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187 results on '"Olivier Maury"'

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

Author

Gyula Tircsó, Nadège Hamon, Gyoergy Trencseny, Kamel Hadj-Kaddour, Mélanie Onofre, Christophe Nguyen, Eniko Molnar, Raphaël Tripier, Olivier Maury, Cyrille Monnereau, Laura Abad Galán, János Kiss, Jonathan Mendy, Maryline Beyler, Magali Gary-Bobo, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Debrecen Egyetem [Debrecen], École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

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

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

Published
2021
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2. Pyclen-Based Ln(III) Complexes as Highly Luminescent Bioprobes for In Vitro and In Vivo One- and Two-Photon Bioimaging Applications

Author

Olivier Maury, Sophie Brasselet, Raphaël Tripier, Jean-Christophe Mulatier, Nadir Bettache, Marie Maynadier, Magali Gary-Bobo, Maryline Beyler, Christophe Nguyen, Alexei Grichine, Nadège Hamon, Chantal Andraud, Alain Duperray, Amandine Roux, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), NanoMedSyn, Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), MOSAIC (MOSAIC), Institut FRESNEL (FRESNEL), Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), NanoMedSyn (NMS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
Lanthanide, [SDV]Life Sciences [q-bio], 010402 general chemistry, Quantum mechanics, 01 natural sciences, Biochemistry, Catalysis, Colloid and Surface Chemistry, Two-photon excitation microscopy, In vivo, Lanthanides, Microscopy, Structural isomer, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation, Zebrafish, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Ligand, Chemistry, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, Biological imaging, Antennas, Luminescence
Abstract

International audience; In addition to the already described ligand L4a, two pyclen-based lanthanide chelators, L4b and L4c, bearing two specific picolinate two-photon antennas (tailor-made for each targeted metal) and one acetate arm arranged in a dissymmetrical manner, have been synthesized, to form a complete family of lanthanide luminescent bioprobes: [EuL4a], [SmL4a], [YbL4b], [TbL4c], and [DyL4c]. Additionally, the symmetrically arranged regioisomer L4a′ was also synthesized as well as its [EuL4a′] complex to highlight the astonishing positive impact of the dissymmetrical N-distribution of the functional chelating arms. The investigation clearly shows the high performance of each bioprobe, which, depending on the complexed lanthanide, could be used in various applications. Each presents high brightness, quantum yields, and lifetimes. Staining of the complexes into living human breast cancer cells was observed. In addition, in vivo two-photon microscopy was performed for the first time on a living zebrafish model with [EuL4a]. No apparent toxicity was detected on the growth of the zebrafish, and images of high quality were obtained.

Published
2020
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3. Regioselective Monohalogenation and Homo/Hetero Dihalogenation of Benzothioxanthene Monoimide

Author

Olivier Maury, Magali Allain, Pierre Josse, Laura Abad Galán, Clément Dalinot, Pablo Simón Marqués, Philippe Blanchard, Clément Cabanetos, José María Andrés Castán, and Cyrille Monnereau

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Halogenation, Regioselectivity, 02 engineering and technology, Physical and Theoretical Chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, 3. Good health
Abstract

Through the preparation and characterization of five new derivatives, the regioselective mono and di, homo and hetero, halogenation of the benzothioxanthene (BTXI) core is demonstrated herein. All structurally solved by X-ray crystallography, these complementary functionalized building blocks open doors to the design of new symmetrical and asymmetrical π-conjugated systems based on this promising but still under-explored rylene.

Published
2020
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4. Aza-BODIPY Platform: Toward an Efficient Water-Soluble Bimodal Imaging Probe for MRI and Near-Infrared Fluorescence

Author

Pierre-Simon Bellaye, Olivier Maury, Célia S. Bonnet, Jacques Pliquett, Océane Florès, Bertrand Collin, Franck Denat, Sandra Même, Ewen Bodio, Laura Abad Galán, Robin Lescure, Christine Goze, Agnès Pallier, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER, Même, Sandra, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, 010405 organic chemistry, Singlet oxygen, Quantum yield, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Wavelength, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Surface modification, Physical and Theoretical Chemistry, Absorption (chemistry), Boron, Excitation
Abstract

In this study, an original aza-BODIPY system comprising two Gd3+ complexes has been designed and synthesized for magnetic resonance imaging/optical imaging application, by functionalization of the boron center. This strategy enabled to obtain a positively-charged bimodal probe, which displays an increased water-solubility, optimized photophysical properties in the near-infrared region, and very promising relaxometric properties. The absorption and emission wavelengths are 705 and 741 nm respectively, with a quantum yield of around 10 % in aqueous media. Moreover, the system does not produce singlet oxygen upon excitation, which would be toxic for tissues. The relaxivity obtained is high at intermediate fields (16.1 mM-1.s-1 at 20 MHz and 310 K) and competes with that of bigger or more rigid systems. A full relaxometric and 17O NMR study and fitting of the data using the Lipari-Szabo approach showed that this high relaxivity can be explained by the size of the system and the presence of some small aggregates. These optimized photophysical and relaxometric properties highlight the potential use of such systems for future bimodal imaging studies.

Published
2020
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5. Disentangling diverse responses to climate change among global marine ecosystem models

Author

Colleen M. Petrik, Travis C. Tai, Jason D. Everett, Nicolas Barrier, Ryan F. Heneghan, Tyler D. Eddy, Eric D. Galbraith, Olivier Maury, Juliano Palacios-Abrantes, Jeroen Steenbeek, Cheryl S. Harrison, Derek P. Tittensor, Marta Coll, Hubert Du Pontavice, William W. L. Cheung, Julia L. Blanchard, Phoebe A. Woodworth-Jefcoats, Catherine M. Bulman, Anthony J. Richardson, Jan Volkholz, Maite Erauskin-Extramiana, Didier Gascuel, Jose A. Fernandes-Salvador, Jérôme Guiet, Australian Research Council, European Commission, Agence Nationale de la Recherche (France), Jarislowsky Foundation, Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Fisheries and Oceans Canada, MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Écologie et santé des écosystèmes (ESE), AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institute for the Oceans and Fisheries, University of British Columbia (UBC), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-INSTITUT AGRO Agrocampus Ouest, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017), and Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-AGROCAMPUS OUEST

Subjects
0106 biological sciences, 010504 meteorology & atmospheric sciences, [SDE.MCG]Environmental Sciences/Global Changes, Climate change, Aquatic Science, Oceanography, 01 natural sciences, Modelling, Ecosystem services, Marine ecology, Structural uncertainty, Marine ecosystem, 14. Life underwater, Organism, 0105 earth and related environmental sciences, Trophic level, Biomass (ecology), business.industry, 010604 marine biology & hydrobiology, Scale (chemistry), Environmental resource management, Geology, Redistribution (cultural anthropology), 15. Life on land, FishMIP, Fish MIP, MIP, Climatic change, Climate Action, Fish, 13. Climate action, [SDE]Environmental Sciences, Environmental science, business, Fishery oceanography
Abstract

16 pages, 6 figures, 3 tables, supplementary data https://doi.org/10.1016/j.pocean.2021.102659.-- Code and data availability: The experimental protocol in this paper has no code associated with it. Forcing data from CMIP5 used for the protocol, and the FishMIP model outputs presented in this paper are available on the ISIMIP servers (https://www.isimip.org/), Climate change is warming the ocean and impacting lower trophic level (LTL) organisms. Marine ecosystem models can provide estimates of how these changes will propagate to larger animals and impact societal services such as fisheries, but at present these estimates vary widely. A better understanding of what drives this inter-model variation will improve our ability to project fisheries and other ecosystem services into the future, while also helping to identify uncertainties in process understanding. Here, we explore the mechanisms that underlie the diversity of responses to changes in temperature and LTLs in eight global marine ecosystem models from the Fisheries and Marine Ecosystem Model Intercomparison Project (FishMIP). Temperature and LTL impacts on total consumer biomass and ecosystem structure (defined as the relative change of small and large organism biomass) were isolated using a comparative experimental protocol. Total model biomass varied between −35% to +3% in response to warming, and -17% to +15% in response to LTL changes. There was little consensus about the spatial redistribution of biomass or changes in the balance between small and large organisms (ecosystem structure) in response to warming, an LTL impacts on total consumer biomass varied depending on the choice of LTL forcing terms. Overall, climate change impacts on consumer biomass and ecosystem structure are well approximated by the sum of temperature and LTL impacts, indicating an absence of nonlinear interaction between the models’ drivers. Our results highlight a lack of theoretical clarity about how to represent fundamental ecological mechanisms, most importantly how temperature impacts scale from individual to ecosystem level, and the need to better understand the two-way coupling between LTL organisms and consumers. We finish by identifying future research needs to strengthen global marine ecosystem modelling and improve projections of climate change impacts, JDE was funded by Australian Research Council Discovery Projects DP150102656 and DP190102293. MC, JS, NB and OM received financial support by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 817578 (Triatlas project). CH received funding from the Open Philanthropy Project. NB and OM also acknowledge the support of the French ANR project CIGOEF (grant ANR-17-CE32-0008-01). DPT acknowledges funding from the ISI-MIP project to support a workshop on this topic, and the Jarislowsky Foundation. EDG received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 682602, BIGSEA). RFH was funded by the Spanish Ministry of Science, Innovation and Universities through the Acciones de Programación Conjunta Internacional (PCIN-2017-115). MC acknowledges the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S) to the Institute of Marine Science (ICM-CSIC). TDE acknowledges funding from the ISIMIP project to support a workshop on this topic and the Fisheries and Oceans Canada Atlantic Fisheries Fund. All authors declare no conflict of interest with respect to this study. JAFS received funding from the European Union’s Horizon 2020 FutureMARES project (#869300).

Published
2021
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6. Influence of Divalent Cations in the Protein Crystallization Process Assisted by Lanthanide-Based Additives

Author

Olivier Maury, Sebastiano Di Pietro, François Riobé, Sylvain Engilberge, Guillaume Pilet, R. Talon, Adeline Robin, Seigo Shima, Zaynab Alsalman, Elise Dumont, Anthony D'Aléo, Tristan Wagner, Alessio Bartocci, Eric Girard, Amandine Roux, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie structurale (IBS - UMR 5075), 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), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Max Planck Institute for Terrestrial Microbiology, Max-Planck-Gesellschaft, Max Planck Institute for Marine Microbiology, ANR-13-BS07-0007,Ln23,Complexes de lanthanide comme nouveaux chevaux de Troie pour la détermination structurale de protéines(2013), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Models, Molecular, Lanthanide, Cations, Divalent, Inorganic chemistry, Supramolecular chemistry, Crystal structure, Crystallography, X-Ray, 010402 general chemistry, Crystals, Lanthanoid Series Elements, 01 natural sciences, Adduct, Divalent, law.invention, Inorganic Chemistry, Transmetalation, Transition metal, Coordination Complexes, law, [CHIM]Chemical Sciences, Particle Size, Physical and Theoretical Chemistry, Crystallization, chemistry.chemical_classification, Molecular Structure, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], 010405 organic chemistry, Chemistry, Additives, Crystals, Crystallization, Alcohols, Crystal structure, Additives, 0104 chemical sciences, Crystallography, Alcohols, X-ray crystallography, Chemical stability, Protein crystallization
Abstract

International audience; Lanthanide complexes are now widely used as powerful auxiliaries for protein crystallisation to improve the crucial nucleation and phasing steps. We systematically analysed the influence of the commercial crystallisation kit composition on the efficiency of two lanthanide additives [Na]$_3$[Eu(DPA)$_3$] and Tb-Xo4, we developed. This study revealed that our initial the trisdipicolinate complex presents a lower chemical stability and a strong tendency to self-crystallisation detrimental for its use in highthroughput robotised crystallisation platform. In particular, we reported herein the crystal structures of (Mg(H$_2$O)$_6$)$_3$ [Eu(DPA)$_3$]$_2$•7H$_2$O (1),{(Ca(H$_2$O)$_4$)$_3$[Eu(DPA)$_3$]$_2$}$_n$•11nH$_2$O (2) and {Cu(DPA)(H$_2$O)$_2$}$_n$ (3) resulting from spontaneous crystallisation in the presence of divalent alkaline earth cation or transmetallation. On the other hand, the Tb-Xo4 is perfectly soluble in the crystallisation media, stable in the presence of alkaline-earth dications and slowly decomposed (within days) by trans-metalation with transition metals. The original structure of [Tb$_4$L$_4$(H$_2$O)$_4$]Cl$_4$•15H$_2$O (4) is also described. In this article, we also discussed the potential beneficial interactions between the crystallisation mixture components and Tb-Xo4 leading to the formation of more complex adducts observed in the case of the AdKA protein crystallisation, like {AdkA/Tb-Xo4/Mg$^{2+}$ /glycerol} in the protein binding sites. The observation of such multi-components adducts illustrates the complexity and the versatility of the supramolecular chemistry occurring at the surface of proteins.

Published
2021
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7. Exploring the Concept of Dimerization-Induced Inter System Crossing: at the Origins of Spin-Orbit Coupling Selection Rules

Author

Olivier Maury, Tangui Le Bahers, Chantal Andraud, Pablo Simón Marqués, Philippe Blanchard, Elise Dumont, Clément Cabanetos, Joachim Galiana, José María Andrés Castán, Clément Dalinot, Laura Abad Galán, Cyrille Monnereau, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
Physics, Work (thermodynamics), 010405 organic chemistry, Supramolecular chemistry, Spin–orbit interaction, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Molecular engineering, Coupling (physics), Intersystem crossing, Photochemotherapy, Chemical physics, Materials Chemistry, Molecule, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Dimerization, Quantum
Abstract

Singlet-triplet interconversions (intersystem crossing, ISC) in organic molecules are at the basis of many important processes in cutting-edge photonic applications (organic light-emitting devices, photodynamic therapy, etc.). Selection rules for these transitions are mainly governed by the spin-orbit coupling (SOC) phenomenon. Although the SOC relies on complex relativistic phenomena, theoreticians have, with time, developed increasingly sophisticated and efficient approaches to gain access to a satisfactory evaluation of its magnitude. However, recent works have highlighted the remarkable and somehow unexpected efficiency of dimers of small conjugated molecules in terms of ISC quantum yields, whose origin has not been completely investigated. In this work, we bring a coupled experimental and theoretical analysis of the origin of the unusually large ISC efficiency on a series of such dimers that differ by their nature (covalent or supramolecular). We show that considering the dynamical nature of the SOC, and especially its dependence on angular orientations between the dimer subunits sometimes overlooked in the literature, it is necessary to rationalize some counterintuitive experimental observations. This combined experimental and theoretical work paves the way for new molecular engineering rules for SOC control.

Published
2021
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8. Chiral Benzothiazole Monofluoroborate Featuring Chiroptical and Oxygen-Sensitizing Properties: Synthesis and Photophysical Studies

Author

Bruno Baguenard, Stephan Guy, Olivier Maury, Frédéric Gendron, David M. Perrin, Emmanuel Gras, Amina Bensalah-Ledoux, Omar Sadek, Laura Abad Galán, Boris Le Guennic, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Matériaux et nanostructures photoniques (MNP), Institut Lumière Matière [Villeurbanne] (ILM), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, University of British Columbia (UBC), O.S. acknowledges support from Université Toulouse III and the French-Canadian Research Fund (FCRF). B.B., S.G., A.B.-L., B.L.G., O.M., L.A.G., O.S., and E.G. acknowledge support from Agence Nationale de la Recherche (ANR-18-CE07-0016/ANR-19-CE29-0012-02). F.G. and B.L.G. acknowledge support from the European Research Council (ERC-CoG MULTIPROSMM, Grant Agreement 7255184). F.G. thanks the Région Bretagne for its support (SAD 18006-LnCPLSMM). F.G. and B.L.G. thank the French GENCI/IDRIS-CINES centers for high-performance computing resources (allocations A0020800649 and A0040800649)., ANR-18-CE07-0016,CatSAmy,CatalyseurS à base d'agrégats Amyloïdes.(2018), ANR-19-CE29-0012,SMMCPL,Luminescence polarisée circulairement de molécules-aimants à base de lanthanide(2019), European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, medicine.medical_treatment, Photodynamic therapy, 010402 general chemistry, Ligands, 01 natural sciences, Stereocenter, Absorption, Physical Phenomena, chemistry.chemical_compound, medicine, Molecule, [CHIM]Chemical Sciences, Singlet state, Benzothiazoles, Boron, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Absolute configuration, Stereoisomerism, Combinatorial chemistry, Chiral resolution, 3. Good health, 0104 chemical sciences, Oxygen, Benzothiazole, chemistry, Mixtures, Enantiomer, Molecular structure
Abstract

International audience; Advances in personalized medicine are prompting the development of multimodal agents, that is, molecules that combine properties promoting various diagnostic and therapeutic applications. General approaches exploit chemical conjugation of therapeutic agents with contrast agents or the design of multimodal nanoplatforms. Herein, we report the design of a single molecule that exhibits potential for different diagnostic modes as well as the ability to sensitize oxygen, thus offering potential for photodynamic therapy. Exceptionally, this work involves the synthesis and chiral resolution of an enantiomeric pair of chiral monofluoroborates that contain a stereogenic boron atom. Combining experimental and theoretical chiroptical studies allowed the unambiguous determination of their absolute configuration. Photophysical investigations established the ability of this compound to sensitize oxygen even in the absence of heavy atoms within its structure. The synthesis of a chiral benzothiazole monofluoroborate paves a way to multimodal diagnostic tools (fluorescence and nuclear imaging) while also featuring potential therapeutic applications owing to its ability to activate oxygen to its singlet state for use in photodynamic therapy.

Published
2021
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9. Homodinuclear lanthanide 9-anthracenecarboxylate complexes: Field induced SMM and NIR-luminescence

Author

Olivier Maury, Berta Casanovas, Mercè Font-Bardia, Saskia Speed, and Ramon Vicente

Subjects
Lanthanide, Magnetisme, Luminescence, Field (physics), 010405 organic chemistry, Chemistry, Relaxation (NMR), Magnetism, Rare earth metals, Luminescència, Metalls de terres rares, Atmospheric temperature range, 010402 general chemistry, 01 natural sciences, Magnetic susceptibility, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, Magnetization, Crystallography, Materials Chemistry, Antiferromagnetism, Physical and Theoretical Chemistry
Abstract

Six homodinuclear lanthanide complexes with formula [Ln2(μ2-9-AC)4(9-AC)2(phen)2] (Ln(III) = Nd (1), Eu (2), Gd (3), Tb (4), Er (5) and Yb (6) are reported and complexes 1–3 and 6 are structurally characterized. 9-HAC = 9-anthracenecarboxylic acid, phen = 1,10-phenanthroline. The luminescence properties of compounds 1–6 have been studied at different temperatures in the solid state and show the sensitization of the 4f–4f emission bands in the NIR range for compounds 1, 5 and 6. The molar magnetic susceptibility measurements of 1–6 in the 2–300 K temperature range indicate weak antiferromagnetic exchange for the isotropic Gd(III) compound 3. Furthermore, slow relaxation of the magnetization is found in complexes 5 and 6 with effective energy barriers of 9.5 cm−1 (0.1 T) and 22.7 cm−1 (0.15 T), respectively.

Published
2019
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10. A 'Multi‐Heavy‐Atom' Approach toward Biphotonic Photosensitizers with Improved Singlet‐Oxygen Generation Properties

Author

Olivier Maury, Tangui Le Bahers, Raphaël Tripier, Margaux Galland, Chantal Andraud, N. Lascoux, Alain Duperray, Akos Banyasz, Yannick Guyot, Cyrille Monnereau, Alexei Grichine, Marie Maynadier, Christophe Nguyen, Magali Gary-Bobo, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut Lumière Matière [Villeurbanne] (ILM), Université de Lyon-Université de Lyon, NanoMedSyn, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and NanoMedSyn (NMS)

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

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

Published
2019
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11. Near-infrared dyes for two-photon absorption in the short-wavelength infrared: strategies towards optical power limiting

Author

Simon Pascal, Olivier Maury, Chantal Andraud, Sylvain David, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Range (particle radiation), Materials science, 010405 organic chemistry, business.industry, Infrared, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Near-infrared spectroscopy, Physics::Optics, Optical power, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Chromophore, 010402 general chemistry, 01 natural sciences, Two-photon absorption, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Wavelength, Optoelectronics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Absorption (electromagnetic radiation), business
Abstract

International audience; This work provides an overview of the recent advances in the field of two-photon absorbing chromophores active in the short-wavelength infrared (SWIR) spectral range. Herein the common strategies and main structure-properties relationships that lead to a near-infrared (NIR) electronic absorption of chromophores are described. A complete review of the molecules that feature two-photon absorption (2PA) beyond 1100 nm is presented for the purpose of further use in optical power limiting applications in the SWIR band. Recent progresses in the development of optical power limiting in this particular spectral region are reported with emphasis on the use of two-photon induced excited state absorption (ESA) process as optical power limiting enhancer.

Published
2021
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12. Investigation of the K 4 [Fe(CN) 6 ]-Mediated Mono- and Bis-Palladium-Catalyzed Cyanation of the Benzothioxanthene Core

Author

José María Andrés Castán, Olivier Maury, Pablo Simón Marqués, Magali Allain, Clément Cabanetos, Philippe Blanchard, Laura Abad Galán, Tangui Le Bahers, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nitrile, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Core (manufacturing), Cyanation, 010402 general chemistry, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Polymer chemistry, Structural isomer, [CHIM]Chemical Sciences, Imide, ComputingMilieux_MISCELLANEOUS, Palladium
Abstract

International audience; The pallado-catalyzed cyanation of benzothioxanthene imide (BTXI) derivatives is explored herein. Once optimized on the monobromo BTXI, mild reaction conditions were successfully applied to the dibromo derivative affording two regioisomers that have been isolated and structurally solved. Additional hydrogen-deuterium exchange experiments were carried out to support a proposed mechanism involving the formation of a five-membered palladacycle intermediate in the bay area. In addition to impact the structural, photo physical and electrochemical properties of the BTXI core, nitrile moieties were successfully used as orthogonal protecting groups thus opening doors to new design principles.

Published
2021
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13. Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral YbIII-Single-Molecule Magnet

Author

Stephan Guy, Frédéric Gendron, Bruno Baguenard, Fabrice Pointillart, Vincent Dorcet, Olivier Maury, Claudia Lalli, Bertrand Lefeuvre, Amina Bensalah-Ledoux, Jessica Flores Gonzalez, Olivier Cador, Carlo Andrea Mattei, François Riobé, Boris Le Guennic, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique de l'ENS Lyon (Phys-ENS), École normale supérieure de Lyon (ENS de Lyon)-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Matériaux et nanostructures photoniques (MNP), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), 725184, European Commission, SMMCPL ANR-19-CE29-0012-02, Agence Nationale de la Recherche, ANR-19-CE29-0012,SMMCPL,Luminescence polarisée circulairement de molécules-aimants à base de lanthanide(2019), European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), École normale supérieure - Lyon (ENS Lyon)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Ytterbium, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, Ion, chemistry.chemical_compound, medicine, Single Molecule Magnet, [CHIM]Chemical Sciences, Single-molecule magnet, triad, 010405 organic chemistry, Organic Chemistry, Near-infrared spectroscopy, Triad (anatomy), circularly polarized luminescence, ytterbium, General Chemistry, 0104 chemical sciences, Crystallography, medicine.anatomical_structure, chemistry, Magnet, chiral ancillary ligand, Luminescence, Tetrathiafulvalene
Abstract

International audience; A field-induced chiral Yb III Single-Molecule Magnet (SMM) displayed an unprecedented near-infrared circularly polarized luminescence (NIR-CPL) in solid-state. The bridging bis(1,10-phenantro[5,6b])tetrathiafulvalene triad ( L ) allowed an efficient sensitization of the NIR 2 F 5/2 → 2 F 7/2 emission while the NIR-CPL is associated to the f-f transitions of the Yb III ion bearing chiral β-diketonate derived-camphorate ancillary ligands.

Published
2021
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14. Benzothiadiazole substituted aza-BODIPY dyes: two-photon absorption enhancement for improved optical limiting performances in the SWIR range

Author

Gérard Berginc, Boris Le Guennic, Olivier Maury, David J. Hagan, Carl Brännlund, Sylvain David, Cesar Lopes, Chantal Andraud, Denis Jacquemin, Hao-Jung Chang, Eric W. Van Stryland, Mykailo V Bondar, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Central Florida [Orlando] (UCF), Swedish Defense Research Agency (FOI), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Thales LAS France, National Academy of Sciences of Ukraine (NASU), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Aza-bodipy dyes, 010405 organic chemistry, Chemistry, Organic Chemistry, Optical power, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Two-photon absorption, Catalysis, 0104 chemical sciences, Delocalized electron, two photon absorption, Intramolecular force, nonlinear optic, Moiety, Molecule, [CHIM]Chemical Sciences, optical limitation, Absorption (electromagnetic radiation), Spectroscopy, photophysics
Abstract

International audience; Aza-boron dipyrromethenes (aza-BODIPYs) presenting a benzothiadiazole substitution on upper positions are described. The strong electron-withdrawing effect of the benzothiadiazole moiety permits enhancement of the accepting strength and improves the delocalization of the aza-BODIPY core to attain a significant degree of electronic communication between the lower donating groups and the upper accepting groups. The nature of the intramolecular charge transfer is studied both experimentally and theoretically. Linear spectroscopy highlighted the strongly redshifted absorption and emission of the synthesized molecules with recorded fluorescence spectra over 1000 nm. Nonlinear optical properties were also investigated. Strong enhancement of the two-photon absorption of the substituted dyes compared with the unsubstituted one (up to 4520 GM at 1300 nm) results in an approximately 15-20 % improvement of the optical power limiting performances. These dyes are therefore a good starting point for further improvement of optical power limiting in the short-wave IR range.

Published
2021
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15. Solid-state: Versus solution investigation of a luminescent chiral BINOL-derived bisphosphate single-molecule magnet

Author

Vincent Montigaud, Frédéric Gendron, Nicolas Giraud, François Riobé, Fabrice Pointillart, Boris Le Guennic, Olivier Maury, Olivier Cador, Carlo Andrea Mattei, Vincent Dorcet, Claudia Lalli, Sandrine Denis-Quanquin, Gilles Argouarch, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), 725184SA18006-LnCPLSMMEuropean Research Council, ERCCentre National de la Recherche Scientifique, CNRSUniversité de Rennes 1, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)

Subjects
Computational investigation, Circular dichroism, Materials science, Luminescence, Coordination polymer, Dichroism, Polymers, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Ligands, 01 natural sciences, Dysprosium compounds, Nuclear magnetic resonance, Inorganic Chemistry, Paramagnetism, chemistry.chemical_compound, Mononuclear structures, Stereochemistry, [CHIM]Chemical Sciences, Single-molecule magnet, HOMO/LUMO, One dimensional, 010405 organic chemistry, Ligand, Electronic circular dichroism, Coordination Polymers, Molecules, Crystal-field splitting, 0104 chemical sciences, Crystallography, Enantiopure drug, chemistry, Dichloromethane, Crystal field theory, Magnets, Optimized structures, Structural transformation
Abstract

International audience; The enantiopure coordination polymer [Dy(hfac)3((S/R)-L)]n ([(S/R)-1]n) involving a BINOL-derived bisphosphate ligand (S/R)-L is reported. Paramagnetic NMR and computational investigations demonstrated the formation of mononuclear species [(S/R)-1] in CH2Cl2 solution and its optimized structure was determined. The experimental electronic circular dichroism signals of (S/R)-L were strongly enhanced after metal coordination [(S/R)-1]. Both polymeric and mononuclear structures displayed field-induced Single-Molecule Magnet (SMM) behaviour with similar multi-relaxation processes due to the retention of crystal-field splitting determined by CASSCF calculations, despite the strong structural transformation between the two media. The HOMO ? LUMO transition of the (S)-L ligand induced the classical Dy(iii) emission at 77 K that was correlated with the magnetic properties. [(S)-1]n is described as one-dimensional assembly of chiral luminescent Single-Ion Magnets (SIMs).

Published
2021
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16. Luminescence, chiroptical, magnetic and ab initio crystal-field characterizations of an enantiopure helicoidal Yb( iii ) complex

Author

Stephan Guy, Amina Bensalah-Ledoux, Francesco Zinna, Guillaume Pilet, Laure Guy, Lorenzo Di Bari, Sebastiano Di Pietro, François Riobé, Olivier Cador, Olivier Maury, Boris Le Guennic, Yannick Guyot, Virginie Placide, Bruno Baguenard, Fabrice Pointillart, Laura Abad Galán, Frédéric Gendron, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Pisa - Università di Pisa, Matériaux et nanostructures photoniques (MNP), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Luminescence (LUMINESCENCE), Laboratoire des Multimatériaux et Interfaces (LMI), F.G and B.L.G thank the French GENCI/IDRIS‐CINES center for high‐performance computing resources. F.G. andB.L.G. acknowledge the Stratégie d’Attractivité Durable (SAD18006—LnCPLSMM). Authors acknowledge supportfrom Agence Nationale de la Recherche (SMMCPL ANR-19-CE29-0012-02) and the European Research Councilunder the European Union’s Horizon 2020 research and innovation program (ERC-CoG MULTIPROSMM, Grantagreement No. 725184). All authors are indebted to J.-H. van Vleck for illuminating the richness and complexity oflanthanide optical spectra., ANR-19-CE29-0012,SMMCPL,Luminescence polarisée circulairement de molécules-aimants à base de lanthanide(2019), European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université de Lyon-Université de Lyon

Subjects
Materials science, Field (physics), 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Ab initio, Electronic structure, 010402 general chemistry, 01 natural sciences, Molecular physics, Spectral line, 0104 chemical sciences, Inorganic Chemistry, Crystal, Ab initio quantum chemistry methods, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Wave function, Luminescence
Abstract

International audience; The electronic structure of a chiral Yb(III)-based complex is fully determined by taking advantage of experimental magnetic, luminescence, and chiroptical (NIR-ECD and CPL) characterizations in combination with ab initio wavefunction calculations. The combined use of these techniques allows determining with high resolution the electronic structure diagram as well as the nature of the different states involved in the magnetic and chiroptical properties of the investigated complex. The crystal-field picture deduced from spectroscopic measurements (absorption and emission) is used to reproduce the magnetic properties. Subsequently, advanced ab initio calculations demonstrate that global chiroptical spectra correspond to the sum of entangled transitions with similar or opposite polarizations.

Published
2021
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17. Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Author

Amandine Roux, Lucca Neupert, Hubert Wadepohl, Laura Abad-Galán, Olivier Maury, Michael Gast, Peter Comba, Patrick Cieslik, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universität Heidelberg, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Lanthanide, Luminescence, Hot Paper, Quantum yield, Photophysics, Quantum Yield, Ligands, 010402 general chemistry, Lanthanoid Series Elements, 01 natural sciences, Catalysis, chemistry.chemical_compound, Lanthanides, Nonadentate ligand, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Emission spectrum, Coordination geometry, Square antiprismatic molecular geometry, Full Paper, 010405 organic chemistry, Ligand, Chemistry, Organic Chemistry, General Chemistry, Full Papers, Bridged Bicyclo Compounds, Heterocyclic, 0104 chemical sciences, 3. Good health, Crystallography, Excited state, Nonane
Abstract

EuIII, TbIII, GdIII and YbIII complexes of the nonadentate bispidine derivative L2 (bispidine=3,7‐diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X‐ray crystallography reveals full encapsulation by the nonadentate ligand L2 that enforces to all LnIII cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C4v symmetry). The well‐resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long‐lived excited states and high emission quantum yields ([EuIIIL2]+, H2O, 298 K, τ=1.51 ms, ϕ=0.35; [TbIIIL2]+, H2O, 298 K, τ=1.95 ms, ϕ=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes., EuIII, TbIII, GdIII and YbIII complexes of a nonadentate bispidine derivative were successfully synthesized and their emission properties studied. The X‐ray crystallography reveals full encapsulation by the nonadentate ligand, and the identical emission spectra in the solid state and in solution confirm equal structures in both media. As therefore expected, this results in long‐lived excited states and high emission quantum yields, making these complexes a possible basis for interesting biological probes.

Published
2021
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18. Next-generation ensemble projections reveal higher climate risks for marine ecosystems

Author

Jason S. Link, Marta Coll, Eric D. Galbraith, Jérôme Guiet, Jose A. Fernandes-Salvador, Gregory L. Britten, Didier Gascuel, William W. L. Cheung, Julia L. Blanchard, John P. Dunne, Yunne-Jai Shin, Elizabeth A. Fulton, Ryan F. Heneghan, Matthias Büchner, Jasmin G. John, Tyler D. Eddy, Daniele Bianchi, Heike K. Lotze, Charles A. Stock, Camilla Novaglio, Nicolas Barrier, Laurent Bopp, Jeroen Steenbeek, Derek P. Tittensor, Olivier Maury, Jonathan Rault, Kelly Ortega-Cisneros, Lynne J. Shannon, Colleen M. Petrik, Juliano Palacios-Abrantes, Hubert Du Pontavice, Anthony J. Richardson, Jason D. Everett, Andrea Bryndum-Buchholz, Cheryl S. Harrison, Villy Christensen, MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Laboratoire de Météorologie Dynamique (UMR 8539) (LMD), Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-École des Ponts ParisTech (ENPC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département des Géosciences - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Massachusetts Institute of Technology (MIT), Interférométrie (LCAR), Laboratoire Collisions Agrégats Réactivité (LCAR), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institute for the Oceans and Fisheries, University of British Columbia (UBC), NOAA Geophysical Fluid Dynamics Laboratory (GFDL), National Oceanic and Atmospheric Administration (NOAA), Institució Catalana de Recerca i Estudis Avançats (ICREA), Écologie et santé des écosystèmes (ESE), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), NOAA National Marine Fisheries Service (NMFS), Dalhousie University [Halifax], Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), University of Aberdeen, Institute for Marine and Antarctic Studies and Centre for Marine Socioecology, University of Tasmania [Hobart, Australia] (UTAS), Jarislowsky Foundation, Natural Sciences and Engineering Research Council of Canada, Australian Research Council, European Commission, Ministerio de Ciencia, Innovación y Universidades (España), UK Research and Innovation, Global Challenges Research Fund, One Ocean Hub, Simons Foundation, Belmont Forum, BiodivERsA, Agencia Estatal de Investigación (España), Ocean Frontier Institute, Agence Nationale de la Recherche (France), California Ocean Protection Council, Alfred P. Sloan Foundation, Extreme Science and Engineering Discovery Environment (US), National Oceanic and Atmospheric Administration (US), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, University of Texas Rio Grande Valley [Brownsville, TX] (UTRGV), Louisiana State University (LSU), Queensland University of Technology [Brisbane] (QUT), University of California [Los Angeles] (UCLA), University of California (UC), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Potsdam Institute for Climate Impact Research (PIK), Instituto de Ciencias del Mar de Barcelona (ICM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Centre for Fisheries Ecosystems Research (CFER), Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN), University of Queensland [Brisbane], Commonwealth Scientific and Industrial Research Organisation [Canberra] (CSIRO), University of New South Wales [Sydney] (UNSW), Basque Research and Technology Alliance (BRTA), AZTI - Tecnalia, McGill University = Université McGill [Montréal, Canada], Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-INSTITUT AGRO Agrocampus Ouest, University of Cape Town, University of Wisconsin-Madison, Texas A&M University [College Station], Princeton University, and ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017)

Subjects
0106 biological sciences, 010504 meteorology & atmospheric sciences, Environmental Science and Management, [SDE.MCG]Environmental Sciences/Global Changes, Climate change, Environmental Science (miscellaneous), 01 natural sciences, Physical Geography and Environmental Geoscience, Article, Atmospheric Sciences, Ecosystem, Marine ecosystem, 14. Life underwater, Life Below Water, 0105 earth and related environmental sciences, Ecological modelling, Marine biology, Coupled model intercomparison project, Biomass (ecology), business.industry, 010604 marine biology & hydrobiology, Environmental resource management, Climate-change ecology, Primary production, 15. Life on land, Climate Action, 13. Climate action, Environmental science, Climate model, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, business, Social Sciences (miscellaneous)
Abstract

22 pages, 5 figures, 1 table, supplementary information https://doi.org/10.1038/s41558-021-01173-9.-- Data availabilityAll standardized forcing variables from the ESMs are available at https://doi.org/10.48364/ISIMIP.575744.1; all outputs from the MEMs are available via ISIMIP (https://www.isimip.org/gettingstarted/data-access/).-- Code availabilityAll code used to analyse simulations is available at https://github.com/Fish-MIP/CMIP5vsCMIP6, Projections of climate change impacts on marine ecosystems have revealed long-term declines in global marine animal biomass and unevenly distributed impacts on fisheries. Here we apply an enhanced suite of global marine ecosystem models from the Fisheries and Marine Ecosystem Model Intercomparison Project (Fish-MIP), forced by new-generation Earth system model outputs from Phase 6 of the Coupled Model Intercomparison Project (CMIP6), to provide insights into how projected climate change will affect future ocean ecosystems. Compared with the previous generation CMIP5-forced Fish-MIP ensemble, the new ensemble ecosystem simulations show a greater decline in mean global ocean animal biomass under both strong-mitigation and high-emissions scenarios due to elevated warming, despite greater uncertainty in net primary production in the high-emissions scenario. Regional shifts in the direction of biomass changes highlight the continued and urgent need to reduce uncertainty in the projected responses of marine ecosystems to climate change to help support adaptation planning, This work was supported by the Jarislowsky Foundation (D.P.T.), the Natural Sciences and Engineering Research Council of Canada Discovery Grant programme (D.P.T., H.K.L., T.D.E., W.W.L.C., J.P.-A. and V.C.); Australian Research Council (ARC) Discovery Projects DP170104240 (J.L.B. and C.N.), DP190102293 (J.L.B., C.N., A.J.R., J.D.E. and D.P.T.) and DP150102656 (J.D.E.); the European Union’s Horizon 2020 research and innovation programme under grant agreements 817578 (TRIATLAS) (M.C., J.S., L.S., O.M., L.B., Y.-J.S., N.B. and J.R.), 869300 (FutureMARES) (J.A.F.-S.,Y.-J.S. and M.C.) and 862428 (MISSION ATLANTIC (J.A.F.-S, Y.-J.S. and M.C.); the Spanish National Project ProOceans (PID2020-118097RB-I00) (M.C. and J.S.); the Open Philanthropy Project (C.S.H.); the United Kingdom Research and Innovation (UKRI) Global Challenges Research Fund (GCRF) One Ocean Hub (NE/S008950/1) (K.O.-C. and L.S.); the Simons Foundation (nos. 54993, 645921) (G.L.B.); the Belmont Forum and BiodivERsA under the BiodivScen ERA-Net COFUND programme (SOMBEE project, ANR-18-EBI4-0003-01) (Y.-J.S. and N.B.); the MEOPAR Postdoctoral Fellowship Award 2020–2021 and the Ocean Frontier Institute (Module G) (A.B.-B.); the French ANR project CIGOEF (grant ANR-17-CE32-0008-01) (O.M., L.B. and J.R.); the California Ocean Protection Council Grant C0100400, the Alfred P. Sloan Foundation and the Extreme Science and Engineering Discovery Environment (XSEDE) allocation TG-OCE170017 (D.B. and J.G.); the National Oceanographic and Atmospheric Association (NA20OAR4310441, NA20OAR4310442) (C.M.P.). M.C. acknowledges the Severo Ochoa Centre of Excellence accreditation (CEX2019-000928-S) to the Institute of Marine Science (ICM-CSIC)

Published
2021
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19. Capturing The Dynamic Association Between A Tris-Dipicolinate Lanthanide Complex And A Decapeptide: A Combined Paramagnetic NMR And Molecular Dynamics Exploration

Author

Sandrine Denis-Quanquin, Elise Dumont, Olivier Maury, Alessio Bartocci, Florence Szczepaniak, François Riobé, Nicolas Giraud, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)

Subjects
Lanthanide, Tris, Magnetic Resonance Spectroscopy, Static Electricity, education, Molecular Conformation, General Physics and Astronomy, macromolecular substances, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Lanthanoid Series Elements, Paramagnetism, chemistry.chemical_compound, Molecular dynamics, Coordination Complexes, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Conformational sampling, Peptide structure, Picolinic Acids, health care economics and organizations, chemistry.chemical_classification, 010405 organic chemistry, Biomolecule, technology, industry, and agriculture, [INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation, 0104 chemical sciences, Microsecond, chemistry, Chemical physics, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract

In the realm of biomolecules, peptides can present a large diversity of structures. Our study sheds new light on the structural interplay between a tris-dipicolinate lanthanide probe and a decapeptide SASYKTLPRG. Although a rather trivial, electrostatically driven interaction was expected, the combination of paramagnetic NMR and molecular dynamics simulations reveals a highly dynamic association process and allows for providing extensive insights into the interaction sites and their occupancy. This study highlights the importance of a large conformational sampling to reconcile characteristic time in NMR with molecular dynamics simulations, where sampling in the microsecond range is needed. This study opens the door for a detailed mechanistic elucidation of the early steps of lanthanide complex-peptide or lanthanide complex–protein interaction or self-assembly processes.

Published
2020
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20. Impacts of Ion‐Pairing Effects on Linear and Nonlinear Photophysical Properties of Polymethines Dyes

Author

Olivier Maury, Joseph W. Perry, Simon Pascal, San-Hui Chi, Chantal Andraud, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)

Subjects
chemistry.chemical_classification, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 02 engineering and technology, Electronic structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Two-photon absorption, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Delocalized electron, chemistry, Chemical physics, Absorption band, Physical and Theoretical Chemistry, Counterion, Cyanine, 0210 nano-technology, Absorption (electromagnetic radiation), Heptamethine dyes
Abstract

International audience; The two-photon absorption (2PA) and photophysics of heptamethine dyes featuring cyanine or dipolar electronic structures has been compared for the first time. The perfectly delocalized cyanine system is classically characterized by a two-photon transition matching the vibronic component of its lower energy absorption band. The dipolar species is generated by ion-pairing with a hard counterion in non-dissociating solvent and displays significant optical properties modifications, including dramatic hypochromic shift of absorption, weaker emission and 2PA matching the lower energy transition, thus revealing symmetry breaking within the polymethine electronic structure. 2

Published
2020
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21. Poly-halogenated aza-bodipy dyes with improved solubility as a versatile synthetic platform for the design of photonic materials

Author

Guillaume Pilet, Olivier Maury, Sylvain David, Gérard Berginc, Chantal Andraud, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Improved solubility, Chemistry, Nonlinear optics, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Photonic metamaterial, Materials Chemistry, Alkoxy group, Aza-bodipy, [CHIM]Chemical Sciences, Solubility, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

The optimization of the solubility in organic solvents of halogenated aza-dipyrromethenes was achieved by substitution of the upper phenyl moieties by branched long alkoxy chains (1f) or by using an OMe–OHex–OMe pattern (1h). These results allowed us to prepare original tetra-halogenated aza-dipyrromethenes that were used as a synthetic platform to access highly functionalized aza-bodipy dyes for various potential applications including PDT, imaging, or nonlinear optics.

Published
2020
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22. Cationic Biphotonic Lanthanide Luminescent Bioprobes Based on Functionalized Cross-Bridged Cyclam Macrocycles

Author

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

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

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

Published
2020
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23. Nitration of benzothioxanthene: towards a new class of dyes with versatile photophysical properties

Author

Philippe Blanchard, Magali Allain, Cyrille Monnereau, Pablo Simón Marqués, Olivier Maury, Clément Cabanetos, José María Andrés Castán, Shi Li, Chad Risko, Clément Dalinot, Laura Abad Galán, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), School of Economics and Business Administration (School of Economics and Business Administration), Beijing Normal University (BNU), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry and Biochemistry, and Center for Organic Electronics and Photonics, Georgia Institute of Technology [Atlanta], École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
chemistry.chemical_classification, Primary (chemistry), 010405 organic chemistry, Nitro compound, General Chemistry, 010402 general chemistry, 01 natural sciences, Chemical reaction, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Nitration, Materials Chemistry, [CHIM]Chemical Sciences, Amine gas treating, Azide, ComputingMilieux_MISCELLANEOUS
Abstract

The selective mono-nitration of benzothioxanthane (BTXI) is demonstrated herein. This leap opens doors to a wide range of chemical reactions since the nitro compound was successfully reduced to a primary amine that was, in turn, converted into an azide. Beyond this chemical achievement, this new series of functionalized BTXI was fully characterized, including from a photophysical point of view, expanding the scope of this promising rylene to build a new electroactive π-conjugated platform for electronic organic purposes.

Published
2020
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24. High-Performance Optical Power Limiting Filters at Telecommunication Wavelengths: When Aza-BODIPY Dyes Bond to Sol-Gel Materials

Author

Gérard Berginc, Denis Jacquemin, Boris Le Guennic, Olivier Maury, Denis Chateau, Sylvain David, Cesar Lopes, Hao-Jung Chang, Linda H. Karlsson, Stephane Parola, Chantal Andraud, Mykhailo V. Bondar, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Central Florida [Orlando] (UCF), Swedish Defense Research Agency (FOI), National Academy of Sciences of Ukraine (NASU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Thales LAS France, Totalförsvarets Forskningsinstitut, FOI, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, Infrared, Optical power, 02 engineering and technology, 010402 general chemistry, Short wave infrared, 01 natural sciences, Two-photon absorption, Limiter, Sol-gels, Optical power limiters, [CHIM]Chemical Sciences, Sol-gel process, Physical and Theoretical Chemistry, Optical power limiting, Infrared radiation, Doping concentration, Dyes, Two photon absorption, Sol-gel, Optical properties, business.industry, Chromophore, Two photon processes, 021001 nanoscience & nanotechnology, Chromophores, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Wavelength, Light intensity, General Energy, Optoelectronics, Incident intensity, 0210 nano-technology, business, Telecommunication wavelengths, Photochemical stability
Abstract

International audience; An optical power limiter (OPL) device can change its optical properties depending on the input light intensity: it is ideally transparent at low incident power and presents a decrease in transmission when the incident intensity increases. This phenomenon can be used for protection of optical sensors. This paper presents the design of a functionalized aza-BODIPY chromophore, combining good nonlinear two-photon absorption and exited-state absorption in the short-wave infrared range (1300-1600 nm). The aza-BODIPY chromophores also show excellent thermal and photochemical stabilities. Their covalent grafting to a sol-gel matrix leads to the formation of class II sol-gel materials that allows for extraordinary doping concentrations of up to 280 mol·L-1 (40 wt %), which results in highly efficient OPL performances at 1550 nm. © 2020 American Chemical Society.

Published
2020
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25. Climate Change-Induced Emergence of Novel Biogeochemical Provinces

Author

Thomas L. Frölicher, Vicky W. Y. Lam, Gabriel Reygondeau, Colette C. C. Wabnitz, Olivier Maury, William W. L. Cheung, University of British Columbia (UBC), Climate and Environmental Physics [Bern] (CEP), Physikalisches Institut [Bern], Universität Bern [Bern]-Universität Bern [Bern], MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Universität Bern [Bern] (UNIBE)-Universität Bern [Bern] (UNIBE), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017)

Subjects
0106 biological sciences, Biogeochemical provinces, lcsh:QH1-199.5, 010504 meteorology & atmospheric sciences, Novel habitat, 530 Physics, [SDE.MCG]Environmental Sciences/Global Changes, Biome, Biodiversity, Climate change, pelagic environment, Ocean Engineering, lcsh:General. Including nature conservation, geographical distribution, Aquatic Science, marine biogeography, Oceanography, Spatial distribution, 01 natural sciences, Ecosystem services, novel ocean climate, 14. Life underwater, lcsh:Science, 550 Earth sciences & geology, 0105 earth and related environmental sciences, Water Science and Technology, Global and Planetary Change, 010604 marine biology & hydrobiology, Global warming, environmental niche model, Representative Concentration Pathways, physical oceanography, 15. Life on land, Species distribution (niche) model, Earth system science, 13. Climate action, Environmental science, lcsh:Q, Physical geography, [SDE.BE]Environmental Sciences/Biodiversity and Ecology
Abstract

WOS:000579835900001; International audience; The global ocean is commonly partitioned into 4 biomes subdivided into 56 biogeochemical provinces (BGCPs) following the accepted partition proposed by Longhurst in 1998. Each province corresponds to a unique regional environment that shapes biodiversity and constrains ecosystem structure and functions. BGCPs are dynamic entities that change their spatial extent and position with climate and are expected to be pertubated in the near future by global climate change. Here, we characterize the changes in spatial distribution of BGCPs from 1950 to 2100 using three earth system models under two representative concentration pathways (RCP 2.6 and 8.5). We project a reorganisation of current distribution of BGCPs driven mostly by a poleward shift of their distributions (18.4 km in average per decade). Projection of the future distribution of BGCPs also revealed the emergence of new climate that has no analogue with past and current environmental conditions experienced by BGCPs . This novel environmental conditions, here named No-Analogue BGCPs State (NABS), will expand from 2040 to 2100 at a rate of 4.3 Mkm2 per decade (1.2% of the global ocean). We subsequently quantified the potential amount of marine species and fisheries catch that would experience such novel environmental conditions to roughly evaluate NABS impact on ecosystem services.

Published
2020
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26. Differing marine animal biomass shifts under 21st century climate change between Canada’s three oceans

Author

Heike K. Lotze, Olivier Maury, Christensen, Andrea Bryndum-Buchholz, Eric D. Galbraith, Julia L. Blanchard, Derek P. Tittensor, Wwl Cheung, F Prentice, MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), and Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0106 biological sciences, Canada Exclusive Economic Zone, 010504 meteorology & atmospheric sciences, [SDE.MCG]Environmental Sciences/Global Changes, Climate change, canada exclusive economic zone, Fish stock, fish-mip, 01 natural sciences, Ecosystem services, Fish-MIP, Marine ecosystem, 14. Life underwater, lcsh:Science, 0105 earth and related environmental sciences, Biomass (ecology), Multidisciplinary, 010604 marine biology & hydrobiology, Exclusive economic zone, 15. Life on land, Fishery, climate change, Arctic, 13. Climate action, projection uncertainty, Environmental science, marine ecosystem models, Marine protected area, lcsh:Q, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, lcsh:L, ensemble modeling, lcsh:Education
Abstract

Identificadors digitals: Digital object identifier for the 'European Research Council' (http://dx.doi.org/10.13039/501100000781) and Digital object identifier for 'Horizon 2020' (http://dx.doi.org/10.13039/501100007601) Unidad de excelencia María de Maeztu CEX2019-000940-M Under climate change, species composition and abundances in high-latitude waters are expected to substantially reconfigure with consequences for trophic relationships and ecosystem services. Outcomes are challenging to project at national scales, despite their importance for management decisions. Using an ensemble of six global marine ecosystem models we analyzed marine ecosystem responses to climate change from 1971 to 2099 in Canada's Exclusive Economic Zone (EEZ) under four standardized emissions scenarios. By 2099, under business-as-usual emissions (RCP8.5) projected marine animal biomass declined by an average of −7.7% (±29.5%) within the Canadian EEZ, dominated by declines in the Pacific (−24% ± 24.5%) and Atlantic (−25.5% ± 9.5%) areas; these were partially compensated by increases in the Canadian Arctic (+26.2% ± 38.4%). Lower emissions scenarios projected successively smaller biomass changes, highlighting the benefits of stronger mitigation targets. Individual model projections were most consistent in the Atlantic and Pacific, but highly variable in the Arctic due to model uncertainties in polar regions. Different trajectories of future marine biomass changes will require regional-specific responses in conservation and management strategies, such as adaptive planning of marine protected areas and species-specific management plans, to enhance resilience and rebuilding of Canada's marine ecosystems and commercial fish stocks.

Published
2020
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27. Tracking Crystallophore Nucleating Properties: Setting Up a Database for Statistical Analysis

Author

Sebastiano Di Pietro, François Riobé, Tao Jiang, Eric Girard, Olivier Maury, Amandine Roux, Zaynab Alsalman, Sylvain Engilberge, Bruno Franzetti, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie structurale (IBS - UMR 5075), 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), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
0303 health sciences, Database, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Computer science, General Chemistry, 010402 general chemistry, Condensed Matter Physics, Tracking (particle physics), computer.software_genre, Phaser, 01 natural sciences, 0104 chemical sciences, law.invention, 03 medical and health sciences, law, [CHIM]Chemical Sciences, General Materials Science, Statistical analysis, Crystallization, Representation (mathematics), Protein crystallization, computer, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology
Abstract

In this article, the principle of a database aimed at facilitating the understanding of the unique protein nucleating properties of the Crystallophore is presented. A first analysis allows us to compare the efficiency of Tb-Xo4 with the new Lu-Xo4 variant, featuring improved phasing properties. Then, the concept of subset-of-interest is introduced to reveal potential antagonistic/synergistic effects between Tb-Xo4 and physico-chemical parameters of the crystallisation kits such as pH. The overall approach may be of interest for any studies working on solutions dedicated to improve the nucleating step in protein crystallization.TOC GraphicSynopsisA database and associated representation tools are highlighted to understand nucleating properties of the crystallophore.

Published
2020
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28. Efficient Photomodulation of Visible Eu(III) and Invisible Yb(III) Luminescences using DTE Photochromic Ligands for Optical Encryption

Author

Lucie Norel, François Riobé, Olivier Maury, Olivier Galangau, Thierry Roisnel, Stéphane Rigaut, Hassan Al Sabea, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Universite de Rennes 1, Ecole Normale Superieure de Lyon, CNRS Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Materials science, near infrared, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Ion, Biomaterials, Photochromism, Electrochemistry, luminescence, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, chemistry.chemical_classification, lanthanide ions, business.industry, Near-infrared spectroscopy, Polymer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, photochromism, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Optical encryption, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Optoelectronics, anti-counterfeiting, Naked eye, 0210 nano-technology, Luminescence, business
Abstract

International audience; This work describes a class of complex combining three dithienylethene units and a lanthanide ion used as an optical system displaying a double encryption method i) a colorful code, drawn and erased under UV and visible irradiations respectively, due to coloration and discoloration of the photochromic entities, and ii) a concomitant gradual disappearance and progressive restoration of the associated lanthanide ion luminescence triggered with the same stimuli. The innovation of the system stems from the emission color tunability, i.e., with either a lanthanide ion emitting only in the visible range (Eu3+) or with another lanthanide ion emitting only in the near infrared (NIR) range (Yb3+), therefore observable, or not, to the naked eye. This system is the very first one to achieve efficient repeatable modulation of pure NIR luminescence on photochemical command. Furthermore, it is proven to be highly efficient when embedded in a PDMS polymer opening real opportunities for practical applications as anti-counterfeiting.

Published
2020
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29. Luminescence-Driven Electronic Structure Determination in a Textbook Dimeric Dy(III)-based Single Molecule Magnet

Author

Frédéric Gendron, François Riobé, Boris Le Guennic, Guglielmo Fernandez Garcia, Guillaume Pilet, Olivier Maury, Djamila Guettas, Olivier Cador, Thierry Roisnel, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), École normale supérieure - Lyon (ENS Lyon), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), ANR-15-CE29-0019-02, Agence Nationale de la Recherche, ERCAdG 267746, H2020 European Research Council, École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), ANR-15-CE29-0019,ReDivaLan,Transfert électronique dans les organolanthanides : une approche spectroscopique et théorique(2015), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Université de Lyon

Subjects
Lanthanide, Magnetism, Acetylacetone, Supramolecular chemistry, chemistry.chemical_element, Electronic structure, 010402 general chemistry, 01 natural sciences, Catalysis, Supramolecular Chemistry, chemistry.chemical_compound, luminescence, Single Molecule Magnet, Dysprosium, [CHIM]Chemical Sciences, Single-molecule magnet, Crystal field, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, Organic Chemistry, General Chemistry, 0104 chemical sciences, 3. Good health, Crystallography, Luminescence
Abstract

A textbook dysprosium dinuclear complex based on acetylacetone ligands, [Dy2 (acac)4 (μ2 -acac)2 (H2 O)2 ], has been synthesized and fully characterized. This simple dimeric lanthanide complex shows well-resolved solid-state luminescence and behaves as a single-molecule magnet under zero DC field. A seminal crystal-field approach is used to marry both magnetism and luminescence in the frame of an energetic picture.

Published
2020
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30. Efficient luminescence control in dithienylethene functionalized cyclen macrocyclic lanthanide complexes

Author

Olivier Galangau, Raphaël Tripier, Nadège Hamon, Lucie Norel, Hassan Al Sabea, Stéphane Rigaut, François Riobé, Olivier Maury, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Rennes 1, Centre National de la Recherche Scientifique, Ministère de l'Education Nationale, de l'Enseignement Superieur et de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

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

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

Published
2020
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31. Synthesis, characterization and use of benzothioxanthene imide based dimers

Author

Olivier Maury, Olivier Alévêque, Ludovic Favereau, Pablo Simón Marqués, Gregory C. Welch, Sergey V. Dayneko, José María Andrés Castán, Clément Cabanetos, Laura Abad Galán, Clément Dalinot, Magali Allain, Philippe Blanchard, MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Calgary, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse Caractérisation Analyse de la Matière (ScanMAT), Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SADAM ANR-16-CE07-0015-01, Agence Nationale de la Recherche, Mitacs, SEPOMO 722651, H2020 Energy, ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Fabrication, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Relationship analysis, Metals and Alloys, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Characterization (materials science), chemistry.chemical_compound, chemistry, Chemical engineering, Materials Chemistry, Ceramics and Composites, OLED, 0210 nano-technology, Imide
Abstract

International audience; The synthesis of benzothioxanthene imide based dimers is reported herein. Subtle chemical modifications were carried out and their impact on the optical and electrochemical properties was investigated for a better structure-property relationship analysis. The icing on the cake was that these new structures were used as light emitting materials for the fabrication and demonstration of the first BTXI-based OLEDs.

Published
2020
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32. Evaluating the Potential Impacts of the Diurnal Vertical Migration by Marine Organisms on Marine Biogeochemistry

Author

Olivier Aumont, Stelly Lefort, Olivier Maury, Laurent Bopp, Nucleus for European Modeling of the Ocean (NEMO R&D ), Laboratoire d'Océanographie et du Climat : Expérimentations et Approches Numériques (LOCEAN), Institut Pierre-Simon-Laplace (IPSL (FR_636)), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Institut de Recherche pour le Développement (IRD)-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Institut de Recherche pour le Développement (IRD)-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), Laboratoire de Météorologie Dynamique (UMR 8539) (LMD), Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-École des Ponts ParisTech (ENPC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département des Géosciences - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), ANR-09-CEPL-0003,MACROES(2009), ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017), Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)-Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL)

Subjects
diurnal vertical, 0106 biological sciences, diurnal vertical migration, Atmospheric Science, Biogeochemical cycle, 010504 meteorology & atmospheric sciences, Mesopelagic zone, [SDV]Life Sciences [q-bio], migration, 01 natural sciences, Carbon cycle, biogeochemistry, Ecosystem model, carbon cycle, Environmental Chemistry, Ecosystem, 14. Life underwater, Diel vertical migration, 0105 earth and related environmental sciences, General Environmental Science, ecosystem, Global and Planetary Change, Biomass (ecology), 010604 marine biology & hydrobiology, Biogeochemistry, ocean, Oceanography, 13. Climate action, [SDE]Environmental Sciences, Environmental science, export
Abstract

International audience; Diurnal vertical migration (DVM) of marine organisms is an ubiquitous phenomenon in the ocean that generates an active vertical transport of organic matter. However, the magnitude and consequences of this flux are largely unknown and are currently overlooked in ocean biogeochemical models. Here we present a global model of pelagic ecosystems based on the ocean biogeochemical model NEMO-PISCES that is fully coupled to the upper trophic levels model Apex Predators ECOSystem Model, which includes an explicit description of migrating organisms. Evaluation of the model behavior proved to be challenging due to the scarcity of suitable observations. Nevertheless, the model appears to be able to simulate approximately both the migration depth and the relative biomass of migrating organisms. About one third of the epipelagic biomass is predicted to perform DVM. The flux of carbon driven by DVM is estimated to be 1.05 +/- 0.15 PgC/year, about 18% of the passive flux of carbon due to sinking particles at 150 m. Comparison with local studies suggests that the model captures the correct magnitude of this flux. Oxygen is decreased in the mesopelagic domain by about 5 mmol m(-3) relative to simulations of an ocean without DVM. Our study concludes that DVM drives a significant and very efficient flux of carbon to the mesopelagic domain, similar in magnitude to the transport of DOC. Relative to a model run without DVM, the consequences of this flux seem to be quite modest on oxygen, due to compensating effects between DVM and passive fluxes.

Published
2018
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33. Global biogeochemical provinces of the mesopelagic zone

Author

Stephanie A. Henson, Philippe Koubbi, Lionel Guidi, Tracey Sutton, Brian R. MacKenzie, Olivier Maury, Gabriel Reygondeau, Martine Fioroni, Grégory Beaugrand, Laboratoire d'océanographie de Villefranche (LOV), Observatoire océanologique de Villefranche-sur-mer (OOVM), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d’Océanologie et de Géosciences (LOG) - UMR 8187 (LOG), Centre National de la Recherche Scientifique (CNRS)-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de la Mer de Villefranche (IMEV), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Institut national des sciences de l'Univers (INSU - CNRS)-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD [France-Nord])

Subjects
Ocean, 0106 biological sciences, Biogeochemical cycle, 010504 meteorology & atmospheric sciences, Range (biology), Mesopelagic zone, Twilight zone, 01 natural sciences, Latitude, mesopelagic, Ecosystem, 14. Life underwater, ComputingMilieux_MISCELLANEOUS, [SDU.STU.OC]Sciences of the Universe [physics]/Earth Sciences/Oceanography, Ecology, Evolution, Behavior and Systematics, Macroecology, biogeochemical provinces, 0105 earth and related environmental sciences, geography, geography.geographical_feature_category, Ecology, 010604 marine biology & hydrobiology, environmental division, Pelagic zone, 15. Life on land, Oceanography, 13. Climate action, macroecology, Oceanic basin, Geology
Abstract

Aim Following the biogeographical approach implemented by Longhurst for the epipelagic layer, we propose here to identify a biogeochemical 3-D partition for the mesopelagic layer. The resulting partition characterizes the main deep environmental biotopes and their vertical boundaries on a global scale, which can be used as a geographical and ecological framework for conservation biology, ecosystem-based management and for the design of oceanographic investigations. Location The global ocean. Methods Based on the most comprehensive environmental climatology available to date, which is both spatially and vertically resolved (seven environmental parameters), we applied a combination of clustering algorithms (c-means, k-means, partition around medoids and agglomerative with Ward's linkage) associated with a nonparametric environmental model to identify the vertical and spatial delineation of the mesopelagic layer. Results First, we show via numerical interpretation that the vertical division of the pelagic zone varies and, hence, is not constant throughout the global ocean. Indeed, a latitudinal gradient is found between the epipelagic–mesopelagic and mesopelagic–bathypelagic vertical limits. Second, the mesopelagic layer is shown here to be composed of 13 distinguishable Biogeochemical Provinces. Each province shows a distinct range of environmental conditions and characteristic 3-D distributions. Main conclusions The historical definition of the mesopelagic zone is here revisited to define a 3-D geographical framework and characterize all the deep environmental biotopes of the deep global ocean. According to the numerical interpretation of mesopelagic boundaries, we reveal that the vertical division of the zone is not constant over the global ocean (200–1,000 m) but varies between ocean basin and with latitude. We also provide evidence of biogeochemical division of the mesopelagic zone that is spatially structured in a similar way than the epipelagic in the shallow waters but varies in the deep owing to a change of the environmental driving factors.

Published
2017
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34. Luminescence and Single‐Molecule‐Magnet Behaviour in Lanthanide Coordination Complexes Involving Benzothiazole‐Based Tetrathiafulvalene Ligands

Author

Fabrice Pointillart, François Riobé, Olivier Cador, Olivier Maury, Boris Le Guennic, Hideki Fujiwara, Yosuke Kishi, Bertrand Lefeuvre, Louis Cornet, Lahcène Ouahab, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Osaka Prefecture University, Conseil Régional de Bretagne, ANR-13-BS07-0022-01, ANR, Agence Nationale de la Recherche, ERDF, European Regional Development Fund, FEDER, Federación Española de Enfermedades Raras, CNRS, Centre National de la Recherche Scientifique, ANR-13-BS07-0022,SCOSIMLIGHT,Effet d'une irradiation lumineuse sur des ions aimants à transition de spin incorporant des ligands redox(2013), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Luminescence, Stereochemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Coordination complex, Inorganic Chemistry, Crystal, chemistry.chemical_compound, Lanthanides, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Single-molecule magnet, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, 0104 chemical sciences, 3. Good health, Ligand effects, Crystallography, Benzothiazole, Single-molecule magnets, Dysprosium, Sulfur heterocycles, Tetrathiafulvalene
Abstract

The two 4-[6-(1,3-benzothiazol-2-yl)pyridin-3-yl]-4',5'-bis(methylthio)tetrathiafulvene (L1) and 4-[6-(1,3-benzothiazol-2-yl)pyridin-3-yl]-4',5'-(ethylenedithio)tetrathiafulvene (L2) ligands have been elaborated and six new coordination complexes of lanthanide ions, namely [Ln2(hfac)6(L1)2]C6H14xCH2Cl2 (Ln = Dy and x = 0.25 (1); Ln = Yb and x = 0.30 (2)), [Ln(hfac)3(L2)] (Ln = Dy (3), Yb (4)) and [Ln(tta)3(L1)] (Ln = Yb (5), Er (6)) (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate; tta- = 2-thenoyltrifluoroacetylacetonate), have been characterized by X-ray diffraction on single crystals. Compounds 1-6 have been identified as mononuclear complexes with different crystal packing depending on the nature of the ancillary and tetrathiafulvalene-based ligands. The two dysprosium derivatives 1 and 3 displayed Single-Molecule Magnet behaviour in zero-applied magnetic field. While the near-infrared luminescence of 2 and 4 is almost undetectable, the change of ancillary ligands switched on the YbIII (5) and ErIII (6) luminescence.

Published
2017
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35. Linked sustainability challenges and trade-offs among fisheries, aquaculture and agriculture

Author

Eric D. Galbraith, Lindsay Davidson, Andrea Bryndum-Buchholz, Julia L. Blanchard, Tyler D. Eddy, Richard S. Cottrell, Elizabeth A. Fulton, William W. L. Cheung, Kirsty L. Nash, Reg Watson, Heike K. Lotze, Matthias Büchner, Olivier Maury, Christoph Müller, John P. Dunne, Joshua Elliott, Simon Jennings, Nicholas K. Dulvy, Derek P. Tittensor, David A. Carozza, Sea Around Us Project (SAUP), University of British Colombia, CSIRO Marine and Atmospheric Research (CSIRO-MAR), Commonwealth Scientific and Industrial Research Organisation [Canberra] (CSIRO), Department of Computer Science, Hong Kong Baptist University (HKBU), University of Chicago, Earth to Ocean Research Group (SFU), Simon Fraser University (SFU.ca), NOAA Geophysical Fluid Dynamics Laboratory (GFDL), National Oceanic and Atmospheric Administration (NOAA), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Potsdam Institute for Climate Impact Research (PIK), School of Geography, and University of North London

Subjects
0106 biological sciences, Conservation of Natural Resources, 010504 meteorology & atmospheric sciences, [SDE.MCG]Environmental Sciences/Global Changes, Climate Change, Fisheries, Aquaculture, 01 natural sciences, 12. Responsible consumption, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, 11. Sustainability, 14. Life underwater, Ecology, Evolution, Behavior and Systematics, 0105 earth and related environmental sciences, 2. Zero hunger, Sustainable development, Adaptive capacity, Food security, Ecology, business.industry, 010604 marine biology & hydrobiology, 1. No poverty, Capacity building, Agriculture, Biodiversity, 15. Life on land, Fishery, 13. Climate action, Sustainability, Food systems, Fisheries management, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, business
Abstract

International audience; Fisheries and aquaculture make a crucial contribution to global food security, nutrition and livelihoods. However, the UN Sustainable Development Goals separate marine and terrestrial food production sectors and ecosystems. To sustainably meet increasing global demands for fish, the interlinkages among goals within and across fisheries, aquaculture and agriculture sectors must be recognized and addressed along with their changing nature. Here, we assess and highlight development challenges for fisheries-dependent countries based on analyses of interactions and trade-offs between goals focusing on food, biodiversity and climate change. We demonstrate that some countries are likely to face double jeopardies in both fisheries and agriculture sectors under climate change. The strategies to mitigate these risks will be context-dependent, and will need to directly address the trade-offs among Sustainable Development Goals, such as halting biodiversity loss and reducing poverty. Countries with low adaptive capacity but increasing demand for food require greater support and capacity building to transition towards reconciling trade-offs. Necessary actions are context-dependent and include effective governance, improved management and conservation, maximizing societal and environmental benefits from trade, increased equitability of distribution and innovation in food production, including continued development of low input and low impact aquaculture.

Published
2017
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36. Can schooling regulate marine populations and ecosystems?

Author

Olivier Maury, MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), and Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
School, DYNAMICS, 0106 biological sciences, TAIL BEAT FREQUENCY, [SDE.MCG]Environmental Sciences/Global Changes, FISH SCHOOLS, Foraging, Fishing, Population, PREY, Density-dependence, Aquatic Science, Biology, ANIMAL GROUPS, 010603 evolutionary biology, 01 natural sciences, Population density, shoal, YELLOWFIN TUNA, Predation, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, Population resilience, Ecosystem, High fecundity, 14. Life underwater, education, Phase transition, Ecological stability, education.field_of_study, PREDATION, Ecology, 010604 marine biology & hydrobiology, Swarm behaviour, Geology, MODEL, swarm, School, shoal, swarm, MULTIBEAM SONAR, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, BEHAVIOR, Auto-organized groups
Abstract

International audience; Schools, shoals and swarms are pervasive in the oceans. They have to provide very strong advantages to have been selected and generalized in the course of evolution. Auto-organized groups are usually assumed to provide facilitated encounters of reproduction partners, improved protection against predation, better foraging efficiency, and hydrodynamic gains. However, present theories regarding their evolutionary advantages do not provide an unambiguous explanation to their universality. In particular, the mechanisms commonly proposed to explain grouping provide little support to the formation of very large groups that are common in the sea (e.g. Rieucau et al., 2014). From literature review, data analysis and using a simple mathematical model, I show that large auto-organized groups appear at high population density while only small groups or dispersed individuals remain at low population density. Following, an analysis of tuna tagging data and simple theoretical developments show that large groups are likely to expose individuals to a dramatic decrease of individual foraging success and simultaneous increase of predatory and disease mortality, while small groups avoid those adverse feedbacks and provide maximum foraging success and protection against predation, as it is usually assumed. This would create an emergent density-dependent regulation of marine populations, preventing them from outbursts at high density, and protecting them at low density. This would be a major contribution to their resilience and a crucial process of ecosystems dynamics. A two-step evolutionary process acting at the individual level is proposed to explain how this apparently suicidal behaviour could have been selected and generalized. It explains how grouping would have permitted the emergence of extremely high fecundity life histories, despite their notorious propensity to destabilize populations. The potential implications of the "grouping feedback" on population resilience, ecosystem stability and the persistence of marine biodiversity are discussed. The risk of harvesting marine species with fishing gears that enable catching dispersed individuals (such as longline, gillnet, trawl or using fishing aggregative devices for instance) is underlined. Finally, tropical tunas are used to exemplify the potential importance of schooling in shaping complex life histories and species interaction.

Published
2017
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37. Picolinate-Appended Tacn Complexes for Bimodal Imaging: radiolabeling, relaxivity, photophysical and electrochemical studies

Author

Olivier Maury, Gyula Tircsó, Patricia Le Saëc, Véronique Patinec, Christophe Bucher, Margaux Galland, Amaury Guillou, Réka Anna Gogolák, Alain Faivre-Chauvet, Amandine Roux, Raphaël Tripier, Maryline Beyler, Balázs Váradi, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Department of Physical Chemistry [Debrecen, Hungary] (Faculty of Science and Technology), University of Debrecen Egyetem [Debrecen], Nuclear Oncology (CRCINA-ÉQUIPE 13), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Gy.T. acknowledges financial support arriving form the Hungarian National Research, Development and Innovation Office (NKFIH K-120224 project), János Bolyai Research Scholarship of the Hungarian Academy of Sciences and European Regional Development Fund under the project GINOP-2.3.2-15-2016-00008., École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016), Bernardo, Elizabeth, École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Oncologie nucléaire (CRCINA - Département NOHMAD - Equipe 13), Centre de recherche de Cancérologie et d'Immunologie / Nantes - Angers (CRCINA), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), and Université de Nantes (UN)-Université de Nantes (UN)

Subjects
Models, Molecular, chemistry.chemical_element, Quantum yield, bimodal, [SDV.CAN]Life Sciences [q-bio]/Cancer, Zinc, π-conjugated antenna, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, Inorganic Chemistry, Metal, Electron transfer, [SDV.CAN] Life Sciences [q-bio]/Cancer, Transition metal, Coordination Complexes, luminescence, Picolinic Acids, Molecular Structure, 010405 organic chemistry, Chemistry, tacn, Fluorescence, 0104 chemical sciences, PET, Copper Radioisotopes, Isotope Labeling, visual_art, visual_art.visual_art_medium, Physical chemistry, Radiopharmaceuticals, Luminescence, IRM
Abstract

International audience; Based on our previous works involving two 1,4,7-triazacyclononane (tacn)-based ligands Hno2py1pa (1-Picolinic acid-4,7-bis(pyridin-2-ylmethyl)-1,4,7-triazacyclononane) and Hno1pa (1-Picolinic acid-1,4,7-triazacyclononane), we report here the synthesis of analogues bearing picolinate-based π-conjugated ILCT (Intra-Ligand Charge Transfer) transition antenna (HL1, HL2), using regiospecific N-functionalization of the tacn skeleton and their related transition metal complexes (e.g. Cu 2+ , Zn 2+ and Mn 2+). Coordination properties as well as their photophysical and electrochemical properties were investigated in order to quantify the impact of such antenna on the luminescent or relaxometric properties of the complexes. The spectroscopic properties of the targeted ligands and metal complexes have been studied using UV-Vis absorption and fluorescence spectrocopies. While the zinc complex formed with HL1 possesses a moderate quantum yield of 5%, complexation of Cu 2+ led to an extinction of the luminescence putatively attributed to a photo-induced electron transfer, as supported by spectroscopic and electrochemical evidences. The [Mn(L2)] + complex is characterized by a fluorescence quantum yield close to 8% in CH 2 Cl 2. The potential interest of such systems as bimodal probes has been assessed from radiolabeling experiments conducted on HL1 and 64 Cu 2+ as well as confocal microscopy analyses and from relaxometric studies carried out on the cationic [Mn(L2)] + complex. These results showed that HL1 can be used for radiolabeling, with a radiochemical conversion of 40% in 15 minutes at 100°C. Finally, the relaxivity values obtained for [Mn(L2)] + , r 1p = 4.80 mM-1 .s-1 and r 2p = 8.72 mM-1 .s-1 , make the Mn(II) complex an ideal candidate as a probe for Magnetic Resonance Imaging.

Published
2019
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38. Dual Light and Redox Control of NIR Luminescence with Complementary Photochromic and Organometallic Antennae

Author

Olivier Galangau, Hassan Al Sabea, Lucie Norel, Christophe Bucher, Hussein Hijazi, Rémi Métivier, Thierry Roisnel, Stéphane Rigaut, François Riobé, Olivier Maury, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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 Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-12-BS07-0010-01, Agence Nationale de la Recherche, Centre National de la Recherche Scientifique, Université de Rennes 1, GDR MCM-2, ANR-12-BS07-0010,RuOxLux,Modulation redox de la luminescence à l'aide de complexes organométalliques du ruthénium associés à une unité luminescente(2012), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Ytterbium, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, 3. Good health, 0104 chemical sciences, Ion, Ruthenium, Photochromism, Colloid and Surface Chemistry, chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract

International audience; With the help of a judicious association between dithienylethene (DTE) units, an ytterbium ion, and a ruthenium carbon-rich complex, we describe (i) the efficient (on/off) switching of pure NIR luminescence with a photochromic unit absorbing in the UV range and (ii) the association of electrochemical and photochemical control of this NIR emission in a single system with nondestructive readout.

Published
2019
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39. Evidencing under-barrier phenomena in a Yb( iii ) SMM: a joint luminescence/neutron diffraction/SQUID study

Author

Christophe Morell, Frédéric Guégan, Julie Jung, Béatrice Gillon, François Riobé, Olivier Maury, Jean-François Jacquot, Dominique Luneau, Boris Le Guennic, Yannick Guyot, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, LLB - Nouvelles frontières dans les matériaux quantiques (NFMQ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut Lumière Matière [Villeurbanne] (ILM), Université de Lyon-Université de Lyon, Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), ANR-15-CE29-0019-02, Agence Nationale de la Recherche, Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-École normale supérieure - Lyon (ENS Lyon), Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), 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)-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), OM and FR are grateful to ANR (REDIVALAN ANR-15-CE29-0019-02 and SCOSIMLIGHT ANR-13-BS07-0022-01) for financial support., ANR-15-CE29-0019,ReDivaLan,Transfert électronique dans les organolanthanides : une approche spectroscopique et théorique(2015), ANR-13-BS07-0022,SCOSIMLIGHT,Effet d'une irradiation lumineuse sur des ions aimants à transition de spin incorporant des ligands redox(2013), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-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)-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), Chemometrics and theoretical chemistry. - Chimiométrie et chimie théorique, and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Ytterbium, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Relaxation (NMR), Neutron diffraction, Ab initio, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, 0104 chemical sciences, law.invention, Inorganic Chemistry, SQUID, Magnetization, chemistry, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physics::Atomic Physics, 0210 nano-technology, Luminescence, Joint (geology)
Abstract

International audience; We report the synthesis, spectroscopic and magnetic characterisation and ab initio investigation of a new mononuclear ytterbium based complex, [YbTp2NO3], and discuss the physical mechanisms underlying the slow relaxation of its magnetisation in a moderate static field and at low temperature.

Published
2019
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40. Unraveling the Two-Photon and Excited State Absorptions of Aza-BODIPY Dyes for Optical Power Limiting in the SWIR Band

Author

Gérard Berginc, Joseph W. Perry, Nikolay S. Makarov, Boris Le Guennic, Denis Jacquemin, Patrick Feneyrou, Pierre-Antoine Bouit, Olivier Maury, Siwar Chibani, Simon Pascal, Chantal Andraud, Sylvain David, Quentin Bellier, San-Hui Chi, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry and Biochemistry, and Center for Organic Electronics and Photonics, Georgia Institute of Technology [Atlanta], Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Thales Research and Technology [Palaiseau], THALES [France], Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and THALES

Subjects
Physics, business.industry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Optical power, 02 engineering and technology, Limiting, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nonlinear optical, General Energy, Two-photon excitation microscopy, Position (vector), Excited state, Aza-bodipy, Optoelectronics, Physical and Theoretical Chemistry, 0210 nano-technology, Focus (optics), business, ComputingMilieux_MISCELLANEOUS
Abstract

We describe the linear and nonlinear optical properties of substituted aza-boron-dipyrromethene (aza-BODIPY) dyes with a focus on the impact of the spatial position and electronic nature of the sub...

Published
2019
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41. Global ensemble projections reveal trophic amplification of ocean biomass declines with climate change

Author

Heike K. Lotze, Jan Volkholz, Jacob Schewe, Susa Niiranen, David A. Carozza, Julia L. Blanchard, Yunne-Jai Shin, Tilla Roy, Charles A. Stock, Andrea Bryndum-Buchholz, Steve Mackinson, Derek P. Tittensor, Tyler D. Eddy, William W. L. Cheung, Matthias Büchner, Philippe Verley, Boris Worm, Miranda C. Jones, Elizabeth A. Fulton, Eric D. Galbraith, Jose A. Fernandes, Manuel Barange, Simon Jennings, Olivier Maury, Laurent Bopp, John P. Dunne, Ricardo Oliveros-Ramos, Tiago H. Silva, Nicolas Barrier, Daniele Bianchi, Nicola D. Walker, Marta Coll, Jeroen Steenbeek, Catherine M. Bulman, Villy Christensen, Natural Sciences and Engineering Research Council of Canada, V. Kann Rasmussen Foundation, Agence Nationale de la Recherche (France), Department for Environment, Food & Rural Affairs (UK), European Commission, Federal Ministry of Education and Research (Germany), Australian Research Council, Department of Computer Science, Hong Kong Baptist University (HKBU), Department of Earth and Planetary Sciences [Montréal] (EPS), McGill University = Université McGill [Montréal, Canada], GLOBEC IPO, Plymouth Marine Laboratory, Laboratoire de physique des océans (LPO), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS), Fisheries Centre, University of British Columbia, University of British Columbia (UBC), Institute of Marine Sciences / Institut de Ciències del Mar [Barcelona] (ICM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), NOAA Geophysical Fluid Dynamics Laboratory (GFDL), National Oceanic and Atmospheric Administration (NOAA), CSIRO Marine and Atmosphere Research [Hobart], Commonwealth Scientific and Industrial Research Organisation [Canberra] (CSIRO), School of Geography, University of North London, Stockholm University, Instituto del Mar del Peru (IMARPE), Food Science, FFUP, Potsdam-Institut für Klimafolgenforschung (PIK), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Chimie des Interactions Plasma-Surface (ChIPS) (ChIPS), Université de Mons-Hainaut, Ecopath International Initiative Research Association, Botanique et Modélisation de l'Architecture des Plantes et des Végétations (UMR AMAP), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut National de la Recherche Agronomique (INRA)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut de Recherche pour le Développement (IRD [France-Sud]), Defence Science and Technology Laboratory (Dstl), Ministry of Defence (UK) (MOD), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut National de la Recherche Agronomique (INRA)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD [France-Sud]), McGill University, Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), and Consejo Superior de Investigaciones Científicas [Spain] (CSIC)

Subjects
0106 biological sciences, Aquatic Organisms, Food Chain, 010504 meteorology & atmospheric sciences, Climate Change, Oceans and Seas, Fisheries, Climate change, Atmospheric sciences, [SDV.BID.SPT]Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, 01 natural sciences, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, Theoretical, Effects of global warming, Models, global ecosystem modeling, Animals, Marine ecosystem, Intercomparison, 14. Life underwater, Biomass, Trophic cascade, uncertainty, 0105 earth and related environmental sciences, Trophic level, Biomass (ecology), marine food webs, Multidisciplinary, Ensemble forecasting, Ecology, 010604 marine biology & hydrobiology, climate change impacts, Fishes, 15. Life on land, [SDV.BV.BOT]Life Sciences [q-bio]/Vegetal Biology/Botanics, Biological Sciences, Models, Theoretical, Food web, Climate Action, model intercomparison, 13. Climate action, Environmental science, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Model
Abstract

6 pages, 5 figures, supporting information https://doi.org/10.1073/pnas.1900194116.-- All data reported in this paper are archived and publicly available at http://dataservices.gfz-potsdam.de/pik/showshort.php?id=escidoc:2956913., While the physical dimensions of climate change are now routinely assessed through multimodel intercomparisons, projected impacts on the global ocean ecosystem generally rely on individual models with a specific set of assumptions. To address these single-model limitations, we present standardized ensemble projections from six global marine ecosystem models forced with two Earth system models and four emission scenarios with and without fishing. We derive average biomass trends and associated uncertainties across the marine food web. Without fishing, mean global animal biomass decreased by 5% (±4% SD) under low emissions and 17% (±11% SD) under high emissions by 2100, with an average 5% decline for every 1 °C of warming. Projected biomass declines were primarily driven by increasing temperature and decreasing primary production, and were more pronounced at higher trophic levels, a process known as trophic amplification. Fishing did not substantially alter the effects of climate change. Considerable regional variation featured strong biomass increases at high latitudes and decreases at middle to low latitudes, with good model agreement on the direction of change but variable magnitude. Uncertainties due to variations in marine ecosystem and Earth system models were similar. Ensemble projections performed well compared with empirical data, emphasizing the benefits of multimodel inference to project future outcomes. Our results indicate that global ocean animal biomass consistently declines with climate change, and that these impacts are amplified at higher trophic levels. Next steps for model development include dynamic scenarios of fishing, cumulative human impacts, and the effects of management measures on future ocean biomass trends, Financial support was provided by the German Federal Ministry of Education and Research through ISI-MIP (Grant01LS1201A1), the European Union’s Horizon 2020 Research and Innovation Program (Grant 678193), and the Ocean Frontier Institute (Module G). We acknowledge additional financial support as follows: to H.K.L., W.W.L.C., and B.W. from the Natural Sciences and Engineering Research Council (NSERC) of Canada; to D.P.T. from the Kanne Rasmussen Foundation Denmark; to A.B.-B. from the NSERC Transatlantic Ocean Science and Technology Program; to W.W.L.C. and T.D.E. from the Nippon Foundation-Nereus Program; to E.D.G., M.C. and J. Steenbeek from the European Union’s Horizon 2020 Re-search and Innovation Program (Grants 682602 and 689518); to E.A.F., J.L.B., andT.R. from Commonwealth Scientific and Industrial Research Organization and the Australian Research Council; to N.B., L.B., and O.M. from the French Agence Nationale de la Recherche and Pôle de Calcul et de Données pour la Mer; and to S.J. from the UK Department of Environment, Food and Rural Affairs

Published
2019
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42. Divalent Thulium Crown Ether Complexes with Field-Induced Slow Magnetic Relaxation

Author

Grégory Nocton, Olivier Maury, Carole Duboc, Mathieu Xémard, Florian Molton, Olivier Cador, Boris Le Guennic, Marie Cordier, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), 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 des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), CNRS, Ecole polytechnique, IR-RPE CNRS FR3443 network, École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Lanthanide, Spintronics, 010405 organic chemistry, Ligand, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Coordination complex, law.invention, Inorganic Chemistry, Thulium, chemistry, Chemical physics, law, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Ground state, Electron paramagnetic resonance, Crown ether
Abstract

International audience; The tailoring of the coordination chemistry around f-element centers is a crucial step for the development of compounds with slow magnetic relaxation, including single-molecule magnets (SMMs), which have great potential in molecular spintronics and for future quantum computing devices. Lanthanide ions are particularly interesting because the predominant electrostatic model of their bonding allows rationalizing their coordination symmetry. However, to the best of our knowledge, the redox properties of the lanthanides are not taken into account for the design of SMMs, and therefore all SMMs reported to date contain lanthanide ions in their trivalent oxidation state. In this Article, divalent lanthanide compounds presenting field-induced slow magnetic relaxation are reported. The rational design and synthesis of two TmII complexes with the 18-crown-6 ligand are presented along with their emission and EPR properties, which help to probe the desired nature of the ground state, that is, maximizing the anisotropy. The observed magnetic properties demonstrate their slow magnetic relaxation behavior in a moderate external magnetic field.

Published
2019
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43. Helicenic Complexes of Lanthanides: Influence of the f-Element on the Intersystem Crossing Efficiency and Competition between Luminescence and Oxygen Sensitization

Author

Chantal Andraud, Vincent Dorcet, Jiang-Kun Ou-Yang, Olivier Maury, Jeanne Crassous, Olivier Cador, Margaux Galland, Nidal Saleh, Cyrille Monnereau, Fabrice Pointillart, François Riobé, Boris Le Guennic, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-16-CE07-0015-01, Agence Nationale de la Recherche, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0015,SADAM,Diagnostiquer et guérir par des agents azamacrocycliques multimodaux(2016)

Subjects
Lanthanide, 010405 organic chemistry, Singlet oxygen, media_common.quotation_subject, medicine.medical_treatment, chemistry.chemical_element, Photodynamic therapy, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Oxygen, Competition (biology), 3. Good health, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, medicine.anatomical_structure, Intersystem crossing, chemistry, medicine, Luminescence, Sensitization, ComputingMilieux_MISCELLANEOUS, media_common
Abstract

International audience

Published
2019
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44. Damage-related protein turnover explains inter-specific patterns of maintenance rate and suggests modifications of the DEB theory

Author

Olivier Maury, Olivier Aumont, Jean-Christophe Poggiale, MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Institut de Recherche pour le Développement (IRD), Institut méditerranéen d'océanologie (MIO), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), Nucleus for European Modeling of the Ocean (NEMO R&D ), Laboratoire d'Océanographie et du Climat : Expérimentations et Approches Numériques (LOCEAN), Institut Pierre-Simon-Laplace (IPSL (FR_636)), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Institut de Recherche pour le Développement (IRD)-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Institut de Recherche pour le Développement (IRD)-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU), ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)-Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-École polytechnique (X)-Centre National d'Études Spatiales [Toulouse] (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)

Subjects
0106 biological sciences, [SDV.EE]Life Sciences [q-bio]/Ecology, environment, Protein - protein interaction, 010604 marine biology & hydrobiology, Scale (chemistry), High variability, Protein turnover, Aquatic Science, Oceanography, 010603 evolutionary biology, 01 natural sciences, Orders of magnitude (bit rate), Order (biology), DEB theory, Statistics, Maximum size, Add-my-Pet, Constant (mathematics), Scaling, Ecology, Evolution, Behavior and Systematics, Mathematics
Abstract

Maintenance is the energy that living organisms are bound to use to maintain their structure in a viable state. It includes all the metabolic and physiological costs that are not directly associated to the production of biomass (growth and reproduction) or to development (maturation). In the framework of the DEB theory, somatic maintenance rate can either be proportional to organism structural volume V or, more marginally, to structural surface V 2/3. Being mostly associated to similar metabolic processes, volume specific maintenance costs are not expected to vary substantially at both intra-and interspecific levels. In the DEB theory, the volume-specific maintenance rate is therefore supposed to keep constant from birth to death and to remain approximately constant between species. However, a recent meta-analysis of DEB parameters estimated using the Add-my-Pet collection (Kooijman, 2014) reveals troubling patterns apparently violating this inter-specific scaling rule and challenging the DEB theory. It is indeed shown in this study that empirically-derived volume-specific maintenance rates scale approximately with, and display a very high variability around this trend. Overall, estimated maintenance rates in Add-my-Pet span over three to four orders of magnitude, thus invalidating the assumption of constant maintenance rate between species, which underpins the covariation rules for parameter values of the DEB theory. In an attempt to address this major problem for the DEB theory, we propose a simple physiological mechanism that would simultaneously explain the apparent decrease of volume-specific maintenance rate with ultimate size and its apparent variability for a given range of maximum size. Our proposition consists in making protein (and more generally structure) turnover explicit in maintenance and linking protein damage rate to aerobic metabolism and the production of ROS, which are decreasing with both structural volume and maximum structural volume. We show that this implies that the actual volume specific maintenance rate varies both at the intra- and inter-specific levels in a range very similar to what is observed in the Add-my Pet data estimations. If true, this implies that the apparent decrease of volume-specific maintenance rate with ultimate size is an artefact and it requires modifications of the standard DEB theory in order to capture empirical inter-specific scaling patterns of DEB parameters while keeping the consistency of the theory at both intra- and inter-specific levels.

Published
2019
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45. Twenty-first-century climate change impacts on marine animal biomass and ecosystem structure across ocean basins

Author

Heike K. Lotze, Simon Jennings, Marta Coll, William W. L. Cheung, Derek P. Tittensor, Olivier Maury, Julia L. Blanchard, Andrea Bryndum-Buchholz, Eric D. Galbraith, V. Kann Rasmussen Foundation, Natural Sciences and Engineering Research Council of Canada, Federal Ministry of Education and Research (Germany), Institute of Marine Sciences / Institut de Ciències del Mar [Barcelona] (ICM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD)

Subjects
0106 biological sciences, Aquatic Organisms, marine animal biomass, 010504 meteorology & atmospheric sciences, ocean basins, Marine ecosystem models, 01 natural sciences, Ecosystem services, Body Size, Climate change, Ensemble modeling, Biomass, uncertainty, Marine animal biomass, General Environmental Science, Global and Planetary Change, Biomass (ecology), projections, geography.geographical_feature_category, Ecology, Uncertainty, Ocean basins, oxygen limitation, communities, Oceanography, model intercomparison, climate change, marine ecosystem models, ensemble modeling, Oceans and Seas, future projection, coastal, 010603 evolutionary biology, Models, Biological, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, Environmental Chemistry, Animals, Marine ecosystem, Ecosystem, 14. Life underwater, biogeography, 0105 earth and related environmental sciences, global ocean, geography, model, Primary production, 15. Life on land, Future projection, Sea surface temperature, 13. Climate action, fisheries, Environmental science, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Oceanic basin, Model intercomparison
Abstract

14 pages, 5 figures, 1 table, supporting information https://doi.org/10.1111/gcb.14512, Climate change effects on marine ecosystems include impacts on primary production, ocean temperature, species distributions, and abundance at local to global scales. These changes will significantly alter marine ecosystem structure and function with associated socio‐economic impacts on ecosystem services, marine fisheries, and fishery‐dependent societies. Yet how these changes may play out among ocean basins over the 21st century remains unclear, with most projections coming from single ecosystem models that do not adequately capture the range of model uncertainty. We address this by using six marine ecosystem models within the Fisheries and Marine Ecosystem Model Intercomparison Project (Fish‐MIP) to analyze responses of marine animal biomass in all major ocean basins to contrasting climate change scenarios. Under a high emissions scenario (RCP8.5), total marine animal biomass declined by an ensemble mean of 15%–30% (±12%–17%) in the North and South Atlantic and Pacific, and the Indian Ocean by 2100, whereas polar ocean basins experienced a 20%–80% (±35%–200%) increase. Uncertainty and model disagreement were greatest in the Arctic and smallest in the South Pacific Ocean. Projected changes were reduced under a low (RCP2.6) emissions scenario. Under RCP2.6 and RCP8.5, biomass projections were highly correlated with changes in net primary production and negatively correlated with projected sea surface temperature increases across all ocean basins except the polar oceans. Ecosystem structure was projected to shift as animal biomass concentrated in different size‐classes across ocean basins and emissions scenarios. We highlight that climate change mitigation measures could moderate the impacts on marine animal biomass by reducing biomass declines in the Pacific, Atlantic, and Indian Ocean basins. The range of individual model projections emphasizes the importance of using an ensemble approach in assessing uncertainty of future change, Financial support was provided by the German Federal Ministry of Education and Research (BMBF, grant no. 01LS1201A1) and through the Inter‐Sectoral Impact Model Intercomparison Project (ISI‐MIP). ABB acknowledges financial support from the NSERC CREATE Transatlantic Ocean Science and Technology Program (TOSST), HKL from the Natural Sciences and Engineering Research Council (NSERC) of Canada, and DPT from the Kann Rasmussen Foundation, Denmark

Published
2019
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46. Synthesis of the New Cyanine-Labeled Bacterial Lipooligosaccharides for Intracellular Imaging and in Vitro Microscopy Studies

Author

Andrea Sala, Chantal Andraud, Fabio A. Facchini, Francesco Peri, Flaviana Di Lorenzo, Thomas R Huser, Olivier Maury, Tung Cheng Wang, Simon Pascal, Lenny Zaffaroni, Florent Cochet, Christelle Serba, Department of Biotechnology and Biosciences, Università degli Studi di Milano-Bicocca = University of Milano-Bicocca (UNIMIB), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemical Sciences, Complesso Universitario Monte Sant'Angelo, University of Naples Federico II = Università degli studi di Napoli Federico II, Wang, T, Cochet, F, Facchini, F, Zaffaroni, L, Serba, C, Pascal, S, Andraud, C, Sala, A, Di Lorenzo, F, Maury, O, Huser, T, Peri, F, Università degli Studi di Milano-Bicocca [Milano] (UNIMIB), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Università degli studi di Napoli Federico II

Subjects
Lipopolysaccharides, Lipopolysaccharide, media_common.quotation_subject, Fluorescent Dye, Biomedical Engineering, Pharmaceutical Science, Bioengineering, 02 engineering and technology, Carbocyanine, In Vitro Techniques, 01 natural sciences, chemistry.chemical_compound, CHIM/06 - CHIMICA ORGANICA, Fluorescence microscope, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Internalization, ComputingMilieux_MISCELLANEOUS, media_common, Fluorescent Dyes, Pharmacology, Microscopy, Bacteria, Endocytosi, 010405 organic chemistry, Chemistry, In Vitro Technique, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Colocalization, Carbocyanines, 021001 nanoscience & nanotechnology, Subcellular localization, Endocytosis, 0104 chemical sciences, Cell biology, Toll-Like Receptor 4, CHIM/08 - CHIMICA FARMACEUTICA, TLR4, 0210 nano-technology, Bacterial outer membrane, Intracellular, Biotechnology
Abstract

Endotoxin (lipooligosaccharide, LOS, and lipopolysaccharide, LPS) is the major molecular component of Gram-negative bacteria outer membrane, and very potent pro-inflammatory substance. Visualizing and tracking the distribution of the circulating endotoxin is one of the fundamental approaches to understand the molecular aspects of infection with subsequent inflammatory and immune responses, LPS also being a key player in the molecular dialogue between microbiota and host. While fluorescently labeled LPS has previously been used to track its subcellular localization and colocalization with TLR4 receptor and downstream effectors, our knowledge on lipopolysaccharide (LOS) localization and cellular activity remains almost unexplored. In this study, LOS was labeled with a novel fluorophore, Cy7N, featuring a large Stokes-shifted emission in the deep-red spectrum resulting in lower light scattering and better imaging contrast. The LOS-Cy7N chemical identity was determined by mass spectrometry, and immunoreactivity of the conjugate was evaluated. Interestingly, its application to microscopic imaging showed a faster cell internalization compared to LPS-Alexa488, despite that it is also CD14-dependent and undergoes the same endocytic pathway as LPS toward lysosomal detoxification. Our results suggest the use of the new infrared fluorophore Cy7N for cell imaging of labeled LOS by confocal fluorescence microscopy, and propose that LOS is imported in the cells by mechanisms different from those responsible for LPS uptake.

Published
2019
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47. Paramagnetic DOSY: An Accurate Tool for the Analysis of the Supramolecular Interactions between Lanthanide Complexes and Proteins

Author

Olivier Maury, Marc-André Delsuc, Nicolas Giraud, Sandrine Denis-Quanquin, François Riobé, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut de Génétique et de Biologie Moléculaire et Cellulaire (IGBMC), Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Supramolecular chemistry, Analytical chemistry, Pulse sequence, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Small molecule, Catalysis, 0104 chemical sciences, Paramagnetism, Crystallography, Protein structure, Titration, Diffusion (business)
Abstract

International audience; Diffusion ordered NMR is implemented to determine accurately the mobility of paramagnetic tris-dipicolinate lanthanide complexes that are versatile probes of protein structure. It is shown that diffusion coefficient ratios can be measured with an accuracy of 1 % using a standard BPPLED pulse sequence, which allows for observing significant, though weak, variations when different species are interacting with the paramagnetic compound. We demonstrate that this approach is complementary to classical chemical shift titration experiments, and that it can be applied successfully to probe the supramolecular dynamic interactions between lanthanide complexes and small molecules on the one hand, or to determine rapidly their affinity for a targeted protein.

Published
2016
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48. Nano‐Nonanuclear Mixed‐Lanthanide Clusters [Eu 9– x Tb x ] Featuring Tunable Dual Luminescence Properties

Author

Christian Reber, Alexandra Fateeva, Florian Lepoivre, Ylane Malicet, Cristina M. Balogh, Guillaume Pilet, Djamila Guettas, Dominique Luneau, Emel Önal, Olivier Maury, and Camille Sonneville

Subjects
Lanthanide, 010405 organic chemistry, Chemistry, 010402 general chemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, 3. Good health, Ion, Inorganic Chemistry, Crystal, Crystallography, Nano, Inductively coupled plasma, Spectroscopy, Luminescence, Powder diffraction
Abstract

Five Tb3+/Eu3+ mixed nonanuclear clusters with the general formula [Eu9–xTbx(acac)16(µ3-OH)8(µ4-O)(µ4-OH)] ([Eu9–xTbx], x = 0.9–8.1, acac = acetylacetonate) were synthesized. Characterization by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) highlight a near-perfect match between the amounts of Tb3+ and Eu3+ ions input in the reaction mixture and the amounts in the clusters. The luminescence properties of these [Eu9–xTbx] clusters were investigated thoroughly in the solid state, and a strong energy transfer from the Tb3+ to Eu3+ emitters was evidenced. Thus, these nano-nonanuclear 4f clusters, which can be viewed as square pyramids that share one top, exhibit dual luminescence that can be adjusted by controlling the ratio of the lanthanide ions within the crystal architecture.

Published
2016
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49. The Ecosystem Approach to Fisheries: Reconciling Conservation and Exploitation

Author

Frédéric Ménard, Sophie Bertrand, Olivier Maury, François Le Loc'h, Florent Renaud, Lynn Shannon, Arnaud Bertrand, Souad Kifani, Marta Coll, Philippe Cury, Yunne-Jai Shin, Philippe Gros, Institut de Recherche pour le Développement (IRD), Institut de Recherche pour le Développement (IRD [France-Sud]), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut de Recherche pour le Développement (IRD), Institute of Marine Sciences / Institut de Ciències del Mar [Barcelona] (ICM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), 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 méditerranéen d'océanologie (MIO), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Toulon (UTLN), André Monaco, Patrick Prouzet, Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Consejo Superior de Investigaciones Científicas [Spain] (CSIC), Institut de Recherche pour le Développement (IRD)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Humboldt, 0106 biological sciences, Marine conservation, Benguela, Fisheries science, species conservation, 010604 marine biology & hydrobiology, OS, Pelagic zone, 010603 evolutionary biology, 01 natural sciences, Fishery, marine resources exploitation, Marine Strategy Framework Directive, Geography, marine strategy framework directive, Habitat, 13. Climate action, ecosystem approach to fisheries, Marine ecosystem, Ecosystem, 14. Life underwater, Fisheries management, marine ecosystems, [SDE.BE]Environmental Sciences/Biodiversity and Ecology
Abstract

International audience; Marine fisheries have a direct impact on the resources they exploit but also indirectly affect other species, habitats and the way ecosystems work. Ecosystem approach to fisheries (EAF) is a major aspect for the exploitation of marine resources and conservation of species. An ecosystem is set formed by a community of living beings and their biological, geological, edaphic, hydrological, climatic environment. Organisms are distributed as patches across a wide continuum of spatiotemporal scales. The marine strategy framework directive (MSFD) proposes an ecosystem approach for the assessment of the marine environment. Bottom-up control of predator fish through small pelagic fish has been noticed in the Benguela and Humboldt Current and in Guinea, since several predator fish suffer when their prey stock collapses. The scientific community needs to set up a long-term scientific strategy in order to enhance its ability to provide suitable competences for the ecosystem approach to marine resources.

Published
2016
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50. Redox-Modulations of Photophysical and Single-molecule Magnet Properties in Ytterbium Complexes Involving Extended-TTF Triads

Author

Vladimir K. Cherkasov, Frédéric Gendron, Viacheslav Kuropatov, François Riobé, Vincent Dorcet, Boris Le Guennic, Bertrand Lefeuvre, Olivier Cador, Olivier Maury, Fabrice Pointillart, Jessica Flores Gonzalez, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), École normale supérieure - Lyon (ENS Lyon), G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences [Moscow] (RAS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), 725184, ERC_, European Research Council, International, 18-53-15004, Российский Фонд Фундаментальных Исследований (РФФИ), PRC 199001, Centre National de la Recherche Scientifique, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Absorption spectroscopy, Semiquinone, extended-tetrathiafulvalene, Pharmaceutical Science, Protonation, Crystallography, X-Ray, 010402 general chemistry, 01 natural sciences, Article, Analytical Chemistry, Coordination complex, lcsh:QD241-441, Computational Chemistry, X-Ray Diffraction, lcsh:Organic chemistry, Drug Discovery, Benzoquinones, luminescence, electro-activity, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Single-molecule magnet, Physical and Theoretical Chemistry, Density Functional Theory, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, single-molecule magnet, Quenching (fluorescence), Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Quinones, Temperature, ytterbium, 3. Good health, 0104 chemical sciences, Quinone, Crystallography, Spectrometry, Fluorescence, Chemistry (miscellaneous), Magnets, Molecular Medicine, Luminescence, Oxidation-Reduction
Abstract

The reaction between the 2,2&rsquo, benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate triad (H2SQ) and the metallo-precursor [Yb(hfac)3]2H2O led to the formation of a dinuclear coordination complex of formula [Yb2(hfac)6(H2SQ)]0.5CH2Cl2 (H2SQ-Yb). After chemical oxidation of H2SQ in 2,2&rsquo, cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q), the latter triad reacted with the [Yb(hfac)3]2H2O precursor to give the dinuclear complex of formula [Yb2(hfac)6(Q)] (Q-Yb). Both dinuclear compounds have been characterized by X-ray diffraction, DFT optimized structure and electronic absorption spectra. They behaved as field-induced Single-Molecule Magnets (SMMs) nevertheless the chemical oxidation of the semiquinone to quinone moieties accelerated by a factor of five the relaxation time of the magnetization of Q-Yb compared to the one for H2SQ-Yb. The H2SQ triad efficiently sensitized the YbIII luminescence while the chemical oxidation of H2SQ into Q induced strong modification of the absorption properties and thus a quenching of the YbIII luminescence for Q-Yb. In other words, both magnetic modulation and luminescence quenching are reached by the oxidation of the protonated semiquinone into quinone.

Published
2020
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