( 17 )). Since the reduced dinuclear species [Mo 2 Cp 2 (CO) 2 (μ-SMe) 2 ] and the related oxo-compound [Mo 2 Cp 2 (CO)(O)(μ-SMe) 2 ] are sometimes isolated as minor products, the anionic reagent can play a secondary role as a reductant in these reactions in addition to its main role as a nucleophile. The electronic properties of the donor carbon atoms of the cyclopentadienyl rings and of the terminal ligands L, together with the nature of the anionic reagent, are the dominant factors controlling selective formation of 4 – 12 and 17 . Tetrafluoroboric acid reacts with the substituted cyclopentadiene derivatives 9 , 11 and 12 to form new functionalised cyclopentadienyl derivatives, [Mo 2 (η 5 -C 5 H 5 )(η 5 -C 5 H 4 R)(CO) 2 (μ-SMe) 3 ](BF 4 ) (R = Me ( 13) , Bu n ( 14 ) or Ph ( 15 )). New complexes have been characterised by spectroscopic and chemical methods, supplemented for 5 , 6 and 12 by X-ray diffraction studies at 100 K.

Published
2005

12. Comparative studies of new pyranylidene-based sensitizers bearing single or double anchoring groups for dye-sensitized solar cells

Author

Mohammed Boujtita, Yann Pellegrin, Laurianne Wojcik, Sébastien Gauthier, Fabrice Odobel, Denis Jacquemin, Aurélien Planchat, Nicolas Le Poul, Patricia Guevara Level, Nadine Szuwarski, Françoise Robin-le Guen, 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), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank the Région des Pays de la Loire, for financial support via LUMOMAT program. This work used the computational resources of the CCIPL installed in Nantes, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Nantes - Faculté des Sciences et des Techniques, and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Anchoring dyes, 020209 energy, Substituent, γ-pyranylidene, Anchoring, Photovoltaic performance, Electron donor, 02 engineering and technology, Dye-sensitized solar cells, Electrochemistry, Photochemistry, 7. Clean energy, chemistry.chemical_compound, Substituent effect, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, TD-DFT calculations, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, Moiety, General Materials Science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Renewable Energy, Sustainability and the Environment, Photovoltaic system, Energy conversion efficiency, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dye-sensitized solar cell, chemistry, Single and double, 0210 nano-technology
Abstract

International audience; Mono- and di-anchoring γ-pyranylidene-based organic dyes featuring D–π–A and D–(π–A)2 architectures have been engineered as sensitizers for applications in Dye-Sensitized Solar Cells (DSSCs). Their photophysical, electrochemical and photovoltaic properties were further investigated. TD-DFT calculations were performed to rationalize the trends observed in the optical and electrochemical properties of the dyes. The investigation of the photovoltaic performances of this series of new dyes provided structure–property relationships where their Power Conversion Efficiencies (PCE) could be correlated to structural features, such as the length of the π-conjugated spacer, the nature of the substituents on the pyranylidene electron donor moiety and the number of anchoring groups. Dye-Sensitized Solar Cells based on mono-anchoring dyes were more efficient than the corresponding cells based on di-anchoring analogues due to high dye loading. The highest Power Conversion Efficiency of 5.23% was achieved with the mono-anchoring 17a dye containing t-butyl substituent groups on the pyranylidene fragment and with one thienyl π-conjugated spacer.

Published
2020

13. The reduction of molecular oxygen by iron porphyrins

Author

Bernard Boitrel, Amandine Didier, David Ricard, Maurice L’Her, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), and boitrel, bernard

Subjects
inorganic chemicals, Cytochrome, biology, 010405 organic chemistry, General Chemical Engineering, Inorganic chemistry, Active site, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Electrochemistry, Electrocatalyst, 01 natural sciences, Porphyrin, Oxygen, [ CHIM ] Chemical Sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymer chemistry, [CHIM] Chemical Sciences, biology.protein, Cytochrome c oxidase, [CHIM]Chemical Sciences, Graphite
Abstract

Molecular assemblies have been synthesised to reproduce the structure of the cytochrome c oxidase (C c O) active site and to explore the roles played by its different features. It was discovered that a single iron porphyrin, adsorbed at the surface of a graphite electrode, is a selective catalyst for the four-electron reduction of dioxygen to water, at pH 7. To cite this article: D. Ricard et al., C. R. Chimie 5 (2002) 33–36

Published
2002

14. Unexpected formation of the novel mixed μ-oxo, μ-sulfido, bis(μ-thiolato) compound [Mo(IV)2Cp2(μ-O)(μ-S)(μ-SMe)2]

Author

Kenneth W. Muir, Philippe Schollhammer, Jean Talarmin, François Y. Pétillon, Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Stereochemistry, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, [ CHIM ] Chemical Sciences, 0104 chemical sciences, Inorganic Chemistry, Bond length, chemistry.chemical_compound, chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Bond cleavage, Derivative (chemistry)
Abstract

cited By 7; International audience; A novel example of C-S bond cleavage in a dimolybdenum derivative leads to the formation of the quadruply bridged compound [Mo(IV)2Cp2(μ-O)(μ-S)(μ-SMe)2]. This μ-oxo species is formed by reaction of the chloro-bridged complex [Mo(III)2Cp2(μ-Cl)(μ-SMe)3] with PhCCLi and subsequent hydration at the dimolybdenum site. The Mo-Mo bond length of 2.4900(3)Å in [Mo2Cp2(μ-O)(μ-S)(μ-SMe)2] is unusually short. © 2001 Elsevier Science B.V.

Published
2001

15. Cis- and trans-Bis(1-phenyl-2,3,4,5-tetramethylphosphole)tetracarbonylmolybdenum(0), [Mo(CO)4(tmpPh)2]. Syntheses and structures

Author

Philippe Schollhammer, François Y. Pétillon, Jean Talarmin, Kenneth W. Muir, René Rumin, Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Stereochemistry, Trans effect, Organic Chemistry, Phosphole, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, [ CHIM ] Chemical Sciences, 0104 chemical sciences, Inorganic Chemistry, Metal, chemistry.chemical_compound, chemistry, Molybdenum, visual_art, Materials Chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isomerization, Cis–trans isomerism
Abstract

cited By 7; International audience; 1-Phenyl-2,3,4,5-tetramethylphosphole reacts with [Mo(CO)6] to give the mono- and bis(phosphole) complexes [Mo(CO)5L] and cis- and trans-[Mo(CO)4L2], where L=C4Me4PPh (tmpPh). The new complexes have been characterised by spectroscopic methods, supplemented by single-crystal X-ray analyses in the case of the bis(phosphole) isomers. The isomeric bis-tmpPh complexes show little evidence of the overcrowding which is thought to lengthen bonds and distort the metal coordination in the corresponding bis-PPh3 and bis-PCy3 isomers. The structural basis for the greater stability of the trans isomers is briefly considered: the cis→trans isomerisation typically involves little change in the mean Mo-CO distance, whereas there is a marked shortening of the Mo-P bonds. © 2001 Elsevier Science B.V.

Published
2001

16. Tuning the lipophilic nature of pyclen-based 90Y3+ radiopharmaceuticals for β-radiotherapy

Author

Mariane Le Fur, Raphaël Tripier, Maryline Beyler, Olivier Fougère, Nicolas Lepareur, Olivier Rousseaux, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire Guerbet, Nutrition, Métabolismes et Cancer (NuMeCan), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), CRLCC Eugène Marquis (CRLCC), Laboratoire Guerbet / Guerbet Research, Université de Rennes (UR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and GINOP-2.3.2-15-2016-00008, European Regional Development Fund

Subjects
[SDV]Life Sciences [q-bio], Biophysics, Nanoparticle, 010402 general chemistry, Ligands, 01 natural sciences, Biochemistry, digestive system, Brain cancer, Biomaterials, chemistry.chemical_compound, picolinate, Ethiodized Oil, lipophilicity, Chelation, Yttrium Radioisotopes, 90Y radiolabeling, Picolinic Acids, Alkyl, Carbon chain, chemistry.chemical_classification, biodegradable nanoparticles, Radiotherapy, 010405 organic chemistry, Ligand, internal radiotherapy, Metals and Alloys, pyclen, Lipiodol®, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, chemistry, Chemistry (miscellaneous), Lipophilicity, Malic acid, Radiopharmaceuticals, Azabicyclo Compounds
Abstract

Pyclen-dipicolinate chelates proved to be very efficient chelators for the radiolabeling with β–-emitters such as 90Y. In this study, a pyclen-dipicolinate ligand functionalized with additional C12 alkyl chains was synthesized. The radiolabeling with 90Y proved that the addition of saturated carbon chains does not affect the efficiency of the radiolabeling, whereas a notable increase in lipophilicity of the resulting 90Y radiocomplex was observed. As a result, the compound could be extracted in Lipiodol® and encapsulated in biodegrable pegylated poly(malic acid) nanoparticles demonstrating the potential of lipophilic pyclen-dipicolinate derivatives as platforms for the design of radiopharmaceuticals for the treatment of liver or brain cancers by internal radiotherapy.

Published
2021

17. Complexation of C -Functionalized Cyclams with Copper(II) and Zinc(II): Similarities and Changes When Compared to Parent Cyclam Analogues

Author

Hélène Bernard, David Esteban-Gómez, Mi Hee Lim, Marie Cordier, Guy Royal, Rita Delgado, Gunhee Kim, Evan Lelong, Raphaël Tripier, Jong-Min Suh, Carlos Platas-Iglesias, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Korea Advanced Institute of Science and Technology (KAIST), Centro de Investigaciones Científicas Avanzadas (CICA), Facultade de Ciencias, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Instituto de Tecnologia Química e Biológica António Xavier (ITQB), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)

Subjects
C-functionalization, chemistry.chemical_element, Zinc, 010402 general chemistry, Electrochemistry, Ligands, 01 natural sciences, law.invention, Inorganic Chemistry, chemistry.chemical_compound, law, Polymer chemistry, Cyclam, Molecule, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Conformation, Electron paramagnetic resonance, 010405 organic chemistry, Crystal structure, N-methylation, Copper, 0104 chemical sciences, chemistry, Metals, transition metal ions, Absorption (chemistry), configuration, Single crystal, Molecular structure
Abstract

International audience; Herein, we report a comprehensive coordination study of the previously reported ligands cyclam, CB-cyclam, TMC, DMC, and CB-DMC and of their C-functional analogues, cyclam-E, CB-cyclam-E, TMC-E, DMC-E, and CB-DMC-E. This group of ligands includes cyclam, cross-bridged cyclams, their di- or tetramethylated derivatives, and the analogues bearing an additional hydroxyethyl group on one β-N position of the ring. The Cu(II) and Zn(II) complexes of these macrocycles have been highlighted previously for the biological interest, but the details of their structures in the solid state and in solution remained largely unexplored. In particular, we analyzed the impact that adding noncoordinating N-methyl and C-hydroxyethyl functionalities has in the structures of the complexes. All the Cu(II) and Zn(II) complexes were synthesized and investigated using single crystal X-ray diffraction and NMR, electronic absorption, and EPR spectroscopies, along with DFT studies. Dissociation kinetics experiments in acidic conditions and electrochemical studies were also performed. Special attention was paid to analyze the different configurations present in solution and in the solid state, as well as the impact of the C-appended hydroxyethyl group on the coordination behavior. Various ratios of the trans-I, trans-III, and cis-V configurations have been observed depending on the degree of N-methylation and the presence of the ethylene cross-bridge.

Published
2021

18. Reactions of dinuclear and polynuclear complexes XIX. Rearrangements of terminal or disubstituted alkyne ligands present in homo- and heterodinuclear complexes of cobalt and molybdenum during reactions with molybdenum and cobalt carbonyl compounds: Formation of trinuclear and tetranuclear clusters

Author

Kenneth W. Muir, René Rumin, François Y. Pétillon, Pierre Abiven, Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_element, Alkyne, 010402 general chemistry, Ring (chemistry), Heterotrimetallics, 01 natural sciences, Biochemistry, Medicinal chemistry, [ CHIM ] Chemical Sciences, Inorganic Chemistry, chemistry.chemical_compound, Cobalt carbonyl, Heterotetrametallics, Materials Chemistry, Cluster (physics), Moiety, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Tetrahydrofuran, chemistry.chemical_classification, Molybdenum, 010405 organic chemistry, Organic Chemistry, Cobalt, Phosphido, 0104 chemical sciences, chemistry, Alkylidyne
Abstract

International audience; The dicobalt alkyne complex [Co2(μ-PhC≢CH)(CO)6] 1a reacted with [Mo2(η5-C5H5)2CO)4] in refluxing tetrahydrofuran (THF) to give the μ3-alkylidyne trinuclear cluster [Co2Mo(η5-C5H5)(μ3 -CCH2Ph)(CO)8] 3 as the major product. Possible routes to the formation of 3 have been investigated. Among the identified minor products from this reaction were [CoMo2(η5-C5H5)2(μ 3-CCH2Ph)(CO)7] 4, [Co2Mo2(η5-C5H5)2(μ4-PhC2H)(μ-CO)4(CO)4] 5 and [Co3Mo(η5-C5H5)2(μ 4-PhC2H)(μ-CO)2(CO)5] 6. In contrast, when the related dicobalt complexes [Co2(μ-CF3C≢CR) (CO)6] (R=CF3 (1b), H (1c)), which contain alkynes with more strongly electron-withdrawing substituents, were heated with [Mo2(η5-C5H5)2(CO)4] in THF only mixed-dinuclear complexes [(η5-C5H5)(CO)2Mo(μ-CF3C2R)Co(CO)3](Mo-Co) (R=H (7a), CF3 (7b)) were formed. The reaction of the mixed-dinuclear complex 7b with [Co(η5-C5H5)(CO)2] led to the mixed-tetranuclear butterfly cluster [Co2Mo2(η5-C5H5)3(μ-CO)(CO)3] 8. The thermal reaction of 1b with the phosphido compound [Mo2(η5-C5H5)2(μ-C O)(μ-PPh2)2] gave rise to a single product, [Mo2(η5-C5H5)2(μ-P Ph2)_μ-PPh2Co2(μ-CF3C2CF3)(CO)5₍CO)2] 9, in which a phenyl ring of the (μ-phosphido)dimolybdenum moiety is π-bonded to one of the two cobalt atoms. Spectroscopic data for the new complexes are discussed.

Published
1998

19. Electrooxidation of porphyrin free bases: Fate of the π-cation radical

Author

Yves Le Mest, Roger Guilard, Claude Inisan, Jean-Yves Saillard, Alain Tabard, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Ingénierie Moléculaire pour la Séparation et les Applications des Gaz (LIMSAG), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Ingénierie Moléculaire pour la Séparation et les Applications des Gaz (UMR 5633) (LIMSAG), Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
010405 organic chemistry, Radical, Free base, Protonation, General Chemistry, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, Porphyrin, Chemical reaction, [ CHIM ] Chemical Sciences, Catalysis, 0104 chemical sciences, law.invention, Metal, chemistry.chemical_compound, chemistry, law, visual_art, Materials Chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Electron paramagnetic resonance
Abstract

International audience; In contrast to metalloporphyrins with non-electroactive metal centres, the π-cation radicals of porphyrin free bases (H2OEP, H2TPP, H2CdiE) electrogenerated in strictly anhydrous solvents are not stable and give rise to a quantitative chemical reaction. Conjunction of electrochemical and spectroscopic data (UV/VIS, EPR and NMR) demonstrates unambiguously that the porphyrin skeleton is not modified during the chemical reaction. The reaction product is the protonated free base, and thus the free base can be regenerated by reduction of the protons.

Published
1998

20. Phosphonodithioester-amine coupling in water: a fast reaction to modify the surface of liposomes

Author

Paul-Alain Jaffrès, Dany Jeanne Dit Fouque, Aurélien Dupont, Mathieu Berchel, Montassar Khalil, Aurore Fraix, Salvatore Sortino, Antony Memboeuf, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), University of Catania [Italy], Biosit : biologie, santé, innovation technologique (SFR UMS CNRS 3480 - INSERM 018), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), and Université de Rennes (UR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )

Subjects
liposomes, réaction dans l’eau, [SDV]Life Sciences [q-bio], Kinetics, education, Phospholipid, 010402 general chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, Reaction rate constant, Amphiphile, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, réaction click, amphiphiles, Liposome, no metal, reaction in water, sans métal, 010405 organic chemistry, Organic Chemistry, food and beverages, Combinatorial chemistry, 0104 chemical sciences, Coupling (electronics), chemistry, click chemistry, Click chemistry, Amine gas treating
Abstract

International audience; The incorporation of lipophilic phosphonodithioesters in phospholipid formulations generates clickable liposomes that react with amines. The kinetics of this metal free phosphonodithioester-amine coupling (PAC) on liposomes in water is reported and can be classified as a fast reaction with a second order rate constant of k ≈ 8 × 102 M-1 s-1. The PAC reaction represents a versatile strategy to functionalize liposomes.

Published
2021

21. Synthetic alkyl-ether-lipid promotes TRPV2 channel trafficking trough PI3K/Akt-girdin axis in cancer cells and increases mammary tumour volume

Author

Audrey Gambade, Marie Potier-Cartereau, Yann Fourbon, Philippe Bougnoux, Romain Félix, Sana Kouba, David Ternant, François Carreaux, Maxime Guéguinou, Ana Bouchet, Paul-Alain Jaffrès, Thomas Harnois, Christophe Vandier, Olivier Mignen, Aurélie Chantôme, Christophe Arnoult, Jean-Pierre Haelters, Thibauld Oullier, Séverine Marionneau-Lambot, Aubin Penna, Günther Weber, Gaëlle Simon, Nutrition, croissance et cancer (U 1069) (N2C), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM), Groupe innovation et ciblage cellulaire (GICC), EA 7501 [2018-...] (GICC EA 7501), Université de Tours (UT), Institut de Recherche en Santé de l'Université de Nantes (IRS-UN), The Enteric Nervous System in gut and brain disorders [U1235] (TENS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN), Signalisation et Transports Ioniques Membranaires (STIM), Université de Poitiers-Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), 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), Inserm UMR 1227 Immunothérapies et Pathologies Lymphocytaires B, Hôpital Morvan - CHRU de Brest (CHU - BREST ), INCa, Ligue Nationale Contre le Cancer, Region Centre Val de Loire (LIPIDS project of ARD2020-Biomédicaments), INSERM, Cancéropôle Grand Ouest, the association 'CANCEN' and Tours Hospital oncology association 'ACORT'. M. Guéguinou, Y. Fourbon and A. Gambade held fellowships from the 'Region Centre', 'Ministère de l'Enseignement Supérieur et de la Recherche'., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Tours-Institut National de la Santé et de la Recherche Médicale (INSERM), Université de Tours, and Université de Poitiers-Université de Tours-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Physiology, [SDV]Life Sciences [q-bio], Metastasis, 03 medical and health sciences, Transient receptor potential channel, chemistry.chemical_compound, 0302 clinical medicine, medicine, [CHIM]Chemical Sciences, Molecular Biology, Protein kinase B, PI3K/AKT/mTOR pathway, Constitutive Ca2+ entry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Breast cancer cell migration, Cancer, Cell migration, Cell Biology, medicine.disease, 3. Good health, Cell biology, TRPV2, 030104 developmental biology, Cancer cell, lipids (amino acids, peptides, and proteins), Alkyl-ether-lipid, 030217 neurology & neurosurgery, Edelfosine
Abstract

International audience; The Transient Receptor Potential Vanilloid type 2 (TRPV2) channel is highly selective for Ca2+ and can be activated by lipids, such as LysoPhosphatidylCholine (LPC). LPC analogues, such as the synthetic alkyl-ether-lipid edelfosine or the endogenous alkyl-ether-lipid Platelet Activating Factor (PAF), modulates ion channels in cancer cells. This opens the way to develop alkyl-ether-lipids for the modulation of TRPV2 in cancer. Here, we investigated the role of 2-Acetamido-2-Deoxy-l-O-Hexadecyl-rac-Glycero-3-PhosphatidylCholine (AD-HGPC), a new alkyl-ether-lipid (LPC analogue), on TRPV2 trafficking and its impact on Ca2+ -dependent cell migration. The effect of AD-HGPC on the TRPV2 channel and tumour process was further investigated using calcium imaging and an in vivo mouse model. Using molecular and pharmacological approaches, we dissected the mechanism implicated in alkyl-ether-lipids sensitive TRPV2 trafficking. We found that TRPV2 promotes constitutive Ca2+ entry, leading to migration of highly metastatic breast cancer cell lines through the PI3K/Akt-Girdin axis. AD-HGPC addresses the functional TRPV2 channel in the plasma membrane through Golgi stimulation and PI3K/Akt/Rac-dependent cytoskeletal reorganization, leading to constitutive Ca2+ entry and breast cancer cell migration (without affecting the development of metastasis), in a mouse model. We describe, for the first time, the biological role of a new alkyl-ether-lipid on TRPV2 channel trafficking in breast cancer cells and highlight the potential modulation of TRPV2 by alkyl-ether-lipids as a novel avenue for research in the treatment of metastatic cancer.

Published
2021

22. TE1PA as Innovating Chelator for 64Cu Immuno-TEP Imaging: A Comparative in Vivo Study with DOTA/NOTA by Conjugation on 9E7.4 mAb in a Syngeneic Multiple Myeloma Model

Author

Alain Faivre-Chauvet, Raphaël Tripier, Nathalie Le Bris, Thomas Le Bihan, Patricia Le Saëc, Mickaël Bourgeois, Clément Bailly, Catherine Saï-Maurel, Michel Chérel, Anne-Sophie Navarro, Nuclear Oncology (CRCINA-ÉQUIPE 13), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Cyclotron ARRONAX [Saint-Herblain], ARRONAX - (GIP) Groupement d'Intérêt Public [Saint-Herblain] (Institut de Recherche Public), Institut de Cancérologie de l'Ouest [Angers/Nantes] (UNICANCER/ICO), UNICANCER, Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), and Bernardo, Elizabeth

Subjects
Biodistribution, medicine.drug_class, Biomedical Engineering, Pharmaceutical Science, [SDV.CAN]Life Sciences [q-bio]/Cancer, Bioengineering, 02 engineering and technology, Monoclonal antibody, 01 natural sciences, chemistry.chemical_compound, [SDV.CAN] Life Sciences [q-bio]/Cancer, In vivo, medicine, DOTA, ComputingMilieux_MISCELLANEOUS, Pharmacology, biology, 010405 organic chemistry, Chemistry, Organic Chemistry, 021001 nanoscience & nanotechnology, Ligand (biochemistry), In vitro, 0104 chemical sciences, Cell culture, biology.protein, Cancer research, Antibody, 0210 nano-technology, Biotechnology
Abstract

Following the successful synthesis of a C-functionalized version of the TE1PA ligand, a monopicolinate cyclam, we looked to demonstrate its in vivo properties versus DOTA and NOTA, after conjugation on the 9E7.4 rat antibody, an IgG2a against CD138 murine, which has relevant properties for multiple myeloma targeting. For each ligand, different conjugation approaches had been considered to select the most appropriate for the comparative study. The p-SCN-Bn-TE1PA, NHS-DOTA, and p-SCN-Bn-NOTA were finally chosen for conjugation and radiolabeling tests. For in vivo comparison, we used a model of subcutaneous grafted mice with 5T33 tumor cells. In vitro tests and immuno-PET study highlighted 64Cu-9E7.4-p-SCN-Bn-NOTA as the least attractive. Further competitive biodistribution and hepatic metabolic studies at 2, 24, and 48 h post-injection (100 μg radiolabeled with 10 MBq of 64Cu) were then performed with the 64Cu-9E7.4-p-SCN-Bn-TE1PA and 64Cu-9E7.4-NHS-DOTA. Results show a better in vivo resistance of 64Cu-9E7.4-p-SCN-Bn-TE1PA to transchelation compared to 64Cu-9E7.4-NHS-DOTA, especially at later times. This was confirmed with 64Cu-9E7.4-p-SCN-Bn-NOTA at 48 h PI. 64Cu-9E7.4-p-SCN-Bn-TE1PA also demonstrated an excellent hepatic clearance. 64Cu-9E7.4-p-SCN-Bn-TE1PA displayed an overall superiority compared to 64Cu-9E7.4-NHS-DOTA and 64Cu-9E7.4-p-SCN-Bn-NOTA in terms of in vivo stability, reinforcing the usefulness of the p-SCN-Bn-TE1PA ligand for 64Cu immuno-PET imaging.

Published
2019

23. A 'Multi‐Heavy‐Atom' Approach toward Biphotonic Photosensitizers with Improved Singlet‐Oxygen Generation Properties

Author

Olivier Maury, Tangui Le Bahers, Raphaël Tripier, Margaux Galland, Chantal Andraud, N. Lascoux, Alain Duperray, Akos Banyasz, Yannick Guyot, Cyrille Monnereau, Alexei Grichine, Marie Maynadier, Christophe Nguyen, Magali Gary-Bobo, 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), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut Lumière Matière [Villeurbanne] (ILM), Université de Lyon-Université de Lyon, NanoMedSyn, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), 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 Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and NanoMedSyn (NMS)

Subjects
Lanthanide, Gadolinium, chemistry.chemical_element, O2, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Two-photon excitation microscopy, Atom, TACN, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Two-photon microscopy, Bromine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Singlet oxygen, Organic Chemistry, Intersystem crossing, General Chemistry, Gd Complex, 0104 chemical sciences, chemistry, Photodynamic Therapy, Absorption (chemistry), [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

Dr. Y. Bretonnière and Dr. M. Rémond for their help in the preparation of Pluronic nanoparticles.IAB platform was co-funded thanks to grants of ‘‘Association pour la Recherche sur le Cancer’’ (ARC, Villejuif, France),‘‘Ligue Contre le Cancer’’ (LCC Ise`re/Arde`che) and the CPER program. The authors thank C. Chamot and the PLATIM Imaging and Microscopy platform for theaccess to the femtosecond laser system.We thank MRI (Montpellier RIO Imaging platform) for confocal imaging facilities. Dr. T. Le Bahers thanks the ‘‘Pole Scientifique de Modélisation Numérique (PSMN)“ for its computational resources.; International audience; The TACN based gadolinium complex exhibits high two-photon absorption cross-section combined with near-unity 1O2 generation. The very large inter system crossing efficiency induced by the combination of bromine atom and heavy rare-earth element was corroborated with theoretical calculations. The 1O2 generation properties of micellar suspensions under two-photon activation lead to tumour cells death introducing the potential of such structures for theranostic applications; Le complexe de gadolinium à base de TACN présente une section efficace d'absorption à deux photons combinée à une génération de 1O2 proche de l'unité. La très grande efficacité de croisement intersystème induite par la combinaison d'un atome de brome et d'un lanthanide a été corroborée par des calculs théoriques. Les propriétés de génération 1O2 des suspensions micellaires sous activation à deux photons entraînent la mort des cellules tumorales, ce qui introduit le potentiel de telles structures pour des applications théranostiques.

Published
2019

24. Insights into the radical-radical and radical-substrate dimerization processes for substituted phenylmethylenepyrans

Author

Pascal Le Poul, Isidoro López, Sébastien Gauthier, Laurianne Wojcik, Frédéric Gloaguen, Nolwenn Cabon, Nicolas Le Poul, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Financial support by Agence Nationale pour la Recherche (ANR-13-BSO7-0018), Conseil Général du Finistère, and Université de Bretagne Occidentale. I.L. acknowledges support from the European Commission under the Campus Prestige progamme (PRESTIGE-2015-2-0019)., ANR-13-BS07-0018,COMEBAC,COmplexes à Valence MixtE Bis(µ-oxo)CuIICuIII pour l'ACtivation de Liaisons C-H(2013), European Project: PRESTIGE 2015-2-0019,PRESTIGE, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, Dimer, Population, Substituent, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, chemistry.chemical_compound, radical dimerization, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, low-temperature voltammetry, Electrochemistry, [CHIM]Chemical Sciences, education, Voltammetry, education.field_of_study, [CHIM.ORGA]Chemical Sciences/Organic chemistry, ab initio calculations, Intermolecular force, 021001 nanoscience & nanotechnology, methylenepyran, 0104 chemical sciences, C-C bond making, chemistry, Radical ion, Electrophile, Cyclic voltammetry, 0210 nano-technology
Abstract

International audience; The electrochemically-induced CC bond making/breaking for six differently R-substituted phenylmethylenepyrans has been investigated by voltammetry in organic media. All compounds display an irreversible oxidation peak whose potential is fully dependent on the electrophilic property of the substituent R. The electrochemical oxidation yields bis-pyrylium compounds by σ-σ CC bond formation. The initial methylenepyrans are recovered by cleavage of the CC bond through electrochemical reduction of the bis-pyrylium species. According to the voltammetric analysis, the mechanistic pathway, radical-radical or radical-substrate, for the intermolecular dimerization is fully R-dependent. Electronic structure calculations show that the spin population in the radical cation and the strength of the σ-σ CC bond in the dimer strongly depend on the nature of R. In addition, low-temperature electrochemical voltammetry (175 K), and room-temperature high scan rate cyclic voltammetry have been used to unravel the kinetics of the CC bond formation.

Published
2019

25. Design and Synthesis of Hybrid PEGylated Metal Monopicolinate Cyclam Ligands for Biomedical Applications

Author

Fatima Aouidat, Stefania Filosa, Stella Donato, Rosarita Tatè, Zakaria Halime, Rosalba Moretta, Raphaël Tripier, Luca De Stefano, Jolanda Spadavecchia, Ilaria Rea, Chimie, Structures et Propriétés de Biomatériaux et d'Agents Thérapeutiques (CSPBAT), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris 13 (UP13)-Institut Galilée-Université Sorbonne Paris Cité (USPC), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institute for Microelectronics and Microsystems [Naples], Naples-National Research Council, Institute of Genetics and Biophysics, Consiglio Nazionale delle Ricerche (CNR), Institute of Biosciences and Bioresources, National Research Council of Italy, Institute of Genetics and Biophysics Adriano Buzzati-Traverso (IGB), and Consiglio Nazionale delle Ricerche [Roma] (CNR)

Subjects
General Chemical Engineering, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Article, Nanomaterials, lcsh:Chemistry, symbols.namesake, chemistry.chemical_compound, Dynamic light scattering, Cyclam, [CHIM]Chemical Sciences, Chelation, Hybrid PEGylated, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, chemistry, lcsh:QD1-999, symbols, Chemical stability, 0210 nano-technology, Raman spectroscopy, Nuclear chemistry
Abstract

International audience; In this study, we report, for the first time, the synthesis of two original nanosystems, based on gold Au(III) and copper Cu(II): simple gold−copper nanoparticles (Cu 0 AuNPs) and enriched monopicolinate cyclam (L1)−Cu(II)−Au(III)-complex (L1@Cu 2+ AuNPs). The two nanomaterials differ substantially by the chelation or not of the Cu(II) ions during the NPs synthesis process. The two hybrid nanoparticles (Cu 0 AuNPs; L1@Cu 2+ AuNPs) were deeply studied from the chemical and physical point of view, using many different analytical techniques such as Raman and UV−vis spectroscopy, electron transmission microscopy, and dynamic light scattering. Both nanosystems show morphological and good chemical stability at pH 4 values and in physiological conditions during 98 h. Undifferentiated and neural differentiated murine embryonic stem cells were used as a model system for in vitro experiments to reveal the effects of NPs on these cells. The comparative study between Cu 0 AuNPs and L1@Cu 2+ AuNPs highlights that copper chelated in its +2 oxidation state in the NPs is more functional for biological application.

Published
2019

26. Methylthiazolyl Tacn Ligands for Copper Complexation and Their Bifunctional Chelating Agent Derivatives for Bioconjugation and Copper-64 Radiolabeling: An Example with Bombesin

Author

Véronique Patinec, Luís M. P. Lima, Nicolas Le Poul, Amaury Guillou, Raphaël Tripier, David Esteban-Gómez, Carlos Platas-Iglesias, Rita Delgado, Mark Bartholomä, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Instituto de Tecnologia Química e Biológica António Xavier (ITQB), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Departamento de Química Fundamental, Universidade da Coruña, Department of Nuclear Medicine, and Saarland University [Saarbrücken]

Subjects
Models, Molecular, 64Cu-labeling, Potentiometric titration, Molecular Conformation, chemistry.chemical_element, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Conjugated system, Ligands, radiopharmaceutical, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, bifunctionalization, chemistry.chemical_compound, Piperidines, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation, Physical and Theoretical Chemistry, Bifunctional, Chelating Agents, Aza Compounds, methylthiazolyl, Bioconjugation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Water, tacn, Hydrogen-Ion Concentration, Combinatorial chemistry, Copper, 0104 chemical sciences, Copper Radioisotopes, chemistry, Isotope Labeling, Quantum Theory, Bombesin, Chemical stability, Copper-64
Abstract

International audience; We present here the synthesis of two new bifunctionalized azachelators, no2th-EtBzNCS and Hno2th1tha, as bioconjugable analogues of two previously described di- and trimethylthiazolyl 1,4,7-triazacyclononane (tacn) ligands, no2th and no3th, for potential uses in copper-64 (64Cu) positron emission tomography imaging. The first one bears an isothiocyanate group on the remaining free nitrogen atom of the tacn framework, while the second one presents an additional carboxylic function on one of the three heterocyclic pendants. Their syntheses required regiospecific N-functionalization of the macrocycles. In order to investigate their suitability for in vivo applications, a complete study of their copper(II) chelation was performed. The acid–base properties of the ligands and their thermodynamic stability constants with copper(II) and zinc(II) cations were determined using potentiometric techniques. Structural studies were conducted in both solution and the solid state, consolidated by theoretical calculations. The kinetic inertness in an acidic medium of both copper(II) complexes was determined by spectrophotometry, while cyclic voltammetry experiments were performed to evaluate the stability at the copper(I) redox state. UV–vis, NMR (of the zinc complexes), electron paramagnetic resonance spectroscopy, and density functional theory studies showed excellent agreement between the solution structures of the complexes and their crystallographic data. These investigations unambiguously prove that these bifunctional derivatives display similar coordination properties as their no2th and no3th counterparts, opening the door to targeted bioapplications. The no2th-EtBzNCS and Hno2th1tha ligands were then conjugated to a bombesin antagonist peptide for targeting the gastrin-releasing peptide receptor (GRPr). To highlight the potential of the two chelators for radiopharmaceutical development, the 64Cu-radiolabeling properties, in vitro stability, and binding affinity to GRPr of the corresponding bioconjugates were determined. Altogether, the results of this work warrant the further development of 64Cu-based radiopharmaceuticals comprising our novel bifunctional chelators.

Published
2019

27. Substitution of unsaturated lipid chains by thioether-containing lipid chains in cationic amphiphiles: physicochemical consequences and application for gene delivery

Author

Olivier Lozach, Mathieu Berchel, Tristan Montier, Laure Deschamps, Gilles Paboeuf, Rosy Ghanem, Véronique Vié, Tony Le Gall, Paul-Alain Jaffrès, Amal Bouraoui, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Génétique, génomique fonctionnelle et biotechnologies (UMR 1078) (GGB), EFS-Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Synthèse Caractérisation Analyse de la Matière (ScanMAT), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Chimie du CNRS (INC), RF20160501669, Association Vaincre la Mucoviscidose, PS2009_15628, French Muscular Dystrophy Association, Centre National de la Recherche Scientifique, Institut National de la Santé et de la Recherche Médicale, Brest Metropole, Association Gaétan Saleün (Brest-France), AFM, Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
thiol-ene click reaction, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 02 engineering and technology, Sulfides, Gene delivery, 010402 general chemistry, 01 natural sciences, Biochemistry, thioether, Supramolecular assembly, lipids, Turn (biochemistry), Surface-Active Agents, chemistry.chemical_compound, Thioether, Cations, Amphiphile, Humans, Moiety, Physical and Theoretical Chemistry, Degree of unsaturation, Chemistry, Physical, [CHIM.ORGA]Chemical Sciences/Organic chemistry, compression isotherm, Organic Chemistry, Gene Transfer Techniques, Cationic polymerization, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, transfection, chemistry, cationic amphiphiles, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions
Abstract

International audience; The hydrophobic moiety of cationic amphiphiles plays an important role in the transfection process because its structure has an impact on both the type of the supramolecular assembly and the dynamic properties of these assemblies. The latter have to exhibit a compromise between stability and instability to efficiently compact then deliver DNA into target cells. In the present work, we report the synthesis of new cationic amphiphiles featuring a thioether function at different positions of two 18-atom length lipid chains and we study their physicochemical properties (anisotropy of fluorescence and compression isotherms) with analogues possessing either oleyl (C181) or stearyl (C180) chains. We show that the fluidity of cationic lipids featuring a thioether function located close to the middle of each lipid chain is intermediate between that of oleyl- and stearyl-containing analogues. These properties are also supported by the compression isotherm assays. When used as carriers to deliver a plasmid DNA, thioether-containing cationic amphiphiles demonstrate a good ability to transfect human-derived cell lines, with those incorporating such a moiety in the middle of the chain being the most efficient. This work supports the use of a thioether function as a possible alternative to unsaturation in aliphatic lipid chains of cationic amphiphiles to modulate physicochemical behaviours and in turn biological activities such as gene delivery ability.; La partie hydrophobe des composés amphiphiles joue un rôle important lors des processus de transfection puisque sa structure influence l’assemblage supramoléculaire et la dynamique de ces assemblages. Cette dynamique doit être un compromis entre stabilité et instabilité pour compacter et apporter l’ADN jusqu’aux cellules cibles. Dans cette étude, nous décrivons la synthèse de nouveaux amphiphiles cationiques comportant une fonction thioéther à différente position d’une chaine contenant dans son squelette 18 atomes. Nous rapportons également leurs propriétés physico-chimiques et comparons les résultats avec des amphiphiles comportant une chaine insaturée (chaine oleyle) ou saturée (chaine stéaryle). Nous montrons que la fluidité des assemblages supramoléculaires des amphiphiles comportant une fonction thioéther proche du milieu de chaine est intermédiaire à celle des composés possédant une chaine oleyles et stéaryle. Ces résultats sont aussi en accord avec les résultats des isothermes de compression. Ces nouveaux amphiphiles ont été utilisés en transfection et montrent de très bonnes efficacités pour les composés où la fonction thioéther se trouve proche du milieu de la chaine lipidique. Ce travail montre que ce nouveau type de chaine lipidique présente une alternative à l’utilisation des chaines mono-insaturée (oleyle) pour la conception de composés amphiphiles utilisés ici pour la transfection

Published
2019

28. High-valence CuIICuIII species in action: demonstration of aliphatic C–H bond activation at room temperature

Author

Christian Philouze, Amélie Durand, Aurore Thibon-Pourret, Nicolas Le Poul, Catherine Belle, James A. Isaac, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie Moléculaire de Grenoble (ICMG), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
aliphatic C–H bond activation, Reactive intermediate, chemistry.chemical_element, CuII, Oxidative phosphorylation, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, CuIICuIII, C h bond, Valence (chemistry), 010405 organic chemistry, Chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Copper, Toluene, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, C-H bond activation, copper, Ceramics and Composites, CuIII, Stoichiometry
Abstract

International audience; The electrochemically generated CuIICuIII mixed-valence species promotes activation of strong aliphatic C–H bonds (i.e. toluene) at room temperature. The mechanistic pathway turns from stoichiometric to catalytic upon addition of base, hence demonstrating that such high-valence dicopper species can be key reactive intermediates in copper-based oxidative processes.

Published
2019

29. Thio-ether functionalized glycolipid amphiphilic compounds reveal a potent activator of SK3 channel with vasorelaxation effect

Author

Côme Pasqualin, Véronique Maupoil, Alicia Bauduin, Maxime Guéguinou, Bei Li Zhang, Hélène Couthon, Aurélie Chantôme, Christophe Vandier, Charlotte M. Sevrain, Karine Mahéo, Delphine Fontaine, Paul-Alain Jaffrès, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Nutrition, croissance et cancer (U 1069) (N2C), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM), Signalisation et Transports Ioniques Membranaires (STIM), Université de Poitiers-Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Tours-Institut National de la Santé et de la Recherche Médicale (INSERM), and Université de Poitiers-Université de Tours-Centre National de la Recherche Scientifique (CNRS)

Subjects
Male, Cell Survival, Small-Conductance Calcium-Activated Potassium Channels, Stereochemistry, Thio, Ether, 01 natural sciences, Biochemistry, Sulfone, Surface-Active Agents, 03 medical and health sciences, chemistry.chemical_compound, Thioether, glycolipide, Cell Movement, Amphiphile, Animals, Humans, [CHIM]Chemical Sciences, Sulfhydryl Compounds, Patch clamp, Rats, Wistar, Physical and Theoretical Chemistry, Cells, Cultured, Ion channel, vasorelaxation, 030304 developmental biology, amphiphiles, 0303 health sciences, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, canaux ioniques, Sulfoxide, Rats, 0104 chemical sciences, Vasodilation, chemistry, Glycolipids, Ethers, activateur
Abstract

International audience; The modulation of SK3 ion channels can be efficiently and selectively achieved by using the amphiphilic compound Ohmline (a glyco-glycero-ether-lipid). We report herein a series of Ohmline analogues featuring the replacement of one ether function by a thioether function located at the same position or shifted close to its initial position. The variation of the lipid chain length and the preparation of two analogues featuring either one sulfoxide or one sulfone moiety complete this series. Patch clamp measurements indicate that the presence of the thioether function (compounds 7 and 17a) produces strong activators of SK3 channels, whereas the introduction of a sulfoxide or a sulfone function at the same place produces amphiphiles devoid of an effect on SK3 channels. Compounds 7 and 17a are the first amphiphilic compounds featuring strong activation of SK3 channels (close to 200% activation). The cytosolic calcium concentration determined from fluorescence at 3 different times for compound 7b (13 min, 1 h, 24 h) revealed that the effect is different suggesting that the compound could be metabolized over time. This compound could be used as a strong SK3 activator for a short time. The capacity of 7b to activate SK3 was then used to induce vasorelaxation via an endothelium-derived hyperpolarization (EDH) pathway. For the first time, we report that an amphiphilic compound can affect the endothelium dependent vasorelaxation.; Des analogues de l’Ohmline, contenant une fonction soufrée, sont décrits et testés comme modulateur des canaux ioniques SK3. Deux puissants activateurs sont identifiés. Néanmoins leur effet est limité dans le temps. Il est suggéré que ces composés, dotés d’une fonction thioéther, soient oxydés en sulfoxide et sulfone au cours du temps conduisant à une modification de leur activité. Un compose inhibiteur est également identifié mais son manque de sélectivité pourrait expliquer l’absence d’effet sur les entrées calciques associé à l’inhibition des canaux SK3. Finalement, il est montré pour la première fois qu’un composé amphiphile (l’un des activateurs des canaux SK3) présente un effet de vasorelaxation.

Published
2021

30. Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for 64 Cu-PET Imaging: Synthesis, Physicochemical Studies, Radiolabeling, and Bioimaging

Author

Séverine Marionneau-Lambot, Nathalie Saffon-Merceron, Michel Chérel, Mourad Elhabiri, Valérie Mazan, Nathalie Le Bris, Richard C. Knighton, Loïc J. Charbonnière, Thibault Troadec, Thomas Le Bihan, Patricia Le Saëc, Raphaël Tripier, Alain Faivre-Chauvet, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Troadec, Thibault, Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-IDEX-0007,NExT (I-SITE),NExT (I-SITE)(2016)

Subjects
Organophosphorus compounds, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, Reaction mechanisms, Potentiometric titration, chemistry.chemical_element, 010402 general chemistry, Ligands, 01 natural sciences, Dissociation (chemistry), Inorganic Chemistry, chemistry.chemical_compound, Cyclam, Pyridine, [CHIM.RADIO] Chemical Sciences/Radiochemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, 010405 organic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Combinatorial chemistry, Copper, Phosphonate, 0104 chemical sciences, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, chemistry, Lipophilicity, Chemical stability, Stability, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

International audience; Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection–alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid state (X-ray diffraction analysis) and in solution (EPR and UV–vis spectroscopies). Potentiometric studies combined with spectrometry have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demonstrated a set of features emerging from the combination of picolinates and phosphonate units: high stability in vivo, fast clearance from the body via renal elimination, and most interestingly, very low fixation in the liver. This is in contrast with what was observed for monopicolinate cyclam (te1pa), which had a non-negligible accumulation in the liver, owing probably to its different charge and lipophilicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo64Cu-PET imaging.

Published
2021

31. Oxo-functionalised mesoionic NHC nickel complexes for selective electrocatalytic reduction of CO 2 to formate

Author

Martin Albrecht, Peter Broekmann, Frédéric Gloaguen, Motiar Rahaman, Philippe Schollhammer, Alexander V. Rudnev, Abhijit Dutta, Simone Bertini, Universität Bern [Bern], Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, and Russian Academy of Sciences [Moscow] (RAS)

Subjects
chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 7. Clean energy, 01 natural sciences, 12. Responsible consumption, Catalysis, chemistry.chemical_compound, 540 Chemistry, Environmental Chemistry, Chelation, Formate, Oxo-functionalised mesoionic NHC nickel complexes, Ni, 010405 organic chemistry, Ligand, Mesoionic, Pollution, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Nickel, chemistry, Yield (chemistry), CO 2, H2, 570 Life sciences, biology, Carbene
Abstract

International audience; Strategies for the conversion of CO2 to valuable products are paramount for reducing the environmental risks associated with high levels of this greenhouse gas and offer unique opportunities for transforming waste into useful products. While catalysts based on nickel as an Earth-abundant metal for the sustainable reduction of CO2 are known, the vast majority produce predominantly CO as a product. Here, efficient and selective CO2 reduction to formate as a synthetically valuable product has been accomplished with novel nickel complexes containing a tailored C,O-bidentate chelating mesoionic carbene ligand. These nickel(II) complexes are easily accessible and show excellent catalytic activity for electrochemical H+ reduction to H2 (from HOAc in MeCN), and CO2 reduction (from CO2-saturated MeOH/MeCN solution) with high faradaic efficiency to yield formate exclusively as an industrially and synthetically valuable product from CO2. The most active catalyst precursor features the 4,6-di-tert-butyl substituted phenolate triazolylidene ligand, tolerates different proton donors including water, and reaches an unprecedented faradaic efficiency of 83% for formate production, constituting the most active and selective Ni-based system known to date for converting CO2 into formate as an important commodity chemical.

Published
2021

32. Complexation of Mn(II) by Rigid Pyclen Diacetates: Equilibrium, Kinetic, Relaxometric, Density Functional Theory, and Superoxide Dismutase Activity Studies

Author

Raphaël Tripier, Norbert Lihi, Gyula Tircsó, José L. Barriada, Nadège Hamon, Ferenc K. Kálmán, Enikő Molnár, Viktória Nagy, Balázs Váradi, Carlos Platas-Iglesias, Imre Tóth, David Esteban-Gómez, Zoltán Garda, Kristof Pota, Éva Tóth, University of Debrecen Egyetem [Debrecen], Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centro de Investigacións Científicas Avanzadas (CICA), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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 RENARD, NICOLAS

Subjects
Ethylenediaminetetraacetic acid, SOD activity, Acetates, 010402 general chemistry, Ligands, 01 natural sciences, Medicinal chemistry, Dissociation (chemistry), Oxalate, Inorganic Chemistry, Metal, chemistry.chemical_compound, Blood serum, Coordination Complexes, [CHIM] Chemical Sciences, Humans, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Density Functional Theory, Manganese, Molecular Structure, 010405 organic chemistry, Superoxide, Ligand, Superoxide Dismutase, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Stereoisomerism, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 0104 chemical sciences, Mn(II) complexes, Kinetics, chemistry, visual_art, Pyclen, visual_art.visual_art_medium, Chemical stability, Relaxivity, Azabicyclo Compounds, MRI
Abstract

International audience; We report the Mn(II) complexes with two pyclen-based ligands (pyclen = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene) functionalized with acetate pendant arms at either positions 3,6 (3,6-PC2A) or 3,9 (3,9-PC2A) of the macrocyclic fragment. The 3,6-PC2A ligand was synthesized in five steps from pyclen oxalate by protecting one of the secondary amine groups of pyclen using Alloc protecting chemistry. The complex with 3,9-PC2A is characterized by a higher thermodynamic stability [log KMnL = 17.09(2)] than the 3,6-PC2A analogue [log KMnL = 15.53(1); 0.15 M NaCl]. Both complexes contain a water molecule coordinated to the metal ion, which results in relatively high 1H relaxivities (r1p = 2.72 and 2.91 mM–1 s–1 for the complexes with 3,6-PC2A and 3,9-PC2A, respectively, at 25 °C and 0.49 T). The coordinated water molecule displays fast exchange kinetics with the bulk in both cases; the rates (kex298) are 140 × 106 and 126 × 106 s–1 for [Mn(3,6-PC2A)(H2O)] and [Mn(3,9-PC2A)(H2O)], respectively. The two complexes were found to be remarkably inert with respect to their dissociation, with half-lives of 63 and 21 h, respectively, at pH = 7.4 in the presence of excess Cu(II). The r1p values recorded in blood serum remain constant at least over a period of 120 h. Cyclic voltammetry experiments show irreversible oxidation features shifted to higher potentials with respect to [Mn(EDTA)(H2O)]2– (H4EDTA = ethylenediaminetetraacetic acid) and [Mn(PhDTA)(H2O)]2– (H4PhDTA = phenylenediamine-N,N,N′,N′-tetraacetic acid), indicating that the PC2A complexes reported here have a lower tendency to stabilize Mn(III). The superoxide dismutase activity of the Mn(II) complexes was tested using the xanthine/xanthine oxidase/p-nitro blue tetrazolium chloride assay at pH = 7.8. The Mn(II) complexes of 3,6-PC2A and 3,9-PC2A are capable of assisting decomposition of the superoxide anion radical. The kinetic rate constant of the complex of 3,9-PC2A is smaller by 1 order of magnitude than that of 3,6-PC2A.

Published
2021

33. Development of pyrene-based fluorescent ether lipid as inhibitor of SK3 ion channels

Author

Aurélie Chantôme, Marion Papin, Hélène Couthon, Alicia Bauduin, Paul-Alain Jaffrès, Jose Requejo-Isidro, Christophe Vandier, Laure Deschamps, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Nutrition, croissance et cancer (U 1069) (N2C), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Tours, Centro Nacional de Biotecnología [Madrid] (CNB-CSIC), Biocomputing Unit [Madrid], We are grateful to Ana M. Bouchet for constructive scientific discussions and critical assistance for OP2 cellular internalization experiments and Isabelle Domingo for technical assistance. This study was funded by Institut National du Cancer (INCA N°2018-151), the University of Brest, the University of Tours, the Région Bretagne and Région Centre-Val de Loire, INSERM, CNRS, Canceropôle Grand Ouest, La Ligue Nationale Contre le Cancer and the CANCEN Association. AB is grateful for a PhD fellowship from 'La Ligue contre le Cancer' and 'région Bretagne' and for a mobility grant from the university of Brest. We thank the platforms (NMR and mass spectrometry) from the University of Brest., Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), and CCSD, Accord Elsevier

Subjects
Small-Conductance Calcium-Activated Potassium Channels, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 01 natural sciences, 03 medical and health sciences, chemistry.chemical_compound, Cell Movement, Cell Line, Tumor, Drug Discovery, [CHIM] Chemical Sciences, SK3, Potassium Channel Blockers, Humans, [CHIM]Chemical Sciences, Patch clamp, membrane, Ion channel, Fluorescent Dyes, 030304 developmental biology, Pharmacology, amphiphiles, 0303 health sciences, Liposome, Pyrenes, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Bilayer, Organic Chemistry, canaux ioniques, General Medicine, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Fluorescence, 0104 chemical sciences, HEK293 Cells, Ether lipid, Monomer, chemistry, Biophysics, Pyrene, fluorescence, Glycolipids
Abstract

We report the synthesis of three bioactive pyrene-based fluorescent analogues of Ohmline which is the most efficient and selective inhibitor of SK3 ion channel. The interaction of these Ohmline-pyrene (OP1-3) with liposomes of different composition reveals that only OP2 and OP3 are readily integrated into liposomes. Fluorescence measurements indicate that, depending on their concentration, OP2 and OP3 exist either as monomer or as a mixture of monomer and excimers within the liposome bilayer. Among the three Ohmline Pyrene compounds (OP1-3) only OP2 is able to reduce SK3 currents and is the first efficient fluorescent modulator of SK3 channel as revealed by patch clamp measurements (- 71.3 ± 13.3% at 10 mM) and by its inhibition of SK3-dependent cancer cell migration at (32.5% ± 4.8% at 1 mM). We also report the first fluorescence study on living breast cancer cells (MDA-MB-231) showing that OP2 is rapidly integrated in bio-membranes followed by cell internalization., Nous décrivons la synthèse d’analogues de l’Ohmline comportant au niveau de la partie lipidique une sonde fluorescente de type pyrène. Nous montrons que l’un d’entre eux (le composé OP2) est capable de réduire les courants potassiques SK3 de 71% et de réduire la migration cellulaire SK3-dépendante de 32%. Il s’agit, à notre connaissance, du premier inhibiteur des canaux ioniques SK3 de nature amphiphile et fluorescent.

Published
2021

34. Pyclen-Based Ligands Bearing Pendant Picolinate Arms for Gadolinium Complexation

Author

Olivier Rousseaux, Gyula Tircsó, Gwladys Nizou, David Esteban-Gómez, Maryline Beyler, Nadège Hamon, Ferenc K. Kálmán, Olivier Fougère, Carlos Platas-Iglesias, Raphaël Tripier, Enikő Molnár, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), University of Debrecen Egyetem [Debrecen], Laboratoire Guerbet, Centro de Investigaciones Científicas Avanzadas (CICA), Facultade de Ciencias, and Centro de Investigacións Científicas Avanzadas (CICA)

Subjects
Steric effects, Ions, 010405 organic chemistry, Ligand, Picolinic acid, Molecules, 010402 general chemistry, Ligands, 01 natural sciences, Medicinal chemistry, Dissociation (chemistry), 0104 chemical sciences, Inorganic Chemistry, NMR spectra database, chemistry.chemical_compound, Monomer, chemistry, Molecule, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Water binding, Solution chemistry, Macrocycles
Abstract

International audience; We report the synthesis of two pyclen-based regioisomer ligands (pyclen = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene) functionalized with picolinic acid pendant arms either at positions 3,9-pc2pa (L5) or 3,6-pc2pa (L6) of the macrocyclic fragment. The ligands were prepared by the regiospecific protection of one of the amine nitrogen atoms of the macrocycle using Boc and Alloc protecting groups, respectively. The X-ray structure of the Gd(III) complex of L5 contains trinuclear [(GdL5)3(H2O)3]3+ entities in which the monomeric units are joined by μ2-η1:η1-carboxylate groups. However, the 1H and 89Y NMR spectra of its Y(III) analogue support the formation of monomeric complexes in solution. The Tb(III) complexes are highly luminescent, with emission quantum yields of up to 28% for [TbL5]+. The luminescence lifetimes recorded in H2O and D2O solutions indicate the presence of a water molecule coordinated to the metal ion, as also evidenced by the 1H relaxivities measured for the Gd(III) analogues. The Gd(III) complexes present very different exchange rates of the coordinated water molecule (kex298 = 87.1 × 106 and 1.06 × 106 s–1 for [GdL5]+ and [GdL6]+, respectively). The very high water exchange rate of [GdL5]+ is associated with the steric hindrance originating from the coordination of the ligand around the water binding site, which favors a dissociatively activated water exchange process. The Gd(III) complexes present rather high thermodynamic stabilities (log KGdL = 20.47 and 19.77 for [GdL5]+ and [GdL6]+, respectively). Furthermore, these complexes are remarkably inert with respect to their acid-assisted dissociation, in particular the complex of L5.

Published
2020

35. Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

Author

Héloïse Dossmann, David Gatineau, Antony Memboeuf, Hervé Clavier, Denis Lesage, Yves Gimbert, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Valence (chemistry), Ligand, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Interaction energy, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, chemistry.chemical_compound, Electronic effect, Physical chemistry, Molecular orbital, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron configuration, Physical and Theoretical Chemistry, Ionization energy, Organometallic chemistry
Abstract

International audience; In organometallic chemistry, and especially in the catalysis area, accessing the finest tuning of a catalytic reaction pathway requires a detailed knowledge of the steric and electronic influence of the ligands bound to the metal center. Usually, the M-L bond between a ligand and a metal is depicted by the Dewar-Chatt-Duncanson model involving two opposite interactions, a σ-donor and a π-acceptor effect of the ligand. The experimental evaluation of these effects is essential and complementary to in-depth theoretical approaches that are able to provide a detailed description of the M-L bond. In this work, we present a study of LMo(CO)5 complexes with L being various tertiary phosphines ligands by means of mass-selected high-resolution photoelectron spectroscopy (PES) performed with synchrotron radiation, DFT and energy decomposition analyses (EDA) combined with the natural orbitals for chemical valence (NOCV) analysis. These methods enable a separated access of the σ-donor and π-acceptor effects of ligands by probing either the electronic configuration of the complex (PES) or the interaction of the ligand with the metal (EDA). Three series of PX3 ligands with various electronic influence are investigated: the strong donating alkyl substituents (PMe3, PEt3 and PiPr3), the intermediate PPhxMe(3-x) (x = 0-3) set and the PPhxPyrl(3-x) set (x = 0-3 with Pyrl being the strong electron withdrawing pyrrolyl group C4H4N). For each complex, their adiabatic and vertical ionization energies (IEs) could be determined with a 0.03 eV precision. Experiment and theory show an excellent agreement, either for the IEs determination or for the electronic effect analysis. The ability to interpret the spectra is shown to depend on the character of the ligand. “Innocent” ligands provide the spectra the most straightforward to analyze whereas the “non-innocent” ligands (which are ionized prior to the metal center) render the analysis more difficult due to an increased number of molecular orbitals in the energy range considered. A very good linear correlation is finally found between the measured adiabatic ionization energies and the interaction energy term obtained by EDA for each of these two types of ligands which opens interesting perspective for the prediction of ligand characters.

Published
2020

36. Why Cobalt macrocyclic complexes are not efficient catalysts for the oxygen reduction reaction, under acidic conditions

Author

Claudie Miry, Maurice L'Her, Frédéric Gloaguen, Emmanuel Ngameni, Laboratoire d'Analyses de Surveillance et d'Expertise de la Marine (LASEM), Service de Santé des Armées, Laboratoire de Chimie analytique, Université de Yaoundé I, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
inorganic chemicals, General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Oxygen reduction reaction, Metal, chemistry.chemical_compound, Aqueous acidic solution, Oxidation state, Cyclam, Electrochemistry, [CHIM]Chemical Sciences, Lewis acids and bases, Hydrogen peroxide, Cobalt macrocyclic complexes, 021001 nanoscience & nanotechnology, Demetallation, 0104 chemical sciences, 3. Good health, chemistry, visual_art, visual_art.visual_art_medium, 0210 nano-technology, Platinum, Cobalt, (ORR)
Abstract

International audience; The activation of the oxygen reduction reaction (ORR) is of a primary importance for the development of fuel cells. Cobalt macrocyclic complexes, e.g. those of porphyrins, phthalocyanines, tetraazaannulenes (TAA), cyclam, have been tested in order to replace platinum, the best catalyst but a rare and expensive metal. However it has been noted in some studies that these complexes suffer from degradation in an acidic environment. Suspicions have already been expressed that such degradation are caused by hydrogen peroxide or demetallation, but the reason for the loss of activity of these catalysts has never been experimentally established. In the present work, it has been clearly demonstrated that cobalt complexes are stable in the presence of acids when the metal centre is at the Co(III) oxidation state but are demetallated when it is reduced to the Co(II) oxidation state, which occurs during the oxygen reduction reaction. Co2+ is a borderline Lewis acid in Pearson's classification and thus can be substituted by H+ in an acidic environment.

Published
2020

37. Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Author

Ghosh, Pradip, Vos, Sander, Lutz, Martin, Gloaguen, Frederic, Schollhammer, Philippe, Moret, Marc‐etienne, Klein Gebbink, Robertus J. M., Sub Organic Chemistry and Catalysis, Sub Crystal and Structural Chemistry, Organic Chemistry and Catalysis, Crystal and Structural Chemistry, Universiteit Utrecht, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Protonation, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Heterolysis, Medicinal chemistry, DFT, proton reduction, Catalysis, chemistry.chemical_compound, Deprotonation, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, cobalt complex, [CHIM]Chemical Sciences, electrocatalysis, Methylene, Acetonitrile, 010405 organic chemistry, Chemistry, Hydrogen bond, Ligand, Organic Chemistry, diimine ligand, General Chemistry, 3. Good health, 0104 chemical sciences, Intramolecular force
Abstract

International audience; Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF 4 ) 2 . This complex comprises two bis(1‐methyl‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)methane (HBMIM Ph2 ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF 4 ) 2 by either electrochemical or chemical means, one of its HBMIM Ph2 ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF 4 ) regenerates protonated complex [ 1 ](BF 4 ) 2 . In presence of acetic acid in acetonitrile solvent [ 1 ](BF 4 ) 2 shows electrocatalytic proton reduction with a k obs of ~200 s ‐1 at an overpotential of 590 mV. Mechanistic investigations supported by Density Functional Theory (BP86) reveal that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C–H bond of the HBMIM Ph2 ligand and a Co II –H bond through formal heterolytic splitting of the latter. These results represent the joint involvement of a base metal‐hydride and a C–H bond in electrocatalytic proton reduction and are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.

Published
2020

38. Expanding the Scope of Pyclen-Picolinate Lanthanide Chelates to Po-Tential Theranostic Applications

Author

Olivier Rousseaux, Pascal V. Grundler, Raphaël Tripier, Maryline Beyler, Chiara Favaretto, Gwladys Nizou, Olivier Fougère, Nicholas P. van der Meulen, Carlos Platas-Iglesias, Nathalie Saffon-Merceron, Cristina Müller, Francesca Borgna, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Paul Scherrer Institute (PSI), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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), Departamento de Química Fundamental, Universidade da Coruña, Guerbet Group, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
Lanthanide, Ligand, Potentiometric titration, Solid-state, chemistry.chemical_element, Terbium, chemistry.chemical_compound, Optical imaging, chemistry, Computational chemistry, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, DOTA, [CHIM]Chemical Sciences, Chelation
Abstract

A family of three picolinate pyclen based ligands, previously investigated for the complexation of Y3+ and some lanthanide ions (Gd3+, Eu3+), was studied with 161Tb and 177Lu in view of potential radiotherapeutic applications. The set of six Tb3+ and Lu3+ complexes was synthesized and fully characterized. The coordination properties in the solid state and in solution were thoroughly studied. Potentiometric titrations, corroborated by DFT calculations, showed the very high stability constants of the Tb3+ and Lu3+ complexes, which are associated to remarkable kinetic inertness. A complete radiolabeling study performed with both 161Tb and 177Lu radionuclides, including experiments with regard to the stability with and without scavengers and kinetic inertness using challenging agents, proved that the ligands could reasonably compete with the DOTA analogue. To conclude, the potential of using the same ligand for both radiotherapy and optical imaging was highlighted for the first time.

Published
2020

39. A Diiron Hydrogenase Mimic Featuring a 1,2,3-Triazolylidene

Author

Martin Albrecht, Philippe Schollhammer, Catherine Elleouet, Simone Bertini, François Y. Pétillon, Andrea Mele, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Universität Bern [Bern], CNRS (Centre National de la Recherche Scientifique), the Université de Bretagne Occidentale, are also acknowl-edged for financial support., European Project: 675020,H2020,H2020-MSCA-ITN-2015,NoNoMeCat(2016), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), and Universität Bern [Bern] (UNIBE)

Subjects
Proton, 010405 organic chemistry, Mesoionic carbene, Mesoionic, proton reductions, General Medicine, General Chemistry, Hydrogenase mimic, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Bioinspired model, 3. Good health, 0104 chemical sciences, lcsh:Chemistry, chemistry.chemical_compound, Proton reduction, chemistry, lcsh:QD1-999, Hydrogenase, [CHIM]Chemical Sciences, Cyclic voltammetry, Diiron complex, Carbene
Abstract

A novel complex featuring a mesoionic carbene [Fe2(CO)5(trz)(?-pdt)] (1) (trz = 1-phenyl-l,3-methyl,4-butyl-1,2,3-triazol-5-ylidene), was synthesized and spectroscopically and structurally characterized. The reductive behaviour of this compound in the presence and in the absence of acid (CH3CO2H) was examined by cyclic voltammetry (CV) that revealed the lack of efficient activity towards proton reduction.

Published
2020

40. Synthesis, Conformational Analysis, and Complexation Study of an Iminosugar-Aza-Crown, a Sweet Chiral Cyclam Analog

Author

Ana Ardá, Jesús Jiménez-Barbero, Yves Blériot, Alexandra Bordes, Thibault Troadec, Matthieu Sollogoub, Antonio Franconetti, Mickaël Ménand, Flavie Perrin, Ana Poveda, Raphaël Tripier, Jérôme Désiré, Jérôme Guillard, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Cell Biology and Stem Cells Unit (CICbioGUNE), Technologic Park of Bizkaia, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Basque Foundation for Science (Ikerbasque), and University of the Basque Country [Bizkaia] (UPV/EHU)

Subjects
Letter, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Carbohydrates, Iminosugar, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Redox, 0104 chemical sciences, Glycan, Molecular Recognition, NMR , interactions, chemistry.chemical_compound, chemistry, Cations, Cyclam, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation, Conformation, Redox reactions, Physical and Theoretical Chemistry, Macrocycles
Abstract

A new family of chiral C2 symmetric tetraazamacrocycles, coined ISAC for IminoSugar Aza-Crown, incorporating two iminosugars adopting a 4C1 conformation is disclosed. Multinuclear NMR experiments on the corresponding Cd2+ complex show that the ISAC is a strong chelator in water and its tetramine cavity adopts a conformation similar to that of the parent Cd−cyclam complex. Similar behavior is observed with Cu2+ in solution, with enhanced stability compared to the Cu−cyclam complex.

Published
2020

41. Cationic Biphotonic Lanthanide Luminescent Bioprobes Based on Functionalized Cross-Bridged Cyclam Macrocycles

Author

Amandine Roux, Damien Curton, Maryline Beyler, Raphaël Tripier, Véronique Patinec, Anh Thy Bui, Sophie Brasselet, Olivier Maury, Jean-Christophe Mulatier, Alexei Grichine, Jonathan Mendy, Chantal Andraud, François Riobé, Alain Duperray, Boris Le Guennic, Yannick Guyot, RENARD, NICOLAS, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Luminescence (LUMINESCENCE), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), MOSAIC (MOSAIC), Institut FRESNEL (FRESNEL), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors are grateful to the referees for careful reading of the paper and valuable suggestions and comments. The authors also acknowledge support of the Ministère de l'Enseignement Supérieur et de la Recherche, the Centre National de la Recherche Scientifique, the Institut National de la Santé et de la Recherche Médicale and the Agence Nationale de la Recherche (SADAM ANR‐16‐CE07‐0015‐02). M.B. and R.T. thanks the ‘‘Service Commun de RMN’’ of the University of Brest. Confocal and 2P facility of the IAB platform was co‐funded thanks to grants of 'Association pour la Recherche sur le Cancer' (ARC, Villejuif, France), 'Ligue vs Cancer' (LCC Isère/Ardèche) and the CPER program. B.L.G. thanks the French GENCI‐CINES center for high‐performance computing resources., 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), Université de Lyon-Université de Lyon, Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
Lanthanide, Ytterbium, Macrocyclic Compounds, Luminescence, chemistry.chemical_element, 02 engineering and technology, Europium(III), 010402 general chemistry, Photochemistry, 01 natural sciences, Lanthanoid Series Elements, chemistry.chemical_compound, Coordination Complexes, Cations, Cell Line, Tumor, Cyclam, [CHIM] Chemical Sciences, Humans, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Ytterbium(III), Two-photon microscopy, Density Functional Theory, Photons, Aqueous solution, Luminescent Agents, Spectroscopy, Near-Infrared, Molecular Structure, Chemistry, Optical Imaging, Cationic polymerization, Bioprobe, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 021001 nanoscience & nanotechnology, Bioimaging, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Solvent, 0210 nano-technology, Europium
Abstract

Cationic lanthanide complexes are generally able to spontaneously internalize into living cells. Following our previous works based on diMe-cyclen framework, a second generation of cationic water-soluble lanthanide complexes based on a constrained cross-bridged cyclam macrocycle functionalized with donor-p-conjugated picolinate antennas has been prepared with europium(III) and ytterbium(III). Their spectroscopic properties were thoroughly investigated in various solvents and rationalized with the help of DFT calculations. A significant improvement is observed in the case of the Eu3+ complex, while the Yb3+ analogous conserve an excellent brightness in aqueous solvent. Two-photon (2P) microscopy imaging experiments on living T24 human cancer cells confirmed the spontaneous internalization of the probes and images with good signal-to-noise have been obtained in the classical NIR-to-visible configuration with Eu3+ luminescent bioprobe and in the NIR-to-NIR with the Yb3+ one.

Published
2020

42. Unexpected Trends in the Stability and Dissociation Kinetics of Lanthanide(III) Complexes with Cyclen-Based Ligands across the Lanthanide Series

Author

Éva Tóth, Goran Angelovski, Aurora Rodríguez-Rodríguez, Viktória Nagy, Véronique Patinec, Ferenc K. Kálmán, Gyula Tircsó, Zoltán Garda, David Esteban-Gómez, Rosa Pujales-Paradela, Raphaël Tripier, Carlos Platas-Iglesias, University of Debrecen Egyetem [Debrecen], Departamento de Química Fundamental, Universidade da Coruña, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), MR Neuroimaging Agents Group, Max Planck Institute for Biological Cybernetics, Max-Planck-Gesellschaft-Max-Planck-Gesellschaft, Centre de biophysique moléculaire (CBM), 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
Lanthanide, 010405 organic chemistry, Protonation, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, inertie, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Cyclen, picolinate, chemistry, Stability constants of complexes, Molecule, Chemical stability, lanthanides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate, Physical and Theoretical Chemistry, acetate, thermodynamique
Abstract

International audience; We report a detailed study of the thermodynamic stability and dissociation kinetics of lanthanide complexes with two ligands containing a cyclen unit, a methyl group, a picolinate arm, and two acetate pendant arms linked to two nitrogen atoms of the macrocycle in either cis (1,4-H3DO2APA) or trans (1,7-H3DO2APA) positions. The stability constants of the Gd3+ complexes with these two ligands are very similar, with log KGdL values of 16.98 and 16.33 for the complexes of 1,4-H3DO2APA and 1,7-H3DO2APA, respectively. The stability constants of complexes with 1,4-H3DO2APA follow the usual trend, increasing from log KLaL = 15.96 to log KLuL = 19.21. However, the stability of [Ln(1,7-DO2APA)] complexes decreases from log K = 16.33 for Gd3+ to 14.24 for Lu3+. The acid-catalyzed dissociation rates of the Gd3+ complexes differ by a factor of ∼15, with rate constants (k1) of 1.42 and 23.5 M–1 s–1 for [Gd(1,4-DO2APA)] and [Gd(1,7-DO2APA)], respectively. This difference is magnified across the lanthanide series to reach a 5 orders of magnitude higher k1 for [Yb(1,7-DO2APA)] (1475 M–1 s–1) than for [Yb(1,4-DO2APA)] (5.79 × 10–3 M–1 s–1). The acid-catalyzed mechanism involves the protonation of a carboxylate group, followed by a cascade of proton-transfer events that result in the protonation of a nitrogen atom of the cyclen unit. Density functional theory calculations suggest a correlation between the strength of the Ln–Ocarboxylate bonds and the kinetic inertness of the complex, with stronger bonds providing more inert complexes. The 1H NMR resonance of the coordinated water molecule in the [Yb(1,7-DO2APA)] complex at 176 ppm provides a sizable chemical exchange saturation transfer effect thanks to a slow water exchange rate of (15.9 ± 1.6) × 103 s–1.; L'arrangement des atomes donneurs de ligand autour de l'ion lanthanide provoque des différences dramatiques dans les stabilités thermodynamiques et la cinétique de dissociation des complexes de lanthanides, comme le démontre l'étude des complexes avec deux ligands à base de régioisomères du cyclen, contenant un bras picolinate et deux bras acétate soit en position 1,7 ou 1,4 de la structure macrocyclique.

Published
2020

43. Enabling Indium Channels for Mass Cytometry by Using Reinforced Cyclam-Based Chelating Polylysine

Author

Raphaël Tripier, Maryline Beyler, Alexandre Bouzekri, Vladimir Baranov, Yefeng Zhang, Laura Grenier, Nick Zabinyakov, Taunia Closson, Peng Liu, Olga Ornatsky, Jothir Mayanantham Pichaandi, Mitchell A. Winnik, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Fluidigm Canada Inc. (Fluidigm), Department of Chemistry [University of Toronto], University of Toronto, and R.T. and M.B. acknowledge the Ministère de l’Enseignement Supérieur et de la Recherche, the Centre National de la Recherche Scientifique and they thank the 'Région Bretagne' and Fluidigm for the ARED and industrial fellowships respectively for L.G. thesis.

Subjects
Models, Molecular, Immunoconjugates, Polymers, Biomedical Engineering, Pharmaceutical Science, Bioengineering, HL-60 Cells, Indium, Cell Line, chemistry.chemical_compound, Jurkat Cells, picolinate, Biotin, Heterocyclic Compounds, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Cyclam, Humans, [CHIM]Chemical Sciences, Mass cytometry, Biotinylation, Polylysine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Fluorescein isothiocyanate, Indium(III), Chelating Agents, Fluorescent Dyes, Pharmacology, Bioconjugation, biology, Cyclam cross-bridged, Conjugate acid-base pairs, Organic Chemistry, Antibodies, Monoclonal, NeutrAvidin, Antigens, CD20, Flow Cytometry, Combinatorial chemistry, chemistry, Polymer solutions, Metals, biology.protein, CyTOF, Fluorescein-5-isothiocyanate, Biotechnology
Abstract

The synthesis of a polylysine polymer functionalized with the previously reported astonishingly inert [In(cb-te2pa)]+ chelate was performed. A biotin end group allowed the conjugation to biotinylated beads by the intermediary of a fluorescein isothiocyanate/neutravidin receptor. High quality imaging mass cytometry trials, based on 115In detection were performed to highlight the behavior of the material. Anti-CD20 antibody was labeled by the so-obtained In(III)-modified polylysine using the biotin/neutravidin interaction. Ramos (CD20[+]) and HL-60 (CD20[-]) cell lines were costained with the In(III)-modified bioconjugate by finding the best staining conditions. Both immunofluorescence microscopy (IF-M) and mass cytometry analyses confirmed the specific binding of anti-CD20 onto Ramos cells. CyTOF histograms constructed on the 115In detection allowed us to define and to separate, with a good signal-to-noise ratio, two populations (Ramos and HL-60). The inertness of In(III)-MCP-NAv over a three-month storage period was proved by performing new functionality tests involving Jurkat cells (CD20[-]) and multiparametric trials involving the 115In channel. The results ensure a promising future use of the previously announced [In(cb-te2pa)]+ complex-based polymers for mass cytometry.

Published
2020

44. Reactivities of cyclam derivatives with metal–amyloid-β

Author

Evan Lelong, Hélène Bernard, Mi Hee Lim, Nathalie Le Bris, Raphaël Tripier, Dong-Wook Kim, Gunhee Kim, Juhye Kang, Jong-Min Suh, Korea Advanced Institute of Science and Technology (KAIST), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Pohang University of Science and Technology (POSTECH), and Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS)

Subjects
Metal ions in aqueous solution, 010402 general chemistry, medicine.disease_cause, amyloïde-β, Cu(II), 01 natural sciences, Inorganic Chemistry, Metal, chemistry.chemical_compound, Cyclam, medicine, [CHIM]Chemical Sciences, Chelation, MESH: amyloïde-β, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Ternary complex, chemistry.chemical_classification, Reactive oxygen species, 010405 organic chemistry, Chemistry, Small molecule, Combinatorial chemistry, 0104 chemical sciences, MESH: maladie d’Alzheimer, Zn(II), visual_art, visual_art.visual_art_medium, maladie d’Alzheimer, Oxidative stress
Abstract

Amyloid-β (Aβ) aggregation and metal ion dyshomeostasis are found to be pathological features upon the progress of Alzheimer's disease (AD). In addition, Aβ and metal ions are reported to interact with each other forming metal–Aβ complexes, which can affect the aggregation of Aβ and cause oxidative stress via the production of reactive oxygen species (ROS). To disrupt metal coordination to Aβ and control the reactivities of metal–Aβ, metal chelating agents have been tested. Herein, a series of azamacrocyclic compounds with different properties of Cu(II) and Zn(II) binding and Aβ interaction were rationally selected under criteria based on structural and functional variations on the backbone of Cyclam. The series contains Cyclam, its N-methylated and cross-bridged (N-methylated or not) analogs, as well as their C-appended hydroxyethyl derivatives, and some of them have been newly synthesized. The reactivities of the cyclam derivatives towards the aggregation of metal–Aβ and the generation of ROS mediated by metal–Aβ were evaluated. Their modulative reactivities towards metal–Aβ could be achieved by generating a ternary complex with metal–Aβ and chelating the metal ion from metal–Aβ. Moreover, the toxicity induced by metal–Aβ in living cells was alleviated by the cyclam derivatives capable of regulating metal–Aβ aggregation and metal–Aβ-triggered ROS formation. Overall, our studies illustrate new examples of azamacrocyclic metal chelators that alter the interactions between metal ions and Aβ and subsequently modify the reactivities of metal–Aβ, with an indication of how the slight structure–property difference can influence such effects of small molecules.

Published
2020

45. In Vivo Albumin‐Binding of a C ‐Functionalized Cyclam Platform for 64 Cu‐PET/CT Imaging in Breast Cancer Model

Author

Thomas Le Bihan, Cathryn H.S. Driver, Raphaël Tripier, Thomas Ebenhan, Nathalie Le Bris, Jan Rijn Zeevaart, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and South African Nuclear Energy Corporation Radiochemistry and NuMeRI PreClinical Imaging Facility (SANECR-NuMeRi_PCIF)

Subjects
Biodistribution, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, TE3A, Breast cancer, In vivo, Drug Discovery, Cyclam, Radioligand, medicine, [CHIM]Chemical Sciences, 64-Cu PET, General Pharmacology, Toxicology and Pharmaceutics, Pharmacology, Bioconjugation, 010405 organic chemistry, tumor targeting, Organic Chemistry, Albumin, EPR effect, medicine.disease, Blood proteins, 0104 chemical sciences, 3. Good health, 010404 medicinal & biomolecular chemistry, chemistry, Cancer research, Molecular Medicine
Abstract

International audience; An improved glucose‐chelator‐albumin bioconjugate (GluCAB) derivative, GluCAB‐2Mal, has been synthesized and studied for in vivo 64Cu‐PET/CT imaging in breast cancer mice models together with its first‐generation analogue GluCAB‐1Mal. The radioligand works on the principle of tumor targeting through the enhanced permeability and retention (EPR) effect with a supportive role played by glucose metabolism. [64Cu]Cu‐GluCAB‐2Mal (99 % RCP) exhibited high serum stability with immediate binding to serum proteins. In vivo experiments for comparison between tumor targeting of [64Cu]Cu‐GluCAB‐2Mal and previous‐generation [64Cu]Cu‐GluCAB‐1Mal encompassed microPET/CT imaging and biodistribution analysis in an allograft E0771 breast cancer mouse model. Tumor uptake of [64Cu]Cu‐GluCAB‐2Mal was clearly evident with twice as much accumulation as compared to its predecessor and a tumor/muscle ratio of up to 5 after 24 h. Further comparison indicated a decrease in liver accumulation for [64Cu]Cu‐Glu‐CAB‐2Mal.

Published
2020

46. Efficient luminescence control in dithienylethene functionalized cyclen macrocyclic lanthanide complexes

Author

Olivier Galangau, Raphaël Tripier, Nadège Hamon, Lucie Norel, Hassan Al Sabea, Stéphane Rigaut, François Riobé, Olivier Maury, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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), Université de Rennes 1, Centre National de la Recherche Scientifique, Ministère de l'Education Nationale, de l'Enseignement Superieur et de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Ytterbium, Photoluminescence, Materials science, chemistry.chemical_element, europium(III), 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Photochromism, chemistry.chemical_compound, Cyclen, Polymer chemistry, luminescence, lanthanides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Dithienylethylene, 010405 organic chemistry, Yttrium, photochromism, 0104 chemical sciences, molecular switch, azamacrocycles, chemistry, Europium, Luminescence, ytterbium(III)
Abstract

International audience; We report the synthesis of an original ligand scaffold and the corresponding yttrium(III), europium(III) and ytterbium(III) complexes. All three compounds show reversible photochromism with high photo-conversions. Photoluminescence experiments demonstrate that this design is adapted for both europium and ytterbium emission switching. The OFF/ON luminescence ratio are excellent in the case of europium (4 to 8 %) and still quite good in the case of ytterbium (around 13 %); Nous présentons la synthèse d'un ligand original et ses complexes d'yttrium (III), d'europium (III) et d'ytterbium (III). Les trois composés présentent un photochromisme réversible avec des photo-conversions élevées. Les expériences de photoluminescence démontrent que le conception est adapté tant pour la commutation de l’émission de l'europium et de l'ytterbium. Le rapport de luminescence OFF/ON est excellent dans le cas de l'europium (4 à 8%) et encore assez bon dans le cas de l'ytterbium (environ 13%)

Published
2020

47. A different approach: highly encapsulating macrocycles being used as organic tectons in the building of CPs

Author

Carlos J. Laglera-Gándara, Andrés de Blas, Raphaël Tripier, Agustín Esteban-Muriel, Teresa Rodríguez-Blas, Marta Mato-Iglesias, Maryline Beyler, Centro de Investigaciones Científicas Avanzadas (CICA), Facultade de Ciencias, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Coordination polymer, General Chemistry, Polymer, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Pb(II), X-ray diffraction, Crystallography, Perchlorate, chemistry.chemical_compound, coordination polymer, chemistry, Atomic orbital, Cyclam, [CHIM]Chemical Sciences, General Materials Science, cross-bridged cyclam, Single crystal, Lone pair, Linker
Abstract

International audience; For the first time, an azamacrocycle has been used to build Pb(II) 1D coordination polymers. Cross-bridged cyclam H2cb-teapa, that has a strong proton sponge behaviour, adopts a zwitterionic form and therefore acts as the external bridge rather than coordinating Pb(II) in an endocyclic way. The resulting 1D coordination polymer of formula {[Pb(Cl)(H2cb-teapa)]ClO4}n has been analysed by single crystal X-ray diffraction. Interestingly, the polymer adopts a singular tube-like structure, which results from the alternation of the  and  enantiomers generated by the layout of the arms of the organic linker.; Pour la première fois, un azamacrocycle a été utilisé pour construire des polymères de coordination 1D du Pb(II). Le cyclam renforcé H2cb-teapa, qui a fort caractère d’éponge à protons, adopte une forme zwitterionique qui lui permet de jouer le rôle de pont externe plutôt que de complexer le Pb(II) de manière endocyclique. Le polymère de coordination 1D de formule {[Pb(Cl)(H2cb-teapa)]ClO4}n a été analysé par diffraction des rayons X. Le polymère adopte une structure tubulaire qui résulte de l’alternance des énantiomères  et  générés par la disposition des bras de l’espaceur organique H2cb-teapa.

Published
2020

48. A Squaraine-based Dipicolylamine Derivative Acting as a Turn-on Mercury(II) Fluorescent Probe in Water

Author

Judite Costa, Hélène Bernard, Rita Delgado, Catarina V. Esteves, Raphaël Tripier, Instituto de Tecnologia Química e Biológica António Xavier (ITQB), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), CBT-iMed.UL, and Faculdade de Farmácia da Universidade de Lisboa

Subjects
inorganic chemicals, Coordination sphere, Potentiometric titration, 010402 general chemistry, 01 natural sciences, Catalysis, Photoinduced electron transfer, Metal, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Aqueous solution, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 0104 chemical sciences, cation, mercury complex, Dipicolylamine, Fluorescent Probe, visual_art, visual_art.visual_art_medium, Titration, Chemical stability
Abstract

International audience; A symmetrical squaraine-based ligand, sbdpa, bearing two dipicolylamine (dpa) units, was synthesized for the first time, using an environment friendly procedure, such as one-pot and solvent-free reaction. The sbdpa ligand was found to have a small blue-green emission, in aqueous solution, due to a photoinduced electron transfer (PET) mechanism. Metal complexes of sbdpa with a large panel of cations, Na+, K+, Ag+, Mg2+, Ca2+, Ba2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, and Pb2+, were prepared in aqueous buffered solution and screened, in search of a selective response for one of them. A turn-on fluorescence response was then found only for Hg2+, as a consequence of a chelation-enhanced fluorescence (CHEF) effect that disrupts the PET mechanism in sbdpa. Subsequently, the complexation behaviour of Hg2+ with sbdpa was investigated in aqueous solution by potentiometric titrations and other spectroscopic techniques. The acid-base reactions of the ligand were also studied by potentiometry, as well as by 1H-NMR and UV-vis titrations. For comparison purposes, the complexation of two other divalent cations, Cu2+ and Zn2+, was also assessed by potentiometry. Additionally, results are compared with dpa all along the study. Both mono- and dinuclear complexes of sbdpa were found for the three metal cations studied having the mercury(II) complex the largest thermodynamic stability. These findings support a stronger uptake of Hg2+ cation by sbdpa, possibly involving at least one oxygen atom from the squaraine moiety on its coordination sphere.

Published
2020

49. Ruthenium(II) Polypyridyl Complexes as Photosensitizers for Antibacterial Photodynamic Therapy: A Structure-Activity Study on Clinical Bacterial Strains

Author

Ulrich Jonas, Gilles Lemercier, Katrin-Stephanie Tücking, Julian Ravel, Holger Schönherr, Sylviane Chevreux, Tristan Montier, Tony Le Gall, Franck Thétiot, Génétique, génomique fonctionnelle et biotechnologies (UMR 1078) (GGB), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-EFS-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Siegen, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
Methicillin-Resistant Staphylococcus aureus, Luminescence, Light, medicine.medical_treatment, Substituent, activity relationships, chemistry.chemical_element, antibacterial agents, Photodynamic therapy, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, Ruthenium, Structure-Activity Relationship, chemistry.chemical_compound, Antibiotic resistance, Coordination Complexes, Antibiotic therapy, Drug Discovery, Escherichia coli, medicine, [CHIM]Chemical Sciences, General Pharmacology, Toxicology and Pharmaceutics, Pharmacology, chemistry.chemical_classification, Reactive oxygen species, Photosensitizing Agents, Molecular Structure, Singlet Oxygen, biology, 010405 organic chemistry, Organic Chemistry, ruthenium(II) polypyridyl complexes structure, photosensitizers, biology.organism_classification, Combinatorial chemistry, Anti-Bacterial Agents, 3. Good health, 0104 chemical sciences, photodynamic therapy, chemistry, Luminescent Measurements, Pseudomonas aeruginosa, Molecular Medicine, Antibacterial activity, Bacteria, Phenanthrolines
Abstract

International audience; As a growing public health concern, the worldwide spread of antimicrobial resistance urges the development of new therapies. Antibacterial photodynamic therapy (a‐PDT) may be an alternative to conventional antibiotic therapy. Herein we report the synthesis and characterization of seven original reactive oxygen species (ROS)‐producing ruthenium(II) polypyridyl complexes. These are part of a collection of 17 derivatives varying in terms of the nature of the substituent(s), molecular symmetry, electrical charge, and counterions. They were characterized by considering 1) their physical properties (absorption coefficient at irradiation wavelength, 1O2 generation quantum yield, luminescence) and 2) their antibacterial activity in a series of photodynamic assays using Gram‐positive and Gram‐negative bacteria of clinical relevance. The results unveiled some structure–activity relationships: one derivative that combines multiple beneficial features for a‐PDT was effective against all the bacteria considered, regardless of their Gram status, species, or antibiotic resistance profile. This systematic study could guide the design of next‐generation ruthenium‐based complexes for enhanced antibacterial photodynamic strategies.

Published
2018

50. Electrochemical and Theoretical Investigations of the Oxidatively Induced Reactivity of the Complex [Fe2 (CO)4 (κ2 -dmpe)(μ-adtBn )] Related to the Active Site of [FeFe] Hydrogenases

Author

François Y. Pétillon, Salma Mohamed Bouh, Federica Arrigoni, Philippe Schollhammer, Luca De Gioia, Catherine Elleouet, Giuseppe Zampella, Dipartimento di Biotecnologie e Bioscienze, Università degli Studi di Milano-Bicocca [Milano] (UNIMIB), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Department of Biotechnologies and Biosciences, Arrigoni, F, Mohamed Bouh, S, Elleouet, C, Pétillon, F, Schollhammer, P, De Gioia, L, and Zampella, G

Subjects
Isocyanide, azadithiolate bridge, 010402 general chemistry, 01 natural sciences, Catalysis, Catalysi, hydrogenase models, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reactivity (chemistry), hydrogenase model, Acetonitrile, Dichloromethane, biology, 010405 organic chemistry, Ligand, oxidative processes, Organic Chemistry, Active site, General Chemistry, density functional calculation, oxidative processe, 3. Good health, 0104 chemical sciences, Crystallography, electrochemistry, chemistry, density functional calculations, biology.protein, Density functional theory, Cyclic voltammetry
Abstract

International audience; Electrochemical oxidation of the complex [Fe2(CO)4(κ2‐dmpe)(µ‐adtBn)] (adtBn = (SCH2)2NCH2C6H5, dmpe = Me2PCH2CH2PMe2) (1) has been studied by cyclic voltammetry (CV) in acetonitrile and in dichloromethane in presence of various substrates L (L =MeCN, trimethylphosphite, isocyanide). The oxidized species, [1‐MeCN](PF6)2, [1‐(P(OMe)3)2](PF6)2 and [1‐(RNC)4](PF6)2 (R = tButyl, Xylyl), have been prepared and characterized by IR, NMR spectroscopies and, excepted [1‐MeCN](PF6)2, by X‐ray diffraction analysis. The crystallographic structures of the new FeIIFeII complexes reveal in any case that the association of one additional ligand (P(OMe)3 or RNC) occurs and, according to the nature of the substrates, further substitutions of one or three carbonyl groups, by P(OMe)3 or RNC, respectively, arise. Density functional theory (DFT) calculations have been performed for elucidating and discriminating, in each case, the mechanisms leading to the corresponding oxidized species. Moreover, the different degree of ligand substitution in the diiron core has been theoretically rationalized.

Published
2018

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