Author: "Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA )" - Searchworks@Jio Institute Digital Library Search Results

Your search keyword '"Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA )"' showing total 808 results

Start Over Author "Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA )"

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

1. Immobilization of Monolayers Incorporating Cu Funnel Complexes onto Gold Electrodes. Application to the Selective Electrochemical Recognition of Primary Alkylamines in Water

Author: Ivan Jabin, Gaël De Leener, Yann R. Leroux, Ana Gabriela Porras-Gutierrez, Corinne Lagrost, Diana Over, Philippe Hapiot, Nicolas Le Poul, Olivia Reinaud, Jeremy Mertens, François Reniers, Ferdinand Evoung-Evoung, Yves Le Mest, Angélique Lascaux, Laboratoire de Chimie Organique, Université Libre de Bruxelles [Bruxelles] ( ULB ), 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 ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Université libre de bruxelles, Service de chimie analytique et chimie des interfaces (CHANI), 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 ), Fonds de la Recherche Scientifique-FNRS [FRFC 2.4.617.10.F], Agence Nationale de la Recherche [ANR10-BLAN-714], De Brouckere-Solvay fund, Michel Kaisin fund, Université libre de Bruxelles (ULB), 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), Service de chimie analytique et chimie des interfaces (CHANI), 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), Université Libre de Bruxelles [Bruxelles] (ULB), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université Paris Diderot - Paris 7 (UPD7), 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), 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 (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: aqueous-solution, Inorganic chemistry, Alkyne, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Redox, Catalysis, beta-cyclodextrin, active-sites, Colloid and Surface Chemistry, aliphatic-amines, Monolayer, neutral molecules, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, copper complex, chemistry.chemical_classification, Aqueous solution, Chemistry, metal-surfaces, self-assembled monolayers, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Copper, 0104 chemical sciences, alkyl amines, induced electroclick, Electrode, Cyclic voltammetry, 0210 nano-technology
Abstract: International audience; The immobilization of a copper calix[6]azacryptand funnel complex on gold-modified electrodes is reported. Two different methodologies are described. One is based on alkyne-terminated thiol self assembled monolayers. The other relies on the electrografting of a calix[4]arene platform bearing diazonium functionalities at its large rim and carboxylic functions at its small rim, which is post-functionalized with alkyne moieties. In both cases, the CuAAC electroclick methodology proved to be the method of choice for grafting the calix[6]azacryptand onto the monolayers. The surface-immobilized complex was fully characterized by surface spectroscopies and electrochemistry in organic and aqueous solvents. The Cu complex display a well-defined quasi-reversible system in cyclic voltammetry associated with the Cu(II)/Cu(I) redox process. Remarkably, this-redox process triggers a powerful selective detection of primary alkylamines in water at a micromolar level, based on a cavitary recognition process.
Published: 2016

2. Cellular responses of Pacific oyster ( Crassostrea gigas ) gametes exposed in vitro to polystyrene nanoparticles

Author: Mathieu Berchel, Ika Paul-Pont, Philippe Soudant, Kevin Tallec, Arnaud Huvet, Nelly Le Goïc, Christophe Lambert, Carmen González-Fernández, Marc Suquet, Laboratoire des Sciences de l'Environnement Marin (LEMAR) ( LEMAR ), Institut de Recherche pour le Développement ( IRD ) -Institut Français de Recherche pour l'Exploitation de la Mer ( IFREMER ) -Université de Brest ( UBO ) -Institut Universitaire Européen de la Mer ( IUEM ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Français de Recherche pour l'Exploitation de la Mer - Brest ( IFREMER ), Institut Français de Recherche pour l'Exploitation de la Mer ( IFREMER ), 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, French doctoral research grant from Ifremer (50%), Region Bretagne (50%), ANR-15-CE34-0006-02,NANO,ANR-15-CE34-0006-02, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Français de Recherche pour l'Exploitation de la Mer - Brest (IFREMER Centre de Bretagne), Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), 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), ANR-15-CE34-0006,Nanoplastics,Microplastiques, nanoplastiques dans l'environnement marin: caractérisation, impacts et évaluation des risques sanitaires.(2015), and Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, Oyster, Environmental Engineering, [SDV]Life Sciences [q-bio], Health, Toxicology and Mutagenesis, Gametes, 010501 environmental sciences, 01 natural sciences, [ CHIM ] Chemical Sciences, [ SDE ] Environmental Sciences, 03 medical and health sciences, Oysters, biology.animal, [CHIM]Chemical Sciences, Environmental Chemistry, Animals, 14. Life underwater, Crassostrea, 0105 earth and related environmental sciences, biology, [ SDV ] Life Sciences [q-bio], Chemistry, ACL, Public Health, Environmental and Occupational Health, technology, industry, and agriculture, Cellular responses, General Medicine, General Chemistry, Adhesion, Pacific oyster, biology.organism_classification, Pollution, Sperm, In vitro, Polystyrene nanoparticles, 030104 developmental biology, Germ Cells, [SDE]Environmental Sciences, Toxicity, Biophysics, Nanoparticles, Polystyrenes, Nanoplastics, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Plastics, Water Pollutants, Chemical
Abstract: International audience; While the detection and quantification of nano-sized plastic in the environment remains a challenge, the growing number of polymer applications mean that we can expect an increase in the release of nanoplastics into the environment by indirect outputs. Today, very little is known about the impact of nano-sized plastics on marine organisms. Thus, the objective of this study was to investigate the toxicity of polystyrene nanoplastics (NPs) on oyster (Crassostrea gigas) gametes. Spermatozoa and oocytes were exposed to four NPs concentrations ranging from 0.1 to 100 mg L−1 for 1, 3 and 5 h. NPs coated with carboxylic (PS-COOH) and amine groups (PS-NH2) were used to determine how surface properties influence the effects of nanoplastics. Results demonstrated the adhesion of NPs to oyster spermatozoa and oocytes as suggested by the increase of relative cell size and complexity measured by flow-cytometry and confirmed by microscopy observations. A significant increase of ROS production was observed in sperm cells upon exposure to 100 mg L−1 PS-COOH, but was not observed with PS-NH2, suggesting a differential effect according to the NP-associated functional group. Altogether, these results demonstrate that the effects of NPs occur rapidly, are complex and are possibly associated with the cellular eco-corona, which could modify NPs behaviour and toxicity.
Published: 2018

3. Selection of Collision Energies in Proteomics Mass Spectrometry Experiments for Best Peptide Identification: Study of Mascot Score Energy Dependence Reveals Double Optimum

Author: Károly Vékey, Antony Memboeuf, Lilla Turiák, Tibor András Rokob, Dany Jeanne Dit Fouque, Ágnes Révész, László Drahos, MS Proteomics Research Group, Hungarian Academy of Sciences (MTA), Hungarian Academy of Sciences, Chemical Research Center (HAS CRC), Mass Spectrometry Department, Theoretical Chemistry Research Group, 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), Hungarian Academy of Sciences [Budapest], Hungarian Academy of Sciences, Chemical Research Center ( HAS CRC ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), and Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: Proteomics, 0301 basic medicine, Spectrometry, Mass, Electrospray Ionization, Electrospray, collision energy, peptide fragmentation, Collision-induced dissociation, Normal Distribution, Analytical chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Mass spectrometry, Tandem mass spectrometry, 01 natural sciences, Biochemistry, Spectral line, 03 medical and health sciences, Tandem Mass Spectrometry, Mascot score, curve fitting, Humans, Trypsin, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Amino Acid Sequence, mass spectrometry, Physics, Escherichia coli Proteins, 010401 analytical chemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, [ CHIM.INOR ] Chemical Sciences/Inorganic chemistry, General Chemistry, Collision, Peptide Fragments, 0104 chemical sciences, 030104 developmental biology, Curve fitting, optimization, HeLa Cells
Abstract: International audience; Collision energy is a key parameter determining the information content of beam-type collision induced dissociation tandem mass spectrometry (MS/MS) spectra, and its optimal choice largely affects successful peptide and protein identification in MS-based proteomics. For an MS/MS spectrum, quality of peptide match based on sequence database search, often characterized in terms of a single score, is a complex function of spectrum characteristics, and its collision energy dependence has remained largely unexplored. We carried out electrospray ionization-quadrupole-time of flight (ESI-Q-TOF)-MS/MS measurements on 2807 peptides from tryptic digests of HeLa and E. coli at 21 different collision energies. Agglomerative clustering of the resulting Mascot score versus energy curves revealed that only few of them display a single, well-defined maximum; rather, they feature either a broad plateau or two clear peaks. Nonlinear least-squares fitting of one or two Gaussian functions allowed the characteristic energies to be determined. We found that the double peaks and the plateaus in Mascot score can be associated with the different energy dependence of b- and y-type fragment ion intensities. We determined that the energies for optimum Mascot scores follow separate linear trends for the unimodal and bimodal cases with rather large residual variance even after differences in proton mobility are taken into account. This leaves room for experiment optimization and points to the possible influence of further factors beyond m/z.
Published: 2018

4. Synthesis and Biological Evaluation of Bolaamphiphilic Sophorolipids

Author: Inge N. A. Van Bogaert, Tom Coenye, Olivier Lozach, Tristan Montier, Wim Soetaert, Petra Rigole, Elisabeth Delbeke, Mathieu Berchel, Sophie Roelants, Jonas Everaert, Kevin Van Geem, Martha Brennich, Paul-Alain Jaffrès, Christian V. Stevens, Niki Baccile, Tony Le Gall, SynBioC Research Group [Ghent], Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering [Gent], Universiteit Gent = Ghent University [Belgium] (UGENT)-Universiteit Gent = Ghent University [Belgium] (UGENT), Department of Materials, Textiles and Chemical Engineering (LCT), Universiteit Gent = Ghent University [Belgium] (UGENT), Department of Biotechnology (InBio), 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), 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), IBISA ' SynNanoVect ' platform, Université de Brest (UBO)-IFR148 ScInBioS, Service de génétique moléculaire et d'histocompatibilité, Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), Département Universitaire de Médecine Générale (DUMG), Laboratory of Pharmaceutical Microbiology, Institut Laue-Langevin (ILL), ILL, Synchrotron Crystallography Group, European Molecular Biology Laboratory [Grenoble] (EMBL), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Bio Base Europe Pilot Plant, Centre for Synthetic Biology, EFS-Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Brestois Santé Agro Matière (IBSAM), Ghent University [Belgium] ( UGENT ) -Ghent University [Belgium] ( UGENT ), Department of Materials, Textiles and Chemical Engineering ( LCT ), Ghent University [Belgium] ( UGENT ), Department of Biotechnology ( InBio ), 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, Génétique, génomique fonctionnelle et biotechnologies (UMR 1078), EFS-Université de Brest ( UBO ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ), Université de Brest ( UBO ) -IFR148 ScInBioS, Centre Hospitalier Régional Universitaire de Brest ( CHRU Brest ), Département Universitaire de Médecine Générale ( DUMG ), Université de Brest ( UBO ), Institut Laue-Langevin ( ILL ), European Molecular Biology Laboratory [Grenoble] ( EMBL ), Laboratoire de Chimie de la Matière Condensée de Paris ( LCMCP ), Centre National de la Recherche Scientifique ( CNRS ) -Collège de France ( CdF ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ), RENARD, NICOLAS, Universiteit Gent = Ghent University (UGENT)-Universiteit Gent = Ghent University (UGENT), and Universiteit Gent = Ghent University (UGENT)
Subjects: General Chemical Engineering, Bolaamphiphile, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Aldehyde, Reductive amination, [ CHIM ] Chemical Sciences, Minimum inhibitory concentration, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Amphiphile, [CHIM] Chemical Sciences, Environmental Chemistry, [CHIM]Chemical Sciences, bolaamphiphiles, transfection efficiency, chemistry.chemical_classification, Minimum bactericidal concentration, antimicrobial activity, Renewable Energy, Sustainability and the Environment, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Sophorolipid, quaternary ammonium salt, Sophorolipids, General Chemistry, self-assembly, 021001 nanoscience & nanotechnology, Antimicrobial, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Combinatorial chemistry, 0104 chemical sciences, chemistry, 0210 nano-technology, chemical modification
Abstract: New synthetic pathways are proposed for the synthesis of a new set of bolaamphiphilic derivatives starting from microbiologically produced sophorolipids. A total set of 43 new derivatives was synthesized Via reductive amination of a previously synthesized sophorolipid aldehyde with diamines and primary amines. The new derivatives were evaluated for their antimicrobial activity against Gram-negative and Gram-positive bacteria. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) values were determined for the active compounds. Transfection efficiencies were also evaluated for some of the deprotected derivatives via the assessment of their capacity to transfect three different eukaryotic cell lines in vitro. Finally, the self-assembly properties were evaluated for the deprotected derivatives. Antimicrobial activities were mostly observed for the peracetylated mono- or dicationic bolaamphiphiles and only the deprotected monocationic bolaamphiphile with an octadecyl chain on the nitrogen atom was eligible for the evaluation of its transfection properties. Evaluation of the self-assembly properties indicated that the presence of an octadecyl chain was necessary for micelle formation. Both micelle formation and the net charge of the compounds seem to have an influence on the antimicrobial activity and transfection efficiency. These results are promising for use of bolaamphiphilic sophorolipids in medical and self-assembly applications., Dans ce travail de nouveaux composés amphiphiles cationiques sont préparés à partir de sophoro lipides. Ces composés sont formulés en solution liposomales et évaluées pour leurs propriétés bactéricides et pour la transfection. Des analyses physico-chimiques montrent des assemblages sous forme de micelles
Published: 2018
Full Text: View/download PDF

5. Chemoselective guest-triggered shaping of a polynuclear Cu II calix[6]complex into a molecular host

Author: Olivia Reinaud, Yves Le Mest, Nicolas Le Poul, Sarah Richard, Gaëtan Le Duc, Jean-Noël Rebilly, 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), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-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 Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-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 ), 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 et des Matériaux d'Orsay ( ICMMO ), and Université Paris-Sud - Paris 11 ( UP11 ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: 010405 organic chemistry, Ligand, Chemistry, Stereochemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, macromolecular substances, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Binding site
Abstract: International audience; A new calix[6]arene scaffold bearing a tris-imidazole binding site at the small rim and three tetradentate aza ligands at the large rim was synthesized. The system binds three CuII ions at the large rim sites and is unable to bind a fourth one, which remains in solution. The charge repulsion between the complexes, together with the flexibility of the scaffold, disorganizes the small rim site for binding and prevents its use for host–guest studies. Although the presence of MeCN or DMF guests does not alter this state, the addition of a heptylamine guest, which further displays Brønsted basicity, restores its receptor ability by stabilizing the extra CuII ion at the tris-imidazole site with concomitant guest encapsulation and binding of an exo hydroxo ligand. This chemoselective nuclearity switch yields a tetranuclear complex in which the guest backbone is preorganized in front of three potentially reactive Cu(II) complexes, reminiscent of polynuclear CuII enzyme active sites.
Published: 2017

6. Phosphorescent cyclometalated platinum( ii ) complexes with phenyldiazine N^C ligands

Author: Mariia Hruzd, Samia Kahlal, Nicolas le Poul, Laurianne Wojcik, Marie Cordier, Jean-Yves Saillard, Julián Rodríguez-López, Françoise Robin-le Guen, Sébastien Gauthier, Sylvain Achelle, 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), Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), and M. H. acknowledges the Région Bretagne, France and Conseil Départemental des Côtes d'Armor, France for her PhD funding (MMLum project).
Subjects: Inorganic Chemistry, expert elicitation, Chemical risk assessment chemical risk matrix expert elicitation real work situation, real work situation, Chemical risk assessment, chemical risk matrix, [CHIM]Chemical Sciences
Abstract: International audience; A series of phosphorescent platinum(II) complexes containing various phenyldiazine-type bidentate N^C ligands have been successfully synthesized and characterized. Structural modifications have been made to bidentate cyclometalating ligands regarding the nature of the diazine ring (pyrimidine, pyrazine and quinazoline), the substituent groups at the C4 position of the pyrimidine ring (OCH3, CF3) and the EDGs at the para position of the Pt atom (OCH3, Ph, NPh2, carbazol). In addition, the electronic properties of the azaheterocyclic ancillary ligand have been modulated in this series of complexes (pyridine, 4-methoxy-pyridine or pyrimidine). X-ray diffraction studies have been performed on three complexes, revealing Pt(II) ions in a distorted square-planar geometrical environment with no Pt(II)⋯Pt(II) interactions but with moderate π–π interactions in the solid-state structure. Electrochemical and computational studies suggest a ligand-centered reduction on the diazine ligands with, in some cases, additional contribution from the azaheterocyclic ancillary ligand, whereas oxidation occurs on the Pt-phenyl ring substituent moieties. All complexes exhibit phosphorescence emission ranging from green to red/near-infrared, both in solution and in the solid state. Complexes bearing a 2-(3-methoxyphenyl)pyrimidine ligand show the best PLQY of the series, up to 52% in a CH2Cl2 solution and 20% in the solid state. Furthermore, the solid state PLQY of one of the near-infrared emitting phenylquinazoline complex has been found to be 6%.
Published: 2023

7. Iodine footprint: Moving towards environmental responsibility

Author: Raphel Jomaah, Jean-Alix Barrat, Raphaël Tripier, Julien Ognard, Samy Ammari, Douraied Ben Salem, School of Medicine [University of Wollongong], Faculty of Science, Medicine and Health [Wollongong], University of Wollongong [Australia]-University of Wollongong [Australia], Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), 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), Laboratoire de Traitement de l'Information Medicale (LaTIM), Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre Hospitalier Régional Universitaire de Brest (CHRU Brest)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Institut Brestois Santé Agro Matière (IBSAM), Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), LaBoratoire d'Imagerie biOmédicale MultimodAle Paris-Saclay (BIOMAPS), Service Hospitalier Frédéric Joliot (SHFJ), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut Gustave Roussy (IGR), Zambonino-Infante, José-Luis, and Département d'imagerie médicale [Gustave Roussy]
Subjects: Radiological and Ultrasound Technology, Radiology, Nuclear Medicine and imaging, Neurology (clinical), [SDV.IB.MN]Life Sciences [q-bio]/Bioengineering/Nuclear medicine, [SDV.IB.MN] Life Sciences [q-bio]/Bioengineering/Nuclear medicine
Abstract: International audience; No abstract available
Published: 2023

8. Copper(<scp>ii</scp>) and zinc(<scp>ii</scp>) complexation with N-ethylene hydroxycyclams and consequences on the macrocyclic backbone configuration

Author: Nancy AlHaddad, Evan Lelong, Jong-Min Suh, Marie Cordier, Mi Hee Lim, Guy Royal, Carlos Platas-Iglesias, Hélène Bernard, Raphaël Tripier, 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), 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), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Universidade da Coruña, Ministere de l'Enseignement Superieur et de la Recherche, Centre National de la Recherche Scientifique, and Brest Metropole
Subjects: Inorganic Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry
Abstract: International audience; We report a series of four cyclams and cross-bridged cyclams, N-functionalized by one hydroxyethyl arm, which may incorporate additional methyl(s) group(s). The Cu(II) and Zn(II) complexes of these ligands were synthesized and fully characterized. The investigation of the metal complexes in solid-state and in solution was carried via X-ray diffraction, NMR, EPR, absorption spectroscopy and DFT calculations. The influence of N-functionalization on their structural/stereochemical properties, electrochemical behavior and kinetic inertness was carefully studied and identified. N-Functionalization by a hydroxyethyl group did not influence importantly the stereochemical properties of the complexes. However, it stabilized the complexes kinetically and electrochemically. As for N-methylation, it induces significant distortion of the coordination geometry, decreasing the kinetic inertness of the complexes and stabilizing Cu+. Overall, this work expanded the family of cyclam and cross-bridged cyclam metal complexes and provides a detailed analysis of their structural features. The rather large body of data accumulated for this family of complexes provides opportunities to design systems with pre-determined properties for specific applications.
Published: 2022

9. Production d'hydrogène solaire par photosynthèse artificielle

Author: Cornet, Jean-François, Dauchet, Jérémi, Gros, Fabrice, Vourc’h, Thomas, Gloaguen, Frédéric, Institut Pascal (IP), Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA)-Institut national polytechnique Clermont Auvergne (INP Clermont Auvergne), Université Clermont Auvergne (UCA)-Université Clermont Auvergne (UCA), 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: [SPI]Engineering Sciences [physics], hydrogène renouvelable, carburants solaires, photoréacteurs, cellules photoélectrochimiques, [CHIM]Chemical Sciences
Abstract: International audience; Cet article traite de la production photoréactive d’hydrogène à partir d’eau etd’énergie solaire, connue également sous le nom de photosynthèse artificielle. Sontabordés les recherches sur de nouveaux photocatalyseurs pour photolyser efficacementla molécule d’eau et les recherches en sciences de l’ingénieur pour développer les deuxtechnologies envisageables pour la production d’hydrogène solaire, à savoir lesphotoréacteurs et les cellules photo-électrochimiques. Les paramètres clé pour laconception et l’optimisation de ces technologies, ainsi que les performances maximalesaccessibles, sont présentés et discutés sur la base de l’analyse de modèles deconnaissances unifiés.
Published: 2023

10. Highly inert Cu(ii) complexes of C-aryl bifunctional cyclam-picolinates with remarkable Cu-64-labelling and biodistribution

Author: Julie Pineau, Luís M. P. Lima, Marie M. Le Roy, Séverine Marionneau-Lambot, Marie Cordier, Patricia Le Saëc, Jan Rijn Zeevaart, Cathryn H. S. Driver, Alain Faivre-Chauvet, Nathalie Le Bris, Raphaël Tripier, 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), Instituto de Tecnologia Química e Biológica António Xavier (ITQB), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Centre de Recherche en Cancérologie et Immunologie Intégrée Nantes-Angers (CRCI2NA ), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Institut 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), and South African Nuclear Energy Corporation [Pretoria] (NECSA)
Subjects: Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; Cyclam-picolinate chelators were functionalized via click chemistry with an additional carboxyl group for subsequent bioconjugation to antibodies or for the modification of the overall charge of the corresponding Cu-64-radiocomplexes. The C-aryl functionalization strategy developed here preserves the chemical properties of the radiocomplexes whilst deeply enhancing their applications within nuclear medicine.
Published: 2023

11. 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

12. 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

13. Locally Induced and Self-Induced 'Electroclick' onto a Self-Assembled Monolayer: Writing and Reading with SECM under Unbiased Conditions

Author: Christophe Orain, Philippe Hapiot, Yann R. Leroux, Yves Le Mest, Sebastien Lhenry, Nicolas Le Poul, Nathalie Cosquer, Françoise Conan, Olivia Reinaud, 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), 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 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 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 ) -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 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), Université Paris Descartes - Paris 5 (UPD5)-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), 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: chemistry.chemical_classification, Microscopy, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Analytical chemistry, Substrate (chemistry), Alkyne, Self-assembled monolayer, Surfaces and Interfaces, Condensed Matter Physics, Photochemistry, Coupling reaction, Catalysis, Scanning electrochemical microscopy, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Monolayer, Electrochemistry, Molecule, General Materials Science, Spectroscopy
Abstract: International audience; Localized “electroclick” was achieved on azido-terminated self-assembled monolayers using Scanning Electrochemical Microscopy (SECM) in feedback mode, in which the substrate is not electrically connected (unbiased conditions). The method allows both the local immobilization of diverse functional moieties and the monitoring of each modification step at a micrometer scale. Conditions of the “click” coupling reaction were optimized especially to avoid the deposit of metallic copper by the choice of a specific ligand to stabilize the Cu(I) species. The catalytic efficiency in localized “electroclick” reaction of Cu(II)TMPA (TMPA: tris(2-pyridylmethyl)amine) as the “click” catalyst was compared with a derivative containing an alkyne group Cu(II)6eTMPA, the same molecule playing the role of the catalyst and the substrate. Evidences for surface self-catalysis propagation are demonstrated through SECM imaging showing a random 2D progression of the catalytic modification.
Published: 2014

14. Reactions of the μ-alkyne-dicobalt complexes [Co2(CO)6(μ-CF3–CC–R)] (R=CF3, H) with [Co2Cp2(μ-SMe)2]: substitution and insertion leading to novel thiolato-alkyne tetra- and tricobalt clusters

Author: François Y. Pétillon, René Rumin, Kenneth W. Muir, 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), 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: Alkyne, chemistry.chemical_element, 010402 general chemistry, 010403 inorganic & nuclear chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Inorganic Chemistry, Metal, Materials Chemistry, Cluster (physics), [CHIM]Chemical Sciences, Molecule, Physical and Theoretical Chemistry, chemistry.chemical_classification, biology, Chemistry, Ligand, Organic Chemistry, biology.organism_classification, 0104 chemical sciences, Crystallography, visual_art, Yield (chemistry), visual_art.visual_art_medium, Tetra, Cobalt
Abstract: cited By 9; International audience; The bis(μ-thiolato)dicobalt complex [Co2Cp2(μ-SMe)2] (1) reacts with alkyne-cobalt complexes [Co2(CO)6(μ-F3CCCR)] (2) to give tri- and tetranuclear cobalt cluster compounds. When R=CF3 the main product is [Co2(CO)4(μ-CF3C2CF 3)μ-Co2Cp2(μ-SMe)2] (3) but the trinuclear cluster [Co3Cp(CO)4(μ-SMe)2(μ-CF 3C2CF3)] (4) is also obtained in low yield. When R=H the products are the isomeric clusters [Co3Cp(CO)4(μ-SMe)2(μ-CF 3C2H)] (5 and 6), [Co3Cp2(CO)3(μ-SMe)(μ-CF 3C2CH)] (7) and [CpCo(CO)2]. The solid state structures of 3, 4, 5 and 7 have been established by X-ray analysis. The 50 electron triangular cluster 4 has weak Co-Co bonds [2.573(1), 2.800(1), 2.838(1) Å]. The alkyne ligand bridges the shortest of these bonds in perpendicular fashion. 5 and 7 contain open chain tricobalt units [Co-Co 2.39-2.57 Å] more typical of 50 electron M3 species. In these complexes the alkyne is π-bonded to the central metal atom and σ-bonded to both terminal cobalt atoms. Variable temperature NMR indicates that 5, 6 and 7 each exist in solution as interconverting isomers which differ in the configuration at one sulphur atom. For 5 the activation parameters [ΔH‡=64 kJ mol-1 and ΔS‡=-85 J K-1 mol-1] were obtained spectroscopically. In the solid, molecules of 7 contain an asymmetrically bridging carbonyl [Co-C 1.833(4) and 2.050(3) Å] which is not detectable in the solution spectra. © 2001 Elsevier Science B.V.
Published: 2001

15. Application of 3-Quinolinoyl Picket Porphyrins to the Electroreduction of Dioxygen to Water: Mimicking the Active Site of Cytochromec Oxidase

Author: Maurice L’Her, Amandine Didier, Bernard Boitrel, David Ricard, 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), 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 ), and Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS
Subjects: Porphyrins, Hemeprotein, Reducing agent, Iron, chemistry.chemical_element, Photochemistry, Electrochemistry, [ CHIM ] Chemical Sciences, Biochemistry, Oxygen, Electron Transport Complex IV, O-O activation, cytochrome c oxidase, [CHIM]Chemical Sciences, Cytochrome c oxidase, Binding site, Molecular Biology, ComputingMilieux_MISCELLANEOUS, Binding Sites, biology, Chemistry, Molecular Mimicry, Organic Chemistry, Active site, heme proteins, oxidoreductases, electrochemistry, Reducing Agents, biology.protein, Molecular Medicine, Indicators and Reagents, Spectrophotometry, Ultraviolet, Oxidation-Reduction, Copper
Abstract: International audience
Published: 2001

16. Evolution of rafts (morphotypes ratio, size structure, biomass), phenolic content and polysaccharide quality of holopelagic Sargassum species during their drift until their stranding

Author: Dromard, Charlotte R., Stiger-Pouvreau, Valerie, Charles, P., Kergosien, Nolwenn, Cerantola, Stephane, Cosquer, Nathalie, Berline, Leo, Changeux, Thomas, Thibaut, Thierry, Deslandes, Eric, Connan, Solene, Biologie des Organismes et Ecosystèmes Aquatiques (BOREA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université des Antilles (UA), Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 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 méditerranéen d'océanologie (MIO), and Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDV.EE]Life Sciences [q-bio]/Ecology, environment
Abstract: International audience
Published: 2022

17. Annual cycle of humic substances in a temperate estuarine system affected by agricultural practices

Author: Ricardo Riso, Benoît Pernet-Coudrier, François Quentel, Gaël Durrieu, Matthieu Waeles, Cyril Tissot, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 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), Littoral, Environnement, Télédétection, Géomatique (LETG - Brest), Littoral, Environnement, Télédétection, Géomatique UMR 6554 (LETG), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Université d'Angers (UA)-École Pratique des Hautes Études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Brest (UBO)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-Institut de Géographie et d'Aménagement Régional de l'Université de Nantes (IGARUN), Université de Nantes (UN)-Université de Nantes (UN)-Université de Caen Normandie (UNICAEN), Université de Nantes (UN)-Université de Nantes (UN), Laboratoire des Sciences de l'Environnement Marin (LEMAR) ( LEMAR ), Centre National de la Recherche Scientifique ( CNRS ) -Université de Brest ( UBO ) -Institut Français de Recherche pour l'Exploitation de la Mer ( IFREMER ) -Institut Universitaire Européen de la Mer ( IUEM ), Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Université de Brest ( UBO ) -Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ), 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 ), PROcessus de Transfert et d'Echanges dans l'Environnement - EA 3819 ( PROTEE ), Université de Toulon ( UTLN ), Littoral, Environnement, Télédétection, Géomatique ( LETG - Brest ), Littoral, Environnement, Télédétection, Géomatique ( LETG ), Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Normandie Université ( NU ) -Université d'Angers ( UA ) -Université de Nantes ( UN ) -École pratique des hautes études ( EPHE ) -Université de Brest ( UBO ) -Université de Rennes 2 ( UR2 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Caen Normandie ( UNICAEN ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Normandie Université (NU)-Université d'Angers (UA)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Brest (UBO)-Université de Rennes 2 (UR2), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Géographie et d'Aménagement Régional de l'Université de Nantes (IGARUN)
Subjects: 0106 biological sciences, 010504 meteorology & atmospheric sciences, [SDE.MCG]Environmental Sciences/Global Changes, Fluvial, 01 natural sciences, [ SHS.ENVIR ] Humanities and Social Sciences/Environmental studies, [ SHS.GEO ] Humanities and Social Sciences/Geography, [ SDE ] Environmental Sciences, Geochemistry and Petrology, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Dissolved organic carbon, Temperate climate, Organic matter, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, chemistry.chemical_classification, Hydrology, geography, geography.geographical_feature_category, 010604 marine biology & hydrobiology, Estuary, 15. Life on land, Plankton, Annual cycle, [ SDU.STU.GC ] Sciences of the Universe [physics]/Earth Sciences/Geochemistry, 6. Clean water, [ SDE.MCG ] Environmental Sciences/Global Changes, chemistry, 13. Climate action, Environmental chemistry, [SHS.ENVIR]Humanities and Social Sciences/Environmental studies, Soil water, [SDE]Environmental Sciences, Environmental science, [ CHIM.ANAL ] Chemical Sciences/Analytical chemistry
Abstract: International audience; Although widely studied for their chemical structures and properties (e.g., metal complexation, growth stimulation of planktonic species), humic substances (HS) have been very poorly quantified in fluvial and estuarine waters. In this monthly basis study, we determined HS concentrations (by Adsorptive Square Wave Cathodic Stripping Voltammetry) along the entire river-seawater gradient of the Penzé estuary (NW France), with the aim to characterize the export of these compounds. In this watershed where agricultural activities are predominant, manuring activities were identified as being the main source of dissolved organic carbon (DOC) and HS. HS concentrations varied usually within a narrow range in fluvial waters, i.e., 1.8 ± 0.4 mgC L−1 (150 ± 40 μM), but increased significantly as the first flood of autumn occurred (>4 mgC L−1 in river and upper estuary). At this time, HS accounted for a very high proportion of DOC (>80%). As evidenced by the increasing contribution of HS to DOC, and by the increasing contribution of small colloidal HS species; this autumnal flood increase should be attributed to a greater retention and transformation of organic matter on soils over the hotter, drier, and lighter period preceding the first autumnal flood. In the mixing zone, HS displayed mostly conservative behaviour, although some removals were occasionally observed. Overall, our study suggests that preservation of HS could be relatively important during their transfer across macrotidal temperate estuaries, at least in systems affected by agricultural practices.
Published: 2013

18. 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

19. 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

20. 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

21. Rhodium-based cathodes with ultra-low metal loading to increase the sustainability in the hydrogen evolution reaction

Author: Gema Pérez, Guillermo Díaz-Sainz, Lucía Gómez-Coma, Lucía Álvarez-Miguel, Aymeric Garnier, Nolwenn Cabon, Alfredo Ortiz, Frederic Gloaguen, Inmaculada Ortiz, Universidad de Cantabria [Santander], 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), 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 of this work would like to show their gratitude to the financial support from the European Regional Development Fund in the framework of the Interreg Atlantic program through the project 'HYLANTIC'-EAPA_204/2016'. The Spanish Ministry of Science and Innovation has also supported this work through the project PLEC2021-007718. Besides, we thank M.-L. Rouget (Pôle Spectrométrie Ocean, IUEM Brest) and Dr. M. Waeles (LEMAR, UBO Brest) for their help in elemental ICP-MS analysis, Dr. S. Rioual (Lab-STICC, UBO Brest) for his help in XPS analysis, and P. Elies (SC PIMM, UBO Brest) for his help in SEM-EDX analysis. The authors thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF)., and Universidad de Cantabria
Subjects: Low-metal loading, Process Chemistry and Technology, Chemical Engineering (miscellaneous), HER, PEM Electrolyzer, Organometallic catalysis, Rh-based electrocatalysts, [CHIM.CATA]Chemical Sciences/Catalysis, Pollution, Waste Management and Disposal, Hydrogen evolution reaction
Abstract: Climate change mitigation is one of the main global challenges in the 21st century. In this context, the recent 26th United Nations Climate Change Conference of the Parties (COP26-Glasgow) claimed for searching urgent and efficient measures to reduce and ultimately avoid CO2 emissions. Thus, many efforts from the scientific community focus on the research of new and renewable energy sources (RES). Among other approaches, green hydrogen, which comes from water electrolysis, is a promising candidate to be considered in the energy panorama. However, commercial electrolyzers are provided with Pt/C and Ir-based electrocatalytic materials, which are expensive and not abundant, to catalyze the Hydrogen Evolution Reaction (HER) in safe, stable, inexpensive, and environmentaly friendly conditions. Thus, this work aims to synthesize high-performance and very low metal loading catalysts by immobilizing a Rh-based organometallic complex (RhCp*Cl(phendiamine)]Cl) on a carbon black support following a robust synthesis procedure. Advanced characterization of the synthesized materials confirmed that ultra-low metal loadings in the range of 3.2-4.7 mg·g-1 were successfully reached. Subsequently, Rh-based catalysts were tested in a PEM electrolyzer. For metal loadings as low as 0.0066 mg·cm-2 competitive cell potentials of 1.9V were achieved working with 0.5A·cm-2 geometric current density at 70°C. These results are comparable to those obtained with Pt-based commercial cathodes working under similar operation conditions. Thus, the results of this research make a step forward in the substitution of conventional cathodes for the electrolytic HER by new materials with very low metal loadings. The authors of this work would like to show their gratitude to the financial support from the European Regional Development Fund in the framework of the Interreg Atlantic program through the project “HYLANTIC”-EAPA_204/2016”. The Spanish Ministry of Science and Innovation has also supported this work through the project PLEC2021-007718.
Published: 2022

22. Spectroscopic studies of new series of alkaline earth elements (Mg, Ca, Sr, Ba) correlated metallophosphonates

Author: Ganesan, Parameshwari, Letheux, Geoffrey, Labbé, Christophe, Perez, Olivier, Rueff, Jean-Michel, Jaffrès, Paul-Alain, Cardin, Julien, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), 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), Nanomatériaux, Ions et Métamatériaux pour la Photonique (NIMPH), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN)
Subjects: [PHYS]Physics [physics], [CHIM.MATE]Chemical Sciences/Material chemistry, [SPI.MAT]Engineering Sciences [physics]/Materials
Published: 2022

23. Aerosol-mediated non-viral lung gene therapy: The potential of aminoglycoside-based cationic liposomes

Author: Le Gall, T, Berchel, M, Davies, L, Mottais, A, Ghanem, R, Fautrel, A, Gill, D, Hyde, S, Lehn, P, Lehn, J-M, Lemiègre, L, Benvegnu, T, Jaffrès, P-A, Pitard, B, Montier, T, 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), 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), John Radcliffe Hospital [Oxford University Hospital], University of Oxford, Biosit : biologie, santé, innovation technologique (SFR UMS CNRS 3480 - INSERM 018), 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 ), H2P2 - Histo Pathologie Hight Precision (H2P2), Université de Rennes (UR)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Collège de France (CdF (institution)), 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), Centre de Recherche en Cancérologie et Immunologie Intégrée Nantes-Angers (CRCI2NA ), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Santé, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Immunology and New Concepts in ImmunoTherapy (INCIT), Université d'Angers (UA)-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)-Nantes Université - UFR de Médecine et des Techniques Médicales (Nantes Univ - UFR MEDECINE), Agence Nationale de la Recherche, ANR: ANR-17-CE18-0015-03, Bundesministerium für Bildung und Forschung, BMBF: 16GW0342, ANR-20-AMRB-0009, ANR-17-CE18-0015,VINP,monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes.(2017), ANR-20-AMRB-0009,TARGET-THERAPY,Spatially targeted eradication of antimicrobial-resistant bacteria: Novel polymer-based photodynamic therapy following aerosol lung delivery(2020), Jonchère, Laurent, monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes. - - VINP2017 - ANR-17-CE18-0015 - AAPG2017 - VALID, Spatially targeted eradication of antimicrobial-resistant bacteria: Novel polymer-based photodynamic therapy following aerosol lung delivery - - TARGET-THERAPY2020 - ANR-20-AMRB-0009 - FR-DE AMR Bilateral call - VALID, 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), University of Oxford [Oxford], 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 ), Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centre 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), 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), and 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)
Subjects: Aminoglycoside-based cationic lipids, 0303 health sciences, Structure-activity, Pharmaceutical Science, respiratory system, Article, Cystic fibrosis, Lipidic formulations, 3. Good health, RS1-441, Lung gene therapy, Nebulization, 03 medical and health sciences, Pharmacy and materia medica, aminoglycoside-based cationic lipids, cystic fibrosis, lipidic formulations, lung gene therapy, nebulization, structure-activity, 0302 clinical medicine, 030220 oncology & carcinogenesis, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, 030304 developmental biology
Abstract: International audience; Aerosol lung gene therapy using non-viral delivery systems represents a credible therapeutic strategy for chronic respiratory diseases, such as cystic fibrosis (CF). Progress in CF clinical setting using the lipidic formulation GL67A has demonstrated the relevance of such a strategy while emphasizing the need for more potent gene transfer agents. In recent years, many novel non-viral gene delivery vehicles were proposed as potential alternatives to GL67 cationic lipid. However, they were usually evaluated using procedures difficult or even impossible to implement in clinical practice. In this study, a clinically-relevant administration protocol via aerosol in murine lungs was used to conduct a comparative study with GL67A. Diverse lipidic compounds were used to prepare a series of formulations inspired by the composition of GL67A. While some of these formulations were ineffective at transfecting murine lungs, others demonstrated modest-to-very-efficient activities and a series of structure-activity relationships were unveiled. Lipidic aminoglycoside derivative-based formulations were found to be at least as efficient as GL67A following aerosol delivery of a luciferase-encoding plasmid DNA. A single aerosol treatment with one such formulation was found to mediate long-term lung transgene expression, exceeding half the animal’s lifetime. This study clearly supports the potential of aminoglycoside-based cationic lipids as potent GL67-alternative scaffolds for further enhanced aerosol non-viral lung gene therapy for diseases such as CF. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
Published: 2022

24. Spin Crossover and High-Spin State in Fe(II) Anionic Polymorphs Based on Tripodal Ligands

Author: Françoise Conan, Guillaume Chastanet, Cle Donacier Mekuimemba, Sébastien Pillet, Smail Triki, Nathalie Cosquer, Emmelyne Cuza, 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), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and The authors acknowledge the CNRS (Centre National de la Recherche Scientifique), the 'Université de Brest'. E.C. acknowledges financial support from the 'Région de Bretagne (ARED) and Université de Brest (CDE)'. The University of Bordeaux and Région Nouvelle Aquitaine are also acknowledged.
Subjects: Coordination sphere, Spin states, 010405 organic chemistry, Chemistry, Infrared spectroscopy, 010402 general chemistry, 01 natural sciences, LIESST, 0104 chemical sciences, Inorganic Chemistry, Bond length, Crystallography, Spin crossover, Excited state, Tripodal ligand, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract: International audience; Two new mononuclear Fe(II) polymorphs, [(C2H5)4N]2[Fe(py3C-OEt)(NCS)3]2 (1) and [(C2H5)4N][Fe(py3C-OEt)(NCS)3] (2) (py3C-OEt = tris(pyridin-2-yl)ethoxymethane), have been synthesized and characterized by single-crystal X-ray diffraction, by magnetic and photomagnetic measurements, and by detailed variable-temperature infrared spectroscopy. The molecular structure, in both complexes, is composed of the same anionic [Fe(py3C-OEt)(NCS)3]− complex (two units for 1 and one unit for 2) generated by coordination to the Fe(II) metal center of one tridentate py3C-OEt tripodal ligand and three terminal κN-SCN coligands. Magnetic studies revealed that polymorph 2 displays a high-spin (HS) state over the entire studied temperature range (300–10 K), while complex 1 exhibits an abrupt and complete spin crossover (SCO) transition at ca. 132.3 K, the structural characterizations of which, performed at 295 and 100 K, show a strong modification, resulting from the thermal evolutions of the Fe–N bond lengths and of the distortion parameters (∑ and Θ) of the FeN6 coordination sphere, in agreement with the presence of HS and low-spin (LS) states at 295 and 100 K, respectively. This thermal transition has been also confirmed by the thermal evolution of the maximum absorbance for ν(NCS) vibrational bands recorded in the temperature range 200–10 K. In 1 the signature of a metastable photoinduced HS state has been observed using photomagnetic and photoinfrared spectroscopy, leading to a similar T(LIESST) relaxation temperature (LIESST = light-induced excited spin-state trapping) of 70 K.
Published: 2021

25. Ab initio study of lithium decoration of popgraphene and hydrogen storage capacity of the hybrid nanostructure

Author: A. Lebon, Luis J. Gallego, Pablo Álvarez-Zapatero, A. Herrero, A. Vega, 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), Departamento de Física Teórica, Atómica y Óptica, and Universidad de Valladolid [Valladolid] (UVa)
Subjects: Materials science, Nanostructure, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, law.invention, Hydrogen storage, Physisorption, law, [CHIM]Chemical Sciences, Renewable Energy, Sustainability and the Environment, Graphene, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Fuel Technology, chemistry, Chemisorption, Chemical physics, Density functional theory, Lithium, 0210 nano-technology, Carbon
Abstract: cited By 0; The successful realization of extended ‘5-5-8’ line defects in graphene in a controlled way has suggested the possible formation of a new 2D carbon allotrope consisting in pentagonal-octagonal-pentagonal carbon rings. The mechanical and thermal stability of this nanostructure, called popgraphene, has recently been confirmed on the basis of first-principles calculations. Moreover, it has been proposed as a promising anode material for use in Li-ion batteries with fast charge/discharge rates. In the present paper we perform density functional theory calculations to investigate the hydrogen storage ability of popgraphene. Our calculations show that popgraphene can be decorated in a very stable way by placing Li atoms on the pentagonal carbon rings of both sides of the sheet, leaving free the octagonal carbon rings. In that condition, the Li-decorated popgraphene sheet can bind up to four H2 molecules per unit cell, with an average adsorption energy in a range between physisorption and atomic chemisorption, which would allow for reversible hydrogen storage at moderate temperatures and pressures. Moreover, the gravimetric density of the Li-decorated popgraphene is 4.24 wt%, which is almost equal to the threshold specified by the U.S. Department of Energy for novel hydrogen-storage materials. All these results show that Li-decorated popgraphene nanostructures could be good materials for hydrogen storage. © 2021 Hydrogen Energy Publications LLC
Published: 2021

26. Mimicking the protein access channel to a metal center: effect of a funnel complex on dissociative versus associative copper redox chemistry

Author: Grégory Thiabaud, Françoise Conan, Bénédicte Douziech, Olivia Reinaud, Hélène Colas, Yves Le Mest, Nicolas Le Poul, Corinne Lagrost, Nathalie Cosquer, Ivan Jabin, Philippe Hapiot, Joceline Zeitouny, 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 de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Organique, Université Libre de Bruxelles [Bruxelles] (ULB), Institut des Sciences Chimiques de Rennes (ISCR), 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), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université libre de Bruxelles (ULB), 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 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 (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 ) -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 ), Université Libre de Bruxelles [Bruxelles] ( ULB ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), and 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 )
Subjects: Coordination sphere, Inorganic chemistry, 010402 general chemistry, Ligands, 01 natural sciences, Biochemistry, Redox, Catalysis, Metal, Electron transfer, Colloid and Surface Chemistry, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Calixarene, Organometallic Compounds, Molecule, 010405 organic chemistry, Ligand, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Molecular Mimicry, Proteins, General Chemistry, 0104 chemical sciences, Crystallography, Kinetics, visual_art, visual_art.visual_art_medium, Thermodynamics, Cyclic voltammetry, Oxidation-Reduction, Copper
Abstract: International audience; The control of metal−ligand exchange in a confined environment is of primary importance for understanding thermodynamics and kinetics of the electron transfer process governing the reactivity of enzymes. This study reveals an unprecedented change of the CuII/CuI binding and redox properties through a subtle control of the access to the labile site by a protein channel mimic. The cavity effect was estimated from cyclic voltammetry investigations by comparison of two complexes displaying the same coordination sphere (tmpa) and differing by the presence or absence of a calix[6]arene cone surrounding the metal labile site L. Effects on thermodynamics are illustrated by important shifts of E1/2 toward higher values for the calix complexes. This is ascribable to the protection of the labile site of the open-shell system from the polar medium. Such a cavity control also generates specific stabilizations. This is exemplified by an impressively exalted affinity of the calixarene system for MeCN, and by the detection of a kinetic intermediate, a noncoordinated DMF guest molecule floating inside the cone. Kinetically, a unique dissymmetry between the CuI and CuII ligand exchange capacity is highlighted. At the CV time scale, the guest interconversion is only feasible after reduction of CuII to CuI. Such a redox-switch mechanism results from the blocking of the associative process at the CuII state, imposed by the calixarene funnel. All of this suggests that the embedment of a reactive redox metal ion in a funnel-like cavity can play a crucial role in catalysis, particularly for metallo-enzymes associating electron transfer and ligand exchange.
Published: 2009

27. 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

28. Polyamines and applications. A look at the first workshop in linear and cyclic polyamines chemistry

Author: Denat, Franck, Deniaud, David, Tripier, Raphaël, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), Université de Nantes ( UN ) -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 ), RENARD, NICOLAS, 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 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), 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: [CHIM.INOR] Chemical Sciences/Inorganic chemistry, Polyamines cycliques, coordination, co ordination, extraction/puri fication, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, catalyse, hybrid materials, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Cyclic polyamines, luminescence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, linear polyamines, complexes, vectorisation, catalysis, extraction/Èpur ation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, matÈriaux hybrides, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, [ CHIM.INOR ] Chemical Sciences/Inorganic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, IR M, [CHIM.ORGA] Chemical Sciences/Organic chemistry, polyamines linÈaires, MRI
Abstract: Given their versatile coordination properties, cyclic and linear polyamines are the subject of numerous worksin many research groups. This great interest is mainly related to their use in diverse fields such as removalof metals from liquids, purification of gases, application in catalysis, in sensors, as well as in various probesfor medical applications. This paper summarizes recent results obtained by the French research groupswhich attended the first ìworkshop in linear and cyclic polyamines chemistryî., Les polyamines cycliques et linéaires, bien connues pour leurs propriétés de coordination, sont l’objet des travaux de nombreux groupes de recherche. Cette attention est due à leurs implications dans des domaines très divers comme l’extraction de métaux, la purification des gaz, la catalyse ou la mise en oeuvre de sondes et de vecteurs pour des applications médicales. Cet article résume les résultats récents obtenus par quelques groupes de recherche français, présentés lors des premières Journées d’études scientifiques en chimie des polyamines cycliques et linéaires.
Published: 2008

29. Polyamines : études et applications

Author: Denat, Franck, Deniaud, David, Tripier, Raphaël, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Laboratoire de Synthèse Organique (Hétérochimie organique, organoéléments et matériaux) (LSOHOOM), Université de Nantes (UN)-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), Stern, Christine, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Synthèse Organique (Hétérochimie organique, organoéléments et matériaux) ( LSOHOOM ), Université de Nantes ( UN ) -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: complexes, coordination, vectorisation, extraction/purification, catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, cyclic polyamines, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, hybrid materials, luminescence, ComputingMilieux_MISCELLANEOUS, linear polyamines, MRI
Abstract: International audience
Published: 2008

30. 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

31. Triiron clusters derived from dinuclear complexes related to the active site of [Fe–Fe] hydrogenases: steric effect of the dithiolate bridge on redox properties, a DFT analysis

Author: François Y. Pétillon, C Greco, Maxime Laurans, Catherine Elleouet, Philippe Schollhammer, Ahmad Hobballah, Federica Arrigoni, Schollhammer, P, Elleouet, C, Petillon, F, Arrigoni, F, Greco, C, Hobballah, A, Laurans, M, 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), Dipartimento di Scienza dei Materiali = Department of Materials Science [Milano-Bicocca], and Università degli Studi di Milano-Bicocca [Milano] (UNIMIB)
Subjects: Steric effects, Hydrogenase, biology, 010405 organic chemistry, Chemistry, Active site, Protonation, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Inorganic Chemistry, Crystallography, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, hydrogenases, DFT, triiron clusters, bio-inspired, biomimetic, biology.protein, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cyclic voltammetry
Abstract: International audience; A series of triiron clusters [Fe3(CO)5(2-dppe)(µ-pdtR2)(µ-pdt)] featuring different combination of dithiolate bridges have been prepared by using dinuclear and mononuclear precursors, [Fe2(CO)6(µ-xdt)] (xdt = pdt, pdtEt2, pdtBn2, adtBn) and [Fe(CO)2(2-dppe)(2-pdt)]. Novel triiron compounds, featuring sterically crowded dithiolate bridges (pdtEt2, pdtBn2), were spectroscopically and structurally characterized. Their protonation and redox behaviours are discussed. The effect of the dithiolate bridges on the electrochemical properties (oxidation and reduction) of the complexes [Fe3(CO)5(2-dppe)(µ-xdt)(µ-pdt)] has been examined by cyclic voltammetry and rationalized by DFT calculations. Studies of the protonation of these species and their proton reduction behaviour were considered.
Published: 2021

32. 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

33. 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

34. Syntheses, structural characterisation and magnetic properties of Fe(ii) and Mn(ii) compounds with the pentacyanopropenido ligand; structural characterisation of a substituted pyrazolo[1,5-a]pyrimidine

Author: Emeric Lefebvre, Jean Sala-Pala, Estelle Vigier, Carlos J. Gómez García, Jean-Michel Kerbaol, Mathieu Marchivie, Marek M. Kubicki, Nathalie Cosquer, Françoise Conan, 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), Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), 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 ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Instituto de Ciencia Molecular ( ICMol ), and Universitat de València ( UV )
Subjects: Denticity, Stereochemistry, Zero field splitting, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, [ CHIM ] Chemical Sciences, Catalysis, Metal, Delocalized electron, Materials Chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Isostructural, Bicyclic molecule, 010405 organic chemistry, Chemistry, Hydrogen bond, Ligand, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, [ CHIM.INOR ] Chemical Sciences/Inorganic chemistry, General Chemistry, 0104 chemical sciences, Crystallography, visual_art, visual_art.visual_art_medium
Abstract: International audience; Reactions between the metal(II) salts [M(CH3CN)n](BF4)2 (M = Fe, n = 6; M = Mn, n = 4) and some organic anionic polynitriles were studied. With the pentacyanopropenide anion pcp− [pcp− = (NC)2CC(CN)C(CN)2−], were obtained, according to the experimental conditions, the new complexes [M(pcp)2(H2O)4] (1, M = Fe; 2, M = Mn) and [M(pcp)2] (3, M = Fe; 4 = Mn). Use of the hexacyano-3,4-diazahexadienediide anion [(NC)2CC(CN)NNC(CN)C(CN)22−] instead of pcp− did not afford polynitrile metal complexes but led to a new organic derivative 5, of formula C10N8H2. Crystallographic studies indicated that the isostructural compounds 1 and 2 involve discrete monomeric units with pcp ligands acting with a monodentate coordination mode and having the metal in a pseudooctahedral trans-MN2O4 environment; however, a rich hydrogen bond system gives rise to a 3D array. Complex 3, which presents metal in a pseudooctahedral MN6 environment, has a 3D structure arising from pcp ligands having an unprecedented μ3-coordination mode. Compound 5 is a bicyclic derivative with a pyrazolo[1,5-a]pyrimidine skeleton. In all derivatives, the organic part is essentially planar and involves a strongly delocalized π system. The magnetic properties of the inorganic complexes have been studied in the 2–300 K range. Fit of the magnetic data indicates high spin complexes with weak antiferromagnetic interactions in 2, 3 and 4 and the presence of a significant zero field splitting of the Fe(II) ion in 1.
Published: 2006

35. 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

36. 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

37. 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

38. Pyclen-Based Ln(III) Complexes as Highly Luminescent Bioprobes for In Vitro and In Vivo One- and Two-Photon Bioimaging Applications

Author: Olivier Maury, Sophie Brasselet, Raphaël Tripier, Jean-Christophe Mulatier, Nadir Bettache, Marie Maynadier, Magali Gary-Bobo, Maryline Beyler, Christophe Nguyen, Alexei Grichine, Nadège Hamon, Chantal Andraud, Alain Duperray, Amandine Roux, 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), 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), NanoMedSyn, 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), MOSAIC (MOSAIC), Institut FRESNEL (FRESNEL), 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), 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), NanoMedSyn (NMS), 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), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)
Subjects: Lanthanide, [SDV]Life Sciences [q-bio], 010402 general chemistry, Quantum mechanics, 01 natural sciences, Biochemistry, Catalysis, Colloid and Surface Chemistry, Two-photon excitation microscopy, In vivo, Lanthanides, Microscopy, Structural isomer, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation, Zebrafish, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Ligand, Chemistry, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, Biological imaging, Antennas, Luminescence
Abstract: International audience; In addition to the already described ligand L4a, two pyclen-based lanthanide chelators, L4b and L4c, bearing two specific picolinate two-photon antennas (tailor-made for each targeted metal) and one acetate arm arranged in a dissymmetrical manner, have been synthesized, to form a complete family of lanthanide luminescent bioprobes: [EuL4a], [SmL4a], [YbL4b], [TbL4c], and [DyL4c]. Additionally, the symmetrically arranged regioisomer L4a′ was also synthesized as well as its [EuL4a′] complex to highlight the astonishing positive impact of the dissymmetrical N-distribution of the functional chelating arms. The investigation clearly shows the high performance of each bioprobe, which, depending on the complexed lanthanide, could be used in various applications. Each presents high brightness, quantum yields, and lifetimes. Staining of the complexes into living human breast cancer cells was observed. In addition, in vivo two-photon microscopy was performed for the first time on a living zebrafish model with [EuL4a]. No apparent toxicity was detected on the growth of the zebrafish, and images of high quality were obtained.
Published: 2020

39. Luminescent cyclometalated alkynylplatinum(ii) complexes with 1,3-di(pyrimidin-2-yl)benzene ligands: synthesis, electrochemistry, photophysics and computational studies

Author: Mariia Hruzd, Nicolas le Poul, Marie Cordier, Samia Kahlal, Jean-Yves Saillard, Sylvain Achelle, Sébastien Gauthier, 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), Region Bretagne, France Region Bretagne, and Conseil Departemental des Cotes d'Armor, France
Subjects: Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract: International audience; In this article, we report on a series of cyclometalated chloro- and alkynyl-platinum(ii) complexes bearing various tridentate NCN-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene. The X-ray crystal structures of two alkynyl-platinum(ii) complexes were determined and other structures were DFT-calculated. Electrochemical and DFT-computational studies suggest a ligand-centred reduction on the R-1-substituted NCN ligand, whereas oxidation likely occurs either on the Pt-phenylacetylide moiety and/or the cyclometalated ligand. In CH2Cl2 solution at room temperature, the complexes show phosphorescent emissions ranging from green to orange, depending on the R-1 and R-2 substituents on the ligands. In KBr solid state matrix, excluding complexes bearing a trifluoromethyl substituted ligand, all compounds exhibit red emission. The presence of an alkynyl ancillary ligand has limited influence on absorption and emission spectra except in the case of the complex with the strongly electron-donating diphenylamino R-2 substituent on the alkynyl ligand, for which a significant red-shift was observed. The alkynyl Pt(ii) complex with OMe groups as both R-1 and R-2 substituents shows the best emission quantum yield (0.81 in CH2Cl2 solution) in this series. The full series of DFT calculated band gaps correlated generally well with the electrochemical and absorption data and reasonably model the impact of the substituents on the electronics of these complexes.
Published: 2022

40. 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

41. Phosphonodithioester–Amine Coupling as a Key Reaction Step for the Design of Cationic Amphiphiles Used for Gene Delivery

Author: Montassar Khalil, Alexis Hocquigny, Mathieu Berchel, Tristan Montier, 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), 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), Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), RENARD, NICOLAS, Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-EFS-Institut National de la Santé et de la Recherche Médicale (INSERM)
Subjects: liposomes, réaction dans l’eau, Pharmaceutical Science, 010402 general chemistry, cationic lipids, water reaction, 01 natural sciences, Article, Analytical Chemistry, Surface-Active Agents, QD241-441, Cations, Cell Line, Tumor, [CHIM] Chemical Sciences, Drug Discovery, [CHIM]Chemical Sciences, Humans, Sulfhydryl Compounds, Physical and Theoretical Chemistry, Amines, phospholipids, amphiphiles, [SDV.MHEP] Life Sciences [q-bio]/Human health and pathology, sans métal, 010405 organic chemistry, Organic Chemistry, Gene Transfer Techniques, Esters, reaction click, Lipids, 0104 chemical sciences, Chemistry (miscellaneous), Drug Design, click chemistry, click reaction, nucleic acids delivery, Molecular Medicine, lipids (amino acids, peptides, and proteins), [SDV.MHEP]Life Sciences [q-bio]/Human health and pathology
Abstract: International audience; A convergent synthesis of cationic amphiphilic compounds is reported here with the use of the phosphonodithioester–amine coupling (PAC) reaction. This versatile reaction occurs at room temperature without any catalyst, allowing binding of the lipid moiety to a polar head group. This strategy is illustrated with the use of two lipid units featuring either two oleyl chains or two-branched saturated lipid chains. The final cationic amphiphiles were evaluated as carriers for plasmid DNA delivery in four cell lines (A549, Calu3, CFBE and 16HBE) and were compared to standards (BSV36 and KLN47). These new amphiphilic derivatives, which were formulated with DOPE or DOPE-cholesterol as helper lipids, feature high transfection efficacies when associated with DOPE. The highest transfection efficacies were observed in the four cell lines at low charge ratios (CR = 0.7, 1 or 2). At these CRs, no toxic effects were detected. Altogether, this new synthesis scheme using the PAC reaction opens up new possibilities for investigating the effects of lipid or polar head groups on transfection efficacies.
Published: 2021

42. A roadmap towards pollution prevention and sustainable development of Gadolinium

Author: Stéphane Kremer, Asim Mian, François Cotton, Raphaël Tripier, Douraied Ben Salem, Romaric Loffroy, Jean-Alix Barrat, Sébastien Verclytte, Zarrin Alavi, Yih Yian Sitoh, Julien Ognard, Laboratoire de Traitement de l'Information Medicale (LaTIM), Institut National de la Santé et de la Recherche Médicale (INSERM)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Centre Hospitalier Régional Universitaire de Brest (CHRU Brest)-Université de Brest (UBO)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Lyon Sud [CHU - HCL] (CHLS), Hospices Civils de Lyon (HCL), Centre de Recherche en Acquisition et Traitement de l'Image pour la Santé (CREATIS), Université Jean Monnet [Saint-Étienne] (UJM)-Hospices Civils de Lyon (HCL)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Les Hôpitaux Universitaires de Strasbourg (HUS), Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), National Neuroscience Institute, Lille Catholic Hospitals, Neuropediatric Department, Lille Catholic University, F-59000 Lille, France, Equipe IFTIM [ImViA - EA7535], Centre Hospitalier Universitaire de Dijon - Hôpital François Mitterrand (CHU Dijon)-Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER-UNICANCER-Imagerie et Vision Artificielle [Dijon] (ImViA), Université de Bourgogne (UB)-Université de Bourgogne (UB), 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), CIC Brest, Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Hôpital de la Cavale Blanche, CHRU Brest - Service d'Imagerie médicale (CHU - Brest - HM), Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre Hospitalier Régional Universitaire de Brest (CHRU Brest)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Institut Brestois Santé Agro Matière (IBSAM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), RENARD, NICOLAS, and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Hospices Civils de Lyon (HCL)-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Sustainable development, Radiological and Ultrasound Technology, Gadolinium, chemistry.chemical_element, 010501 environmental sciences, Sustainable Development, 01 natural sciences, 6. Clean water, 030218 nuclear medicine & medical imaging, 03 medical and health sciences, 0302 clinical medicine, chemistry, 13. Climate action, Pollution prevention, [CHIM] Chemical Sciences, Environmental science, Humans, [CHIM]Chemical Sciences, Radiology, Nuclear Medicine and imaging, Neurology (clinical), Environmental Pollution, Environmental planning, 0105 earth and related environmental sciences
Abstract: International audience; Several studies have shown the evidence of GBCAs’environmentalpollution and Gd3+toxicity both in aquatic organisms and humans. This short communication provides a roadmap using recent quan-titative data on GBCAs’consumption, medical use and waste, towardsenvironmental pollution mitigation and sustainable development
Published: 2021

43. Antimicrobial Photodynamic Therapy: Latest Developments with a Focus on Combinatory Strategies

Author: Tony Le Gall, Ulrich Jonas, Ali Balasini, Alizé Hascoët, Franck Thétiot, Tristan Montier, Gilles Lemercier, Holger Schönherr, Mareike Müller, Max Müller, Raphaëlle Youf, INSERM Unit 1018, Universität Siegen [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), Université de Brest (UBO), 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), Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), and Le Gall, Tony
Subjects: Computer science, medicine.medical_treatment, Pharmaceutical Science, Photodynamic therapy, Context (language use), 02 engineering and technology, Review, 010402 general chemistry, 01 natural sciences, antimicrobials, Pharmacy and materia medica, multidrug resistance, medicine, combinatory strategies, Management science, ROS, photosensitizers, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, 021001 nanoscience & nanotechnology, Antimicrobial, 0104 chemical sciences, [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, RS1-441, photodynamic therapy, nanoparticles, 0210 nano-technology
Abstract: International audience; Antimicrobial photodynamic therapy (aPDT) has become a fundamental tool in modern therapeutics, notably due to the expanding versatility of photosensitizers (PSs) and the numerous possibilities to combine aPDT with other antimicrobial treatments to combat localized infections. After revisiting the basic principles of aPDT, this review first highlights the current state of the art of curative or preventive aPDT applications with relevant clinical trials. In addition, the most recent developments in photochemistry and photophysics as well as advanced carrier systems in the context of aPDT are provided, with a focus on the latest generations of efficient and versatile PSs and the progress towards hybrid-multicomponent systems. In particular, deeper insight into combinatory aPDT approaches is afforded, involving non-radiative or other light-based modalities. Selected aPDT perspectives are outlined, pointing out new strategies to target and treat microorganisms. Finally, the review works out the evolution of the conceptually simple PDT methodology towards a much more sophisticated, integrated, and innovative technology as an important element of potent antimicrobial strategies.
Published: 2021

44. Liposome-Mediated Gene Transfer in Differentiated HepaRG™ Cells: Expression of Liver Specific Functions and Application to the Cytochrome P450 2D6 Expression

Author: Manuel Vlach, Hugo Coppens-Exandier, Agnès Jamin, Mathieu Berchel, Julien Scaviner, Christophe Chesné, Tristan Montier, Paul-Alain Jaffrès, Anne Corlu, Pascal Loyer, Nutrition, Métabolismes et Cancer (NuMeCan), Université de Rennes (UR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Bioprédic International, Technopole Atalante Villejean, 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), SynNanoVect, Université européenne de Bretagne - European University of Brittany (UEB)-Plateforme Génomique Santé Biogenouest®-Plateforme IBiSA, 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), and This work was funded by the Institut National de la Santé et de la Recherche Médicale (Inserm), the Centre National de la Recherche Scientifique (CNRS) and the Région Bretagne (Project RGen n°20005405, AAP Transfert de technologies Filières Santé et Biotechnologies 2020). Manuel Vlach was hired for 6 months (project RGEN, n°20005405) and Hugo Coppens-Exandier is a recipient of a fellowship 'Convention Industrielle de Formation par la Recherche » (CIFRE n°221206A10) from the Association Nationale Recherche Technologie (ANRT).
Subjects: Carcinoma, Hepatocellular, HepaRG™ cells, [SDV]Life Sciences [q-bio], retrodifferentiation, cell cycle, transfection, lipofection, lipophosphoramidate, CYP450 2D6, Liver Neoplasms, Cell Differentiation, General Medicine, Transfection, Cytochrome P-450 CYP2D6, Cations, Liposomes, Humans
Abstract: The goal of this study was to establish a procedure for gene delivery mediated by cationic liposomes in quiescent differentiated HepaRG™ human hepatoma cells. We first identified several cationic lipids promoting efficient gene transfer with low toxicity in actively dividing HepG2, HuH7, BC2 and progenitor HepaRG™ human hepatoma cells. The lipophosphoramidate Syn1-based nanovector, which allowed the highest transfection efficiencies of progenitor HepaRG™ cells, was next used to transfect differentiated HepaRG™ cells. Lipofection of these cells using Syn1-based liposome was poorly efficient most likely because the differentiated HepaRG™ cells are highly quiescent. Thus, we engineered the differentiated HepaRG™ Mitogenic medium supplement (ADD1001) that triggered robust proliferation of differentiated cells. Importantly, we characterized the phenotypical changes occurring during proliferation of differentiated HepaRG™ cells and demonstrated that mitogenic stimulation induced a partial and transient decrease in the expression levels of some liver specific functions followed by a fast recovery of the full differentiation status upon removal of the mitogens. Taking advantage of the proliferation of HepaRG™ cells, we defined lipofection conditions using Syn1-based liposomes allowing transient expression of the cytochrome P450 2D6, a phase I enzyme poorly expressed in HepaRG cells, which opens new means for drug metabolism studies in HepaRG™ cells.
Published: 2022

45. Iron Porphyrins as Models of Cytochrome c Oxidase

Author: Boitrel , Bernard, Ricard , David, Richard , Philippe, L'Her , Maurice, 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), 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 ), and Université de Brest ( UBO ) -Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ) -IFR148 ScInBioS
Subjects: Hemeproteins, Models, Molecular, Porphyrins, Iron, structure-activity relationships, dioxygen activation, [ CHIM ] Chemical Sciences, Catalysis, heme proteins, model compounds, Electron Transport Complex IV, Oxygen, Structure-Activity Relationship, Zinc, electrochemistry, cytochrome c oxidase, [CHIM]Chemical Sciences, Oxidation-Reduction
Abstract: International audience; A series of iron porphyrins has been synthesized as models of cytochrome c oxidase; their activity as 4 e-catalysts in the reduction of dioxygen has been studied at pH 7. These compounds have been obtained by grafting very different residues onto the same iron complex, namely tripodal tetraamines, pickets, and straps, in order to change the environment of the metal center. In the case of porphyrins bearing a tripodal cap, the secondary amines have been alkylated with different substituents so as to modify the electronic environment of the distal pocket. Surprisingly,when the iron porphyrin is functionalized with four identical acrylamido pickets, the resulting complex exhibits biomimetic activity in that it catalyzes oxygen reduction with almost no production of hydrogen peroxide. The crystal structure of the redox-inactive zinc(ii) analogue is reported; this shows how the metal influences the spatial arrangement of the four pickets through axial coordination and hydrogen bonding. Even a bis-strapped iron porphyrin, for which no dimerization or self-aggregation can occur at the electrode surface, acts as a 4 eÿ catalyst for O2 reduction. It is thus demonstrated that at pH close to physiological values, the iron porphyrin is an intrinsically efficient catalyst for the reduction ofoxygen to water.
Published: 2001

46. 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

47. 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

48. Electrocatalytic reduction of dioxygen to water by tren-capped porphyrins, functional models of cytochrome c oxidase

Author: Maurice L'Her, David Ricard, Bernard Boitrel, Bruno Andrioletti, boitrel, bernard, Laboratoire de synthèse et d'électrosynthèse organométallique [Dijon] (LSEO), Université de Bourgogne (UB)-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), 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 ) -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: Inorganic chemistry, chemistry.chemical_element, 010402 general chemistry, Photochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Catalysis, Reduction (complexity), Adsorption, [CHIM] Chemical Sciences, Materials Chemistry, [CHIM]Chemical Sciences, Cytochrome c oxidase, Graphite electrode, biology, 010405 organic chemistry, Chemistry, Metals and Alloys, General Chemistry, Copper, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ceramics and Composites, biology.protein
Abstract: International audience; Two different tren-capped porphyrins—in which the two metals, iron and copper, are more or less off-centered—are shown to be efficient catalysts for the reduction of O2 to H2O; surprisingly, their iron-only complexes are shown to be even more effective 4e- catalysts when adsorbed on a graphiteelectrode.
Published: 1999

49. 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

50. Influence of QD photosensitizers in the photocatalytic production of hydrogen with biomimetic [FeFe]-hydrogenase. Comparative performance of CdSe and CdTe

Author: Inmaculada Ortiz, Juan Corredor, Frédéric Gloaguen, Maria J. Rivero, Dulanjan Harankahage, Mikhail Zamkov, University of Cantabria, Bowling Green State University (BGSU), 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 Universidad de Cantabria
Subjects: Environmental Engineering, Materials science, Hybrid systems, Hydrogen, Health, Toxicology and Mutagenesis, 0208 environmental biotechnology, chemistry.chemical_element, 02 engineering and technology, Hydrogenase mimic, 010501 environmental sciences, Photochemistry, 7. Clean energy, 01 natural sciences, CdSe, Catalysis, Electron transfer, [SPI]Engineering Sciences [physics], Hydrogenase, Biomimetics, Quantum Dots, Cadmium Compounds, Environmental Chemistry, Photocatalytic hydrogen production, [CHIM]Chemical Sciences, Selenium Compounds, 0105 earth and related environmental sciences, Hydrogen production, Photosensitizing Agents, Public Health, Environmental and Occupational Health, Quantum dot, General Medicine, General Chemistry, CdTe, Ascorbic acid, Pollution, 020801 environmental engineering, chemistry, Photocatalysis, Tellurium
Abstract: Photocatalytic systems comprising a hydrogenase-type catalyst and CdX (X = S, Se, Te) chalcogenide quantum dot (QD) photosensitizers show extraordinary hydrogen production rates under visible light excitation. What remains unknown is the mechanism of energy conversion in these systems. Here, we have explored this question by comparing the performance of two QD sensitizers, CdSe and CdTe, in photocatalytic systems featuring aqueous suspensions of a [Fe2 (μ-1,2-benzenedithiolate) CO6] catalyst and an ascorbic acid sacrificial agent. Overall, the hydrogen production yield for CdSe-sensitized reactions QDs was found to be 13 times greater than that of CdTe counterparts. According to emission quenching experiments, an enhanced performance of CdSe sensitizers reflected a greater rate of electron transfer from the ascorbic acid (kAsc). The observed difference in the QD-ascorbic acid charge transfer rates between the two QD materials was consistent with respective driving forces for these systems. Financial support from projects RTI2018-099407-B-I00, RTI2018-093310-B-I00, RTC2019-006820-5 (MCIU/AEI/FEDER, UE) and ‘HYLANTIC’-EAPA_204/2016 (Interreg Atlantic/FEDER UE) is gratefully acknowledged. Juan Corredor is grateful to FPI contract grant (BES-2016-079201). MZ and DH were supported by the Award DE-SC0016872 (MZ) funded by the U.S. Department of Energy, Office of Science.
Published: 2021

Catalog

Books, media, physical & digital resources

See catalog results

Searchworks

Select search scope, currently: Articles Catalog books, media & more in Jio Institute collections Articles journal articles & other e-resources

Search

Search Constraints

Refine your results

Search Limiters

Topic

Publication Year Range

Language

Publication Type

Journal

Database

Publisher

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

Search Results

Catalog

Select search scope, currently: Articles

Catalog

books, media & more in Jio Institute collections

Articles

journal articles & other e-resources