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90 results on '"ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)"'

1. In Cellulo Mössbauer and EPR Studies Bring New Evidence to the Long‐Standing Debate on Iron–Sulfur Cluster Binding in Human Anamorsin

Author: Geneviève Blondin, Martin Clémancey, Lucia Banci, Francesca Camponeschi, Simone Ciofi-Baffoni, Sara Matteucci, University of Florence, Department of Chemistry and Magnetic Resonance Center (CERM), Consorzio Interuniversitario Risonanze Magnetiche di Metallo Proteine (CIRMMP), Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)-University of Bologna-Partenaires INRAE, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Department of Chemistry, University of Florence, ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Università degli Studi di Firenze = University of Florence (UniFI), and Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence (UniFI)-University of Bologna/Università di Bologna-Partenaires INRAE
Subjects: Iron-Sulfur Proteins, anamorsin, Protein family, Stereochemistry, metalloproteins, Iron–sulfur cluster, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, 03 medical and health sciences, Spectroscopy, Mossbauer, chemistry.chemical_compound, in cellulo EPR spectroscopy, law, Mössbauer spectroscopy, Iron-sulfur cluster binding, Cluster (physics), Metalloprotein, Humans, in cellulo Mcssbauer spectroscopy, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Electron paramagnetic resonance, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, 010405 organic chemistry, Communication, Electron Spin Resonance Spectroscopy, Intracellular Signaling Peptides and Proteins, General Medicine, General Chemistry, Communications, iron-sulfur clusters, 0104 chemical sciences, chemistry, Iron–Sulfur Clusters, in cellulo Mössbauer spectroscopy, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Biogenesis, Protein Binding
Abstract: Human anamorsin is an iron–sulfur (Fe–S)‐cluster‐binding protein acting as an electron donor in the early steps of cytosolic iron–sulfur protein biogenesis. Human anamorsin belongs to the eukaryotic CIAPIN1 protein family and contains two highly conserved cysteine‐rich motifs, each binding an Fe–S cluster. In vitro works by various groups have provided rather controversial results for the type of Fe–S clusters bound to the CIAPIN1 proteins. In order to unravel the knot on this topic, we used an in cellulo approach combining Mössbauer and EPR spectroscopies to characterize the iron–sulfur‐cluster‐bound form of human anamorsin. We found that the protein binds two [2Fe–2S] clusters at both its cysteine‐rich motifs., A combined in cellulo Mössbauer‐ and EPR‐based approach is applied to address controversial aspects of Fe–S cluster‐binding properties of human anamorsin, a protein involved in the biogenesis of cytosolic [4Fe–4S] cluster‐binding proteins. We show that human anamorsin binds two [2Fe–2S] clusters in‐cell in two highly conserved cysteine‐rich motifs typical of the eukaryotic CIAPIN1 protein family, with different electron‐spin‐relaxation properties.
Published: 2021

2. An [FeFe]‐Hydrogenase Mimic Immobilized through Simple Physiadsorption and Active for Aqueous H 2 Production

Author: Marcello Gennari, Abhishek Dey, Lianke Wang, Estak Ahmed, Carole Duboc, Dibyajyoti Saha, Vincent Artero, Somdatta Ghosh Dey, Department of Chemical Sciences, Indian Association for the Cultivation of Science, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-16-CE92-0012,NiFemim,Catalyseurs bio-inspirés de l'hydrogénase à [NiFe] pour la production d'hydrogène.(2016), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)
Subjects: bio-inspired catalysts, Aqueous solution, H-2 evolution, 010405 organic chemistry, Chemistry, earth-abundant electrocatalysts, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Hydrogenase mimic, 010402 general chemistry, Electrocatalyst, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, heterogeneous electrochemistry, Simple (abstract algebra), Electrochemistry, electrocatalysis
Abstract: International audience; Mimicking hydrogenases with synthetic complexes is a promising strategy for the design of Earth-abundant electrocatalysts for H$_2$ evolution as alternative to platinum. Here, we describe a bio-inspired FeFe electrocatalyst, with a semi-bridging $\mu$-CO ligand, active and stable for H$_2$ evolution in acidic aqueous solutions after its physiadsorption onto carbon-based electrodes.
Published: 2021

3. Ratiometric luminescence detection of copper(I) by a resonant system comprising two antenna/lanthanide pairs

Author: Sergey A. Denisov, Didier Boturyn, Olivier Sénèque, Nathan D. McClenaghan, Céline Cepeda, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-12-BS07-0012,LUMZIF,Doigts de zinc luminescents : vers des sondes optiques proche-infrarouge basées sur les lanthanides pour l'imagerie biologique du zinc(2012), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)
Subjects: Lanthanide, Luminescence, Photoluminescence, chemistry.chemical_element, 010402 general chemistry, Photochemistry, Lanthanoid Series Elements, 01 natural sciences, Ion, Inorganic Chemistry, chemistry.chemical_compound, Coordination Complexes, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Naphthalene, Ions, Millisecond, Luminescent Agents, Molecular Structure, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Tryptophan, [SDV.BBM.BM]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Molecular biology, [CHIM.MATE]Chemical Sciences/Material chemistry, Probe, Copper, 0104 chemical sciences, chemistry, Luminescent Measurements, Peptide
Abstract: International audience; Selective and sensitive detection of Cu(I) is an ongoing challenge due to its important role in biological systems, for example. Herein, we describe a photoluminescent molecular chemosensor integrating two lanthanide ions (Tb$^{3+}$ and Eu$^{3+}$) and respective tryptophan and naphthalene antennas onto a polypeptide backbone. The latter was structurally inspired from copper-regulating biomacromolecules in Gram-negative bacteria and was found to bind Cu$^+$ effectively under pseudobiological conditions (log K$_{Cu}$$^+$ = 9.7 ± 0.2). Ion regulated modulation of lanthanide luminescence in terms of intensity and long, millisecond lifetime offers perspectives in terms of ratiometric and time-gated detection of Cu$^+$. The role of the bound ion in determining the photophysical properties is discussed with the aid of additional model compounds.
Published: 2021

4. Hydrogen Production at a NiO Photocathode Based on a Ruthenium Dye-Cobalt Diimine Dioxime Catalyst Assembly: Insights from Advanced Spectroscopy and Post-operando Characterization

Author: Didier Gasparutto, Benjamin Dietzek, Alexander Schwab, Murielle Chavarot-Kerlidou, Stephan Kupfer, Didier Léonard, Christine Saint-Pierre, Sebastian Bold, Nicolas Queyriaux, Jakob Bruhnke, Carolin Müller, Emmanouil Giannoudis, Vincent Artero, Dmitry Aldakov, Corinne Gablin, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena (IPHT), Center for Energy and Environmental Chemistry (CEEC Jena), Institut des Sciences Analytiques (ISA), 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), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Institute of Physical Chemistry and Center for Energy and Environmental Chemistry Jena, (CEEC- Jena), Surfaces, Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institute for Physical Chemistry and Center for Energy and Environmental Chemistry, This work was supported by the European Commission's Seventh Framework Program (FP7/2007-2013) under grant agreement no. 306398 (FP7-IDEAS-ERC, Project PhotocatH2ode), the Deutsche Forschungsgemeinschaft (German Science Foundation, PHOTOACC project, grant no. KU 3933/2-1), and the French National Research Agency in the framework of the 'Investissements d'avenir' program (ANR15-IDEX-02, Labex ARCANE and CBH-EURGS, ANR-17EURE-0003) and the Franco-German University., ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), European Project: 306398,EC:FP7:ERC,ERC-2012-StG_20111012,PHOTOCATH2ODE(2012), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: dye-sensitized, Materials science, Hydrogen, solar fuels, Photoelectrochemistry, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Catalysis, Artificial photosynthesis, photoelectrochemistry, cobalt catalyst, General Materials Science, Hydrogen production, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Solar fuel, 0104 chemical sciences, Ruthenium, chemistry, 13. Climate action, hydrogen, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Water splitting, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; The production of hydrogen by efficient, low-cost, and integrated photoelectrochemical water splitting processes represents an important target for the ecological transition. This challenge can be addressed thanks to bioinspired chemistry and artificial photosynthesis approaches by designing dye-sensitized photocathodes for hydrogen production, incorporating bioinspired first-row transition metal-based catalysts. The present work r describes the preparation and photoelectrochemical characterization of a NiO photocathode sensitized with a phosphonate-derivatized ruthenium tris-diimine photosensitizer covalently linked to a cobalt diimine dioxime hydrogen-evolving catalyst. Under simulated AM 1.5G irradiation, hydrogen is produced with photocurrent densities reaching 84 +/- 7 mu A.cm(-2), which is among the highest values reported so far for dye-sensitized photocathodes with surface-immobilized catalysts. Thanks to the unique combination of advanced spectroscopy and surface characterization techniques, the fast desorption of the dyad from the NiO electrode and the low yield of electron transfer to the catalyst, resulting in the Co demetallation from the diimine dioxime framework, were identified as the main barriers limiting the performances and the stability of the system. This work therefore paves the way for a more rational design of molecular photocathodes for solar fuel production and represents a further step toward the development of sustainable processes for the production of hydrogen from sunlight and water.
Published: 2021

5. Approaching industrially relevant current densities for hydrogen oxidation with a bioinspired molecular catalytic material

Author: Edmond Gravel, Vincent Artero, Bertrand Reuillard, Pascale Chenevier, Jérémy Schild, Eric Doris, Adina Morozan, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and European Project: 779366,CRESCENDO
Subjects: 010405 organic chemistry, Chemistry, Hydrogen oxidation, General Chemistry, Carbon nanotube, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, 0104 chemical sciences, Active layer, law.invention, Anode, Colloid and Surface Chemistry, Chemical engineering, law, Energy transformation, Current (fluid), Current density
Abstract: International audience; Integration of efficient platinum-group-metal (PGM)-free catalysts to fuel cells and electrolyzers is a prerequisite to their large-scale deployment. Here, we describe the development of a molecular-based anode for the hydrogen oxidation reaction (HOR) through noncovalent integration of a DuBois type Ni bioinspired molecular catalyst at the surface of a carbon nanotube modified gas diffusion layer. This mild immobilization strategy enabled us to gain high control over the loading in catalytic sites. Additionally, through the adjustment of the hydration level of the active layer, a new record current density of 214 ± 20 mA cm$^{–2}$ could be reached at 0.4 V vs RHE with the PGM-free anode, at 25 °C. Near industrially relevant current densities were obtained at 55 °C with 150 ± 20 and 395 ± 30 mA cm$^{–2}$ at 0.1 and 0.4 V overpotentials, respectively. These results further demonstrate the relevance of such molecular approaches for the development of electrocatalytic platforms for energy conversion.
Published: 2021

6. LEAFY protein crystals with a honeycomb structure as a platform for selective preparation of outstanding stable bio-hybrid materials

Author: Sylvie Kieffer-Jaquinod, Philippe Carpentier, Stéphane Ravanel, Renaud Dumas, Julien Pérard, Olivier Hamelin, Stéphane Ménage, Alice Gogny, David Cobessi, Lucile Chiari, Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Biocatalyse (BIOCAT), European Synchrotron Radiation Facility (ESRF), Etude de la dynamique des protéomes (EDyP), BioSanté (UMR BioSanté), Institut National de la Santé et de la Recherche Médicale (INSERM)-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 Grenoble Alpes (UGA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), BioEnergie et Environnement (BEE), Plantes, Stress & Métaux (MetalStress), Physiologie cellulaire et végétale (LPCV), Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), Institut de biologie structurale (IBS - UMR 5075), Régulateurs du développement de la fleur (Flo_RE ), 80|PRIME Program (CNRS), DRF Impulsion program (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-10-INBS-0008,ProFI,Infrastructure Française de Protéomique(2010), GON, Nathalie, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, Grenoble Alliance for Integrated Structural Cell Biology - - GRAL2010 - ANR-10-LABX-0049 - LABX - VALID, and Infrastructure Française de Protéomique - - ProFI2010 - ANR-10-INBS-0008 - INBS - VALID
Subjects: Materials science, chemistry.chemical_element, Nanotechnology, 010402 general chemistry, 01 natural sciences, Mass Spectrometry, symbols.namesake, Honeycomb, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, General Materials Science, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Leafy, Enzymatic digestion, 010405 organic chemistry, Ginkgo biloba, Proteins, [PHYS.COND.CM-MS] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0104 chemical sciences, Ruthenium, Plant Leaves, Honeycomb structure, chemistry, symbols, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Raman spectroscopy, Hybrid material, Protein crystallization, Chromatography, Liquid
Abstract: International audience; Well-organized protein assemblies offer many properties that justify their use for the design of innovative bionanomaterials. Herein, crystals of the oligomerization domain of the LEAFY protein from Ginkgo biloba, organized in a honeycomb architecture, were used as a modular platform for the selective grafting of a ruthenium-based complex. The resulting bio-hybrid crystalline material was fully characterized by UV-visible and Raman spectroscopy and by mass spectrometry and LC-MS analysis after selective enzymatic digestion. Interestingly, insertion of complexes within the tubular structure affords an impressive increase in stability of the crystals, eluding the use of stabilizing cross-linking strategies.
Published: 2021

7. Access to Metal Centers and Fluxional Hydride CoordinationIntegral for CO2 Insertion into [Fe3(μ-H)3]3+ Clusters

Author: Vincent J. Catalano, Dae Ho Hong, Jason Shearer, Leslie J. Murray, Ricardo B. Ferreira, Ricardo Garcia-Serres, Center for Catalysis, Department of Chemistry, University of Florida, University of Florida [Gainesville] (UF), Florida Center for Heterocyclic Chemistry, Department of Chemistry, University of Florida, Department of Chemistry, University of Nevada, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Department of Chemistry, Trinity University, Trinity University, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Tris, Steric effects, 010405 organic chemistry, Hydride, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Solvent, Metal, chemistry.chemical_compound, Crystallography, chemistry, visual_art, Kinetic isotope effect, visual_art.visual_art_medium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, Physical and Theoretical Chemistry, Cyclophane
Abstract: International audience; CO$_2$ insertion into tri(mu-hydrido) triiron(II) clusters ligated by a tris($\beta$-diketiminate) cyclophane is demonstrated to be balanced by sterics for CO$_2$ approach and hydride accessibility. Time-resolved NMR and UV-vis spectra for this reaction for a complex in which methoxy groups border the pocket of the hydride donor (Fe$_3$H$_3$L$^{OMe/Me}$, 4) result in a decreased activation barrier and increased kinetic isotope effect consistent with the reduced sterics. For the ethyl congener Fe$_3$H$_3$L$^{Et/Me}$(2), no correlation is found between rate and reaction solvent or added Lewis acids, implying CO$_2$ coordination to an Fe center in the mechanism. The estimated hydricity (50 kcal/mol) based on observed H/D exchange with BD$_3$ requires Fe-O bond formation in the product to offset an endergonic CO$_2$ insertion. $\mu_3$-hydride coordination is noted to lower the activation barrier for the first CO$_2$ insertion event in DFT calculations
Published: 2021

8. Efficient Electrochemical CO2/CO Interconversion by an Engineered Carbon Monoxide Dehydrogenase on a Gas-Diffusion Carbon Nanotube-Based Bioelectrode

Author: Julien Pérard, Clara Rinaldi, Christine Cavazza, Bruno Guigliarelli, Umberto Contaldo, Alan Le Goff, BioEnergie et Environnement (BEE), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA ), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Bioénergétique et Ingénierie des Protéines (BIP ), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and Département de Chimie Moléculaire - Bioélectrochimie pour les capteurs, l’énergie et les nanomatériaux (DCM - BioCEN)
Subjects: medicine.medical_specialty, bioelectrocatalysis, Inorganic chemistry, carbon monoxide dehydrogenase, Overpotential, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, medicine, [PHYS]Physics [physics], biology, carbon nanotubes, 010405 organic chemistry, Chemistry, Rhodospirillum rubrum, Active site, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, biology.organism_classification, 0104 chemical sciences, Turnover number, Bioelectrochemistry, biology.protein, nickel enzymes, EPR, Carbon monoxide dehydrogenase, CO2 RR
Abstract: International audience; Carbon monoxide dehydrogenase catalyzes the reversible oxidation of CO to CO2. The monofunctional enzyme from Rhodospirillum rubrum (RrCODH) has been extensively characterized in the past, although its use and investigation by bioelectrochemistry have been limited. Here, we developed a heterologous system yielding a highly stable and active recombinant RrCODH in one-step purification, with CO oxidation activity reaching a maximum of 26 500 U.mg(-1), making RrCODH the most active CODH under ambient conditions described so far. Electron paramagnetic resonance was used to precisely characterize the recombinant RrCODH, demonstrating the integrity of the active site. Selective CO2/CO interconversion with maximum turnover frequencies of 150 s(-1) for CO oxidation (1.5 mA cm(-2) at 250 mV overpotential) and 420 s(-1) for CO2 reduction (4.2 mA cm(-2) at 180 mV overpotential) is catalyzed by the recombinant RrCODH immobilized on MWCNT electrodes modified with 1-pyrenebutyric acid adamantyl amide (MWCNTADA), either in a classic three-electrode cell or in specifically designed CO2/CO-diffusing electrodes. This functional device is stable for hours with a turnover number of at least 800 000. The performances of recombinant RrCODH-modified MWCNTADA are close to the best metal-based and molecular-based catalysts. These results greatly increase the benchmark for bioelectrocatalysis of reversible CO2 conversion.
Published: 2021

9. Chimeric Protein–Protein Interface Inhibitors Allow Efficient Inhibition of Type III Secretion Machinery and Pseudomonas aeruginosa Virulence

Author: Rossimiriam Pereira de Freitas, Yung-Sing Wong, Aline Thomas, Sophie Plé, Younes Bouzidi, Antoine Fortuné, Caroline Barette, Flaviane Francisco Hilário, Ina Attrée, Marie-Odile Fauvarque, Tuan-Dung Ngo, Eric Faudry, Pathogenèse bactérienne et réponses cellulaires (PBRC), Biologie du Cancer et de l'Infection (BCI ), 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])-Institut National de la Santé et de la Recherche Médicale (INSERM)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Département de pharmacochimie moléculaire (DPM ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Genetics and Chemogenomics (GenChem), Laboratoire de Biologie à Grande Échelle (BGE - UMR S1038), 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)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Universidade Federal de Minas Gerais [Belo Horizonte] (UFMG), Universidade Federal de Ouro Preto (UFOP), Associations 'Vaincre la mucoviscidose' and 'Gregory Lemarchand', AVIESAN T3SS (ANR PRP1.4), GIS-IBiSA and ChemBioFrance, Froggy platform of the CIMENT infrastructure (https://ciment.ujf-grenoble.fr), which is supported by the Rhône-Alpes region (GRANT CPER07_13 CIRA), ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-15-CE11-0018,HemoPseudo,Pneumonie hémorragique à Pseudomonas aeruginosa : étude de nouvelles stratégies de virulence(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), ANR-10-EQPX-0029,EQUIP@MESO,Equipement d'excellence de calcul intensif de Mesocentres coordonnés - Tremplin vers le calcul petaflopique et l'exascale(2010), Faudry, Eric, Grenoble Alliance for Integrated Structural Cell Biology - - GRAL2010 - ANR-10-LABX-0049 - LABX - VALID, Pneumonie hémorragique à Pseudomonas aeruginosa : étude de nouvelles stratégies de virulence - - HemoPseudo2015 - ANR-15-CE11-0018 - AAPG2015 - VALID, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, CBH-EUR-GS - - CBH-EUR-GS2017 - ANR-17-EURE-0003 - EURE - VALID, Innovative strategies for observing and modelling natural systems - - OSUG@20202010 - ANR-10-LABX-0056 - LABX - VALID, Equipements d'excellence - Equipement d'excellence de calcul intensif de Mesocentres coordonnés - Tremplin vers le calcul petaflopique et l'exascale - - EQUIP@MESO2010 - ANR-10-EQPX-0029 - EQPX - VALID, Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: 0301 basic medicine, [SDV]Life Sciences [q-bio], Protein subunit, 030106 microbiology, Virulence, hybrid molecules, medicine.disease_cause, Type three secretion system, Microbiology, 03 medical and health sciences, medicine, antivirulence, Secretion, biology, protein−protein interface inhibitors, Chemistry, Toxin, Pseudomonas aeruginosa, bacterial resistance, biology.organism_classification, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Fusion protein, Type III secretion system, 030104 developmental biology, Infectious Diseases, click chemistry, [SDV.MP.BAC] Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Bacteria
Abstract: International audience; Pseudomonas aeruginosa (P. aeruginosa) is an opportunistic pathogen naturally resistant to many common antibiotics and acquires new resistance traits at an alarming pace. Targeting the bacterial virulence factors by an antivirulence strategy, therefore, represents a promising alternative approach besides antibiotic therapy. The Type III secretion system (T3SS) of P. aeruginosa is one of its main virulence factors. It consists of more than 20 proteins building a complex syringe-like machinery enabling the injection of toxin into host cells. Previous works showed that disrupting interactions between components of this machinery efficiently lowers the bacterial virulence. Using automated target-based screening of commercial and in-house libraries of small molecules, we identified compounds inhibiting the protein-protein interaction between PscE and PscG, the two cognate chaperones of the needle subunit PscF of P. aeruginosa T3SS. Two hits were selected and assembled using Split/Mix/Click chemistry to build larger hybrid analogues. Their efficacy and toxicity were evaluated using phenotypic analysis including automated microscopy and image analysis. Two nontoxic hybrid leads specifically inhibited the T3SS and reduced the ex vivo cytotoxicity of bacteria and their virulence in Galleria mellonella.
Published: 2019

10. Self-Assembly of a Ginkgo Oligomerization Domain Creates a Sub-10-nm Honeycomb Architecture on Carbon and Silicon Surfaces with Customizable Pores: Implications for Nanoelectronics, Biosensing, and Biocatalysis

Author: Gregory Si Larbi, Denis Mariolle, Emmanuel Thévenon, François Parcy, Pierre-Henri Elchinger, Renaud Dumas, Pierre-Henri Jouneau, Denis Falconet, Raluca Tiron, Elise Jacquier, Régulateurs du développement de la fleur (Flo_RE ), Physiologie cellulaire et végétale (LPCV), 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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), LIPID, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA program Nanoprot 3D, DRF impulsion grant, ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Materials science, Silicon, chemistry.chemical_element, Honeycomb (geometry), Nanotechnology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Domain (software engineering), Nanoelectronics, chemistry, Biocatalysis, General Materials Science, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Self-assembly, 0210 nano-technology, Biosensor, Carbon, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2021

11. Iron Oxidation in Escherichia coli Bacterioferritin Ferroxidase Centre, a Site Designed to React Rapidly with H2O2 but Slowly with O$_2$

Author: Martin Clémancey, Marina Lučić, Dimitri A. Svistunenko, Nick E. Le Brun, Jonathan A. R. Worrall, Geoffrey R. Moore, Michael T. Wilson, Geneviève Blondin, Jacob Pullin, Justin M. Bradley, University of Essex, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), University of East Anglia [Norwich] (UEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Models, Molecular, Metalloproteins | Hot Paper, Photochemistry, medicine.disease_cause, Peroxide, 01 natural sciences, law.invention, chemistry.chemical_compound, law, Electron paramagnetic resonance, Research Articles, 0303 health sciences, biology, Mössbauer spectroscopy, Ceruloplasmin, Bacterioferritin, General Medicine, Oxidation-Reduction, Research Article, EPR spectroscopy, inorganic chemicals, Iron, Radical, Mossbauer spectroscopy, 010402 general chemistry, Catalysis, fast kinetics, 03 medical and health sciences, Bacterial Proteins, Escherichia coli, medicine, ferroxidase center, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 030304 developmental biology, 010405 organic chemistry, fungi, Hydrogen Peroxide, General Chemistry, Cytochrome b Group, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, 0104 chemical sciences, Oxygen, A-site, chemistry, Ferritins, biology.protein, rapid freeze-quenching, Stoichiometry
Abstract: Both O2 and H2O2 can oxidize iron at the ferroxidase center (FC) of Escherichia coli bacterioferritin (EcBfr) but mechanistic details of the two reactions need clarification. UV/Vis, EPR, and Mössbauer spectroscopies have been used to follow the reactions when apo‐EcBfr, pre‐loaded anaerobically with Fe2+, was exposed to O2 or H2O2. We show that O2 binds di‐Fe2+ FC reversibly, two Fe2+ ions are oxidized in concert and a H2O2 molecule is formed and released to the solution. This peroxide molecule further oxidizes another di‐Fe2+ FC, at a rate circa 1000 faster than O2, ensuring an overall 1:4 stoichiometry of iron oxidation by O2. Initially formed Fe3+ can further react with H2O2 (producing protein bound radicals) but relaxes within seconds to an H2O2‐unreactive di‐Fe3+ form. The data obtained suggest that the primary role of EcBfr in vivo may be to detoxify H2O2 rather than sequester iron., The kinetics of E. coli bacterioferritin di‐ferrous ferroxidase centre reacting with O2 and H2O2 shows that H2O2 reacts circa 1000 times faster than O2 implying that the primary in vivo role of the protein is ROS detoxification rather than iron sequestering.
Published: 2021

12. Exploring Coumarins Reduction: NaBH 4 /MeOH versus Nickel Boride Generated In Situ

Author: Catherine Belle, Amaury du Moulinet d'Hardemare, Clarisse Faure, Hélène Jamet, Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: In situ, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 010402 general chemistry, Coumarin, 01 natural sciences, 0104 chemical sciences, Reduction (complexity), chemistry.chemical_compound, chemistry, Chemoselectivity, Nuclear chemistry, Nickel boride
Abstract: International audience; The role of reagents NaBH4/MeOH and nickel boride (Ni2B)generated in situ from NaBH4 and NiCl2, are compared in thereduction process of coumarin and a variety of 3,7-substitutedcoumarins bearing electro-donating (ED-group) or electro-withdrawinggroups (EW-group). Coumarins (chromen-2-ones) areonly reduced by Ni2B to the cyclic chromanones. This providesa useful and very simple reduction method for electron-richcoumarins, which are resistant to many other reducingmethods. DFT calculations underlined the role of substituentselectronic effects in the reactivity. Subsequent methanolysismay open the ring to methyl phenylpropanoate esters andalcohols resulting from their reductions can also be produced.
Published: 2020

13. Ditopic Chelators of Dicopper Centers for Enhanced Tyrosinases Inhibition

Author: Christian Philouze, Elina Buitrago, Lylia Challali, Marc Maresca, Elisabetta Bergantino, Ahcène Boumendjel, Marius Réglier, Marcello Carotti, Luigi Bubacco, Catherine Belle, Clarisse Faure, Hélène Jamet, Renaud Hardré, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Università degli Studi di Padova = University of Padua (Unipd), Département de pharmacochimie moléculaire (DPM), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universita degli Studi di Padova
Subjects: bioinorganic chemistry, copper active sites, ditopic inhibitors, docking, tyrosinases, Chelating Agents, Enzyme Inhibitors, Humans, Structure-Activity Relationship, Agaricales, Monophenol Monooxygenase, Stereochemistry, Tyrosinase, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Melanin, chemistry.chemical_compound, Moiety, Chelation, [CHIM.COOR]Chemical Sciences/Coordination chemistry, chemistry.chemical_classification, biology, 010405 organic chemistry, Organic Chemistry, Active site, General Chemistry, 0104 chemical sciences, Enzyme, chemistry, Docking (molecular), biology.protein, Kojic acid
Abstract: International audience; Tyrosinase enzymes (Tys) are involved in the key steps of melanin (protective pigments) biosynthesis and molecules targeting the binuclear copper active site on tyrosinases represent a relevant strategy to regulate enzyme activities. In this work, we studied the possible synergic effect generated by combination of known inhibitors. For this, derivatives containing kojic acid (KA) and 2-Hydroxypyridine-N-oxide (HOPNO) combined with a thiosemicarbazone (TSC) moiety were synthetized. Their inhibition activities were evaluated on purified tyrosinases from different sources (mushroom, bacterial and human) as well as on melanin production by lysates from human melanoma MNT-1 cell line. Results showed significant enhancement of the inhibitory effects compared to the parent compounds, in particular for HOPNO-TSC. In order to elucidate the interaction mode with the dicopper(II) active site, we investigated the binding studies towards a tyrosinase bio-inspired model of the dicopper(II) center. The structure of the isolated adduct between one ditopic inhibitor (KA-TSC) and the model complex reveals that the binding to a dicopper center can occur with both chelating sites. Computational studies on model complexes and docking studies on enzymes led to the identification of KA and HOPNO moieties as interacting groups with the dicopper active site.
Published: 2020

14. A Mechanistic Rationale Approach Revealed the Unexpected Chemoselectivity of an Artificial Ru-Dependent Oxidase: A Dual Experimental/Theoretical Approach

Author: David Michael Mayes, Sarah Lopez, Chloé Leprêtre, Yohann Moreau, Christine Cavazza, Stéphane Ménage, Caroline Marchi-Delapierre, Serge Crouzy, Nicolai Burzlaff, Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Groupe modélisation et chimie théorique (MCT ), Biocatalyse (BIOCAT), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), ANR-14-CE06-0005,CrystalBall,une enzyme artificielle pour une catalyse hétérogene(2014), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Oxidase test, 010405 organic chemistry, Chemistry, catalysis-oxidation, reaction paths, chemistry.chemical_element, spin flip, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, DUAL (cognitive architecture), 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, computational chemistry, Catalysis, 0104 chemical sciences, Ruthenium, hydroxychlorination, Biocatalysis, epoxidation, artificial enzymes, Chemoselectivity, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract: International audience; Artificial enzymes represent an attractive alternative to design abiotic biocatalysis. EcNikA-Rul, an artificial metalloenzyme developed by embedding a ruthenium-based catalyst into the cavity of the periplasmic nickel-binding protein NikA, was found to efficiently and selectively transform certain alkenes. The objective of this study was to provide a rationale on the enzymatic function and the unexpected substrate-dependent chemoselectivity of EcNikA-Rul thanks to a dual experimental/computational study. We observed that the de novo active site allows the formation of the terminal oxidant via the formation of a ruthenium aquo species that subsequently reacts with the hypervalent iodine of phenyl iodide diacetic acid. The oxidation process relies on a Ru$^{IV}$=0 pathway via a two-step reaction with a radical intermediate, resulting in the formation of either a chlorohydrin or an epoxide. The results emphasize the impact of the protein scaffold on the kinetics of the reaction, through (i) the promotion of the starting oxidizing species via the exchange of a CO ligand with a water molecule; and (ii) the control of the substrate orientation on the intermediate structures, formed after the Ru$^{IV}$=0 attack. When a C alpha attack is preferred, chlorohydrins are formed while an attack on C beta leads to an epoxide. This work provides evidence that artificial enzymes mimic the behavior of their natural counterparts.
Published: 2020

15. Redox polyelectrolyte modified gold nanoparticles enhance the detection of adenosine in an electrochemical split‐aptamer assay

Author: Lucy L. Coria-Oriundo, Yoann Roupioz, Fernando Battaglini, Helena Ceretti, Instituto de Química Física de los Materiales, Medio Ambiente y Energía [Buenos Aires] (INQUIMAE), Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET)-Facultad de Ciencias Exactas y Naturales [Buenos Aires] (FCEyN), Universidad de Buenos Aires [Buenos Aires] (UBA)-Universidad de Buenos Aires [Buenos Aires] (UBA), Universidad Nacional de Ingeniería (UNI), Universidad Nacional de General Sarmiento [Los Polvorines, Buenos Aires] (UNGS), Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes (UGA), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Chemistry, Aptamer, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Polyelectrolyte, 0104 chemical sciences, Colloidal gold, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 0210 nano-technology, Nuclear chemistry
Abstract: International audience; We present an electrochemical sandwich‐type assay based on the splitting of an aptamer into two fragments. Gold nanoparticles are modified with one of the fragments and a redox polyelectrolyte. The first is used as the recognition element, while the other for the electrochemical signal generation. The split‐aptamer used here can detect adenosine, used as a model system for recognizing small molecules. The multiple binding sites on the nanoparticle, along with the high number of redox probes, yield a selective and sensitive assay for adenosine, achieving a limit of detection of 3.1 nM and a linear range up to 75 nM. The obtained results are analyzed in terms of the nanoparticle and electrode architectures. The assay can be easily extended to other small molecules and sandwich assays, representing a promising tool for detecting metabolites at the nanomolar level.
Published: 2020

16. Glucose oxidase bioanodes for glucose conversion and H2O2 production for horseradish peroxidase biocathodes in a flow through glucose biofuel cell design

Author: Olivier Ondel, Michael Holzinger, Caroline Abreu, Serge Cosnier, Alan Le Goff, François Buret, Yannig Nedellec, Ampère, Département Bioingénierie (BioIng), Ampère (AMPERE), École Centrale de Lyon (ECL), Université de Lyon-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-École Centrale de Lyon (ECL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Ampère, Département Energie Electrique (EE), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), platform Chimie NanoBio ICMG FR 2607 (PCN-ICMG), Institute Carnot PolyNat at Grenoble, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: H2O2, Energy Engineering and Power Technology, 02 engineering and technology, Electrolyte, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Horseradish peroxidase, law.invention, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Glucose oxidase, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Cellulose, biology, Renewable Energy, Sustainability and the Environment, Chemistry, Substrate (chemistry), 021001 nanoscience & nanotechnology, Biofuel cells, Cathode, 0104 chemical sciences, Anode, Glucose, Membrane, Flow stacks, Chemical engineering, biology.protein, 0210 nano-technology
Abstract: International audience; Bioelectrocatalytic carbon nanotube pellets comprising glucose oxidase (GOx) at the anode and horseradish peroxidase (HRP) at the cathode were integrated in a glucose/H2O2 flow-through fuel cell setup. The porous bioelectrodes, separated with a cellulose membrane, were assembled in a design allowing the fuel/electrolyte flow through the entire fuel cell with controlled direction. An air saturated 5 mmol L−1 glucose solution was directed through the anode where glucose is used for power conversion and for the enzymatic generation of hydrogen peroxide supplying the HRP biocathode with its substrate. This configuration showed an open circuit voltage (OCV) of 0.6 V and provided 0.7 ± 0.035 mW at 0.41 V. Furthermore, different charge/discharge cycles at 500 Ω and 3 kΩ were applied to show the long term stability of this setup producing 290 μW h (1.04 J) of energy after 48 h. The biofuel cell design further allows a convenient assembly of several glucose biofuel cells in reduced volumes and its connection in parallel or in series.
Published: 2018

17. Efficient Buchwald-Hartwig-Migita Cross-Coupling for DNA Thioglycoconjugation

Author: Océane Théry, Nicolas Probst, Samir Messaoudi, Rémy Lartia, Mouâd Alami, Eric Defrancq, Biomolécules : Conception, Isolement, Synthèse (BioCIS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Molécules bioactives, conception, isolement et synthèse (MBCIS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Timcal Belgium SA, Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Synthèse et étude de systèmes à intêret biologique (SEESIB), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), and Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-SIGMA Clermont (SIGMA Clermont)
Subjects: Spectrometry, Mass, Electrospray Ionization, Glycosylation, Oligonucleotides, chemistry.chemical_element, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Nucleobase, chemistry.chemical_compound, [CHIM]Chemical Sciences, DNA-glycoconjugates, thioglycoconjugation, Sulfhydryl Compounds, thiosaccharide, Chromatography, High Pressure Liquid, Pd catalysis, 010405 organic chemistry, Oligonucleotide, Organic Chemistry, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, Coupling (electronics), chemistry, Divergent synthesis, Palladium, DNA
Abstract: International audience; An efficient method for the thioglycoconjugation of iodinated oligonucleotides by Buchwald-Hartwig-Migita cross-coupling under mild conditions is reported. The method enables divergent synthesis of many different functionalized thioglycosylated ODNs in good yields, without affecting the integrity of the other A, C, and G nucleobases.
Published: 2018

18. Design of interpenetrating chitosan and poly(ethylene glycol) sponges for potential drug delivery applications

Author: Lisa Racine, Rachel Auzély-Velty, Guillaume Costa, Isabelle Texier, Eric Bayma-Pecit, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Polymers and Plastics, Scanning electron microscope, Biocompatible Materials, macromolecular substances, 02 engineering and technology, Semi-interpenetrating network, 010402 general chemistry, 01 natural sciences, Polyethylene Glycols, Chitosan, [SPI]Engineering Sciences [physics], chemistry.chemical_compound, Drug Delivery Systems, Spectroscopy, Fourier Transform Infrared, Polymer chemistry, PEG ratio, Materials Chemistry, Poly(ethylene) glycol, Molecule, Fourier transform infrared spectroscopy, Organic Chemistry, technology, industry, and agriculture, Biomaterial, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Sponges, Drug delivery, 0210 nano-technology, Ethylene glycol
Abstract: International audience; Semi-interpenetrating chitosan (CS)/poly(ethylene glycol) (PEG) sponges were designed by crosslinking PEG in the CS matrix via nucleophilic thiol-yne addition. This reaction does not require the use of any potentially cytotoxic catalytic species and offers possibilities to prepare materials with tunable properties. The molecular structure of the sponges was analyzed by FTIR spectroscopy, which provided evidence of intermolecular interactions between PEG and CS, and the presence of a cross-linked PEG network in the CS matrix. The crosslinked CS/PEG sponges displayed a structure with large interconnected pores (tens of micrometers) as demonstrated by scanning electron miscoscopy, in comparison to blended materials with irregular and smaller pores. The crosslinked sponges also exhibited improved mechanical properties (higher Young's modulus) and stability at physiological pH. All together, these interesting properties open the way for the application of this biomaterial in topical drug delivery.
Published: 2017

19. Electrochemical Characterizations of four Main Redox-metabolites ofPseudomonas Aeruginosa

Author: George G. Malliaras, Maxime Gougis, Julie Oziat, Pascal Mailley, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ecole Natl Super Mines, Dept Bioelect, Ecole Natl Super Mines Gardanne, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: 0301 basic medicine, Electrochemical detection, medicine.disease_cause, Electrochemistry, 01 natural sciences, Redox, Analytical Chemistry, [SPI]Engineering Sciences [physics], 03 medical and health sciences, chemistry.chemical_compound, Pyocyanin, medicine, Metabolites detection, biology, 010405 organic chemistry, Pseudomonas aeruginosa, Quorum Sensing, biology.organism_classification, Combinatorial chemistry, 0104 chemical sciences, Pseudomonas quinolone signal, Quorum sensing, 030104 developmental biology, chemistry, Bacteria
Abstract: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Bacterial identification is of first importance in clinic nowadays. For few years, electrochemistry appears as a reliable route for characterizations outside of laboratories. Nowadays, researchers mainly focus on the opportunistic pathogen Pseudomonas aeruginosa because of its production of the Pyocyanin toxin which has an electrochemical case study behavior. Other P. aeruginosa secreted molecules are also studied in a lesser extent. This work deals with the systematic electrochemical characterizations in aprotic and protic solvents of 4 main metabolites of this bacterium in the view of multispecies detection of P. aeruginosa. We report here the behavior of the 2-Heptyl-4(1H)-quinolone (HHQ), Pseudomonas Quinolone Signal (PQS), Pyocyanin (PYO) and the 2′aminoacetophenone (2-AA). All the mentioned species are clearly visible by using electrochemical techniques (cyclic and square wave voltammetries). The 2 most suitable species for electrochemical detection appear to be PQS and PYO because of their detection at low potential.
Published: 2017

20. An oxime-based glycocluster microarray

Author: David Goyard, Eric Defrancq, Françoise Vinet, Olivier Renaudet, Antoine Hoang, Eugénie Laigre, Pascal Dumy, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-12-JS07-0001,VacSyn,Développement de Vaccins Synthétiques multiantigéniques antitumoraux(2012), European Project: 647938,H2020,ERC-2014-CoG,LEGO(2015), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Universitaire de France (IUF), and Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.)
Subjects: Microarray, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Carbohydrates, Molecular Conformation, Substrate (chemistry), Microarray Analysis, 010402 general chemistry, Oxime, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Thermal oxide, Oximes, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, DNA microarray, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Carbohydrate microarrays represent powerful tools to study and detect carbohydratebinding proteins, pathogens or cells. In this paper, we report two original oximebased methods to prepare surfaces displaying well-defined structures and valency in a given microspot with improved recognition potency with lectins. In a first “direct” approach, fully synthetic aminooxylated glycoclusters have been coated onto aldehyde-activated SiO$_2$ (silicium substrate doped with 50 nm thermic oxide layer). To improve the preparation of the microarray in term of rapidity and simplicity and to provide addressable surfaces on which sugars can be linked chemoselectively as clusters at defined plots, a second “indirect” strategy has been developed using successive oxime ligation steps. In both cases, binding assays with labelled lectins have revealed more potent and selective interaction due to the clustered presentation of sugars. The observed differences of interaction have been confirmed in solution by ITC.
Published: 2017

21. Cyclotriveratrylene-Based Glycoclusters as High Affinity Ligands of Bacterial Lectins fromPseudomonas aeruginosaandBurkholderia ambifaria

Author: Jean-Pierre Dutasta, Alexandre Martinez, Zachary P. Michael, Sébastien Vidal, Alexander Star, Anne Imberty, Nicolas Galanos, Yanan Chen, Emilie Gillon, Chimie Organique 2-Glycochimie (CO2GLYCO), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Department of Chemistry, University of Pittsburgh, University of Pittsburg, 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 Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-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 Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Isothermal microcalorimetry, chemistry.chemical_classification, biology, 010405 organic chemistry, Glycoconjugate, Burkholderia ambifaria, Lectin, Cyclotriveratrylene, Context (language use), General Chemistry, 010402 general chemistry, biology.organism_classification, 01 natural sciences, Combinatorial chemistry, Fucose, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Click chemistry, biology.protein, [CHIM]Chemical Sciences, Organic chemistry
Abstract: International audience; The design of multivalent glycoconjugates has been largely studied using a variety of core scaffolds. Cyclotriveratrylenes (CTV) have been scarcely used in this context. The synthesis of the tri- and hexa-propargylated CTV cores allowed the prepn. of the corresponding glycoclusters with galactose or fucose residues through azide-alkyne "click" chem. Their interactions with bacterial lectins (LecA, LecB and BambL) was confirmed and studied by titrn. microcalorimetry. Adsorption onto carbon nanotubes was then attempted based on the hydrophobic CTV cores. Their incorporation into field effect transistor (FET) devices was accomplished but the data collected largely suggested a poor interaction of CTV-based glycoclusters with the carbon nanotubes leading to non-specific detection of the lectins.
Published: 2016

22. Earth-Abundant Molecular Z-Scheme Photoelectrochemical Cell for Overall Water-Splitting

Author: Masanobu Higashi, Sebastian Bold, Kazuhiko Maeda, Vincent Artero, Ryu Abe, Romain Brisse, Bruno Jousselme, Christopher D. Windle, Murielle Chavarot-Kerlidou, Osamu Ishitani, Hiromu Kumagai, Solar fuels, hydrogen and catalysis (SolHyCat ), 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])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), Department of Chemistry, School of Science, Tokyo Institute of Technology [Tokyo] (TITECH), Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Abber Center of Photonics, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Strategic International Collaborative Research Program (PhotoCAT project) from Japan Science and Technology Agency (JST), JSPS KAKENHI Grant Number 17H06439 in Scientific Research on Innovative Areas 'Innovations for Light-Energy Conversion (I4LEC), ANR-14-JTIC-0004,PhotoCAT,Molecular Photocathodes for CO2 reduction and H2 evolution(2014), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Photocurrent, Hydrogen, Chemistry, Energy conversion efficiency, Analytical chemistry, chemistry.chemical_element, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Photoelectrochemical cell, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, Photocathode, 0104 chemical sciences, Colloid and Surface Chemistry, Water splitting, Faraday efficiency, Visible spectrum
Abstract: International audience; A push-pull organic dye and a cobaloxime catalyst were successfully co-grafted on NiO and CuGaO$_2$ to form efficient molecular photocathodes for H$_2$ production with >80% Faradaic efficiency. CuGaO$_2$ is emerging as a more effective p-type semiconductor in photoelectrochemical cells and yields a photocathode with four-fold higher photocurrent densities and 400 mV more positive onset photocurrent potential compared to the one based on NiO. Such an optimized CuGaO$_2$ photocathode was combined with a TaONǀCoO$_x$ photoanode in a photoelectrochemical cell. Operated in this Z-scheme configuration, the two photoelectrodes produced H$_2$ and O$_2$ from water with 87% and 88% Faradaic efficiency, respectively, at pH 7 under visible light and in the absence of an applied bias, equating to a solar to hydrogen conversion efficiency of 5.4×10$^{−3}$%. This is, to the best of our knowledge, the highest efficiency reported so far for a molecular-based noble metal-free water splitting Z-scheme.
Published: 2019

23. [Cr(ttpy)2]3+ as a multi-electron reservoir for photoinduced charge accumulation

Author: Vincent Maurel, Jérôme Chauvin, Jean-Marie Mouesca, Damien Jouvenot, Alain Deronzier, Frédérique Loiseau, Rajaa Farran, Long Le-Quang, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), 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)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Université Grenoble Alpes (UGA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: education.field_of_study, 010405 organic chemistry, Chemistry, Population, Electron donor, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, chemistry.chemical_compound, Electron transfer, law, Excited state, [CHIM]Chemical Sciences, Cyclic voltammetry, Terpyridine, education, Electron paramagnetic resonance
Abstract: [Cr(ttpy)2]3+ (ttpy = 4'-(4-methylphenyl)-2,2':6,2''-terpyridine) exhibits rich electrochemical and photophysical properties. Cyclic voltammetry performed in CH3CN shows in the cathodic part the presence of three one-electron reversible systems at -0.47, -0.85 and -1.35 V vs. Ag/AgNO3 10-2 M. These systems are attributed to the reduction of the terpyridine ligands with a partial delocalization of the charge on the tolyl for the last reduction event. The three different reduced species were generated by exhaustive electrolysis and characterized by EPR and UV-visible spectroscopy; DFT calculations were performed to locate the spin density of the electrons added during the reduction. Visible light irradiation of [Cr(ttpy)2]3+ induces the population of a luminescent metal-centered excited state with a lifetime of 270 ns in deoxygenated CH3CN. This excited state can be quenched by an electron transfer process with triphenylphosphine (PPh3) or triethanolamine (TEOA). Using TEOA as a sacrificial electron donor, the doubly reduced species (i.e.[Cr(ttpy)2] +) can be generated under continuous irradiation. In the presence of [Ru(bpy)3]2+ as an additional photosensitizer, the photoreduction of [Cr(ttpy)2]3+ towards [Cr(ttpy)2]+ is accelerated. The trinuclear [{RuII(bpy)2(bpy-O-tpy)}2CrIII]7+ complex ([Ru2Cr]7+) in which a CrIII-bis-terpyridine centre is covalently linked to two RuII-tris-bipyridine moieties by oxo bridges has been synthesised. Its electrochemical, photophysical and photochemical properties were investigated in deoxygenated CH3CN. Cyclic voltammetry indicates only a poor electronic communication between the different subunits, whereas luminescence experiments show a strong quenching of the RuII* excited state by an intramolecular process. Continuous irradiation of [Ru2Cr]7+ under visible conditions in the presence of TEOA leads to [Ru2Cr]4+ where three electrons are stored on the [Cr(ttpy)] subunit.
Published: 2019

24. Comparative analysis of nanosystems’ effects on human endothelial and monocytic cell functions

Author: Ruth Prassl, Iwona Cicha, Maya Juenet, Harald Unterweger, Christoph Alexiou, Stefan Lyer, Jasmin Matuszak, Isabelle Texier, Cédric Chauvierre, Amr Alaarg, Didier Letourneur, Gunter Almer, Danielle Franke, Harald Mangge, Philipp Dörfler, Josbert M. Metselaar, Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Otolaryngology, University Hospital Erlangen = Uniklinikum Erlangen, Laboratoire de Recherche Vasculaire Translationnelle (LVTS (UMR_S_1148 / U1148)), Université Paris 13 (UP13)-Université Paris Diderot - Paris 7 (UPD7)-Institut National de la Santé et de la Recherche Médicale (INSERM), University of Twente, Medical University Graz, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), RWTH University Clinic, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), European Project: 309820,EC:FP7:NMP,FP7-NMP-2012-LARGE-6,NANOATHERO(2013), University of Twente [Netherlands], RWTH Aachen University, Biomaterials Science and Technology, University Hospital Erlangen, and Université Paris Diderot - Paris 7 (UPD7)-Université Paris 13 (UP13)-Institut National de la Santé et de la Recherche Médicale (INSERM)
Subjects: 0301 basic medicine, monocytic cell chemotaxis, Cell Survival, Surface Properties, THP-1 Cells, Cell, Cell Culture Techniques, Biomedical Engineering, Nanoparticle, Biocompatible Materials, Cell Communication, 02 engineering and technology, endothelial migration, Toxicology, Monocytes, 03 medical and health sciences, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], Cell Movement, atherothrombosis, Cell Adhesion, Human Umbilical Vein Endothelial Cells, medicine, Humans, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Cells, Cultured, Liposome, Cell chemotaxis, Chemistry, Nanoparticles, atherothrombosis, endothelial-monocyte interactions, endothelial migration, monocytic cell chemotaxis, Chemotaxis, Cell migration, Adhesion, 021001 nanoscience & nanotechnology, n/a OA procedure, 030104 developmental biology, medicine.anatomical_structure, endothelial-monocyte interactions, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Biophysics, Nanoparticles, 0210 nano-technology, Iron oxide nanoparticles
Abstract: International audience; The objective of our work was to investigate the effects of different types of nanoparticles on endothelial (HUVEC) and monocytic cell functions. We prepared and tested 14 different nanosystems comprising liposomes, lipid nanoparticles, polymer, and iron oxide nanoparticles. Some of the tested nanosystems contained targeting, therapeutic, or contrast agent(s). The effect of particles (0-400 mu g/mL) on endothelial-monocytic cell interactions in response to TNF-alpha was investigated using an arterial bifurcation model and dynamic monocyte adhesion assay. Spontaneous HUVEC migration (0-100 mu g/mL nanoparticles) and chemotaxis of monocytic cells towards MCP-1 in presence of particles (0-400 mu g/mL) were determined using a barrier assay and a modified Boyden chamber assay, respectively. Lipid nanoparticles dose-dependently reduced monocytic cell chemotaxis and adhesion to activated HUVECs. Liposomal nanoparticles had little effect on cell migration, but one formulation induced monocytic cell recruitment by HUVECs under non-uniform shear stress by about 50%. Fucoidan-coated polymer nanoparticles (25-50 mu g/mL) inhibited HUVEC migration and monocytic cell chemotaxis, and had a suppressive effect on monocytic cell recruitment under non-uniform shear stress. No significant effects of iron oxide nanoparticles on monocytic cell recruitment were observed except lauric acid and human albumin-coated particles which increased endothelial-monocytic interactions by 60-70%. Some of the iron oxide nanoparticles inhibited HUVEC migration and monocytic cell chemotaxis. These nanoparticle-induced effects are of importance for vascular cell biology and function and must be considered before the potential clinical use of some of the analyzed nanosystems in cardiovascular applications.
Published: 2019
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25. Non-specific interference of cobalt with siderophore-dependent iron uptake pathways

Author: Bénédicte Pesset, Pamela Saint Auguste, Olivier Cunrath, Dirk Bumann, Odile Sismeiro, Julien Pérard, Quentin Perraud, Isabelle Michaud-Soret, Isabelle J. Schalk, Rachel Legendre, Anne Forster, Pierre Fechter, Ana Carballido Lopez, Jean Yves Coppée, Gaëtan L. A. Mislin, Gwenaëlle Graulier, Hugo Varet, Biotechnologie et signalisation cellulaire (BSC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de recherche de l'Ecole de biotechnologie de Strasbourg (IREBS), 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]), Transcriptome et Epigénome (PF2), Institut Pasteur [Paris], Hub Bioinformatique et Biostatistique - Bioinformatics and Biostatistics HUB, Institut Pasteur [Paris]-Centre National de la Recherche Scientifique (CNRS), Focal Area Infection Biology, Biozentrum, University of Basel (Unibas), This work was partly funded by the Centre National de la Recherche Scientifique. O. Cunrath held a fellowship from the French Ministère de la Recherche et de la Technologie (3 years) and the FRM (Fondation pour la Recherche Médicale, 6 months). A. Y. Carballido Lopez held a fellowship from the University of Strasbourg (IDEX) and B. Pesset from the DGA (Direction Générale des l’Armement). J. P. and I. M. S. thank the Laboratory of Excellence GRAL (grant ANR-11-LABX-49-01) and the Labex ARCANE (grant ANR-11-LABX-0003-01). The Transcriptome and Epigenome Platform is a member of the France Génomique consortium (ANR10-NBS-09-08)., We thank Dr A. Boos and P. Ronot (Institut Pluridisciplinaire Hubert Curien, Strasbourg) for their help in the ICP-AES measurements., ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Biologie des Métaux (BioMet), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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), Bioinformatique évolutive - Evolutionary Bioinformatics, Centre National de la Recherche Scientifique (CNRS)-Institut Pasteur [Paris], Université de Strasbourg (UNISTRA)-Institut de recherche de l'Ecole de biotechnologie de Strasbourg (IREBS)-Centre National de la Recherche Scientifique (CNRS), 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), Institut Pasteur [Paris] (IP), and Institut Pasteur [Paris] (IP)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0301 basic medicine, inorganic chemicals, Siderophore, Iron, Biophysics, Down-Regulation, Siderophores, Biochemistry, Models, Biological, Biomaterials, 03 medical and health sciences, chemistry.chemical_compound, Biosynthesis, Bacterial Proteins, Phenols, Operon, medicine, Transcriptional regulation, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Psychological repression, 030102 biochemistry & molecular biology, biology, Chemistry, Metals and Alloys, Transporter, Cobalt, Gene Expression Regulation, Bacterial, biology.organism_classification, Sciences du Vivant [q-bio]/Microbiologie et Parasitologie, Up-Regulation, Thiazoles, 030104 developmental biology, [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, Chemistry (miscellaneous), Pseudomonas aeruginosa, Ferric, Bacterial outer membrane, Oligopeptides, Bacteria, medicine.drug
Abstract: International audience; Much data shows that biological metals other than Fe3+ can interfere with Fe3+ acquisition by siderophores in bacteria. Siderophores are small Fe3+ chelators produced by the microorganisms to obtain access to Fe3+. Here, we show that Co2+ is imported into Pseudomonas aeruginosa cells in a complex with the siderophore pyochelin (PCH) by the ferri-PCH outer membrane transporter FptA. Moreover, the presence of Co2+ in the bacterial environment strongly affects the production of PCH. Proteomic and transcriptomic approaches showed that a decrease of PCH production is associated with repression of the expression of the genes involved in PCH biosynthesis. We used various molecular biology approaches to show that this repression is not Fur-(ferric uptake transcriptional regulator) dependent but due to competition of PCH-Co with PCH-Fe for PchR (transcriptional activator), thus inhibiting the formation of PchR-PCH-Fe and consequently the expression of the PCH genes. We observed a similar mechanism of repression of PCH production, but to a lesser extent, by Ni2+, but not for Zn2+, Cu2+, or Mn2+. Here, we show, for the first time at a molecular level, how the presence of a contaminant metal can interfere with Fe3+ acquisition by the siderophores PCH and PVD.
Published: 2019

26. Trinuclear copper complexes as biological mimics: Ligand designs and reactivities

Author: Lionel Dubois, Elena Salvadeo, Jean-Marc Latour, 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), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_element, Phosphate esters hydrolysis, 010402 general chemistry, 01 natural sciences, Ligand design, Inorganic Chemistry, Materials Chemistry, Oxygen reduction reaction, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Metal catalyst, Physical and Theoretical Chemistry, Binding site, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Dioxygen activation, biology, 010405 organic chemistry, Ligand, Active site, Combinatorial chemistry, Copper, Tris-copper centers, 0104 chemical sciences, chemistry, biology.protein, Molecular oxygen
Abstract: International audience; Tris-copper centers are present at the active site of multicopper oxidases (MCO) which couple the four electron reduction of molecular oxygen to water with the oxidation of substrates. Modelling these sites with small molecular complexes has thus attracted the interest of many groups in the (bio)inorganic community over the past three decades and still appears a challenge. These enzymes and their model complexes presently enjoy a renewed interest as potential non-precious metal catalyst for the Oxygen Reduction Reaction. Moreover recent work has revealed that tris-copper centers can catalyze methane oxidation. Therefore the elaboration of tris-copper system constitutes an important and timely issue. The aim of the present review is to analyze the various attempts at preparing tris-copper complexes in terms of strategy of ligand design. Of course the challenge to be met is to force three independent binding sites to converge and react in concert. Three main approaches have been developed to anchor these binding sites based on the use of (i) a node either (a) a single atom node (tren-based systems and related), or (b) an hexa-atom node (mesityl-based systems and derivatives), (ii) macrocyclic systems, and (iii) combination of mono- and dinuclear sites. The structures of the different systems will be described and analyzed accordingly. Then the various reactivities exhibited by these systems will be presented so as to evaluate how the ligand design influences the reactivity and to discern promising future directions.
Published: 2018

27. ASGPR-Mediated Uptake of Multivalent Glycoconjugates for Drug Delivery in Hepatocytes

Author: Pascale Delangle, Marie Monestier, Elisabeth Mintz, Martine Cuillel, Colette Lebrun, Christelle Gateau, Faustine Robert, Peggy Charbonnier, Olivier Renaudet, Service de Chimie Inorganique et Biologique (SCIB - UMR E3), Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Reconnaissance Ionique et Chimie de Coordination (RICC), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-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 [2016-2019] (UGA [2016-2019]), 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), 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]), Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-11-EMMA-0025,COPDETOX,Chélateurs du cuivre ciblant le foie : un traitement novateur des surcharges hépatiques en cuivre(2011), and ANR-12-JS07-0001,VacSyn,Développement de Vaccins Synthétiques multiantigéniques antitumoraux(2012)
Subjects: Williams Syndrome, Glycoconjugate, ASGPR, receptors, Asialoglycoprotein Receptor, 010402 general chemistry, 01 natural sciences, Biochemistry, Cell Line, Flow cytometry, Inhibitory Concentration 50, Drug Delivery Systems, [SDV.SP.MED]Life Sciences [q-bio]/Pharmaceutical sciences/Medication, Asialoglycoproteins, medicine, Humans, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Receptor, Molecular Biology, chemistry.chemical_classification, Dose-Response Relationship, Drug, Molecular Structure, medicine.diagnostic_test, 010405 organic chemistry, Chemistry, Organic Chemistry, drug targeting, [SDV.MHEP.HEG]Life Sciences [q-bio]/Human health and pathology/Hépatology and Gastroenterology, Hep G2 Cells, Flow Cytometry, 0104 chemical sciences, glycopeptide, Targeted drug delivery, synthetic drugs, Cell culture, Drug Design, Drug delivery, Hepatocytes, Molecular Medicine, Asialoglycoprotein receptor, Glycoconjugates, Copper, HeLa Cells
Abstract: International audience; Liver cells are an essential target for drug delivery in many diseases. The hepatocytes express the asialoglycoprotein receptor (ASGPR), which promotes specific uptake by means of N-acetylgalactosamine (GalNAc) recognition. In this work, we designed two different chemical architectures to treat Wilson's disease by intracellular copper chelation. Two glycoconjugates functionalized with three or four GalNAc units each were shown to enter hepatic cells and chelate copper. Here, we studied two series of compounds derived from these glycoconjugates to find key parameters for the targeting of human hepatocytes. Efficient cellular uptake was demonstrated by flow cytometry using HepG2 human heptic cells that express the human oligomeric ASGPR. Dissociation constants in the nanomolar range showed efficient multivalent interactions with the receptor. Both architectures were therefore concluded to be able to compete with endogeneous asialoglycoproteins and serve as good vehicles for drug delivery in hepatocytes.
Published: 2016

28. Surface plasmon resonance imaging of the conversion of clustered DNA lesions into double strand breaks by Fpg protein

Author: Arnaud Buhot, Thierry Livache, Muriel Jourdan, Julia Pingel, Jean-François Constant, Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Biology, Lesion, 03 medical and health sciences, chemistry.chemical_compound, DNA double strand break, 0302 clinical medicine, abasic site, medicine, lcsh:TA401-492, [CHIM]Chemical Sciences, AP site, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Oligonucleotide, Base excision repair, Molecular biology, 8-Oxoguanine, 3. Good health, Fpg, chemistry, Deoxyribose, DNA glycosylase, 030220 oncology & carcinogenesis, DNA cluster lesion, surface plasmon resonance imaging, 8-oxoguanine, lcsh:Materials of engineering and construction. Mechanics of materials, medicine.symptom, DNA
Abstract: Ionizing radiations induce clustered damage sites known to be severely challenging for the cell's repair machinery. In the present study, we have grafted on a biochip four synthetic oligonucleotide duplexes containing either a single 8-oxoguanine, a single 2'-deoxyribose abasic site or two different clustered damages containing these two lesions on opposite strands. Using a SPR imaging-based DNA array, we qualitatively observed the hierarchy of lesion processing by the base excision repair (BER) enzyme Fpg (Formamidopyrimidine (fapy)-DNA glycosylase). We could notably show that Fpg can convert a cluster of lesions into a potentially lethal double strand break (DSB) and demonstrate that SPR imaging is suitable to investigate the incision steps occurring during the repair process.
Published: 2015

29. Silver nanoparticle fate in mammals: Bridging in vitro and in vivo studies

Author: Mireille Chevallet, Aurélien Deniaud, Marianne Marchioni, Pierre-Henri Jouneau, Isabelle Michaud-Soret, 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 d'Etude des Matériaux par Microscopie Avancée (LEMMA ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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 Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-10-INBS-0005,FRISBI,Infrastructure Française pour la Biologie Structurale Intégrée(2010), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), and Institut de Recherche Interdisciplinaire de Grenoble (IRIG)
Subjects: Biocide, Biodistribution, Future studies, Silver sulfide, 02 engineering and technology, Cellular imaging, 010402 general chemistry, 01 natural sciences, Chloride, Silver nanoparticle, Inorganic Chemistry, chemistry.chemical_compound, In vivo, Materials Chemistry, Electron microscopy, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Silver speciation, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, In vitro, 0104 chemical sciences, Human exposure, Biophysics, Silver nanoparticles, 0210 nano-technology, Sulfur
Abstract: International audience; Silver nanoparticles (AgNPs) are exponentially used in various consumer products including medical devices. This production leads to an increasing human exposure to silver in different forms. Indeed, AgNPs are subject to various transformations in aqueous aerobic conditions that trigger the production of Ag(I) species. The main environmental transformation produces the non-toxic species silver sulfide. Transformations occurring in mammals are more diverse and mainly depend on the interaction of AgNPs with thiol, chloride and proteins. Any of these species have a different impact on AgNPs and induces AgNP dissolution into Ag(I) species, aggregation and/or stabilization. The transformations occurring also depend on the exposure route. The main one is dietary but medical exposure is also growing with the massive use of nanosilver as biocide in medical devices. For the former, AgNP modifications and Ag distribution has been extensively studied using in vitro and in vivo models, while data related to medical use of nanosilver are scarce. However, most of the in vitro and in vivo data often remain inconsistent. In this review, we describe both in vitro, in cellulo and in vivo data about AgNP transformations, silver speciation and biodistribution. We try to reconcile all these data and describe the latest methods for the future studies of AgNP fate in mammals.
Published: 2018

30. Contribution of Mössbauer spectroscopy to the investigation of Fe/S biogenesis

Author: Martin Clémancey, Geneviève Blondin, Jean-Marc Latour, Ricardo Garcia-Serres, 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]), ANR-14-CE09-0026,FRATISCA,Mieux comprendre les stades précoces et tardifs de l'assemblage des noyaux Fe-S dans la mitochondrie(2014), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: 0301 basic medicine, 030102 biochemistry & molecular biology, biology, Chemistry, Iron–sulfur cluster, Vacuole, Mitochondrion, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Biochemistry, Inorganic Chemistry, 03 medical and health sciences, Cytosol, chemistry.chemical_compound, 030104 developmental biology, Iron-sulfur protein, Mössbauer spectroscopy, biology.protein, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Spectroscopy, Biogenesis
Abstract: Fe/S cluster biogenesis involves a complex machinery comprising several mitochondrial and cytosolic proteins. Fe/S cluster biosynthesis is closely intertwined with iron trafficking in the cell. Defects in Fe/S cluster elaboration result in severe diseases such as Friedreich ataxia. Deciphering this machinery is a challenge for the scientific community. Because iron is a key player, 57Fe-Mossbauer spectroscopy is especially appropriate for the characterization of Fe species and monitoring the iron distribution. This minireview intends to illustrate how Mossbauer spectroscopy contributes to unravel steps in Fe/S cluster biogenesis. Studies were performed on isolated proteins that may be present in multiple protein complexes. Since a few decades, Mossbauer spectroscopy was also performed on whole cells or on isolated compartments such as mitochondria and vacuoles, affording an overview of the iron trafficking. This minireview aims at presenting selected applications of 57Fe-Mossbauer spectroscopy to Fe/S cluster biogenesis.
Published: 2018

31. Valence Localization at a Bio-inspired Mixed-Valent {Cu 2 S} 2+ Motif upon Solvation in Acetonitrile: Effect on Nitrous Oxide Reductase (N 2 Or) Activity

Author: Jordan Mangue, Jacques Pécaut, Stéphane Ménage, Stéphane Torelli, Maylis Orio, Charlène Esmieu, 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), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Valence (chemistry), 010405 organic chemistry, Organic Chemistry, Solvation, chemistry.chemical_element, Nitrous-oxide reductase, Bioinorganic chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Copper, Catalysis, 0104 chemical sciences, Delocalized electron, Crystallography, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Spectroscopy, Acetonitrile
Abstract: International audience; We demonstrate, based on experimental and theoretical evidence, that the isolated [2(CH3CN)2]2+ complex prepared in CH3CN and containing a mixed‐valent {Cu2II,IS} core evolves towards a new [2(CH3CN)3]2+ species upon solvation in CH3CN. Unlike its type III structural analogue [2(H2O)(OTf)]+ active toward N2O reduction, this new type I compound is inactive. This outcome opens new perspectives for a rational for N2O activation using bio‐inspired Cu/S complexes, especially on the role of the valence localization/delocalization and the Cu−Cu bond on the reactivity.
Published: 2018

32. An artificial photosynthetic system for photoaccumulation of two electrons on a fused dipyridophenazine (dppz)-pyridoquinolinone ligand

Author: Isabelle Baussanne, Vincent Artero, Jean-Marie Mouesca, Jean-François Lefebvre, Martine Demeunynck, Ying Zhang, Serge Gambarelli, Philipp Traber, Stefanie Gräfe, Benjamin Dietzek, Stephan Kupfer, Julian Schindler, Murielle Chavarot-Kerlidou, 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]), Département de pharmacochimie moléculaire (DPM ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institute of Physical Chemistry, Abbe Center of Photonics, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Institute for Physical Chemistry and Center for Energy and Environmental Chemistry, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)
Subjects: Materials science, 010405 organic chemistry, chemistry.chemical_element, Electron donor, General Chemistry, Electron, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Photochemistry, Solar fuel, 01 natural sciences, 0104 chemical sciences, Catalysis, law.invention, Ruthenium, Electron transfer, symbols.namesake, chemistry.chemical_compound, Chemistry, chemistry, law, [SDE]Environmental Sciences, symbols, Electron paramagnetic resonance, Raman spectroscopy
Abstract: The π-extended ligand of a ruthenium complex stores two photo-generated electrons, mimicking a key step in photosynthesis., Increasing the efficiency of molecular artificial photosynthetic systems is mandatory for the construction of functional devices for solar fuel production. Decoupling the light-induced charge separation steps from the catalytic process is a promising strategy, which can be achieved thanks to the introduction of suitable electron relay units performing charge accumulation. We report here on a novel ruthenium tris-diimine complex able to temporarily store two electrons on a fused dipyridophenazine–pyridoquinolinone π-extended ligand upon visible-light irradiation in the presence of a sacrificial electron donor. Full characterization of this compound and of its singly and doubly reduced derivatives thanks to resonance Raman, EPR and (TD)DFT studies allowed us to localize the two electron-storage sites and to relate charge photoaccumulation with proton-coupled electron transfer processes.
Published: 2018

33. Mercury Trithiolate Binding (HgS3) to a de Novo Designed Cyclic Decapeptide with Three Preoriented Cysteine Side Chains

Author: Colette Lebrun, Olivier Sénèque, Didier Boturyn, Pascale Delangle, Alain Manceau, Anaïs Pujol, Pierre Rousselot-Pailley, Serge Crouzy, Olivier Proux, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), 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), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), 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 Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), European Synchrotron Radiation Facility (ESRF), Ondes et Structures, Institut des Sciences de la Terre (ISTerre), Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie Inorganique et Biologique (SCIB - UMR E3), Institut Nanosciences et Cryogénie (INAC), Université Grenoble Alpes (UGA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire de Géophysique Interne et Tectonophysique (LGIT), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Laboratoire Central des Ponts et Chaussées (LCPC)-Institut des Sciences de la Terre (ISTerre), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut national des sciences de l'Univers (INSU - CNRS)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR), Reconnaissance Ionique et Chimie de Coordination (RICC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Université Grenoble Alpes (UGA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut national des sciences de l'Univers (INSU - CNRS)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Université Joseph Fourier - Grenoble 1 (UJF), Department of Inorganic and Analytical Chemistry, University of Szege, Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST), 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), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), and Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: chemistry.chemical_classification, Trigonal planar molecular geometry, 010405 organic chemistry, Stereochemistry, Electrospray ionization, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Cyclic peptide, 0104 chemical sciences, Inorganic Chemistry, Metal, chemistry, visual_art, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Thiol, visual_art.visual_art_medium, Side chain, [CHIM]Chemical Sciences, Chelation, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Cysteine
Abstract: International audience; Mercury(II) is an unphysiological soft ion with high binding affinity for thiolate ligands. Its toxicity lies in the interactions with low molecular weight thiols including glutathione and cysteine-containing proteins that disrupt the thiol balance and alter vital functions. However, mercury can also be detoxified via interactions with Hg(II)-responsive regulatory proteins such as MerR, which coordinates Hg(II) with three cysteine residues in a trigonal planar fashion (HgS3 coordination). The model cyclodecapeptide P3C, c(GCTCSGCSRP) was designed to promote Hg(II) chelation in a HgS3 coordination environment through the parallel orientation of three cysteine side chains. The binding motif is derived from the dicysteine P2C cyclodecapeptide validated previously as a model for d10 metal transporters containing the binding sequence CxxC. The formation of the mononuclear HgP3C complex with a HgS3 coordination is demonstrated using electrospray ionization mass spectrometry, UV absorption, and 199Hg NMR. Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy indicates that the Hg(II) coordination environment is T-shaped with two short Hg–S distances at 2.45 Å and one longer distance at 2.60 Å. The solution structure of the HgP3C complex was refined based on 1H–1H NMR constraints and EXAFS results. The cyclic peptide scaffold has a rectangular shape with the three binding cysteine side chains pointing toward Hg(II). The HgP3CH complex has a pKa of 4.3, indicating that the HgS3 coordination mode is stable over a large range of pH. This low pKa value suggests that the preorientation of the three cysteine groups is particularly well-achieved for Hg(II) trithiolate coordination in P3C.
Published: 2018

34. A noble metal-free photocatalytic system based on a novel cobalt tetrapyridyl catalyst for hydrogen production in fully aqueous medium

Author: Emmanouil Giannoudis, Murielle Chavarot-Kerlidou, Vincent Artero, Christopher D. Windle, Nicolas Queyriaux, Athanassios G. Coutsolelos, Sylvaine Roy, Jacques Pécaut, 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), University of Crete [Heraklion] (UOC), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), European Project: 229927,EC:FP7:REGPOT,FP7-REGPOT-2008-1,BIOSOLENUTI(2009), European Project: 306398,EC:FP7:ERC,ERC-2012-StG_20111012,PHOTOCATH2ODE(2012), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Aqueous solution, 010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Inorganic chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, Electron donor, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, engineering.material, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Fuel Technology, chemistry, engineering, Photocatalysis, Noble metal, Cobalt, Phosphine, Hydrogen production
Abstract: International audience; The new cobalt tetrapyridyl complex 1(BF4)(2) was characterized and assessed for hydrogen production in fully aqueous solution. Mechanistic information was gained thanks to a fast screening method, using chemical reductants and a Clark microelectrode. Optimal hydrogen production (443 TONs - 3 mL of H-2) was achieved under visible light-driven conditions, in the presence of a noble metal-free photosensitizer, the water soluble porphyrin 2Cl(4), and the ascorbate/tris-(2-carboxyethyl)phosphine (TCEP) sacrificial electron donor system.
Published: 2018

35. Direct Electrochemistry of Bilirubin Oxidase from Magnaporthe orizae on Covalently-Functionalized MWCNT for the Design of High-Performance Oxygen-Reducing Biocathodes

Author: Solène Gentil, Marie Carrière, Serge Cosnier, Alan Le Goff, Sébastien Gounel, Nicolas Mano, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Vectorisation moléculaire et cellulaire, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-RP Rorer-Centre National de la Recherche Scientifique (CNRS), Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques [2016-2019] (DCM - BEA [2016-2019]), Département de Chimie Moléculaire [2016-2019] (DCM [2016-2019]), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie [2017-2019] (CIBEST [2017-2019]), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), 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)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), and ANR-11-LABX-0003/11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Oxidoreductases Acting on CH-CH Group Donors, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Oxygen, Catalysis, Diffusion, [CHIM]Chemical Sciences, Bilirubin oxidase, Hypoxia, Electrodes, ComputingMilieux_MISCELLANEOUS, biology, Organic Chemistry, General Chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Combinatorial chemistry, 0104 chemical sciences, Nanostructures, Magnaporthe, chemistry, Covalent bond, Electrode, Surface modification, Myrothecium verrucaria, 0210 nano-technology
Abstract: Herein, the direct electrochemistry of bilirubin oxidase from Magnaporthe orizae (MoBOD) was studied on CNTs functionalized by electrografting several types of diazonium salts. The functionalization induces favorable or unfavorable orientation of MoBOD, the latter being compared to the well-known BOD from Myrothecium verrucaria (MvBOD). On the same nanostructured electrodes, MoBOD can surpass MvBOD in terms of both current densities and minimal overpotentials. Added to the fact that MoBOD is also highly active at the gas-diffusion electrode (GDE), these findings make MoBOD one of the MCOs with the highest catalytic activity towards the oxygen reduction reaction (ORR).
Published: 2018

36. Chitosan-lipid nanoparticles (CS-LNPs): Application to siRNA delivery

Author: Rachel Auzély-Velty, Özgül Tezgel, Amandine Arnould, Isabelle Texier, Anna Szarpak-Jankowska, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Programme Investissements d'Avenir (Glyco@Alps project no ANR-15-IDEX-02), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: food.ingredient, Biocompatibility, Cell Survival, Surface Properties, Nanoparticle, macromolecular substances, 02 engineering and technology, Transfection, 010402 general chemistry, 01 natural sciences, Lecithin, Hybrid nanocarriers, Fatty Acids, Monounsaturated, Biomaterials, Chitosan, Mice, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], Colloid and Surface Chemistry, food, Zeta potential, Animals, Organic chemistry, Particle Size, RNA, Small Interfering, Cytotoxicity, Drug Carriers, Mitogen-Activated Protein Kinase 3, Phosphatidylethanolamines, Cationic polymerization, technology, industry, and agriculture, 021001 nanoscience & nanotechnology, Lipids, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Drug delivery systems, Quaternary Ammonium Compounds, Chemical engineering, chemistry, NIH 3T3 Cells, Lipid nanoparticles, Nanoparticles, SiRNA delivery, lipids (amino acids, peptides, and proteins), 0210 nano-technology
Abstract: International audience; To benefit from the biocompatibility of lipid nanoparticles associated with the transfection ability of chitosan, small chitosan lipid nanoparticles (CS-LNPs) dedicated to SiRNA delivery were formulated by an easy-to-implement one-step process. Formulations of CS-LNP5 (lipid core stabilized by a shell comprising phospholipids/cationic lipids and hydrophobically modified chitosan) were optimized for their physicochemical properties (size, zeta potential, colloidal stability) according to their shell composition. In particular, amphiphilic chitosan with various molecular weight and C12 degrees of substitution, and different phospholipids and cationic lipids (lecithin, DOTAP, DOPE) were included at the particle surface at different ratios. The ability of the particles for SiRNA complexation, NIH3T3 cell transfection, and ERK1 downregulation, were studied. Lipid nanoparticles formulated with 15,000 g/mol 2% C12 substituted chitosan, DOTAP and DOPE, mediated 40% ERK1 downregulation efficiency, comparable to lipofectamin (TM) RNAimax, while displaying no cytotoxicity up to 500 mu g/mL.
Published: 2018

37. Seven-coordinate lanthanide complexes with a tripodal redox active ligand: structural, electrochemical and spectroscopic investigations

Author: Christian Philouze, Olivier Jarjayes, Jennifer K. Molloy, Fabrice Thomas, Lionel Fedele, Daniel Imbert, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique [2009-2015] (DCM - CIRE [2009-2015]), Département de Chimie Moléculaire [2007-2015] (DCM [2007-2015]), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Dynamique des écosystèmes Caraïbe et biologie des espèces associées (DYNECAR EA 926), and Université des Antilles et de la Guyane (UAG)
Subjects: Lanthanide contraction, Lanthanide, Quenching (fluorescence), Coordination sphere, 010405 organic chemistry, Chemistry, Ligand, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, law, Tripodal ligand, Octahedral molecular geometry, [CHIM]Chemical Sciences, Electron paramagnetic resonance, ComputingMilieux_MISCELLANEOUS
Abstract: The tripodal ligand TREN-(3,5-di-tert-butylsalicylidene)3 (H3L) was synthesized and its tris(phenolato) lanthanide complexes L-Ln (Ln = NdIII, EuIII, TbIII, GdIII, ErIII, YbIII and LuIII) were prepared. The X-Ray crystal structures confirm that each metal ion resides in a similar monocapped octahedral geometry, excluding water molecules from the coordination sphere. The coordination bond distances are in agreement with the lanthanide contraction, with Ln-O bond lengths in the range 2.139-2.216 A. The complexes show three reversible monoelectronic oxidation waves, which are assigned to the successive oxidation of the phenolate moieties to phenoxyl radicals. The L-Nd complex is the easiest to oxidize, with E = 0.11, E = 0.21 and E = 0.34 V vs. Fc+/Fc, due to the larger size of the lanthanide ion. The ΔE1/2 value (ΔE1/2 = E-E) is correlated to the lanthanide radius, with values of 0.10 V for L-Nd and 0.22 V for L-Lu. The monoradical species were persistent in solution, allowing for their characterisation. All exhibit a distinct absorption band at around 445 nm due to the phenoxyl π-π* transitions. The EPR spectrum of L-Lu+ consists of a single resonance at giso = 1.999, confirming the radical nature of the oxidized product. Most of the other complexes (L-Gd, L-Er, L-Yb) show a quenching of the LnIII-based resonances upon oxidation, indicative of magnetic interactions between the metal and the radical spins. The L-Ln (L = Nd, Er, Yb) complexes exhibit a metal-based luminescence upon excitation of the ligand. A significant quenching of the luminescence was observed upon radical formation: 92%, 83% and 79% respectively for L-Nd+, L-Er+ and L-Yb+.
Published: 2018

38. Evaluation of the accuracy of exchangeable copper and relative exchangeable copper (REC) in a mouse model of Wilson's disease

Author: Khémary Um, Sophie Heissat, Anne-Sophie Brunet, Alain Lachaux, Muriel Bost, Olivier Guillaud, Elisabeth Mintz, Jérôme Dumortier, Valérie Hervieu, Amélie Harel, Hôpital Femme Mère Enfant [CHU - HCL] (HFME), Hospices Civils de Lyon (HCL), 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]), Laboratoire Central d'Anatomie et de Cytologie Pathologiques [Hôpital Edouard Herriot - HCL], Hôpital Edouard Herriot [CHU - HCL], Hospices Civils de Lyon (HCL)-Hospices Civils de Lyon (HCL), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-PDOC-0006,EMMA,Effets de l'environnement sur les conflits coévolutifs entre les hôtes et leurs parasites : manipulation parasitaire et automédication au sein du système moustique-malaria humaine.(2011), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: 0301 basic medicine, medicine.medical_specialty, Cirrhosis, chemistry.chemical_element, Chronic liver disease, Biochemistry, Gastroenterology, Inorganic Chemistry, Mice, 03 medical and health sciences, Hepatolenticular Degeneration, Fibrosis, Internal medicine, medicine, Animals, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Aspartate Aminotransferases, Adenosine Triphosphatases, Mice, Knockout, Alanine, REC, Genetic heterogeneity, business.industry, Wild type, Bilirubin, Histology, [SDV.MHEP.HEG]Life Sciences [q-bio]/Human health and pathology/Hépatology and Gastroenterology, Diagnostic test, medicine.disease, Copper, 3. Good health, Mice, Inbred C57BL, Wilson's disease, Disease Models, Animal, 030104 developmental biology, Exchangeable copper, chemistry, Copper-Transporting ATPases, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Mutation, Molecular Medicine, Atp7b(-/-) mice, business, Biomarkers, [SDV.MHEP]Life Sciences [q-bio]/Human health and pathology
Abstract: International audience; Wilson's disease (WD) is caused by mutations in the ATP7B gene responsible for a toxic copper overload mainly in the liver and the central nervous system. Phenotypic heterogeneity may challenge the diagnostic confirmation. Exchangeable copper (CuEXC) has recently been proposed as a new marker of WD, and its ratio to the total serum copper (Cus), Relative Exchangeable Copper (REC = CuEXC/Cus), as a diagnostic marker. This study aimed to investigate whether this could be confirmed in Atp7b-/- mice, an engineered WD animal model. Atp7b-/- (n = 137) and wild type (WT; n = 101) mice were investigated under the same conditions at 6-8, 20, 39, or 50 weeks of age. Twenty-four Atp7b-/- mice received D-penicillamine treatment from 39 to 50 weeks of age. Serum and liver [histology and intrahepatic copper (IHCu)] data were evaluated. In the WT group, all serum and liver data were normal. Atp7b-/- livers developed a chronic injury from isolated moderate inflammation (6-8 weeks: 16/33 = 48%) to inflammatory fibrosis with cirrhosis (50 weeks: 25/25 = 100% and 16/25 = 64% respectively). Cus and CuEXC increased until week 39, whereas IHCu and REC were stable with increasing age and much higher than in WT mice (mean ± SD: 669 ± 269 vs. 13 ± 3 μg/g dry liver and 39 ± 12 vs. 11 ± 3%, respectively). A threshold value of 20% for REC provided a diagnostic sensitivity and specificity of 100%, regardless of sex, age, or the use of D-penicillamine. Eleven weeks of 100 mg/kg D-penicillamine reduced liver fibrosis (p = 0.001), IHCu (p = 0.026) and CuEXC (p = 0.175). In conclusion, this study confirms REC as a WD diagnostic marker in a mouse model of chronic liver disease caused by copper overload. Further studies are needed to assess the usefulness of CuEXC to monitor the evolution of WD, particularly during treatment.
Published: 2018

39. Development of a rubredoxin-type center embedded in a de novo designed three-helix bundle

Author: Tyler B. J. Pinter, Jean-Marc Latour, Vincent L. Pecoraro, Geneviève Blondin, Alison G. Tebo, Nicolai Lehnert, Ricardo Garcia-Serres, Cédric Tard, Olivier Sénèque, Amy L. Speelman, James E. Penner-Hahn, University of Michigan [Ann Arbor], University of Michigan System, Department of Chemistry and Biophysics, University of Michigan, University of Michigan System-University of Michigan System, 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]), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, Protein Conformation, alpha-Helical, Circular dichroism, Iron, Protein design, 010402 general chemistry, Ferric Compounds, 01 natural sciences, Biochemistry, Article, law.invention, Electron Transport, Electron transfer, Protein structure, law, Rubredoxin, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Electron paramagnetic resonance, Helix bundle, 010405 organic chemistry, Magnetic circular dichroism, Chemistry, Circular Dichroism, Rubredoxins, Electron Spin Resonance Spectroscopy, 0104 chemical sciences, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Crystallography, Oxidation-Reduction
Abstract: Protein design is a powerful tool for interrogating the basic requirements for the function of a metal site in a way that allows for the selective incorporation of elements that are important for function. Rubredoxins are small electron transfer proteins with a reduction potential centered near 0 mV (vs normal hydrogen electrode). All previous attempts to design a rubredoxin site have focused on incorporating the canonical CXXC motifs in addition to reproducing the peptide fold or using flexible loop regions to define the morphology of the site. We have produced a rubredoxin site in an utterly different fold, a three-helix bundle. The spectra of this construct mimic the ultraviolet–visible, Mössbauer, electron paramagnetic resonance, and magnetic circular dichroism spectra of native rubredoxin. Furthermore, the measured reduction potential suggests that this rubredoxin analogue could function similarly. Thus, we have shown that an α-helical scaffold sustains a rubredoxin site that can cycle with the desired potential between the Fe(II) and Fe(III) states and reproduces the spectroscopic characteristics of this electron transport protein without requiring the classic rubredoxin protein fold.
Published: 2018

40. Spectroscopic investigations of a semi-synthetic [FeFe] hydrogenase with propane di-selenol as bridging ligand in the binuclear subsite: comparison to the wild type and propane di-thiol variants

Author: Souvik Roy, Sigrun Rumpel, Vincent Artero, Marc Fontecave, Wolfgang Lubitz, Edward J. Reijerse, Constanze Sommer, Christophe Farès, Max-Planck-Institut für Chemische Energiekonversion (MPI-CEC), Max-Planck-Gesellschaft, 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]), Max-Planck-Institut für Kohlenforschung (Coal Research), Chaire Chimie des processus biologiques, Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Open access funding provided by Max Planck Society, ANR-11-LABX-0011,DYNAMO,Dynamique des membranes transductrices d'énergie : biogénèse et organisation supramoléculaire.(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Collège de France - Chaire Chimie des processus biologiques
Subjects: Hydrogenase, Spin states, Stereochemistry, Iron, [FeFe] Hydrogenase, 010402 general chemistry, Ligands, 01 natural sciences, Biochemistry, Redox, law.invention, Nuclear magnetic resonance, Inorganic Chemistry, F161 Organometallic Chemistry, chemistry.chemical_compound, Propane, law, FTIR spectroelectrochemistry, C720 Biological Chemistry, Moiety, Sulfhydryl Compounds, Chalcogenic substitution, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Electron paramagnetic resonance, Selenium Compounds, Original Paper, 010405 organic chemistry, Spectrum Analysis, Selenol, Bridging ligand, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, chemistry, F100 Chemistry, Amine gas treating
Abstract: [FeFe] Hydrogenases catalyze the reversible conversion of H2 into electrons and protons. Their catalytic site, the H-cluster, contains a generic [4Fe–4S]H cluster coupled to a [2Fe]H subsite [Fe2(ADT)(CO)3(CN)2]2−, ADT = µ(SCH2)2NH. Heterologously expressed [FeFe] hydrogenases (apo-hydrogenase) lack the [2Fe]H unit, but this can be incorporated through artificial maturation with a synthetic precursor [Fe2(ADT)(CO)4(CN)2]2−. Maturation with a [2Fe] complex in which the essential ADT amine moiety has been replaced by CH2 (PDT = propane-dithiolate) results in a low activity enzyme with structural and spectroscopic properties similar to those of the native enzyme, but with simplified redox behavior. Here, we study the effect of sulfur-to-selenium (S-to-Se) substitution in the bridging PDT ligand incorporated in the [FeFe] hydrogenase HydA1 from Chlamydomonas reinhardtii using magnetic resonance (EPR, NMR), FTIR and spectroelectrochemistry. The resulting HydA1-PDSe enzyme shows the same redox behavior as the parent HydA1-PDT. In addition, a state is observed in which extraneous CO is bound to the open coordination site of the [2Fe]H unit. This state was previously observed only in the native enzyme HydA1-ADT and not in HydA1-PDT. The spectroscopic features and redox behavior of HydA1-PDSe, resulting from maturation with [Fe2(PDSe)(CO)4(CN)2]2−, are discussed in terms of spin and charge density shifts and provide interesting insight into the electronic structure of the H-cluster. We also studied the effect of S-to-Se substitution in the [4Fe–4S] subcluster. The reduced form of HydA1 containing only the [4Fe–4Se]H cluster shows a characteristic S = 7/2 spin state which converts back into the S = 1/2 spin state upon maturation with a [2Fe]–PDT/ADT complex. Electronic supplementary material The online version of this article (10.1007/s00775-018-1558-4) contains supplementary material, which is available to authorized users.
Published: 2018

41. Polymer translocation under a pulling force: scaling arguments and threshold forces

Author: Timothée Menais, Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Magnetic tweezers, Polymers, Molecular Conformation, FOS: Physical sciences, Chromosomal translocation, 02 engineering and technology, Molecular Dynamics Simulation, Condensed Matter - Soft Condensed Matter, 01 natural sciences, Molecular physics, [PHYS.PHYS.PHYS-COMP-PH]Physics [physics]/Physics [physics]/Computational Physics [physics.comp-ph], Motion, Nanopores, 0103 physical sciences, Pull force, 010306 general physics, Scaling, Mechanical Phenomena, chemistry.chemical_classification, Physics, Range (particle radiation), Membranes, Artificial, DNA, Polymer, 021001 nanoscience & nanotechnology, Nanopore, chemistry, 13. Climate action, Soft Condensed Matter (cond-mat.soft), Probability distribution, 0210 nano-technology
Abstract: DNA translocation through nanopores is one of the most promising strategies for next-generation sequencing technologies. Most experimental and numerical works have focused on polymer translocation biased by electrophoresis, where a pulling force acts on the polymer within the nanopore. An alternative strategy, however, is emerging, which uses optical or magnetic tweezers. In this case, the pulling force is exerted directly at one end of the polymer, which strongly modifies the translocation process. In this paper, we report numerical simulations of both linear and structured (mimicking DNA) polymer models, simple enough to allow for a statistical treatment of the pore structure effects on the translocation time probability distributions. Based on extremely extended computer simulation data, we (i) propose scaling arguments for an extension of the predicted translocation times $\ensuremath{\tau}\ensuremath{\sim}{N}^{2}{F}^{\ensuremath{-}1}$ over the moderate forces range and (ii) analyze the effect of pore size and polymer structuration on translocation times $\ensuremath{\tau}$.
Published: 2017

42. Selective Catalytic Electroreduction of CO2 at Silicon Nanowires (SiNWs) Photocathodes Using Non-Noble Metal-Based Manganese Carbonyl Bipyridyl Molecular Catalysts in Solution and Grafted onto SiNWs

Author: Mollereau, B., Rzechorzek, N. M., Roussel, B. D., Sedru, M., Brink, D., Bailly-Maitre, B., Palladino, F., Medinas, D. B., Domingos, P. M., Hunot, S., Chandran, S., Birman, S., Baron, T., Vivien, D., Duarte, C. B., Ryoo, H. D., Steller, H., Urano, F., Chevet, E., Kroemer, G., Ciechanover, A., Calabrese, E. J., Kaufman, R. J., Hetz, C, 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), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), ANR-11-LABX-0003-01, Agence Nationale de la Recherche, Institut de Chimie Moléculaire de Grenoble, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Laboratoire de Biologie Moléculaire de la Cellule (LBMC), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Institut de Biologie du Développement de Marseille (IBDM), Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Centre National de la Recherche Scientifique (CNRS), Laboratory of Apoptosis and Cancer Biology, Rockefeller University [New York], Oncogenesis Stress Signaling (OSS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-CRLCC Eugène Marquis (CRLCC), Centre de Recherche des Cordeliers (CRC), Université Pierre et Marie Curie - Paris 6 (UPMC)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), Plateforme de métabolomique, Direction de la recherche [Gustave Roussy], Institut Gustave Roussy (IGR)-Institut Gustave Roussy (IGR), Pôle de biologie, Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpital Européen Georges Pompidou [APHP] (HEGP), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpitaux Universitaires Paris Ouest - Hôpitaux Universitaires Île de France Ouest (HUPO)-Hôpitaux Universitaires Paris Ouest - Hôpitaux Universitaires Île de France Ouest (HUPO), Apoptose, cancer et immunité (Equipe labellisée Ligue contre le cancer - CRC - Inserm U1138), Institut Gustave Roussy (IGR)-Centre de Recherche des Cordeliers (CRC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-École pratique des hautes études (EPHE), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Photocurrent, Materials science, Silicon, 010405 organic chemistry, Inorganic chemistry, chemistry.chemical_element, General Chemistry, Manganese, Glassy carbon, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, 0104 chemical sciences, chemistry, Electrode, [CHIM]Chemical Sciences, Cyclic voltammetry, Silicon nanowires
Abstract: International audience; The electrocatalytic redn. of CO2 to CO in hydroorg. medium has been investigated at illuminated (λ \textgreater 600 nm; 20 mW cm-2) hydrogen-terminated silicon nanowires (SiNWs-H) photocathodes using three Mn-based carbonyl bipyridyl complexes as homogeneous mol. catalysts ([Mn(L) (CO)3(CH3CN)](PF6) and [Mn(bpy) (CO)3Br] with L = bpy = 2,2'-bipyridine and dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Systematic comparison of their cyclic voltammetry characteristics with those obtained at flat hydrogen-terminated silicon and traditional glassy carbon electrodes (GCE) enabled us to demonstrate the superior catalytic efficiency of SiNWs-H in terms of cathodic photocurrent densities and overpotentials. For example, the photocurrent densities measured at -1.0 V vs SCE for [Mn(bpy) (CO)3(CH3CN)](PF6) at SiNWs-H exceeded 1.0 mA cm-2 in CO2-satd. CH3CN + 5% vol./vol. H2O, whereas almost zero current was measured at this potential at GCE. Such characteristics have been supported by the energetic diagrams built for the different SiNWs\textbarMn-based catalyst interfaces. The fill factor FF and energy conversion efficiency η calcd. under catalytic conditions were higher for [Mn(bpy or dmbpy) (CO)3(CH3CN)](PF6) (FF = 0.35 and 0.34; η = 3.0 and 2.0%, resp.). Further preparative-scale electrolysis at SiNWs-H photocathode with Mn-based complex catalysts in electrolytic soln. evidenced the quant. conversion of CO2 to CO with a higher stability of the [Mn(dmbpy) (CO)3(CH3CN)](PF6) complex. Finally, in order to develop technol. viable electrocatalytic devices, the elaboration of SiNWs-H photoelectrodes modified with a Mn-based complex has been successfully achieved from an electropolymerizable catalyst, and it was shown that the electrocatalytic activity of the complex was retained after immobilization.
Published: 2015

43. Tuning Optical Properties of Functionalized Gold Nanorods through Controlled Interactions with Organic Semiconductors

Author: Russell J. Composto, Didier Gasparutto, Guillaume Gines, Robert C. Ferrier, Patrice Rannou, Brigitte Pépin-Donat, University of Pennsylvania, Laboratoire Lésions des Acides Nucléiques (LAN), Service de Chimie Inorganique et Biologique (SCIB - UMR E3), Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electronique Moléculaire Organique et Hybride (LEMOH), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), 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)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), University of Pennsylvania [Philadelphia], Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Photoluminescence, Performance, Wavelength, Au Nanorods, Nanoparticle, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Fluorescence, chemistry.chemical_compound, Rhodamine-B, Monolayer, Rhodamine B, Physical and Theoretical Chemistry, Cetrimonium bromide, Monolayers, [PHYS]Physics [physics], Distance, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Organic semiconductor, Amphiphilic Triblock Copolymers, General Energy, Chemical engineering, chemistry, Nanoparticles, Probes, Nanorod, Absorption (chemistry), 0210 nano-technology
Abstract: International audience; A novel nanohybrid assembly consisting of gold nanorods (AuNRs) and organic semiconductors (OSCs) to tune optical properties is presented. OSCs are bound to specific areas of the AUNRs (e.g., end or side) by controlling the surface Chemistry of the AuNRs. AuNRs anisotropically fiinctionalized with cetrimonium bromide (CTAB) cysteine, poly(ethylene oxide) (PEO), and/or DNA. Rhodamine B (RhB) 5(6)-carboxyfluorescein (CF), or c-yanine3 (Cy3) are incubated with the anisotropically functionalized AuNRs. The resulting optical properties of the dispersed AuNRs are characterized via steady-state UVvis absorption and photoluminescence (PL) Spectroscopies as a function Of OSC concentration. We found that CF and RhB adsorb to the AuNR differently depending on the AuNR surface chemistry, which results in unique optical properties of the assembly. The distinctive spectra were used to dotermine the interaction between the OSC and the AuNIL Finally, we found that attaching Cy3 specifically to the ends of the AuNR via a DNA tether results in a larger emission quenching process than when Cy3 is not attached. This method of nanohybrid assembly can be extended to :other metal nanostructures and OSCs. Its generic nature qualifies it as new methodology to precisely assemble nano- and molecular objects with controlled (opto)electronic properties.
Published: 2015

44. Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

Author: Jean-Marc Latour, Xiaoyan Lu, Takehiro Ohta, Takashi Ogura, Seungwoo Hong, Wonwoo Nam, Ritimukta Sarangi, Pascale Maldivi, Yong Min Lee, Mi Sook Seo, Martin Clémancey, Department of Chemistry and Nano Science, EWHA Womans University (EWHA), Department of Chemistry, Sookmyung Women's University , Seoul 04310, Korea., Picobiology Institute, Graduate School of Life Science, University of Hyogo, 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), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Stanford Synchrotron Radiation Lightsource (SSRL SLAC), SLAC National Accelerator Laboratory (SLAC), Stanford University-Stanford University, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and 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])
Subjects: Stereochemistry, Nitrene, Iron, Electrons, 010402 general chemistry, Ligands, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, Antiferromagnetic coupling, Article, Colloid and Surface Chemistry, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cation radical, 010405 organic chemistry, Ligand, Chemistry, Hydrogen bond, General Chemistry, Nonheme iron, 0104 chemical sciences, Macrocyclic ligand, Imines, Oxidation-Reduction
Abstract: International audience; A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [FeV(NTs)(TAML)]- (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [FeV(NTs)(TAML+•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML+•). 2 is a competent oxidant in C-H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.
Published: 2017

45. Rational design of Fe catalysts for olefin aziridination through DFT-based mechanistic analysis

Author: Patrick Dubourdeaux, Pascale Maldivi, Ludovic Castro, Martin Clémancey, Colette Lebrun, Guillaume Coin, Ranjan Patra, Jean-Marc Latour, Jacques Pécaut, 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), Panjab University [Chandigarh], Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-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 [2016-2019] (UGA [2016-2019]), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and 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])
Subjects: Olefin fiber, 010405 organic chemistry, Chemistry, Nitrene, Rational design, Electronic structure, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Computational chemistry, Mechanism (philosophy), Electron affinity, Amine derivatives
Abstract: International audience; Nitrene transfer reactions are increasingly used to access various kinds of amine derivatives but the underlying mechanisms have not been unraveled in most cases. Fe-catalyzed aziridination of alkenes has appeared as a promising route to aziridines which are important derivatives both per se and as intermediates in many synthetic procedures. We report the strong activity and the mechanism of di-iron catalysts for aziridination of styrenes using phenyltosyliodinane (PhI[double bond, length as m-dash]NTs). In addition, we have developed a similar mono-iron catalyst which operates under the same mechanism albeit with a reduced activity. DFT calculations were performed to investigate the structure and electronic structure of the FeIVNTs species of the latter catalyst. They suggest that the reaction pathway leading to the nitrene transfer to the olefin involves a transient charge transfer on the way to a radical intermediate, which is totally consistent with the experimental results. Moreover, these calculations identify the electron affinity (EA) of the active species as one key parameter allowing rationalization of the observations, which opens the way to improving the catalyst efficiency on a rational basis.
Published: 2017

46. Bioinspired catalytic materials for energy-relevant conversions

Author: Vincent Artero, 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), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and 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])
Subjects: [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Renewable Energy, Sustainability and the Environment, Chemistry, Energy Engineering and Power Technology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Maturity (finance), 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Catalysis, Fuel Technology, 13. Climate action, Biochemical engineering, 0210 nano-technology
Abstract: International audience; The structure of active sites of enzymes involved in bioenergetic processes can inspire design of active, stable and cost-effective catalysts for renewable-energy technologies. For these materials to reach maturity, the benefits of bioinspired systems must be combined with practical technological requirements.
Published: 2017

47. Spectroscopic evidence for cofactor-substrate interaction in the radical-SAM enzyme TYW1

Author: Farhad Forouhar, Serge Gambarelli, Ricardo Garcia-Serres, Jean-Marc Latour, Mohamed G. Atta, Phanélie Perche-Letuvée, Velavan Kathirvelu, Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), 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)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Columbia University [New York], ANR-10-BLAN-0737,INSERAD,Modifications post-transcriptionnelles des ARNs de transfert par insertion radicalaire.(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and 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])
Subjects: 0301 basic medicine, Iron-Sulfur Proteins, Pyrococcus abyssi, S-Adenosylmethionine, Stereochemistry, Carboxy-Lyases, Radical, Archaeal Proteins, Coenzymes, Guanosine, Cofactor, Substrate Specificity, Inorganic Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Spectroscopy, Mossbauer, Pyruvic Acid, Moiety, [CHIM]Chemical Sciences, Substrate Interaction, 030102 biochemistry & molecular biology, biology, Electron Spin Resonance Spectroscopy, Nucleosides, [CHIM.CATA]Chemical Sciences/Catalysis, Protein Structure, Tertiary, chemistry, Docking (molecular), biology.protein, Biocatalysis, Mutagenesis, Site-Directed, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Radical SAM, Wybutosine
Abstract: International audience; TYW1 is a metalloenzyme involved in the modifications of guanosine 37 of Phe-tRNA of Eukaryota and Archaea. It catalyzes the second step of Wybutosine biosynthesis, which consists of the formation of the tricyclic compound imG-14 from m1G using pyruvate and SAM (S-adenosyl-methionine) as co-substrates. Two [4Fe-4S] clusters are needed in the catalytic process. One effects the reductive binding of SAM, which initiates the radical reaction that inserts a C-C moiety into m1G. The other [4Fe-4S] cluster binds the pyruvate molecule that provides the C-C motif. Using a combination of EPR and Mössbauer spectroscopy, we have been able to probe the binding of both cofactors to the FeS clusters. The results highlight an interaction between pyruvate and SAM, indicating that they bind in close vicinity inside the catalytic pocket. They also indicate a chelating binding mode of pyruvate to the accessible Fe site of the corresponding FeS cluster. This binding mode has been used to construct a docking model of holoTYW1 with pyruvate and SAM, which is consistent with the spectroscopic findings.
Published: 2017

48. At the very beginning of life on Earth: the thiol-rich peptide (TRP) world hypothesis

Author: Anne Milet, Ibrahim Shalayel, K. V. Raghavendra Rao, Kieu Dung Ly, Yannick Vallée, Gaël De Paëpe, Katharina Märker, Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Magnetic Resonance (RM ), Modélisation et Exploration des Matériaux (MEM), 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)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), 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 Grenoble Alpes [2016-2019] (UGA [2016-2019]), and Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE )
Subjects: 0301 basic medicine, Embryology, Earth, Planet, Origin of Life, Peptide, Tripeptide, Biology, 03 medical and health sciences, chemistry.chemical_compound, Abiogenesis, Thiolactone, Humans, Sulfhydryl Compounds, Amino Acids, Beginning of Human Life, [SDV.BDD]Life Sciences [q-bio]/Development Biology, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Condensation reaction, Combinatorial chemistry, Peptide Fragments, Amino acid, 030104 developmental biology, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Biochemistry, Nucleic acid, Developmental Biology, Cysteine
Abstract: Life developed on Earth probably about 3.8 billion years ago, on a planet that was already largely covered by oceans and where the atmosphere was very humid. The reactions, which may have led to the formation of the first polymers, particularly to the first peptides and nucleic acids, must have been compatible with these conditions. This is the case of the reaction of nitriles with aminothiols, such as cysteine and homocysteine. Since aminonitriles are the probable precursors of amino acids, this condensation reaction has been able to rapidly yield dipeptides, tripeptides, oligomers and even true polymers, each containing thiol functions. These thiol-rich peptides (TRP's) would then have assumed the various catalytic roles that the peptides containing cysteine residues play today. They allowed a rapid bloom of life in the primitive ocean. In this scenario, RNA's are not the first polymers, but have been synthesized, like DNA's, thanks to the catalytic properties of thiols in a mostly TRP world. In this world, due to its ability to form a thiolactone, homocysteine may have played the leading role in enabling the previously formed oligomers to be stappled together, thus accelerating the formation of long peptide chains.
Published: 2017

49. Design of a synthetic luminescent probe from a biomolecule binding domain: selective detection of AU-rich mRNA sequences

Author: Laurent Raibaut, Geoffrey D. Shimberg, William Vasseur, Sarah L. J. Michel, Olivier Sénèque, Christine Saint-Pierre, Jean-Luc Ravanat, 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), Department of Pharmaceutical Sciences, School of Pharmacy, University of Maryland [Baltimore]-University of Maryland [Baltimore], Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), ANR-12-BS07-0012,LUMZIF,Doigts de zinc luminescents : vers des sondes optiques proche-infrarouge basées sur les lanthanides pour l'imagerie biologique du zinc(2012), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and 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])
Subjects: 0301 basic medicine, Zinc finger, chemistry.chemical_classification, Messenger RNA, Tandem, Chemistry, Biomolecule, [SDV]Life Sciences [q-bio], RNA, Sequence (biology), Nanotechnology, RNA-binding protein, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, 03 medical and health sciences, 030104 developmental biology, Binding domain
Abstract: International audience; We report the design of a luminescent sensor based upon the zinc finger (ZF) protein TIS11d, that allows for the selective time-resolved detection of the UUAUUUAUU sequence of the 3 0-untranslated region of messenger RNA. This sensor is composed of the tandem ZF RNA binding domain of TIS11d functionalized with a luminescent Tb 3+ complex on one of the ZFs and a sensitizing antenna on the other. This work provides the proof of principle that an RNA binding protein can be re-engineered as an RNA sensor and, more generally, that tunable synthetic luminescent probes for biomolecules can be obtained by modifying biomolecule-binding domains.
Published: 2017

50. Referenceless pH Sensor using Organic Electrochemical Transistors

Author: Romain Coppard, George G. Malliaras, Pascal Mailley, Róisín M. Owens, Gaëtan Scheiblin, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), EMSE, Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Materials science, Inorganic chemistry, Alkalinity, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Industrial and Manufacturing Engineering, 0104 chemical sciences, Lactic acid, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], chemistry, Mechanics of Materials, medicine, Ph sensing, General Materials Science, medicine.symptom, 0210 nano-technology, Acidosis
Abstract: pH is an extremely important parameter in all biological and most chemical reactions. pH sensing has been speciﬁcally shown to be of paramount importance in many ﬁelds such as environmental science, sport, or healthcare as the acidosis or alkalinity of a solution is a marker of a physiological state. Indeed, pH variation can be indicative of lactate production during infection.[1] Besides, during intensive training, the con-centration of lactic acid in sweat increases,[2] decreasing by this way the pH of the sweat. The normal body pH value is different for each subject, which is why, in most cases, we want to detect variations of pH rather than its absolute value.
Published: 2017

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