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1. A Bioinspired NiII Superoxide Dismutase Catalyst Designed on an ATCUN-like Binding Motif

Author

Olivier Proux, Pawel Guinard, Pascale Maldivi, Magali Douillard, Jacques Pécaut, Carole Duboc, Alan Le Goff, Jérémy Domergue, Colette Lebrun, Pascale Delangle, 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 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 - Chimie Inorganique Redox (DCM - CIRE ), Département de Chimie Moléculaire (DCM), 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), European Synchroton Radiation Facility [Grenoble] (ESRF), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Météo-France, Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE ), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)

Subjects
biology, 010405 organic chemistry, Chemistry, Active site, Protonation, [CHIM.CATA]Chemical Sciences/Catalysis, Inner sphere electron transfer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, Crystallography, Catalytic cycle, law, biology.protein, Outer sphere electron transfer, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reactivity (chemistry), Enzyme kinetics, Physical and Theoretical Chemistry, Electron paramagnetic resonance
Abstract

Nickel superoxide dismutase (NiSOD) is an enzyme that protects cells against O2·-. While the structure of its active site is known, the mechanism of the catalytic cycle is still not elucidated. Its active site displays a square planar NiII center with two thiolates, the terminal amine and an amidate. We report here a bioinspired NiII complex built on an ATCUN-like binding motif modulated with one cysteine, which demonstrates catalytic SOD activity in water (kcat = 8.4(2) × 105 M-1 s-1 at pH = 8.1). Its reactivity with O2·- was also studied in acetonitrile allowing trapping two different short-lived species that were characterized by electron paramagnetic resonance or spectroelectrochemistry and a combination of density functional theory (DFT) and time-dependent DFT calculations. Based on these observations, we propose that O2·- interacts first with the complex outer sphere through a H-bond with the peptide scaffold in a [NiIIO2·-] species. This first species could then evolve into a NiIII hydroperoxo inner sphere species through a reaction driven by protonation that is thermodynamically highly favored according to DFT calculations.

Published
2021
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2. Impact of ionomer structuration on the performance of bio-inspired noble-metal-free fuel cell anodes

Author

Vincent Artero, Fabrice Valentino, Tristan Asset, Tran Ngoc Huan, Nathan Coutard, Bruno Jousselme, Sandrine Lyonnard, Bertrand Reuillard, Pascale Chenevier, Reuben T. Jane, Eugen S. Andreiadis, Solène Gentil, Alan Le Goff, Adina Morozan, Frédéric Maillard, 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), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Electrochimie Interfaciale et Procédés (EIP), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), 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), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), European Project, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Materials science, Nanotechnology, 02 engineering and technology, Carbon nanotube, engineering.material, 010402 general chemistry, 7. Clean energy, 01 natural sciences, law.invention, Catalysis, chemistry.chemical_compound, law, Nafion, Ionomer, General Environmental Science, Nanocomposite, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Chronoamperometry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Anode, chemistry, engineering, General Earth and Planetary Sciences, Noble metal, 0210 nano-technology
Abstract

https://www.sciencedirect.com/science/article/pii/S2667109321000014?via%3Dihub; International audience; Molecular-engineered bio-inspired catalysts hold promise for the next generation of proton-exchange membrane fuel cells (PEMFCs). Yet, their implementation in catalytic layers with Nafion ionomer faces nanocomposite formulation issues. Here, we use various DuBois nickel catalysts immobilized on carbon nanotubes to exemplify how self-assembly at the mesoscale affects H2 oxidation anode performance. We exploited the reversible activity of these catalysts together with potential-step chronoamperometry to locally produce H2 and probe mass transport within the catalyticlayer. Small-angle neutron scattering studies serve to build a model describing how the surface functionalization drives the structuration of the ionomer and affects the diffusion of protons and gas from and to catalytic centers. This study thus demonstrates that implementation of unconventional catalysts in catalytic layers requires the redesign of the whole system of materials. On the basis of such information, catalytic layer formulation was optimized,allowing order-of-magnitude performance enhancement of noble-metal-free PEMFCs

Published
2021
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3. Carbon-nanotube-supported POXA1b laccase and its hydrophobin chimera for oxygen reduction and picomolar phenol biosensing

Author

Alessandra Piscitelli, Ilaria Stanzione, Alan Le Goff, Ilaria Sorrentino, Paola Giardina, Sorrentino, Ilaria, Stanzione, Ilaria, Piscitelli, Alessandra, Giardina, Paola, Goff, Alan Le, Département de Chimie Moléculaire (DCM), and Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanotube, Hydrophobin, Dopamine, [SDV]Life Sciences [q-bio], Biomedical Engineering, Biophysics, Carbon nanotubes, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Anthraquinone, Hydrophobic effect, chemistry.chemical_compound, [CHIM]Chemical Sciences, Laccase, Catechol, Chemistry, Biosensing, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, 0210 nano-technology, Biosensor, TP248.13-248.65, Biotechnology
Abstract

International audience; The immobilization of POXA1b laccase and its hydrophobin-fused chimera was performed at pristine Multiwalled Carbon Nanotube (MWCNT) and MWCNT-modified electrodes by electrografting of a 2-diazoniumanthraquinone salt. The influence of the hydrophobin domain and the MWCNT functionalization with anthraquinone groups towards immobilization of laccase was compared by direct electrochemistry under O 2 and electrochemical biosensing of phenols. The hydrophobin domain affords the stable dispersion of MWCNT in water/ ethanol, while being detrimental to the direct electron transfer between POXA1b and the electrode. On the contrary, the stronger hydrophobic interactions between anthraquinone and laccase affords direct electrochemistry of POXA1b and enabled the design of a highly sensitive phenol biosensor, reaching a limit-of-detection (LOD) of 2 pM and sensitivity of 23,600 mA L mmol − 1 cm − 2 for catechol, and a LOD of 15 nM and sensitivity of 0.053 mA L mmol − 1 cm − 2 for dopamine.

Published
2021
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4. Insights into carbon nanotube-assisted electro-oxidation of polycyclic aromatic hydrocarbons for mediated bioelectrocatalysis

Author

Alan Le Goff, Emerson M. Girotto, Pierre Yves Blanchard, Yuta Nishina, Serge Cosnier, Michael Holzinger, Paulo Henrique M. Buzzetti, Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), State University of Maringá, Research Core for Interdisciplinary Sciences [Okayama] (RCIS), Okayama University, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA ), and 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)

Subjects
genetic structures, Glucose Dehydrogenases, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, law.invention, Fungal Proteins, chemistry.chemical_compound, Electron transfer, Glucose dehydrogenase, law, Materials Chemistry, Polycyclic Aromatic Hydrocarbons, ComputingMilieux_MISCELLANEOUS, health care economics and organizations, Naphthalene, Nanotubes, Carbon, Metals and Alloys, Quinones, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Electrochemical Techniques, Phenanthrene, 021001 nanoscience & nanotechnology, eye diseases, Coronene, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Aspergillus, Glucose, chemistry, Ceramics and Composites, Biocatalysis, Flavin-Adenine Dinucleotide, Pyrene, sense organs, 0210 nano-technology, Oxidation-Reduction, Perylene
Abstract

A series of polycyclic aromatics, naphthalene, phenanthrene, perylene, pyrene, 1-pyrenebutyric acid N-hydroxysuccinimide ester (pyrene NHS) and coronene, were immobilized via π stacking on carbon nanotube (CNT) electrodes and electro-oxidized in aqueous solutions. The obtained quinones were characterized and evaluated for the mediated electron transfer with FAD dependent glucose dehydrogenase during catalytic glucose oxidation.

Published
2021
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5. Electrosynthesis of Pyrenediones on Carbon Nanotube Electrodes for Efficient Electron Transfer with FAD‐dependent Glucose Dehydrogenase in Biofuel Cell Anodes

Author

Emerson M. Girotto, Michael Holzinger, Yuta Nishina, Yannig Nedellec, Bridget Davies, Pierre Yves Blanchard, Paulo Henrique M. Buzzetti, Alan Le Goff, Andrew J. Gross, Serge Cosnier, 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]), Universidade Estadual de Maringá [Maringá] (UEM), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), 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]), and Okayama University

Subjects
Chemistry, Cell, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrosynthesis, 7. Clean energy, 01 natural sciences, Catalysis, 0104 chemical sciences, law.invention, Anode, Electron transfer, medicine.anatomical_structure, Chemical engineering, law, Biofuel, Glucose dehydrogenase, Electrode, Electrochemistry, medicine, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract

International audience; A particularly efficient redox mediator for electron transfer between FAD‐dependent glucose dehydrogenase (FAD‐GDH) and carbon nanotube (CNT) based electrodes can be obtained via electrosynthetic oxidation of pyrene in aqueous buffer solution. 1H‐NMR spectroscopic studies reveal the formation of a 2 : 1 mixture of 1,6‐pyrenedione and 1,8‐pyrenedione at the electrode. The formed pyrenedione exhibits a well‐defined surface‐bound redox system at −0.1 V vs. SCE and provides excellent electron transfer kinetics with this enzyme. Furthermore, the π‐system of pyrenedione allows improved stacking behavior with the CNT walls, leading to enhanced stabilities compared to commonly used mediators like naphthoquinone. The electrosynthesis of pyrenedione for catalytic glucose oxidation is optimal at pH 2 using cyclic voltammetry or chronoamerometry. It is envisioned that the electrosynthetic methodology can be expanded to form different redox mediators for a series of enzymes.

Published
2019
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6. Mononuclear Ni(II) Complexes with a S3O Coordination Sphere Based on a Tripodal Cysteine-Rich Ligand: pH Tuning of the Superoxide Dismutase Activity

Author

Christelle Gateau, Pascale Maldivi, Pascale Delangle, Olivier Proux, Jérémy Domergue, Alan Le Goff, Jacques Pécaut, Carole Duboc, Colette Lebrun, Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-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 (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie Moléculaire de Grenoble (ICMG)-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), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), 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 - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), 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)), 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 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), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)

Subjects
Coordination sphere, Stereochemistry, Superoxide dismutase activity, Ligands, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Superoxide dismutase, Biomimetic Materials, Coordination Complexes, Nickel, [CHIM]Chemical Sciences, Cysteine, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Sulfur Compounds, biology, Superoxide Dismutase, 010405 organic chemistry, Ligand, Chemistry, Hydrogen-Ion Concentration, 3. Good health, 0104 chemical sciences, biology.protein, Oxidation-Reduction
Abstract

The superoxide dismutase (SOD) activity of mononuclear NiII complexes, whose structures are inspired by the NiSOD, has been investigated. They have been designed with a sulfur-rich pseudopeptide li...

Published
2019
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7. 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
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8. Clicked Bifunctional Dendrimeric and Cyclopeptidic Addressable Redox Scaffolds for the Functionalization of Carbon Nanotubes with Redox Molecules and Enzymes

Author

Solène Gentil, Carlo Pifferi, Alan Le Goff, Pierre Rousselot-Pailley, Thierry Tron, Olivier Renaudet, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), 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), 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-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Centre National de la Recherche Scientifique (CNRS)-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)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), and Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanotube, 02 engineering and technology, Surfaces and Interfaces, Carbon nanotube, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Combinatorial chemistry, Redox, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, Ferrocene, law, Dendrimer, Electrochemistry, Click chemistry, Surface modification, General Materials Science, 0210 nano-technology, Bifunctional, Spectroscopy
Abstract

International audience; Carbon nanotube electrodes were modified with ferrocene and laccase using two different click reactions strategies and taking advantage of bifunctional dendrimers and cyclopeptides. Using diazonium functionalization and the efficiency of oxime ligation, the combination of both multiwalled carbon nanotube surfaces and modified dendrimers or cyclopeptides allows the access to a high surface coverage of ferrocene in the order of 50 nmol cm(-2), a 50-fold increase compared to a classic click reaction without oxime ligation of these highly branched macromolecules. Furthermore, this original immobilization strategy allows the immobilization of mono- and bi-functionalized active multicopper enzymes, laccases, via copper(I)-catalyzed azide-allcyne cycloaddition. Electrochemical studies underline the high efficiency of the oxime-ligated dendrimers or cyclopeptides for the immobilization of redox entities on surfaces while being detrimental to electron tunneling with enzyme active sites despite controlled orientation.

Published
2021
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9. An introgression breakthrough left by an anthropogenic contact between two ascidians

Author

Nicolas Bierne, Frédérique Viard, Alan Le Moan, Charlotte Roby, Claire Daguin-Thiébaut, Christelle Fraïsse, Adaptation et diversité en milieu marin (AD2M), Station biologique de Roscoff (SBR), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Tjarno Marine Biological Laboratory, Évolution, Écologie et Paléontologie (Evo-Eco-Paleo) - UMR 8198 (Evo-Eco-Paléo), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences de l'Evolution de Montpellier (UMR ISEM), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Montpellier (UM)-Institut de recherche pour le développement [IRD] : UR226-Centre National de la Recherche Scientifique (CNRS), Adaptation et diversité en milieu marin (ADMM), Institut national des sciences de l'Univers (INSU - CNRS)-Station biologique de Roscoff (SBR), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Évolution, Écologie et Paléontologie (Evo-Eco-Paleo) - UMR 8198 (Evo-Eco-Paléo (EEP)), and Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-École Pratique des Hautes Études (EPHE)

Subjects
0106 biological sciences, anthropogenic hybridization, population genomics, media_common.quotation_subject, tunicates, [SDE.MCG]Environmental Sciences/Global Changes, Allopatric speciation, Introgression, 010603 evolutionary biology, 01 natural sciences, Population genomics, 03 medical and health sciences, introgression hotspots, Genetics, Animals, Humans, Ciona intestinalis, non-indigenous species, Ecology, Evolution, Behavior and Systematics, 030304 developmental biology, media_common, 0303 health sciences, Genome, [SDV.GEN.GPO]Life Sciences [q-bio]/Genetics/Populations and Evolution [q-bio.PE], biology, [SDV.BID.EVO]Life Sciences [q-bio]/Biodiversity/Populations and Evolution [q-bio.PE], Genomics, biology.organism_classification, Biological Evolution, Ciona, Speciation, Taxon, Evolutionary biology, Genetic structure, Hybridization, Genetic, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Biological introductions
Abstract

This zenodo archive contains the vcf files and the R scripts used for thestatistical analyses of the paper "An introgression breakthrough left by an anthropogenic contact between two ascidians" published in Molecular Ecology in 2021. The fastq files processed by the stacks reference pipeline to produce the vcf files in this archive are available on NCBI under the bioproject "PRJNA759193". The analyses of the paper available here are divided in three parts: Analyses of the fine-scale population structure of Ciona intestinalis across the English Channel, the Iroise Sea, and the Bay of biscay Genotype file: Ciona_data1_finescale.vcf.gz Genotype file pruned for physical linkage: Ciona_dataset1_fine_scale_maf_thin.vcf R script file for pop. structure : Finescale_structure_dataset1.R Analyses of the large-scale population structure of C. instestinalis, C. robusta and C. roulei across the Atlantic and the Mediteranean sea Genotype file: Ciona_data2_Largescale.vcf.gz Genotype file pruned for physical linkage: Ciona_dataset2_largescale_maf_thin.vcf R script file for pop. structure : Largescale_structure_dataset2.R Linux + R script file for phylogeny: Phylogeny.R Analyse of introgression from C. robusta into C. intestinalis background: Genotype file: Ciona_data2_Largescale.vcf.gz Ancestry informative genotype: Ciona_diagnistic_SNPs_order.vcf R script for admixture across all chromosome: Ancestry_chromosome.R R script for HMM to detect introgression breakthrough from ancestry informative SNPs: HMM_log10FST+1_3norm_introgression_hotspot.R* *this script is a modified version of the script by Marques et al. (2016) available here: https://github.com/marqueda/HMM-detection-of-genomic-islands

Published
2021
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10. Photoelectrochemically-assisted biofuel cell constructed by redox complex and g-C3N4 coated MWCNT bioanode

Author

Michael Holzinger, Alan Le Goff, Karine Gorgy, Bekir Çakıroğlu, Jérôme Chauvin, Mahmut Özacar, Sakarya University, Biomedical, Magnetic and Semiconductor Materials Research Center (BIMAS-RC), 54187 Sakarya, Turkey, Département de Chimie Moléculaire (DCM), and Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Immobilized enzyme, Biomedical Engineering, Biophysics, 02 engineering and technology, Photochemistry, 7. Clean energy, 01 natural sciences, Redox, law.invention, Electron transfer, law, Glucose dehydrogenase, Electrochemistry, ComputingMilieux_MISCELLANEOUS, Photocurrent, Open-circuit voltage, Chemistry, 010401 analytical chemistry, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, Anode, 0210 nano-technology, Biotechnology
Abstract

Herein, we report a membraneless glucose and air photoelectrochemical biofuel cell (PBFC) with a visible light assisted photobioanode. Flavin adenine dinucleotide dependent glucose dehydrogenase (FADGDH) was immobilized on the combined photobioanode for the visible light assisted glucose oxidation (GCE|MWCNT|g-C3N4|Ru-complex|FADGDH) with a quinone mediated electron transfer. Bilirubine oxidase (BOx) immobilized on MWCNT coated GCE (GCE|BOx) was used as the cathode with direct electron transfer (DET). An improvement of biocatalytic oxidation current was observed by 6.2% due in part to the light-driven electron-transfer. The large oxidation currents are probably owing to the good contacting of the immobilized enzymes with the electrode material and the utilization of light assisted process. Under the visible light, the photobioanode shows an anodic photocurrent of 1.95 μA cm2 at attractively low potentials viz. −0.4 vs Ag/AgCl. The lower-lying conduction band of g-C3N4 as compared to Ru-complexes decreases the rate of hole and electron recombination and enhances the charge transportation. The bioanode shows maximum current density for glucose oxidation up to 6.78 μA cm−2 at 0.2 V vs Ag/AgCl at pH:7. The performance of three promising Ru-complexes differing in chemical and redox properties were compared as electron mediators for FADGDH. Upon illumination, the PBFC delivered a maximum power density of 28.5 ± 0.10 μW cm−2 at a cell voltage of +0.4 V with an open circuit voltage of 0.64 V.

Published
2020
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11. Complexes of the Bis(di-tert-butyl-aniline)amine Pincer Ligand: The Case of Copper

Author

Christian Philouze, Florian Molton, Solène Gentil, Nicolas Leconte, Fabrice Thomas, Alan Le Goff, 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), 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), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA ), 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 (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)-Université Grenoble Alpes (UGA), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)

Subjects
Iminosemiquinones, Electronic structure, Coordination sphere, Spin states, 010405 organic chemistry, Ligand, chemistry.chemical_element, Disproportionation, Radicals, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Copper, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, Deprotonation, chemistry, law, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron paramagnetic resonance, Pincer ligand, Phenylenediamine
Abstract

International audience; TheN,N-bis(2-amino-3,5-di-tert-butylphenyl)amine pincer ligand was coordinated to copper. Depending on the copper source, a mononuclear complex1(+)or a trimer2could be isolated and were structurally characterized. Complex1(+)consists of two deprotonated iminobenzoquinone ligands coordinated to a Cu(I) center. Complex2is trinuclear with a (3:3) (M:L) stoichiometry, featuring a three-fold repetition of a unit made of a Cu(II) center coordinated to a tridentate ligand radical-dianion. In2, the metal ions are bridged by an anilido nitrogen. The coordination sphere of each copper is completed to four by a neighboring iminosemiquinone moiety. Complex1(+)belongs to an electron-transfer series. The paramagnetic complexes1and1(2+)were generated and characterized by EPR and Vis-NIR spectroscopy. Complex1exhibits an isotropic resonance at g = 2.00, which is reminiscent of Cu(I) iminosemiquinone species. The dication1(2+)exhibits a metal-based ground spin state and hence is described as a Cu(II) iminobenzoquinone complex. Both1and1(+)show a NIR band (954, 980 nm) of high intensity (> 20 mm(-1) cm(-1)) assigned to ligand-based charge transfer transitions. Two-electron reduction of1produces2via ligand release and disproportionation. Conversely, oxidation of2affords1(+). Finally, carbon-nanotube-supported complex2is active towards electrocatalytic reduction of H2O2.

Published
2020
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12. Carbon nanotube-based flexible biocathode for enzymatic biofuel cells by spray coating

Author

Didier Chaussy, Ahlem Romdhane, Noémie Lalaoui, Nadège Reverdy-Bruas, Serge Cosnier, Naceur Belgacem, Alan Le Goff, Michael Holzinger, Awatef Ben Tahar, Systèmes Nanobiotechnologiques et Biomimétiques (TIMC-IMAG-SyNaBi), Techniques de l'Ingénierie Médicale et de la Complexité - Informatique, Mathématiques et Applications, Grenoble - UMR 5525 (TIMC-IMAG), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire Génie des procédés papetiers (LGP2 ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-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]), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), and 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])

Subjects
Materials science, Carbon nanotubes, Energy Engineering and Power Technology, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, law.invention, Immobilization, law, Conductive ink, [CHIM]Chemical Sciences, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Laccase, Renewable Energy, Sustainability and the Environment, Biofuel cell, Dispersion, 021001 nanoscience & nanotechnology, Enzymes, 0104 chemical sciences, Chemical engineering, Electrode, Spray coating, 0210 nano-technology, Dispersion (chemistry), Current density, Layer (electronics)
Abstract

International audience; Enzymatic biofuel cells are emerging technologies which gain a lot of interest as a power source for implantable devices. Effective enzyme wiring and simplification of the cell architecture are the main limitations of the fuel cell development nowadays. In the present study, spray coating was used as a reliable process to produce flexible biocathodes. That was achieved through spray coating of a conductive ink formulated by surfactant assisted carbon nanotubes dispersion. A thin continuous layer of carbon nanotubes (CNTs) was successfully coated on top of a gas diffusion layer paper. The film thickness was modulated by varying the CNT load in the ink and the number of deposited layers. It varied between 1 and 7.8 μm for a number of deposited layers between 5 and 100. Laccase enzyme was then wired to printed CNT electrodes thanks to the host-guest interaction between the hydrophobic pocket of laccase and pyrene-adamantane. Electrochemical investigations showed that laccase was effectively wired to the CNTs and presented a favorable orientation toward oxygen reduction. The biocathode current density was dependent of the number of deposited CNT layers and reached an optimum at 170 μA cm−2 for 50 deposited layers.

Published
2018
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13. Towards eco-friendly power sources: In series connected glucose biofuel cells power a disposable ovulation test

Author

Caroline Abreu, Yannig Nedellec, Alan Le Goff, Serge Cosnier, Olivier Ondel, Michael Holzinger, François Buret, 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 (DCM), 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), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), 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]), Région Auvergne-Rhône-AlpesPlate-forme Chimie NanoBio http://icmg.ujf-grenoble.fr/ICMG-SITE/ICMG/index.php?page=ICMG-SITE/IC, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)

Subjects
Battery (electricity), Materials science, Ovulation test, [SDV]Life Sciences [q-bio], Disposable device, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, In series connected stack, Automotive engineering, Stack (abstract data type), Materials Chemistry, Electrical and Electronic Engineering, Eco-Friendly power source, Instrumentation, [SDE.IE]Environmental Sciences/Environmental Engineering, Open-circuit voltage, [SPI.NRJ]Engineering Sciences [physics]/Electric power, Metals and Alloys, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Environmentally friendly, Enzymatic glucose biofuel cells, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Power (physics), Biofuel, 0210 nano-technology, Voltage drop, Biofuel Cells
Abstract

International audience; A disposable ovulation test is operated using a flow stack of 5 in series connected glucose biofuel cells giving an open circuit voltage (OCV) of 3.5 V. Such tests consume at total around 60 μWh of energy and in average 1.7 mW of power during one run of around 12 min which are supplied by a CR1220 3 V lithium button battery in the commercialized device. We replaced this battery by the glucose biofuel cell stack and observed during the measurements and display steps peak currents up to 1.4 mA inducing a voltage drop down to 2.8 V during few seconds (4 mW of power consumption). Even such power peaks are supported by the presented biofuel cell stack assuring the necessary operational cell voltage and current. After the measurements towards Luteinizing Hormone (LH) detection the display remains turned on for 8 min and consumes just 2 μW which allows to reestablish the initial OCV and to run a further test. The presented results demonstrate as proof of concept the suitability of eco-friendly enzymatic glucose biofuel cells as alternative power source for disposable devices.

Published
2018
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14. 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
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15. Correction to: Evolution at two time frames: ancient structural variants involved in post-glacial divergence of the European plaice (Pleuronectes platessa)

Author

Alan Le Moan, Dorte Bekkevold, and Jakob Hemmer-Hansen

Subjects
0106 biological sciences, 0301 basic medicine, Population, Flounder, Polymorphism, Single Nucleotide, 010603 evolutionary biology, 01 natural sciences, Haplogroup, Divergence, European plaice, 03 medical and health sciences, Flatfish, Genetic variation, Genetics, Animals, education, Alleles, Phylogeny, Genetics (clinical), Pleuronectes, education.field_of_study, biology, Phylogenetic tree, Correction, Genetic Variation, biology.organism_classification, humanities, 030104 developmental biology, Evolutionary biology
Abstract

Changing environmental conditions can lead to population diversification through differential selection on standing genetic variation. Structural variant (SV) polymorphisms provide examples of ancient alleles that in time become associated with novel environmental gradients. The European plaice (Pleuronectes platessa) is a marine flatfish showing large allele-frequency differences at two putative SVs associated with environmental variation. In this study, we explored the contribution of these SVs to population structure across the North East Atlantic. We compared genome-wide population structure using sets of RAD-sequencing SNPs with the spatial structure of the SVs. We found that in contrast to the rest of the genome, the SVs were only weakly associated with an isolation-by-distance pattern. Indeed, both SVs showed important variation in haplogroup frequencies, with the same haplogroup increasing both along the salinity gradient of the Baltic Sea, and found in high frequency in the northern-range margin of the Atlantic. Phylogenetic analyses suggested that the SV alleles are much older than the age of the Baltic Sea itself. These results suggest that the SVs are older than the age of the environmental gradients with which they currently co-vary. Altogether, our results suggest that the plaice SVs were shaped by evolutionary processes occurring at two time frames, firstly following their origin, ancient spread and maintenance in the ancestral populations, and secondly related to their current association with more recently formed environmental gradients such as those found in the North Sea-Baltic Sea transition zone.

Published
2021
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16. Molecular engineering of the bio/nano-interface for enzymatic electrocatalysis in fuel cells

Author

Michael Holzinger and Alan Le Goff

Subjects
Renewable Energy, Sustainability and the Environment, Chemistry, Process (engineering), Bioconversion, Energy Engineering and Power Technology, Nanotechnology, Context (language use), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrocatalyst, 01 natural sciences, 0104 chemical sciences, Catalysis, Molecular engineering, Chemical energy, Fuel Technology, Catalytic oxidation, 0210 nano-technology
Abstract

The fascinating topic of converting chemical energy into electric power using biological catalysts, called enzymes, and sustainable fuels motivates a large community of scientists to develop enzymatic fuel cells. Enzymes provide the advantage of catalytic oxidation and reduction processes under ecologically friendly conditions and even in complex media due to their unique specificity. However, this specificity represents a constant challenge since every enzyme has its own distinguished structure and catalytic behaviour. In this context, great efforts have been invested to understand the operational modes of promising enzymes for the bioconversion of energy. The aim is to provide chemical functions and functionalities to enable or to facilitate an electron transfer between the enzymes and the electrode material to reach the maximum efficiency of the electrocatalytic process. Original and high performance examples are summarized here in a non-exhaustive manner focusing on the wiring strategy for a series of enzymes described in the literature.

Published
2018
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17. A High Power Buckypaper Biofuel Cell: Exploiting 1,10-Phenanthroline-5,6-dione with FAD-Dependent Dehydrogenase for Catalytically-Powerful Glucose Oxidation

Author

Xiaohong Chen, Fabien Giroud, Caroline Abreu, Serge Cosnier, Andrew J. Gross, Alan Le Goff, Michael Holzinger, 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]), Biosystèmes Electrochimiques et Analytiques, 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), 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), and 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)

Subjects
Nanotube, bioelectrocatalysis, Dehydrogenase, Buckypaper, Nanotechnology, multicopper oxidases, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Redox, Catalysis, Glucose dehydrogenase, [CHIM]Chemical Sciences, Power density, Chemistry, General Chemistry, electrode, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, FADGDH, Electrode, biocatalyst paper, enzymatic, 0210 nano-technology
Abstract

International audience; Enzymatic biofuel cells generate electrical energy from renewable sources with high selectivity and environmental benefits compared to lithium batteries and traditional fuel cells. For enzymatic fuel cells to become competitive, major improvements in electrode design are required to enhance power density, voltage output, and stability. Here we have developed a freestanding paper biofuel cell comprising redox molecule embedded multiwalled carbon nanotube papers for electrical wiring of enzymes. The drop-coat and one-pot fabrication methods provide flexibility and permit easy scalability of functionalized bioelectrodes via commercially available materials. Buckypaper functionalized with 1,10-phenanthroline-5,6-dione (PLQ) as an efficient electron mediator for fungal-derived FAD-dependent glucose dehydrogenase (FADGDH) shows very high steady-state current densities for glucose oxidation of Imax = 5.38 ± 0.54 mA cm–2 at 0.15 V vs SCE at neutral pH. When coupled with a bioinspired protoporphyrin IX buckypaper cathode, the resulting glucose/O2 fuel cell delivered a power density of 0.65 ± 0.10 mW cm–2 or 24.1 ± 4.7 mW cm–3 at a cell voltage of 0.5 V, limited by the cathode. Galvanostatic and current discharge experiments confirm robust short-term operational performance.

Published
2017
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18. A Darwinian Laboratory of Multiple Contact Zones

Author

Samuel Perini, Kerstin Johannesson, Alan Le Moan, and Carl André

Subjects
Gene Flow, 0106 biological sciences, 0301 basic medicine, Genetic Speciation, Reproductive isolation, Biology, 010603 evolutionary biology, 01 natural sciences, Gene flow, Genetic divergence, 03 medical and health sciences, Genetics, Population, 030104 developmental biology, Variation (linguistics), Evolutionary biology, Genetic variation, Genetic algorithm, Hybridization, Genetic, Biological dispersal, SDG 14 - Life Below Water, Laboratories, Ecology, Evolution, Behavior and Systematics, Selection (genetic algorithm)
Abstract

Barriers to gene flow between divergent populations result in contact (hybrid) zones. Locations where multiple contact zones overlap can be used in comparative studies asking: what mechanisms maintain barriers; what is the origin of the genetic variation involved; and do differences in life history affect the nature of barriers? In a review of 23 marine species' genetic divergence over a postglacial salinity gradient, many showed steep genetic clines supported by divergent selection and/or temporal or spatial segregation. Contacts were primary or secondary and shaped by ancestral variation sometimes involving inversions. The dispersal potential of species seemed less important in shaping clines. Studies of multispecies contact zones will increase our understanding of speciation, but we need to address the taxonomic bias and focus more on postzygotic isolation.

Published
2020
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19. Weak genetic structure despite strong genomic signal in lesser sandeel in the North Sea

Author

Asbjørn Christensen, Jakob Hemmer-Hansen, Belén Jiménez-Mena, Alan Le Moan, Henrik Mosegaard, Dorte Bekkevold, and Mikael van Deurs

Subjects
0106 biological sciences, 0301 basic medicine, Population genetics, Population, Stock management, lcsh:Evolution, 010603 evolutionary biology, 01 natural sciences, Structural variation, 03 medical and health sciences, Food chain, lesser sandeel, Fisheries management, lcsh:QH359-425, Genetics, genetic structure, SDG 14 - Life Below Water, education, Ecology, Evolution, Behavior and Systematics, education.field_of_study, biology, Ammodytes, structural variation, population genetics, Reproductive isolation, Original Articles, biology.organism_classification, 030104 developmental biology, fisheries management, Evolutionary biology, Genetic structure, Biological dispersal, Original Article, Lesser sandeel, General Agricultural and Biological Sciences, Ammodytes marinus, stock management
Abstract

Sandeels are an ecologically important group of fishes; they are a key part of the food chain serving as food for marine mammals, seabirds and fish. Sandeels are further targeted by a large industrial fishery, which has led to concern about ecosystem effects. In the North Sea, the lesser sandeel Ammodytes marinus is by far the most prevalent species of sandeel in the fishery. Management of sandeel in the North Sea plus the Kattegat is currently divided into seven geographical areas, based on subtle differences in demography, population dynamics and results from simulations of larval dispersal. However, little is known about the underlying genetic population structure. In this study, we used 2,522 SNPs derived from restriction site‐associated DNA sequencing (RADseq) typed in 429 fish representing four main sandeel management areas. Our main results showed (a) a lack of a clear spatially defined genetic structure across the majority of genetic markers and (b) the existence of a group of at least 13 SNPs under strong linkage disequilibrium which together separate North Sea sandeel into three haplotype clusters, suggestive of one or more structural variants in the genome. Analyses of the spatial distribution of these putative structural variants suggest at least partial reproductive isolation of sandeel in the western management area along the Scottish coast, supporting a separate management. Our results highlight the importance of the application of a large number of markers to be able to detect weak patterns of differentiation. This study contributes to increasing the genetic knowledge of this important exploited species, and results can be used to improve our understanding of population dynamics and stock structure.

Published
2020
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20. A Nanotube-Supported Dicopper Complex Enhances Pt-free Molecular H-2/Air Fuel Cells

Author

Catherine Belle, Arnab Dutta, Wendy J. Shaw, Vincent Artero, Serge Cosnier, Jennifer K. Molloy, Ahmad Hobballah, Alan Le Goff, Solène Gentil, Gisèle Gellon, Marie Carrière, Fabrice Thomas, 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]), 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]), Pacific Northwest National Laboratory (PNNL), IIT, Chem Dept, 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), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)

Subjects
Nanotube, Materials science, Hydrogen, chemistry.chemical_element, 02 engineering and technology, Electrolyte, Carbon nanotube, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Redox, law.invention, fuel cell, law, bioinspired catalyst, [CHIM]Chemical Sciences, carbon nanotubes, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, Anode, oxygen reduction, Nickel, General Energy, Chemical engineering, chemistry, copper, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

International audience; A dinuclear copper complex mimicking the active site of copper oxidase was designed and p-stacked on a carbon nanotube (CNT) electrode thanks to pendent pyrene groups. The high oxygen reduction reaction activity of such CNT-supported dicopper complexes in pH 4 electrolyte allowed the construction of a Pt-free hydrogen/air fuel cell using bioinspired nickel bis-diphosphine complexes immobilized onto CNT at the anode, with an order-of-magnitude improvement of the performance compared to previous literature data. This bioinspired nickel- and copper-based H-2/air fuel cell reaches a maximum power density of 0.15 mW cm(-2) at 0.25 V and pH 4.

Published
2019
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21. A diethyleneglycol-pyrene-modified Ru(II) catalyst for the design of buckypaper bioelectrodes and the wiring of glucose dehydrogenases

Author

Serge Cosnier, Luminita Fritea, Andrew J. Gross, Alan Le Goff, Karine Gorgy, Bertrand Reuillard, 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]), Centre National de la Recherche Scientifique (CNRS), Laboratoire d'électrochimie organique et de photochimie redox (LEOPR), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), and 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])

Subjects
Chemistry, Buckypaper, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Chemical engineering, law, Glucose dehydrogenase, Electrochemistry, Pyrene, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; A novel water-soluble Ru complex bearing phenanthrolinequinone ligands, diethyleneglycol linkers and pyrene anchoring groups was synthesized. Electrical wiring of NAD-and FAD-dehydrogenases is demonstrated via NADH oxidation and mediated electron transfer respectively. Bioelectrocatalysis is facilitated by the flexible and hydrophilic PEG groups, and strong binding of pyrene groups with the carbon nanotubes (CNTs) of the electrodes. Furthermore, owing to the surfactant properties of the PEG-modified complex, high quality CNT dispersions were obtained for homogeneous buckypaper preparation.

Published
2019
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22. Enzymatic versus Electrocatalytic Oxidation of NADH at Carbon-Nanotube Electrodes Modified with Glucose Dehydrogenases: Application in a Bucky-Paper-Based Glucose Enzymatic Fuel Cell

Author

Sadagopan Krishnan, Noémie Lalaoui, Michael Holzinger, Nicholas Means, Charuksha Walgama, Alan Le Goff, Serge Cosnier, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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])

Subjects
010405 organic chemistry, Inorganic chemistry, chemistry.chemical_element, Buckypaper, Carbon nanotube, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, 0104 chemical sciences, Ruthenium, law.invention, Anode, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, law, Glucose dehydrogenase, Diaphorase, Electrode, Electrochemistry, ComputingMilieux_MISCELLANEOUS
Abstract

In this work, we have designed and compared functionalized carbon-nanotube-based electrodes for the electrocatalytic oxidation of NADH. We show that oxidation of NADH at neutral pH values can be performed by pristine multi-walled carbon nanotubes (MWCNT) and directly wired diaphorase or ruthenium phenanthrolinequinone molecular catalysts. Glucose dehydrogenase was immobilized on these MWCNT electrodes by an activated-ester-modified pyrene linker. Glucose-oxidizing bioelectrodes were compared and integrated into a bucky-paper-based glucose/O2 biofuel cell, using a bilirubin-oxidase-modified bucky-paper cathode. The best configuration was obtained using a NADH-oxidizing molecular catalyst at the anode. The biofuel cell exhibits an open-circuit voltage of 0.62 V and delivers a power output of 0.47 mW cm−2.

Published
2016
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23. A synthetic redox biofilm made from metalloprotein–prion domain chimera nanowires

Author

Vincent Forge, Christophe Horvath, Anaëlle Rongier, Michael Holzinger, Vincent Bouchiat, Anthony L. B. Maçon, Saravanan Rengaraj, Chantal Gondran, Denis Mariolle, Patrice Rannou, Alan Le Goff, Charlotte Vendrely, Marc Fontecave, Nicolas Duraffourg, Kamal Elouarzaki, Lucie Altamura, 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), 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]), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), 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])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Equipe de recherche sur les relations matrice extracellulaire-cellules (ERRMECe), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Laboratoire des matériaux et du génie physique (LMGP ), Institut National Polytechnique de Grenoble (INPG)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Systèmes hybrides de basse dimensionnalité (HYBRID), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), 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), 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)), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Systèmes hybrides de basse dimensionnalité (NEEL - HYBRID), Collège de France - Chaire Chimie des processus biologiques, 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 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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[SDV.BIO]Life Sciences [q-bio]/Biotechnology, Prions, Methanococcus, General Chemical Engineering, Protein design, Nanowire, Nanotechnology, 02 engineering and technology, Microscopy, Atomic Force, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, Electron Transport, Electron transfer, Rubredoxin, Metalloproteins, Metalloprotein, [CHIM]Chemical Sciences, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Electrodes, chemistry.chemical_classification, Nanowires, Chemistry, Rubredoxins, Laccase, Electrochemical Techniques, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Electron transport chain, 0104 chemical sciences, Self-assembly, 0210 nano-technology, Oxidation-Reduction
Abstract

International audience; Engineering bioelectronic components and set-ups that mimic natural systems is extremely challenging. Here we report the design of a protein-only redox film inspired by the architecture of bacterial electroactive biofilms. The nanowire scaffold is formed using a chimeric protein that results from the attachment of a prion domain to a rubredoxin (Rd) that acts as an electron carrier. The prion domain self-assembles into stable fibres and provides a suitable arrangement of redox metal centres in Rd to permit electron transport. This results in highly organized films, able to transport electrons over several micrometres through a network of bionanowires. We demonstrate that our bionanowires can be used as electron-transfer mediators to build a bioelectrode for the electrocatalytic oxygen reduction by laccase. This approach opens opportunities for the engineering of protein-only electron mediators (with tunable redox potentials and optimized interactions with enzymes) and applications in the field of protein-only bioelectrodes.

Published
2016
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24. Diazonium Functionalisation of Carbon Nanotubes for Specific Orientation of Multicopper Oxidases: Controlling Electron Entry Points and Oxygen Diffusion to the Enzyme

Author

Michael Holzinger, Noémie Lalaoui, Alan Le Goff, Serge Cosnier, Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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])

Subjects
Oxidoreductases Acting on CH-CH Group Donors, Surface Properties, Inorganic chemistry, Molecular Conformation, chemistry.chemical_element, Electrons, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrocatalyst, 01 natural sciences, Oxygen, Catalysis, law.invention, Diffusion, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, law, Electrodes, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Diazonium Compounds, biology, Nanotubes, Carbon, Chemistry, Organic Chemistry, Electrochemical Techniques, General Chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Copper, 0104 chemical sciences, Hypocreales, Electrode, Myrothecium verrucaria, Oxidoreductases, 0210 nano-technology, Oxidation-Reduction
Abstract

We report the controlled orientation of bilirubin oxidases (BOD) from Myrothecium verrucaria on multiwalled carbon nanotubes (MWCNTs) functionalised by electrografting of 6-carboxynaphthalenediazonium and 4-(2-aminoethyl)benzenediazonium salts. On negatively charged naphthoate-modified MWCNTs, a high-potential (0.44 V vs. SCE) oxygen reduction electrocatalysis is observed, occurring via the T1 copper centre. On positively charged ammonium-modified MWCNTs, a low-potential (0.15 V) oxygen reduction electrocatalysis is observed, occurring through a partially oxidised state of the T2/T3 trinuclear copper cluster. Finally, chemically modified naphthoate MWCNTs exhibit high bioelectrocatalytic current densities of 3.9 mA cm(-2) under air at gas-diffusion electrode.

Published
2016
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25. Direct Electron Transfer between a Site-Specific Pyrene-Modified Laccase and Carbon Nanotube/Gold Nanoparticle Supramolecular Assemblies for Bioelectrocatalytic Dioxygen Reduction

Author

Michael Holzinger, Yasmina Mekmouche, Noémie Lalaoui, Thierry Tron, Pierre Rousselot-Pailley, Serge Cosnier, Viviane Robert, Alan Le Goff, Reynaldo Villalonga, 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]), 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), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic chemistry, Population, Nanoparticle, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrocatalyst, 01 natural sciences, Reductive amination, Catalysis, law.invention, chemistry.chemical_compound, Electron transfer, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, law, education, ComputingMilieux_MISCELLANEOUS, education.field_of_study, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Chemical engineering, Colloidal gold, Pyrene, 0210 nano-technology
Abstract

Strategies to maximize direct electron transfer (DET) between redox enzymes and electrodes include the oriented immobilization of enzymes onto an electroactive surface. Here, we present a strategy for achieving a controlled orientation of a fungal laccase on carbon nanotube-based electrodes. A homogeneous population of pyrene-modified laccase is obtained via the reductive amination of a unique surface accessible lysine residue engineered near the T1 copper center of the enzyme. Immobilization of the site-specific functionalized enzyme is achieved either via π-stacking of pyrene on pristine CNT electrodes or through pyrene/β-cyclodextrin host guest interactions on β-cyclodextrin-modified gold nanoparticles (β-CD-AuNPs). Contrasting with unmodified and nonspecifically modified (pyrene-NHS) laccase-electrodes, an efficient DET is obtained at these nanostructured assemblies. Modeling the direct bioelectrocatalysis of dioxygen reduction reveals a heterogeneity in ET rates on MWCNT electrodes wheras β-CD-AuNPs ...

Published
2016
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26. From Graphite to Laccase Biofunctionalized Few-Layer Graphene: A 'One Pot' Approach Using a Chimeric Enzyme

Author

Alessandra Piscitelli, Yannig Nedellec, Ilaria Sorrentino, Alan Le Goff, Paola Giardina, Ilaria Stanzione, Sorrentino, I., Stanzione, I., Nedellec, Y., Piscitelli, A., Giardina, P., Le Goff, A., Department of Chemical Sciences, University of Naples Federico II, Napoli, Italy, Département de Chimie Moléculaire (DCM), and Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hydrophobin, Dopamine, Catechols, Nanotechnology, Biosensing Techniques, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Article, Catalysis, law.invention, Nanomaterials, lcsh:Chemistry, Fungal Proteins, Inorganic Chemistry, chemistry.chemical_compound, Protein Domains, law, [CHIM]Chemical Sciences, Graphite, Physical and Theoretical Chemistry, lcsh:QH301-705.5, Molecular Biology, ComputingMilieux_MISCELLANEOUS, Spectroscopy, Laccase, Catechol, Chemistry, Graphene, Organic Chemistry, General Medicine, Enzymes, Immobilized, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Computer Science Applications, lcsh:Biology (General), lcsh:QD1-999, Surface modification, 0210 nano-technology, Biosensor
Abstract

A chimeric enzyme based on the genetic fusion of a laccase with a hydrophobin domain was employed to functionalize few-layer graphene, previously exfoliated from graphite in the presence of the hydrophobin. The as-produced, biofunctionalized few-layer graphene was characterized by electrochemistry and Raman spectroscopy, and finally employed in the biosensing of phenols such as catechol and dopamine. This strategy paves the way for the functionalization of nanomaterials by hydrophobin domains of chimeric enzymes and their use in a variety of electrochemical applications.

Published
2020
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27. Oriented Immobilization of [NiFeSe] Hydrogenases on Covalently and Noncovalently Functionalized Carbon Nanotubes for H 2 /Air Enzymatic Fuel Cells

Author

Christine Cavazza, Hélène Jamet, Alan Le Goff, Syamim Muhamad Che Mansor, Solène Gentil, Serge Cosnier, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Institut de Chimie Moléculaire de Grenoble (ICMG)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut de Biosciences et de Biotechnologies de Grenoble (ex-IRTSV) (BIG), Institut National de la Santé et de la Recherche Médicale (INSERM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)-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]), 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 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 - Biosystèmes Electrochimiques et Analytiques [2009-2015] (DCM - BEA [2009-2015]), Département de Chimie Moléculaire [2007-2015] (DCM [2007-2015]), Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique [2009-2015] (DCM - CIRE [2009-2015]), and Institut National de la Santé et de la Recherche Médicale (INSERM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
Hydrogenase, hydrogen oxidation, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrochemistry, 01 natural sciences, Anthraquinone, Catalysis, law.invention, Hydrophobic effect, hydrogenases, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, diazonium, ComputingMilieux_MISCELLANEOUS, carbon nanotubes, General Chemistry, Quartz crystal microbalance, biofuel cells, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical engineering, chemistry, Covalent bond, 0210 nano-technology
Abstract

International audience; We report the oriented immobilization of [NiFeSe] hydrogenases on both covalently and noncovalently modified carbon nanotubes (CNTs) electrodes. A specific interaction of the [NiFeSe] hydrogenase from Desulfomicrobium baculatum with hydrophobic organic molecules was probed by electrochemistry, quartz crystal microbalance with dissipation monitoring (QCM-D), and theoretical calculations. Taking advantage of these hydrophobic interactions, the enzyme was efficiently wired on anthraquinone and adamantane-modified CNTs. Because of rational immobilization onto functionalized CNTs, the O-2-tolerant [NiFeSe]-hydrogenase is able to efficiently operate in a H-2/air gas-diffusion enzymatic fuel cell.

Published
2018
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28. 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
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29. Design of a reduced-graphene-oxide composite electrode from an electropolymerizable graphene aqueous dispersion using a cyclodextrin-pyrrole monomer. Application to dopamine biosensing

Author

Luminiţa Fritea, Alan Le Goff, Serge Cosnier, Jean-Luc Putaux, Cecilia Cristea, Mihaela Tertis, Robert Săndulescu, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Centre National de la Recherche Scientifique (CNRS), Iuliu Hatieganu University of Medicine and Pharmacy, Analytical Chemistry Department, and University of Medicine and Pharmacy

Subjects
Materials science, Aqueous solution, Nanocomposite, Graphene, General Chemical Engineering, Inorganic chemistry, Oxide, 02 engineering and technology, Glassy carbon, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Monomer, chemistry, Chemical engineering, law, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Pyrrole
Abstract

A new cyclodextrin-modified pyrrole monomer (Py-CD) was synthesized and used both as an aqueous surfactant for the stabilization of aqueous reduced graphene oxide (RGO) dispersion and as an electropolymerizable unit to generate a RGO-polypyrrole composite electrode. This nanocomposite was used in combination with amphiphilic pyrrole derivative for the entrapment of tyrosinase, an enzyme catalyzing the oxidation of phenols and diphenols. Compared to glassy carbon electrodes, these nanostructured electrodes exhibit enhanced electroactive surface area and electrochemical properties and achieve higher performances towards catechol and dopamine biosensing.

Published
2015
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30. New set of candidate gene SNPs and microsatellites to disentangle selective and neutral processes shaping population responses of European flounder (Platichthys flesus) to anthropogenic stress and contrasted environments

Author

Grégory Charrier, Romain Morvezen, Jean Laroche, Alan Le Moan, Bruno Guinand, Nicolas Pédron, José-Luis Zambonino-Infante, Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Français de Recherche pour l'Exploitation de la Mer - Brest (IFREMER Centre de Bretagne), Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), Institut des Sciences de l'Evolution de Montpellier (UMR ISEM), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Montpellier (UM)-Institut de recherche pour le développement [IRD] : UR226-Centre National de la Recherche Scientifique (CNRS), ANR-10-LABX-0019,LabexMER,LabexMER Marine Excellence Research: a changing ocean(2010), Institut de Recherche pour le Développement (IRD)-Institut Universitaire Européen de la Mer (IUEM), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Université de Brest (UBO)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS), Institut Français de Recherche pour l'Exploitation de la Mer - Brest (IFREMER), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-École pratique des hautes études (EPHE)-Université de Montpellier (UM)-Institut de recherche pour le développement [IRD] : UR226-Centre National de la Recherche Scientifique (CNRS), and ANR-10-LABX-0019/10-LABX-0019,LabexMER,LabexMER Marine Excellence Research: a changing ocean(2010)

Subjects
0106 biological sciences, Candidate gene, Range (biology), Platichthys flesus, Population, BHMT, SNP, Flounder, Single-nucleotide polymorphism, 01 natural sciences, 03 medical and health sciences, L-PGDS, Genetics, AMPD, EUROPEAN FLOUNDER, education, Ecology, Evolution, Behavior and Systematics, 030304 developmental biology, European flounder, P53, 0303 health sciences, education.field_of_study, biology, GAPDH, Ecology, ACL, 010604 marine biology & hydrobiology, Multiplexes, biology.organism_classification, Platichthys, Microsatellite, [SDE.BE]Environmental Sciences/Biodiversity and Ecology
Abstract

International audience; Six candidate gene SNP assays and 12 new microsatellites were developed in the European flounder (Platichthys flesus), in order to provide new tools to (1) further investigate signatures of selection suspected on candidate genes, and (2) better depict the neutral evolutionary background shaping the differentiation of populations. All markers were successfully tested in two populations from contrasted estuaries, and should be helpful to better understand the possible adaptive responses of flounder populations to anthropogenic pressures (e.g. global warming, eutrophication, pollutions), over the whole distribution range of the species.

Published
2015
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31. A membraneless air-breathing hydrogen biofuel cell based on direct wiring of thermostable enzymes on carbon nanotube electrodes

Author

Pascale Infossi, Michael Holzinger, Sébastien Gounel, Raoudha Haddad, Anne de Poulpiquet, Michel Mermoux, Elisabeth Lojou, Noémie Lalaoui, Serge Cosnier, Nicolas Mano, Alan Le Goff, Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Bioénergétique et Ingénierie des Protéines (BIP ), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI ), Institut de Chimie du CNRS (INC)-Institut National Polytechnique de Grenoble (INPG)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Université Joseph Fourier - Grenoble 1 (UJF)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), ANR-13-BIME-0003,CAROUCELL,Nanostructuration des anode et cathode pour une biopile à combustible H2/O2(2013), European Project: ANR-11-LABX-0003-01, European Project: ANR-12-BS08-0011-01, 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), Aix Marseille Université (AMU)-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), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)

Subjects
Oxidoreductases Acting on CH-CH Group Donors, Materials science, Hydrogenase, Hydrogen, Bioelectric Energy Sources, Carbon nanotubes, chemistry.chemical_element, Bacillus, Nanotechnology, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, law.invention, law, Materials Chemistry, Bilirubin oxidase, Electrodes, biology, Nanotubes, Carbon, Bacillus pumilus, Air, fungi, Metals and Alloys, Biofuel cell, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Enzymes, Immobilized, 021001 nanoscience & nanotechnology, biology.organism_classification, Cathode, Enzymes, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Anode, Oxygen, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical engineering, chemistry, Electrode, Ceramics and Composites, 0210 nano-technology, Oxidation-Reduction
Abstract

International audience; A biocathode was designed by the modification of a carbon nanotube (CNT) gas-diffusion electrode with bilirubin oxidase from Bacillus pumilus, achieving high current densities up to 3 mA cm−2 for the reduction of O2 from air. A membraneless air-breathing hydrogen biofuel cell was designed by combination of this cathode with a functionalized CNT-based hydrogenase anode.

Published
2015
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32. Assembly and Stacking of Flow-through Enzymatic Bioelectrodes for High Power Glucose Fuel Cells

Author

Olivier Ondel, Michael Holzinger, Caroline Abreu, François Buret, Serge Cosnier, Alan Le Goff, Yannig Nedellec, Andrew J. Gross, 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), Institut National des Sciences Appliquées (INSA)-Université de Lyon-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), Institut National des Sciences Appliquées (INSA)-Université de Lyon-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 (DCM), 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), Laboratoire d'électrochimie organique et de photochimie redox (LEOPR), and Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)

Subjects
Materials science, Stacking, Pellets, Nanotechnology, 02 engineering and technology, Carbon nanotube, Electrolyte, 010402 general chemistry, 01 natural sciences, 7. Clean energy, law.invention, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, General Materials Science, Cellulose, Open-circuit voltage, [SPI.NRJ]Engineering Sciences [physics]/Electric power, technology, industry, and agriculture, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Membrane, chemistry, Chemical engineering, Biofuel, 0210 nano-technology
Abstract

International audience; Bioelectrocatalytic carbon nanotube based pellets comprising redox enzymes were directly integrated in a newly conceived flow-through fuel cell. Porous electrodes and a separating cellulose membrane were housed in a glucose/oxygen biofuel cell design with inlets and outlets allowing the flow of electrolyte through the entire fuel cell. Different flow setups were tested and the optimized single cell setup, exploiting only 5 mmol L-1 glucose, showed an open circuit voltage (OCV) of 0.663 V and provided 1.03 ± 0.05 mW at 0.34 V. Furthermore, different charge/discharge cycles at 500 Ω and 3 kΩ were applied to optimize long-term stability leading to 3.6 J (1 mW h) of produced electrical energy after 48 h. Under continuous discharge at 6 kΩ, about 0.7 mW h could be produced after a 24 h period. The biofuel cell design further allows a convenient assembly of several glucose biofuel cells in reduced volumes and their connection in parallel or in series. The configuration of two biofuel cells connected in series showed an OCV of 1.35 V and provided 1.82 ± 0.09 mW at 0.675 V, and when connected in parallel, showed an OCV of 0.669 V and provided 1.75 ± 0.09 mW at 0.381 V. The presented design is conceived to stack an unlimited amount of biofuel cells to reach the necessary voltage and power for portable electronic devices without the need for step-up converters or energy managing systems.

Published
2017
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33. Synergetic Effects of Combined Nanomaterials for Biosensing Applications

Author

Michael Holzinger, Alan Le Goff, Serge Cosnier, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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])

Subjects
Analyte, Materials science, Energy transfer, Transducers, metals, Nanotechnology, 02 engineering and technology, Review, semiconductors, Biosensing Techniques, lcsh:Chemical technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Signal, Analytical Chemistry, Nanomaterials, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, lcsh:TP1-1185, Electrical and Electronic Engineering, Instrumentation, ComputingMilieux_MISCELLANEOUS, nanomaterials, hybrids, energy transfer, carbon, 021001 nanoscience & nanotechnology, biosensors, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Nanostructures, 0210 nano-technology, Biosensor
Abstract

Nanomaterials have become essential components for the development of biosensors since such nanosized compounds were shown to clearly increase the analytical performance. The improvements are mainly related to an increased surface area, thus providing an enhanced accessibility for the analyte, the compound to be detected, to the receptor unit, the sensing element. Nanomaterials can also add value to biosensor devices due to their intrinsic physical or chemical properties and can even act as transducers for the signal capture. Among the vast amount of examples where nanomaterials demonstrate their superiority to bulk materials, the combination of different nano-objects with different characteristics can create phenomena which contribute to new or improved signal capture setups. These phenomena and their utility in biosensor devices are summarized in a non-exhaustive way where the principles behind these synergetic effects are emphasized.

Published
2017
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34. Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

Author

Yannig Nedellec, Arnab Dutta, Serge Cosnier, Noémie Lalaoui, Alan Le Goff, Wendy J. Shaw, Vincent Artero, Solène Gentil, 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), 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]), Pacific NW Natl Lab, Richland, WA 99352 USA, Chemistry Department, IIT Gandhinagar, Gujarat, India, 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
bio-inspired catalysts, Materials science, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Hydrogen, Proton exchange membrane fuel cell, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, Carbon nanotube, multicopper oxidases, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Redox, Catalysis, Nanomaterials, law.invention, law, [CHIM]Chemical Sciences, 010405 organic chemistry, General Medicine, General Chemistry, biofuel cells, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, Nickel, Chemical engineering, chemistry, nickel complexes, 0210 nano-technology, H2 oxidation
Abstract

International audience; A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2 /2 H+ interconversion from pH 0 to 9, with catalytic preference for H2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm-2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm-2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts.

Published
2017
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35. Electrochemical nanopatterning of an electrogenerated photosensitive poly-[trisbipyridinyl-pyrrole ruthenium(II)] metallopolymer by nanosphere lithography

Author

Alan Le Goff, Robert Săndulescu, Chantal Gondran, Michael Holzinger, Karine Gorgy, Luminita Fritea, Serge Cosnier, Fatima Haddache, Bertrand Reuillard, Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Analytical Chemistry Department, and University of Medicine and Pharmacy

Subjects
Nanostructure, Materials science, Photoelectrochemistry, chemistry.chemical_element, 02 engineering and technology, Glassy carbon, 010402 general chemistry, Photochemistry, 01 natural sciences, lcsh:Chemistry, chemistry.chemical_compound, Electrochemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Pyrrole, Photocurrent, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Ruthenium, chemistry, lcsh:Industrial electrochemistry, lcsh:QD1-999, Nanosphere lithography, Polystyrene, 0210 nano-technology, lcsh:TP250-261
Abstract

900- and 100-nm-diameter polystyrene beads were combined with electrogenerated photosensitive poly-[tris(4,4-bis(3-pyrrol-1-ylpropyloxy)bipyridinyl)ruthenium(II)], (poly-[RuII-pyrrole]), metallopolymer on glassy carbon electrodes. Nanosphere lithography (NSL) with 900-nm-diameter microbead mask affords the realization of a nanostructured polymer (after dissolution of the polystyrene templates) with a typical highly-organized honeycomb nanostructure. NSL with 100-nm-diameter-nanobead mask allowed the achievement of a highly macroporous metallopolymer. The nanostructured Ru(II)-based metallopolymer was characterized by 3D laser scanning confocal microscopy and scanning electron microscopy (SEM). Electrochemical and photoelectrochemical studies demonstrate the enhancement of redox probe diffusion in the polymer layer for nanopatterned poly-[RuII-pyrrole]. This is accompanied with photocurrent enhancement for nanostructured polymer, especially in the case of poly-[RuII-pyrrole] obtained by the 100 nm-nanobead NSL. Keywords: Nanosphere lithography, Ruthenium complexes, Electropolymerization, Metallopolymers, Photoelectrochemistry

Published
2014
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36. Acid-Base Control of Hemilabile Proton-Responsive Protecting Devices in Dimolybdenum, Thiolate-Bridged Complexes

Author

Alan Le Goff, Christine Le Roy, Philippe Schollhammer, François Y. Pétillon, David Vénec, Jean Talarmin, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Base (chemistry), 010405 organic chemistry, Chemistry, Protonation, Crystal structure, 010402 general chemistry, Ligand (biochemistry), Electrochemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, Acetonitrile, Dichloromethane
Abstract

International audience; Dimolybdenum thiolate-bridged complexes [Mo2Cp2(μ-SMe)2(μ-SCH2CH2E)] (E = O (2) or NH (4)) with a proton-dependent protecting device have been synthesized by reaction of [Mo2Cp2(μ-SMe)2(μ-Cl)2] (1) with SCH2CH2EH. The reactivity of the resultant quadruply bridged complexes with acid was investigated in the absence and in the presence of a potential ligand (N2, MeCN, RNC). While the protonation of complexes 2 and 4 under N2 in dichloromethane produced only the oxidized derivatives instead of the desired diazenido compound, ligand binding was observed in MeCN or in the presence of RNC (R = t-Bu, Xyl). Whereas acetonitrile loss from [Mo2Cp2(μ-SMe)2(μ-SCH2CH2OH)(MeCN)2]+ (8+) prevented the isolation and characterization of this species, the t-BuNC analogue (6+) could be characterized by an X-ray crystal structure. The electrochemistry of 2 and 2+ was investigated in CH2Cl2 and in MeCN, both in the absence and in the presence of acid. While the addition of HBF4·Et2O to a dichloromethane solution of 2 only produced 2+ (and presumably H2), 8+ was the major product of the protonation in MeCN.

Published
2014
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37. Non-covalent functionalization of carbon nanotubes with boronic acids for the wiring of glycosylated redox enzymes in oxygen-reducing biocathodes

Author

Michael Holzinger, Alan Le Goff, Serge Cosnier, Bertrand Reuillard, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), 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), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, Materials science, Biomedical Engineering, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 01 natural sciences, Horseradish peroxidase, law.invention, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Organic chemistry, General Materials Science, Glucose oxidase, ComputingMilieux_MISCELLANEOUS, biology, General Chemistry, General Medicine, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Monomer, chemistry, Covalent bond, biology.protein, Surface modification, Pyrene, 0210 nano-technology, Boronic acid
Abstract

We report the non-covalent functionalization of multiwalled carbon nanotubes with pyrene monomers bearing a boronic acid function. These functionalized electrodes were used to wire horseradish peroxidase via formation of a covalent boronic ester bond under mild conditions with the glycosylated enzyme. By attaching glucose oxidase at the same time, a bi-enzymatic system was elaborated and showed efficient bioelectrocatalytic oxygen reduction under physiological conditions.

Published
2014
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38. A double-walled carbon nanotube-based glucose/H2O2 biofuel cell operating under physiological conditions

Author

Michael Holzinger, Charles Agnès, Bertrand Reuillard, Serge Cosnier, Alan Le Goff, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)

Subjects
02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Horseradish peroxidase, Catalysis, law.invention, lcsh:Chemistry, chemistry.chemical_compound, law, Electrochemistry, [CHIM]Chemical Sciences, Glucose oxidase, Hydrogen peroxide, ComputingMilieux_MISCELLANEOUS, biology, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, Anode, chemistry, Biochemistry, Chemical engineering, lcsh:Industrial electrochemistry, lcsh:QD1-999, Electrode, biology.protein, 0210 nano-technology, Peroxidase, lcsh:TP250-261
Abstract

We report the first example of a glucose/H2O2 biofuel cell operating at 5 mM glucose under air at 37 °C in 0.14 M NaCl. At a bienzymatic cathode, the direct wiring of horseradish peroxidase (HRP) achieves the electrocatalytic reduction of H2O2 concomitantly produced during the oxidation of glucose by glucose oxidase (GOx) in the presence of O2. At the bienzymatic anode, the indirect wiring of glucose oxidase achieves electrocatalytic glucose oxidation while catalase removes trace of H2O2 and, in combination with GOx, traces of O2. The bienzymatic catalysis involved GOx at both electrodes. The biofuel cell exhibits OCV of 450 mV and maximum power output of 30 μW cm−2 at 0.3 V in 5 mM glucose and 0.14 M NaCl at 37 °C. This represents a novel alternative to the use of copper oxidases in conventional glucose/O2 biofuel cells for implantable applications. Keywords: Carbon nanotubes, Peroxidase, Glucose oxidase, Biofuel cells, Hydrogen peroxide

Published
2013
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39. Fluorescent and redox tetrazine films by host-guest immobilization of tetrazine derivatives within poly(pyrrole-β-cyclodextrin) films

Author

Karine Gorgy, Luminiţa Fritea, Serge Cosnier, Alan Le Goff, Pierre Audebert, Robert Săndulescu, Laurent Galmiche, 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]), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-Chimie Macromoléculaire (UMR 7615) (LPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Analytical Chemistry Department, and University of Medicine and Pharmacy

Subjects
General Chemical Engineering, Supramolecular chemistry, 02 engineering and technology, 010402 general chemistry, Polypyrrole, Photochemistry, 01 natural sciences, Analytical Chemistry, chemistry.chemical_compound, Tetrazine, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electrochemistry, Glucose oxidase, ComputingMilieux_MISCELLANEOUS, Pyrrole, chemistry.chemical_classification, biology, Cyclodextrin, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, chemistry, Enzyme model, biology.protein, 0210 nano-technology, Biosensor
Abstract

Tetrazines were immobilized onto electrogenerated films of polypyrrole functionalized with β -cyclodextrin. Their immobilization was ascribed to the formation of the inclusion complexes between the tetrazines derivatives and the β -cyclodextrin cavity. We proved that the resulting supramolecular material kept the electrochemical and fluorescent properties of tetrazines. This original architecture was used with success as a “bridge” to immobilize the β -cyclodextrin-tagged glucose oxidase, chosen as an enzyme model, to prove the efficiency of the method to build new supra-biomolecular architectures.

Published
2016
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40. A label-free photoelectrochemical cocaine aptasensor based on an electropolymerized ruthenium-intercalator complex

Author

Nicolas Spinelli, Karine Gorgy, Fatima Haddache, Chantal Gondran, Priyanka Gairola, Alan Le Goff, Serge Cosnier, Eric Defrancq, 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]), and Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM)

Subjects
Stereochemistry, General Chemical Engineering, Aptamer, Photoelectrochemistry, Phenazine, Intercalation (chemistry), chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Ligand (biochemistry), 01 natural sciences, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Ruthenium, chemistry.chemical_compound, Monomer, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electrochemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Pyrrole
Abstract

A photoelectrode was designed by electrodeposition of a pyrrole monomer modified with a polypyridyl Ru(II) complex bearing benzo[i]dipyrido-[3,2-a:2′.3′-c]phenazine (dppn) ligand. Owing to the intercalating properties of these immobilized complexes towards DNA double helix, cocaine aptamer was immobilized on the modified electrodes thanks to its stem-loop configuration in order to design a photoelectrochemical cocaine aptasensor. Especially using a double-fragment aptamer strategy, the binding of cocaine and the formation of the aptamer/cocaine complex was successfully observed and modeled by a Langmuir-Freundlich isotherm, giving access to an apparent dissociation constant K d of 3.8 mmol L −1 . The photoelectrochemical aptasensor exhibits a LOD of 10 nmol L −1 and linear range of 1 10 −8 –5 10 −4 mol L −1 .

Published
2016
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41. Recent advances on enzymatic glucose/oxygen and hydrogen/oxygen biofuel cells: Achievements and limitations

Author

Michael Holzinger, Alan Le Goff, Andrew J. Gross, Serge Cosnier, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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])

Subjects
Materials science, Hydrogen, Energy Engineering and Power Technology, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electronics, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical energy, Electricity generation, chemistry, 13. Climate action, Biofuel, Electric power, 0210 nano-technology, Energy source
Abstract

The possibility of producing electrical power from chemical energy with biological catalysts has induced the development of biofuel cells as viable energy sources for powering portable and implanted electronic devices. These power sources employ biocatalysts, called enzymes, which are highly specific and catalytic towards the oxidation of a biofuel and the reduction of oxygen or hydrogen peroxide. Enzymes, on one hand, are promising candidates to replace expensive noble metal-based catalysts in fuel cell research. On the other hand, they offer the exciting prospect of a new generation of fuel cells which harvest energy from body fluids. Biofuel cells which use glucose as a fuel are particularly interesting for generating electricity to power electronic devices inside a living body. Hydrogen consuming biofuel cells represent an emerging alternative to platinum catalysts due to comparable efficiencies and the capability to operate at lower temperatures. Currently, these technologies are not competitive with existing commercialised fuel cell devices due to limitations including insufficient power outputs and lifetimes. The advantages and challenges facing glucose biofuel cells for implantation and hydrogen biofuel cells will be summarised along with recent promising advances and the future prospects of these exotic energy-harvesting devices.

Published
2016
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42. How the Intricate Interactions between Carbon Nanotubes and Two Bilirubin Oxidases Control Direct and Mediated O2 Reduction

Author

Marie-Thérèse Giudici-Orticoni, Sabine Szunerits, Jad Rouhana, C. Laffon, Philippe Parent, Ievgen Mazurenko, Elisabeth Lojou, Nicolas Mano, Karen Monsalve, Rabah Boukherroub, Alan Le Goff, Bioénergétique et Ingénierie des Protéines (BIP ), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Département de Chimie Moléculaire - Chimie Inorganique Redox (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 d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), ANR-12-BS08-0011,RATIOCELLS,Ingénierie de matériaux poreux et d'enzymes pour le développement de biopiles(2012), ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), European Project, European Project: IdEx Bordeaux (ANR-10-IDEX- 003-02), and Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE )

Subjects
Carbon nanotubes, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, law.invention, Nanomaterials, Bilirubin oxidase, Electron transfer, Adsorption, law, Organic chemistry, General Materials Science, Surface charge, Mediated electron transfer, Electrostatic interactions, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Direct electron transfer, Bioelectrocatalysis, 0210 nano-technology
Abstract

International audience; Due to the lack of a valid approach in the design of electrochemical interfaces modified with enzymes for efficient catalysis, many oxidoreductases are still not addressed by electrochemistry. We report in this work an in-depth study of the interactions between two different bilirubin oxidases, (from the fungus Myrothecium verrucaria and from the bacterium Bacillus pumilus), catalysts of oxygen reduction, and carbon nanotubes bearing various surfacecharges (pristine, carboxylic-, and pyrene-methylamine-functionalized). The surface charges and dipole moment of the enzymes as well as the surface state of the nanomaterials are characterized as a function of pH. An original electrochemical approach allows determination of the best interface for direct or mediated electron transfer processes as a function of enzyme, nanomaterial type, and adsorption conditions. We correlate these experimentalresults to theoric voltammetric curves. Such an integrative study suggests strategies for designing efficient bioelectrochemical interfaces toward the elaboration of biodevices such as enzymatic fuel cells for sustainable electricity production.

Published
2016
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43. Hosting Adamantane in the Substrate Pocket of Laccase: Direct Bioelectrocatalytic Reduction of O 2 on Functionalized Carbon Nanotubes

Author

Rolf David, Hélène Jamet, Michael Holzinger, Alan Le Goff, Serge Cosnier, Noémie Lalaoui, 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]), and Département de Chimie Moléculaire - Chimie Théorique (DCM - CT)

Subjects
Laccase, Chemistry, Adamantane, Inorganic chemistry, Substrate (chemistry), 02 engineering and technology, General Chemistry, Carbon nanotube, Quartz crystal microbalance, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Electron transfer, Chemical engineering, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Pyrene, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

We report the efficient immobilization and orientation of laccase from Trametes versicolor on MWCNT electrodes using 1-pyrenebutyric acid adamantyl amide as a supramolecular linker. We demonstrate the ability of adamantane to specifically interact with the hydrophobic cavity of laccase, while pyrene interacts with MWCNT sidewalls by π–π interactions. Adamantane allows the oriented immobilization of laccases on MWCNT electrodes. Using an anthraquinone-modified pyrene derivative for comparison, adamantane-modified MWCNTs achieve the stable immobilization and orientation of a higher number of enzymes per surface units, as confirmed by electrochemistry, theoretical calculations, and quartz crystal microbalance experiments. Furthermore, the efficient direct electron transfer ensures bioelectrocatalytic oxygen reduction at high half-wave potential of 0.55 V vs SCE accompanied by no kinetic limitation by the heterogeneous electron transfer and maximum current densities of 2.4 mA cm–2.

Published
2016
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44. Direct electron transfer between tyrosinase and multi-walled carbon nanotubes for bioelectrocatalytic oxygen reduction

Author

Bertrand Reuillard, Charles Agnès, Michael Holzinger, Serge Cosnier, Abdelkader Zebda, Alan Le Goff, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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)

Subjects
Tyrosinase, Cyanide, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Redox, Oxygen, lcsh:Chemistry, Electron transfer, chemistry.chemical_compound, Electrochemistry, [CHIM]Chemical Sciences, Bilirubin oxidase, ComputingMilieux_MISCELLANEOUS, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, chemistry, lcsh:Industrial electrochemistry, lcsh:QD1-999, Cyclic voltammetry, 0210 nano-technology, lcsh:TP250-261
Abstract

We report the fabrication of a tyrosinase bioelectrode by mechanical compression of a MWCNT enzyme mixture. Cyclic voltammetry of the nanostructured bioelectrode demonstrated a Direct Electron Transfer (DET) process between tyrosinase, a copper enzyme, and MWCNT. The latter led to an enzyme redox potential of +0.30 V vs SCE, close to the redox potential described for the T3 binuclear copper center. Furthermore, we demonstrate, for the first time, a bioelectrocatalytic reduction of oxygen performed by tyrosinase directly wired within the MWCNT disk. A maximum current density of 0.55 mA cm−2 was recorded by chronoamperometric measurements at 0 V vs SCE. The bioelectrode exhibits excellent stability over time, conserving more than 50% of its activity after one week. DET between MWCNTs and the T3 binuclear copper centers have been further investigated by studying the influence of two tyrosinase inhibitors: benzoic acid and cyanide. As previously reported for “blue” multicopper oxidases, such as bilirubin oxidase and laccase, tyrosinase can achieve oxygen reduction via DET between MWCNT and its T3 binuclear copper center, representing an alternative in the design of oxygen biocathodes for biofuel cells. Keywords: Carbon nanotubes, Multi-copper enzymes, Tyrosinase, Direct electron transfer, Biofuel cells, Oxygen reduction

Published
2012
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45. Electrochemical and Theoretical Studies of the Impact of the Chelating Ligand on the Reactivity of [Fe2(CO)4(κ2-LL)(μ-pdt)]+ Complexes with Different Substrates (LL = IMe-CH2-IMe, dppe; IMe = 1-Methylimidazol-2-ylidene)

Author

Jean Talarmin, Luca De Gioia, Philippe Schollhammer, Dounia Chouffai, François Y. Pétillon, Giuseppe Zampella, Alan Le Goff, and Jean-François Capon

Subjects
010405 organic chemistry, Stereochemistry, Chemistry, Ligand, Organic Chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Dication, Adduct, Inorganic Chemistry, Reactivity (chemistry), Chelation, Propanedithiolate, Physical and Theoretical Chemistry, Cyclic voltammetry
Abstract

The reactivity of [Fe2(CO)4(κ2-LL)(μ-pdt)]+ complexes (pdt = S(CH2)3S, propanedithiolate) with different substrates L′ (L′ = CO, MeCN, P(OMe)3) was investigated electrochemically in order to assess the influence of the chelating ligand κ2-LL (LL = IMe-CH2-IMe (1+), dppe (2+); IMe = 1-methylimidazol-2-ylidene). This latter ligand is effectively shown to affect the reactivity of the cations in different ways: when L′ = CO, the adduct [Fe2(CO)4(μ-CO)(κ2-dppe)(μ-pdt)]+ (2-CO+) was clearly observed by cyclic voltammetry, whereas [Fe2(CO)4(μ-CO)(κ2-IMe-CH2-IMe)(μ-pdt)]+ (1-CO+) was not detected, although DFT calculations show that the energies of the products and the activation barriers to their formation are similar. When L′ = MeCN, the adducts X-MeCN+ with X = 1, 2 are both observed, but the formation is easier when LL = dppe. Finally, the reaction of [Fe2(CO)4(κ2-IMe-CH2-IMe)(μ-pdt)]+ (1+) with P(OMe)3 produces the disubstituted dication [Fe2(CO)2{P(OMe)3}2(κ2-IMe-CH2-IMe)(μ-CO)(μ-pdt)]2+ (42+) via a disprop...

Published
2012
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46. Immobilization of FeFe hydrogenase mimics onto carbon and gold electrodes by controlled aryldiazonium salt reduction: an electrochemical, XPS and ATR-IR study

Author

Serge Palacin, Mathieu Razavet, Marc Fontecave, Phong D. Tran, Fabrice Moggia, Alan Le Goff, Vincent Artero, Bruno Jousselme, Romain Metayé, Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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]), 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), 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, Inorganic chemistry, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, Hydrolysis, chemistry.chemical_compound, Amide, Polymer chemistry, biology, Renewable Energy, Sustainability and the Environment, Chemistry, Active site, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Surface chemistry, Hydrogen evolution reaction, Toluene, 0104 chemical sciences, Modified electrodes, Fuel Technology, Hydrogenase models, Covalent bond, biology.protein, 0210 nano-technology
Abstract

International audience; A dithiolate-bridged hexacarbonyldiiron complex was synthesized from the reaction of the N-hydroxysuccinimide (NHS) ester of lipoic acid with Fe3(CO)12 in toluene. This mimic of the active site of FeFe hydrogenases could be covalently attached, using an NHS ester route, to carbon or gold electrode first decorated with amino functions. Once grafted this complex catalyzes hydrogen electro-evolution under strongly acidic conditions but is rapidly inactivated. We could evidence that the activity loss was due to the elimination of the carbonyl ligands rather than a leaching of the catalyst as a consequence of hydrolysis of the amide linkages.

Published
2010
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47. Synthesis of functionalized alkoxyalkylidene gem-bisphosphonates

Author

Bernard Corbel, Hélène Couthon-Gourvès, Paul-Alain Jaffrès, Alan Le Goff, Jean-Pierre Haelters, Gaëlle Simon, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Allyl bromide, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Carboxylic acid, Organic Chemistry, Aminobisphosphonates, Epoxide, Alcohol, Bisphosphonates, Alkylation, 010402 general chemistry, 01 natural sciences, Biochemistry, Aldehyde, 0104 chemical sciences, Alkoxy methylene bisphosphonates, chemistry.chemical_compound, Drug Discovery, Bisphosphonic acids, Alkoxy group, [CHIM]Chemical Sciences, Organic chemistry, Amine gas treating
Abstract

International audience; We report the synthesis of a series of new functionalized bisphosphonates and bisphosphonic acids with an alkoxy group fixed at the geminal carbon, which is proposed to increase their lipophilicity and so their bioavailability. Subsequently, the alkylation of these alkoxy bisphosphonates with allyl bromide is reported. The reactivity of the allyl group has been studied to give access to alkoxy bisphosphonates functionalized by diverse groups including alcohol, aldehyde, carboxylic acid, epoxide and amine.

Published
2008
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48. First Occurrence of Tetrazines in Aqueous Solution: Electrochemistry and Fluorescence

Author

Serge Cosnier, Reynaldo Villalonga, Luminiţa Fritea, Robert Săndulescu, Alan Le Goff, Pierre Audebert, Laurent Galmiche, Karine Gorgy, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), 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), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-Chimie Macromoléculaire (UMR 7615) (LPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Analytical Chemistry Department, and University of Medicine and Pharmacy

Subjects
Aqueous solution, Supramolecular chemistry, Substituent, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Supramolecular assembly, Inclusion compound, Solvent, chemistry.chemical_compound, Tetrazine, chemistry, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Acetonitrile, ComputingMilieux_MISCELLANEOUS
Abstract

The photophysical and electrochemical properties of tetrazines substituted by linear 2,3-naphtalimide antennas and/or adamantane groups specifically dedicated to host-guest interactions with cyclodextrins are studied both in organic and aqueous media. In acetonitrile solvent, the reduction potential of tetrazine leading to the anion radical is shifted, depending on the electron-withdrawing power of the substituent of the tetrazines. Due to the hydrophobic character of these compounds, their solubilization in aqueous solution is achieved successively in presence of either β-cyclodextrins or gold nanoparticules modified by β-cyclodextrins. We demonstrate that the formation of the inclusion compound tetrazine-cyclodextrin allows the solubilization of the tetrazines in aqueous solution. The supramolecular assemblies obtained in water retain tetrazine's emission properties, yielding a yellow fluorescence.

Published
2015
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49. One-year stability for a glucose/oxygen biofuel cell combined with pH reactivation of the laccase/carbon nanotube biocathode

Author

Olivier Ondel, Michael Holzinger, Noémie Lalaoui, Caroline Abreu, Serge Cosnier, Bertrand Reuillard, François Buret, Alan Le Goff, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), 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), 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), and Ampère, Département Energie Electrique (EE)

Subjects
Bioelectric Energy Sources, Inorganic chemistry, Biophysics, Carbon nanotubes, chemistry.chemical_element, 02 engineering and technology, Carbon nanotube, Glucose biofuel cell, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Oxygen, law.invention, chemistry.chemical_compound, law, Long period, Electrochemistry, Animals, Physical and Theoretical Chemistry, Electrodes, Laccase, Nanotubes, Carbon, Phosphate buffered saline, [SPI.NRJ]Engineering Sciences [physics]/Electric power, General Medicine, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Phosphate, 0104 chemical sciences, Enzyme Activation, Glucose, chemistry, Biochemistry, Biofuel, Direct electron transfer, Glucose oxidation, Hydroxide, Cattle, 0210 nano-technology
Abstract

International audience; This study reports a mixed operational/storage stability of a MWCNT-based glucose biofuel cell (GBFC) over one year. The latter was examined by performing a one hour discharge every day during one month followed by several discharges over a period of 11 months. Under continuous discharge in physiological conditions (5 mM glucose, 37°, pH 7), the GBFC exhibits a 25% power decrease after 1 h of operation. This decrease is mainly due to the deactivation of laccase biocathodes at neutral pH. Nevertheless, the biocathodes can be reversibly reactivated via storage in phosphate buffer (pH 5). Under these conditions, the GBFC finally exhibits 22% of its initial maximum power density after one year at intermittent reactivation/discharge cycles. Although both GBFC electrodes can exhibit one year stability, short-term experiments show that biocathodes are limited by hydroxide inhibition while long-term experiments indicate that bioanodes are likely limited by the stability of the GOx itself. While most of the GBFCs in the literature present stability in the range of several weeks, these results demonstrate the viability of a GBFC for industrial applications in a long period of time.

Published
2015
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50. Fully Oriented Bilirubin Oxidase on Porphyrin-Functionalized Carbon Nanotube Electrodes for Electrocatalytic Oxygen Reduction

Author

Serge Cosnier, Michael Holzinger, Noémie Lalaoui, Alan Le Goff, Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), and 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)

Subjects
Oxidoreductases Acting on CH-CH Group Donors, Porphyrins, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Catalysis, law.invention, Electron Transport, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Bilirubin oxidase, Electrodes, ComputingMilieux_MISCELLANEOUS, Protoporphyrin IX, Nanotubes, Carbon, Organic Chemistry, General Chemistry, Hydrogen-Ion Concentration, Enzymes, Immobilized, 021001 nanoscience & nanotechnology, Porphyrin, Copper, 0104 chemical sciences, chemistry, Biocatalysis, 0210 nano-technology, Oxidation-Reduction
Abstract

The efficient immobilization and orientation of bilirubin oxidase from Myrothecium verrucaria on multi-walled carbon nanotube electrodes by using π-stacked porphyrins as a direct electron-transfer promoter is reported. By comparing the use of different types of porphyrin, the rational effect of the porphyrin structure on both the immobilization and orientation of the enzyme is demonstrated. The best performances were obtained for protoporphyrin IX, which is the natural precursor of bilirubin. These electrodes exhibit full orientation of the enzyme, as confirmed by the observable non-catalytic redox system corresponding to the T1 copper center associated with pure Nernstian electrocatalytic behavior with high catalytic currents of almost 5 mA cm(-2) at neutral pH.

Published
2015
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