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1. BODIPY-based catenane: Synthesis and optical properties

Author

Aurélie Rago, Sylvain David, Eric Framery, Olivier Maury, and Bruno Andrioletti

Subjects
General Chemistry
Abstract

The syntheses of unprecedented bis-triazolyl BODIPY dyes displaying high quantum yields are described. The synthetic approach involves a key alkene metathesis step after templating the two bis-triazolyl dipyrromethenes with Zn, promoting the catenane structure at the expense of the mono-macrocyclic structure. The optical properties of the open form, macrocyclic, and [2]-catenane derivatives are compared. Interestingly, if the fluorescence of both the open and the macrocyclic structure displayed excellent fluorescent properties in dichloromethane, the fluorescence is quenched for the catenane analogue. However, the fluorescence of the catenane can be restored in toluene. A putative explanation for the strong solvent effect is proposed.

Published
2023
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2. Ytterbium(III) Complex with Photochromic Ruthenium(II) Acetylide Ligand: All Visible Light Photoswitching of NIR Luminescence

Author

Pramila Selvanathan, Elsa Tufenkjian, Olivier Galangau, Thierry Roisnel, François Riobé, Olivier Maury, Lucie Norel, Stéphane Rigaut, 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), The authors thank the Université de Rennes 1, the CNRS, the ANR (RuOxLux─ANR-12-BS07-0010-01), and MESR for support. This work was performed using HPC/AI resources from GENCI-[CINES/TGCC] (Grant 2020-AP010811752 and 2021-AP0090811914)., and ANR-12-BS07-0010,RuOxLux,Modulation redox de la luminescence à l'aide de complexes organométalliques du ruthénium associés à une unité luminescente(2012)

Subjects
Inorganic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry
Abstract

International audience; We report a ruthenium(II) bisacetylide complex bearing a photochromic dithienylethene (DTE) acetylide arm and a coordinating bipyridyl on the trans acetylide unit. Its coordination with Yb(TTA)(3) centers (TTA = 2-thenoyltrifluoroacetonate) produces a bimetallic complex in which the dithienylethene isomerization is triggered by both ultraviolet (UV) light absorbed by the DTE unit and 450 nm excitation in a transition of the organometallic moiety. The redox behavior arising from the ruthenium(II) bisacetylide system is fully investigated by cyclic voltammetry and spectroelectrochemistry, revealing a lack of stability of the DTE-closed oxidized state preventing effective redox luminescence switching. On the other hand, the photoswitching of ytterbium(III) near-infrared (NIR) emission triggered by the photochromic reaction is fully operational. The electronic structure of this complex in its different states characterized by strong electronic coupling between the DTE and the ruthenium(II)-based moieties leading to metal-assisted photochromic behavior were rationalized with the help of time-dependent density functional theory (TD-DFT) calculations.

Published
2023
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3. Circularly polarized activity from two photon excitable europium and samarium chiral bioprobes

Author

Silvia Mizzoni, Silvia Ruggieri, Annika Sickinger, François Riobé, Laure Guy, Margaux Roux, Guillaume Micouin, Akos Banyasz, Olivier Maury, Bruno Baguenard, Amina Bensalah-Ledoux, Stéphan Guy, Alexei Grichine, Xuan-Nhi Nguyen, Andrea Cimarelli, Martina Sanadar, Andrea Melchior, and Fabio Piccinelli

Subjects
lanthanide ions, two photon absorption, optical probe, Materials Chemistry, circularly polarized luminescence, General Chemistry
Abstract

Circularly polarized luminescence activity from new cationic water soluble Sm(iii) and Eu(iii) complexes is triggered by one- and two-photon absorption processes. The Eu(iii) complex is shown to be an efficient NIR-to-RED probe in cellulo.

Published
2023
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4. A new G-quadruplex-specific photosensitizer inducing genome instability in cancer cells by triggering oxidative DNA damage and impeding replication fork progression

Author

Marco Deiana, José María Andrés Castán, Pierre Josse, Abraha Kahsay, Darío Puchán Sánchez, Korentin Morice, Natacha Gillet, Ranjitha Ravindranath, Ankit Kumar Patel, Pallabi Sengupta, Ikenna Obi, Eva Rodriguez-Marquez, Lhoussain Khrouz, Elise Dumont, Laura Abad Galán, Magali Allain, Bright Walker, Hyun Seo Ahn, Olivier Maury, Philippe Blanchard, Tangui Le Bahers, Daniel Öhlund, Jonas von Hofsten, Cyrille Monnereau, Clément Cabanetos, and Nasim Sabouri

Subjects
Genetics
Abstract

Photodynamic therapy (PDT) ideally relies on the administration, selective accumulation and photoactivation of a photosensitizer (PS) into diseased tissues. In this context, we report a new heavy-atom-free fluorescent G-quadruplex (G4) DNA-binding PS, named DBI. We reveal by fluorescence microscopy that DBI preferentially localizes in intraluminal vesicles (ILVs), precursors of exosomes, which are key components of cancer cell proliferation. Moreover, purified exosomal DNA was recognized by a G4-specific antibody, thus highlighting the presence of such G4-forming sequences in the vesicles. Despite the absence of fluorescence signal from DBI in nuclei, light-irradiated DBI-treated cells generated reactive oxygen species (ROS), triggering a 3-fold increase of nuclear G4 foci, slowing fork progression and elevated levels of both DNA base damage, 8-oxoguanine, and double-stranded DNA breaks. Consequently, DBI was found to exert significant phototoxic effects (at nanomolar scale) toward cancer cell lines and tumor organoids. Furthermore, in vivo testing reveals that photoactivation of DBI induces not only G4 formation and DNA damage but also apoptosis in zebrafish, specifically in the area where DBI had accumulated. Collectively, this approach shows significant promise for image-guided PDT.

Published
2023
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6. Thiochromenocarbazole imide: a new organic dye with first utility in large area flexible electroluminescent devices

Author

José María Andrés Castán, C. Amruth, Pierre Josse, Laura Abad Galan, Pablo Simón Marqués, Magali Allain, Olivier Maury, Tangui Le Bahers, Philippe Blanchard, Cyrille Monnereau, Gregory C. Welch, Clément Cabanetos, 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), Building Blocks for Future Electronics Laboratory (2B-FUEL), Yonsei University-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-18-EURE-0012,LumoMat-E,Molecular Materials for Organic Electronics/Photonics(2018), and ANR-20-CE05-0029,BTXI-APOGEE,Benzothioxanthene et dérivés : motifs prometteurs pour l'électronique organique(2020)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, General Materials Science
Abstract

International audience; Synthesis and use of the unprecedented thiochromenocarbazole imide (TCI) for the preparation of printed, large-area and flexible OLEDs.

Published
2022
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7. Scenario set-up and forcing data for impact model evaluation and impact attribution within the third round of the Inter-Sectoral Model Intercomparison Project (ISIMIP3a)

Author

Katja Frieler, Jan Volkholz, Stefan Lange, Jacob Schewe, Matthias Mengel, María del Rocío Rivas López, Christian Otto, Christopher P. O. Reyer, Dirk Nikolaus Karger, Johanna T. Malle, Simon Treu, Christoph Menz, Julia L. Blanchard, Cheryl S. Harrison, Colleen M. Petrik, Tyler D. Eddy, Kelly Ortega-Cisneros, Camilla Novaglio, Yannick Rousseau, Reg A. Watson, Charles Stock, Xiao Liu, Ryan Heneghan, Derek Tittensor, Olivier Maury, Matthias Büchner, Thomas Vogt, Tingting Wang, Fubao Sun, Inga J. Sauer, Johannes Koch, Inne Vanderkelen, Jonas Jägermeyr, Christoph Müller, Jochen Klar, Iliusi D. Vega del Valle, Gitta Lasslop, Sarah Chadburn, Eleanor Burke, Angela Gallego-Sala, Noah Smith, Jinfeng Chang, Stijn Hantson, Chantelle Burton, Anne Gädeke, Fang Li, Simon N. Gosling, Hannes Müller Schmied, Fred Hattermann, Jida Wang, Fangfang Yao, Thomas Hickler, Rafael Marcé, Don Pierson, Wim Thiery, Daniel Mercado-Bettín, Matthew Forrest, and Michel Bechtold

Abstract

This paper describes the rationale and the protocol of the first component of the third simulation round of the Inter-Sectoral Impact Model Intercomparison Project (ISIMIP3a, www.isimip.org) and the associated set of climate-related and direct human forcing data (CRF and DHF, respectively). The observation-based climate-related forcings for the first time include high-resolution observational climate forcings derived by orographic downscaling, monthly to hourly coastal water levels, and wind fields associated with historical tropical cyclones. The DHFs include land use patterns, population densities, information about water and agricultural management, and fishing intensities. The ISIMIP3a impact model simulations driven by these observation-based climate-related and direct human forcings are designed to test to what degree the impact models can explain observed changes in natural and human systems. In a second set of ISIMIP3a experiments the participating impact models are forced by the same DHFs but a counterfactual set of atmospheric forcings and coastal water levels where observed trends have been removed. These experiments are designed to allow for the attribution of observed changes in natural, human and managed systems to climate change, rising CH4 and CO2 concentrations, and sea level rise according to the definition of the Working Group II contribution to the IPCC AR6.

Published
2023
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8. Theoretical and experimental analysis of circularly polarized luminescence spectrophotometers for artifact-free measurements using a single CCD camera

Author

bruno baguenard, amina Bensalah-Ledoux, Laure Guy, François Riobé, Olivier Maury, Stephan Guy, Laboratoire de Chimie - UMR5182 (LC), 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
[PHYS]Physics [physics], Multidisciplinary, [CHIM]Chemical Sciences, General Physics and Astronomy, General Chemistry, General Biochemistry, Genetics and Molecular Biology
Abstract

Circularly polarized luminescence (CPL) is a fast growing research field as a complementary chiroptical spectroscopy alternative to the conventional circular dichroism or in the quest of devices producing circularly polarized light for different applications. Because chiroptical signals are generally lower than 0.1%, conventional chiral spectroscopies rely on polarization time modulation requiring step-by-step wavelength scanning and a long acquisition time. High throughput controls motivated the development of CPL spectrophotometers using cameras as detectors and space polarization splitting. However, CPL measurements imposes careful precautions to minimize the numerous artifacts arising from experimental imperfections. Some previous work used complex calibration procedure to this end. Here we present a rigorous Mueller analysis of an instrument based on polarizations space splitting. We show that by using one camera and combining spatial and temporal separation through two switchable circular polarization encoding arms we can record accurate CPL spectra without the need of any calibration. The measurements robustness and their fast acquisition times are exemplified on different chiral emitters.

Published
2023
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9. Multifunctional Helicene‐Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto‐Chiral Dichroism**

Author

Kais Dhbaibi, Maxime Grasser, Haiet Douib, Vincent Dorcet, Olivier Cador, Nicolas Vanthuyne, François Riobé, Olivier Maury, Stéphan Guy, Amina Bensalah‐Ledoux, Bruno Baguenard, Geert L. J. A. Rikken, Cyrille Train, Boris Le Guennic, Matteo Atzori, Fabrice Pointillart, Jeanne Crassous, 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), Université Larbi Tébessi [Tebessa], Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire 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 Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire national des champs magnétiques intenses - Grenoble (LNCMI-G ), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), The French National Research Agency (ANR) and the European Research Council (ERC) are acknowledged for financial support through SMMCPL (ANR-19-CE29-0012-02) and the European Union's Horizon 2020 research and innovation program (ERC-CoG MULTIPROSMM, Grant Agreement No. 725184). MG and BLG thank the French Agreement GENCI/IDRIS-CINES centers for high-performance computing resources., ANR-19-CE29-0012,SMMCPL,Luminescence polarisée circulairement de molécules-aimants à base de lanthanide(2019), and European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017)

Subjects
Single-molecule Magnet, [CHIM]Chemical Sciences, circularly polarized luminescence, ytterbium, General Medicine, General Chemistry, helicene, Catalysis, Magnetochiral Effect
Abstract

International audience; The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as Magneto-Chiral Dichroism (MChD) and Circularly Polarized Luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units, efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a slow magnetic relaxation (SMM) and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Published
2022
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10. Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based 'N

Author

Amélie, Godard, Laura Abad, Galán, Jean, Rouillon, Shaymaa, Al Shehimy, Wassima, Tajani, Charlotte, Cave, Raluca, Malacea-Kabbara, Yoann, Rousselin, Pierre, Le Gendre, Arnaud, Fihey, Mohamed, Bendellaa, Benoit, Busser, Lucie, Sancey, Boris, Le Guennic, Christophe, Bucher, Olivier, Maury, Christine, Goze, and Ewen, Bodio

Abstract

Aza-boron-dipyrromethenes (Aza-BODIPYs) are an increasingly studied class of fluorophores. They can be seen as an azadipyrromethene ("aza-DIPY") ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. The impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined, and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) makes them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this redshift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

Published
2022

11. 'N2O2' Metal-azaDIPY complexes: a new class of NIR-fluorophores

Author

Amélie Godard, Laura Abad Galan, Jean Rouillon, Shaymaa Al Shehimy, Wassima Tajani, Charlotte Cave, Raluca Malacea-Kabbara, Yoann Rousselin, Pierre Le Gendre, Arnaud Fihey, Mohamed Bendellaa, Benoit Busser, Lucie Sancey, Boris Le Guennic, Christophe Bucher, Olivier Maury, Christine Goze, and Ewen Bodio

Abstract

Aza-BODIPYs are an increasingly studied class of fluorophores. They can be seen as an "aza-DIPY" ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. Impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) make them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this red shift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

Published
2022
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12. Multifunctional Helicene-Based Ytterbium(III) Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism

Author

Kais Dhbaibi, Maxime Grasser, Haiet Douib, Vincent Dorcet, Olivier Cador, Nicolas Vanthuyne, françois Riobé, Olivier Maury, Stéphan Guy, Amina Bensalah-Ledoux, Bruno Baguenard, Geert Rikken, Cyrille Train, Boris Le Guennic, Matteo Atzori, Fabrice Pointillart, and Jeanne Crassous

Abstract

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as Magneto-Chiral Dichroism (MChD) and Circularly Polarized Luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units, efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a slow magnetic relaxation (SMM) and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Published
2022
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13. Modulation of the magnetic and photophysical properties in 3d-4f and 4f-4f' heterobimetallic complexes involving a tetrathiafulvalene-based ligand

Author

Haiet Douib, Jessica Flores Gonzalez, Saskia Speed, Vincent Montigaud, Bertrand Lefeuvre, Vincent Dorcet, François Riobé, Olivier Maury, Abdelkrim Gouasmia, Boris Le Guennic, Olivier Cador, Fabrice Pointillart, 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), Université Larbi Tébessi [Tebessa], This work was supported by Région Bretagne, Rennes Métropole, CNRS, Université de Rennes 1, FEDER, the ANR (ANR-13-BS07-0022-01) and the European Commission through the ERC-CoG 725184 MULTIPROSMM (project no. 725184). S. S. would like to thank Obra Social de la Fundació 'La Caixa' and Fundació Universitària Agustí Pedro i Pons for financial support., ANR-13-BS07-0022,SCOSIMLIGHT,Effet d'une irradiation lumineuse sur des ions aimants à transition de spin incorporant des ligands redox(2013), and European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017)

Subjects
Inorganic Chemistry, [CHIM]Chemical Sciences
Abstract

International audience; The reaction between the 2-(1-(2,6-di(pyrazol-1-yl)-4-methylpyridyl)-4,5-(4,5-bis(propylthio)-tetrathiafulvalenyl)-1H-benzimidazol-2-yl)-pyridine ligand (L), 1 equivalent of Ln(hfac)(3)·2H(2)O/Dy(tta)(3)·2H(2)O (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta(-) = 2-thenoyltrifluoroacetonate) and M(hfac)(2)·2H(2)O leads to the formation of heteroleptic 3d-4f dinuclear complexes of formula [MLn(hfac)(5)(L)](n) (M(II) = Cd, Zn, Co, Mn, Ni and Ln(III) = Dy, Yb, Nd) and [ZnDy(tta)(2)(hfac)(3)(L)]·(CH(2)Cl(2)). Their X-ray structures reveal that the two coordination sites are occupied by one Ln(III) ion and one M(II) transition metal respectively. The M(II) ions are coordinated to the benzoimidazolylpyridine (bzip) moiety in a N(2)O(4) coordination sphere, while the Ln(III) ions are coordinated to the 2,6-di(pyrazol-1-yl)-4-pyridine (dpp) moiety in a N(3)O(6) surrounding. When Dy(III) ion is used a field-induced Single-Molecule Magnet (SMM) behavior is detected with a magnetic relaxation time slightly dependent to the nature of the vicinal divalent transition metal. On the other hand, when the Yb(III) is used, intense, moderated or quenched (2)F(5/2) → (2)F(7/2) NIR luminescence is observed when the Yb(III) ion is respectively associated with the Zn(II), Mn(II) and Ni(II)/Co(II) ion. The emission intensity can be modulated in function of the metal-to-ligand charge transfer and d-d transition intensities. The replacement of the divalent transition metal by a trivalent lanthanide leads to the formation of heteroleptic 4f-4f’ dinuclear complexes of formula [Ln(2-x)Ln’(x)(hfac)(6)(L)]·a(CH(2)Cl(2))·b(C(6)H(14)) and [Dy(1.11)Nd(0.89)(tta)(3)(hfac)(3)(L)]. The coordination selectivity is based on the radius. Among the 4f-4f’ series, the Dy(III) derivatives displayed such ion in N(2)O(6) eight-coordinated sphere allowing the observation of SMM behavior. The three compounds [Dy(1.21)Nd(0.79)(hfac)(6)(L)]·2(CH(2)Cl(2))·(C(6)H(14)), [Yb(1.04)Nd(0.96)(hfac)(6)(L)] and [YbPr(hfac)(6)(L)] displayed respectively Nd(III), modarated Yb(III) and intense Yb(III) NIR emissions.

Published
2022
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14. De novo determination of mosquitocidal Cry11Aa and Cry11Ba structures from naturally-occurring nanocrystals

Author

Guillaume Tetreau, Michael R. Sawaya, Elke De Zitter, Elena A. Andreeva, Anne-Sophie Banneville, Natalie A. Schibrowsky, Nicolas Coquelle, Aaron S. Brewster, Marie Luise Grünbein, Gabriela Nass Kovacs, Mark S. Hunter, Marco Kloos, Raymond G. Sierra, Giorgio Schiro, Pei Qiao, Myriam Stricker, Dennis Bideshi, Iris D. Young, Ninon Zala, Sylvain Engilberge, Alexander Gorel, Luca Signor, Jean-Marie Teulon, Mario Hilpert, Lutz Foucar, Johan Bielecki, Richard Bean, Raphael de Wijn, Tokushi Sato, Henry Kirkwood, Romain Letrun, Alexander Batyuk, Irina Snigireva, Daphna Fenel, Robin Schubert, Ethan J. Canfield, Mario M. Alba, Frédéric Laporte, Laurence Després, Maria Bacia, Amandine Roux, Christian Chapelle, François Riobé, Olivier Maury, Wai Li Ling, Sébastien Boutet, Adrian Mancuso, Irina Gutsche, Eric Girard, Thomas R. M. Barends, Jean-Luc Pellequer, Hyun-Woo Park, Arthur D. Laganowsky, Jose Rodriguez, Manfred Burghammer, Robert L. Shoeman, R. Bruce Doak, Martin Weik, Nicholas K. Sauter, Brian Federici, Duilio Cascio, Ilme Schlichting, Jacques-Philippe Colletier, 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), UCLA/DOE Institute for Genomics and Proteomics, University of California [Los Angeles] (UCLA), University of California (UC)-University of California (UC), Groupe Dynamique et Cinétique des processus moléculaires (IBS-DYNAMOP), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Max-Planck-Institut für Medizinische Forschung, Max-Planck-Gesellschaft, Max Planck Institute for Medical Research [Heidelberg], Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory (SLAC), Stanford University-Stanford University, California Baptist University (CBU), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), European Synchroton Radiation Facility [Grenoble] (ESRF), Laboratoire d'Ecologie Alpine (LECA ), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), 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), Stanford University, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-17-CE11-0018,X-in-vivo,Cristallisation in vivo: une nouvelle stratégie pour étudier la structure et la dynamique des protéines dans les lasers à électrons libres et les synchrotrons.(2017)

Subjects
Mosquito Control, Multidisciplinary, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Bacillus thuringiensis, General Physics and Astronomy, General Chemistry, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, General Biochemistry, Genetics and Molecular Biology, Endotoxins, Hemolysin Proteins, Bacterial Proteins, Larva, [CHIM.CRIS]Chemical Sciences/Cristallography, Animals, Nanoparticles, [CHIM]Chemical Sciences
Abstract

Cry11Aa and Cry11Ba are the two most potent toxins produced by mosquitocidal Bacillus thuringiensis subsp. israelensis and jegathesan, respectively. The toxins naturally crystallize within the host; however, the crystals are too small for structure determination at synchrotron sources. Therefore, we applied serial femtosecond crystallography at X-ray free electron lasers to in vivo-grown nanocrystals of these toxins. The structure of Cry11Aa was determined de novo using the single-wavelength anomalous dispersion method, which in turn enabled the determination of the Cry11Ba structure by molecular replacement. The two structures reveal a new pattern for in vivo crystallization of Cry toxins, whereby each of their three domains packs with a symmetrically identical domain, and a cleavable crystal packing motif is located within the protoxin rather than at the termini. The diversity of in vivo crystallization patterns suggests explanations for their varied levels of toxicity and rational approaches to improve these toxins for mosquito control.

Published
2022
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15. Mechanisms underlying the epipelagic ecosystem response to ENSO in the equatorial Pacific ocean

Author

Nicolas Barrier, Matthieu Lengaigne, Jonathan Rault, Renaud Person, Christian Ethé, Olivier Aumont, Olivier Maury, 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)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), Nucleus for European Modeling of the Ocean (NEMO R&D ), Laboratoire d'Océanographie et du Climat : Expérimentations et Approches Numériques (LOCEAN), 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 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)-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)

Subjects
[SDE.MCG]Environmental Sciences/Global Changes, Geology, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Aquatic Science
Abstract

International audience

Published
2023
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16. 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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17. 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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18. 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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19. 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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20. Projecting net primary production in a sea of uncertainty: next steps and why should we care?

Author

Laurent Bopp, Olivier Aumont, Lester Kwiatkowski, Priscilla Le Mezo, Olivier Maury, Roland Séférian, and Alessandro Tagliabue

Abstract

Ocean net primary production (NPP) consists of CO2 fixation by marine phytoplankton and hence supports most marine food webs, fisheries and ocean carbon sequestration. Recent Earth System Model (ESM) projections of NPP changes under global warming scenarios, performed as part of the 6th phase of Coupled Model Intercomparison Project (CMIP6), show large uncertainty both in the magnitude and spatial distribution of NPP, which may have consequences for assessing ecosystem impacts and ocean carbon uptake. NPP uncertainty has increased since the previous intercomparion project (CMIP5), and likely does not even capture the full range of possible outcomes due to the general simplicity of ecosystem parameterizations employed in ESMs and the failure to account for non-climate drivers. Here, we exploit the full set of ESM projections from CMIP6, documenting NPP uncertainties and identifying certain physical and biogeochemical mechanisms that give rise to these uncertainties. We then use different versions of the IPSL ESM to explore (1) the specific role of N-fixation by diazotrophs in the upper ocean and (2) the influence of coupling to higher trophic levels in shaping the response of NPP, marine ecosystems and biogeochemistry to anthropogenic climate change. We show that the response of N-fixation to global warming is a key driver of NPP projection uncertainties in the coming decades, even determining the sign of the global NPP response. Despite contrasting projections of future NPP, all our model versions simulate similar and significant reductions in planktonic biomass. This suggests that plankton biomass may be a more robust indicator than NPP of the potential impact of anthropogenic climate change on marine ecosystems across models. In a second step, we show that an explicit coupling to higher trophic levels modifies the response of lower trophic levels (plankton) and shifts the ecosystem equilibrium, but seems to have limited influence on 21st century anthropogenic carbon uptake under the RCP8.5 high emissions scenario. These results provide new insights regarding the expectations for trophic amplification of climate impacts through the marine food chain and regarding the necessity to explicitly represent marine animals in Earth System Models.

Published
2022
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21. Seasonal forecast of land indicators for decision-making in the field of agriculture, forestry and hydrology

Author

André Chanzy, Patrick bertuzzi, Elisa Kamir, Hendrik Davi, Jean-Luc Dupuy, Nicolas Martin, Guillaume Pouget, Marc Lagier, Olivier Maury, Inaki Garcia de Cortazar, Christian Viel, and Jean-Michel Soubeyroux

Abstract

Many decisions in the field of agriculture, forestry and/or hydrology can get profit from seasonal forecast. However, the skill of such forecast is a critical issue to promote their use in operational context and get profitable decisions. If many methods to assess meteorological forecast performances are available, they are mostly implemented on raw climate variables, while their implementation in sectorial application remains limited to some case studies. In this study a wide range of indicators covering most of the decision-making needs in agriculture, forestry and in some extent to hydrology were considered. These indicators are either direct climate variables, a combination of climate variables, or variables calculated by dynamic models (e.g. a crop model). The study was implemented in southern France using the Méteo-France system 6 1993-2016 hindcast, downscaled using the UERRA reanalysis and the ADAMONT methods available in CS-Tools R package developed in the frame of the MEDSCOPE project. These computed indicators need various climate variables as wind speed, radiation and air humidity while most of the downscaling methods were designed for air temperature and precipitation. The main results are the following.We showed that all variables led to comparable level of accuracy. Seasonal forecasts provide added value compared to climatological forecasts with Brier Skill Scores between 0.05 and 0.20. The predictability of the number of rainy days or the number of days with temperature above a threshold is comparable to those of the corresponding scalar quantities such as cumulative precipitation or mean air temperature. However seasonal forecast of extreme events such as heat waves or drought episodes was not possible. Indicators combining several climatic information such as potential evapotranspiration or fire weather index have comparable predictability than the individual climate variables used in the calculation. With indicators based on dynamic models, the memory effect, i.e. the effect of the system state at the beginning of the forecast period, has a strong impact on the skill scores. We propose a methodology based on an ANOVA to qualify this memory effect by using the F-value. It is shown that when the memory effect is strong (F-value >10) the seasonal forecast does not bring any added value compared to the climatological forecast. An evaluation of the interest of a seasonal forecast in a decision-making framework was carried out by an economic approach. We have based our analysis on the decision making based on the forecast of an event. We show that there is a generic relationship between the AUC score and the gain from the forecast. We show that this relationship depends on the frequency of the decision event, the rarer the event the higher the AUC value must be to have a profitable decision. In our case, a decision based on the detection of a tercile leads to a profitable decision in more than half of the indicators while no indicator leads to a profitable decision when it is based on the detection of a quintile.

Published
2022
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22. De novo determination of mosquitocidal Cry11Aa and Cry11Ba structures from naturally-occurring nanocrystals

Author

Guillaume Tetreau, Michael R. Sawaya, Elke De Zitter, Elena A. Andreeva, Anne-Sophie Banneville, Natalie Schibrowsky, Nicolas Coquelle, Aaron S. Brewster, Marie Luise Grünbein, Gabriela Nass Kovacs, Mark S. Hunter, Marco Kloos, Raymond G. Sierra, Giorgio Schiro, Pei Qiao, Myriam Stricker, Dennis Bideshi, Iris D. Young, Ninon Zala, Sylvain Engilberge, Alexander Gorel, Luca Signor, Jean-Marie Teulon, Mario Hilpert, Lutz Foucar, Johan Bielecki, Richard Bean, Raphael de Wijn, Tokushi Sato, Henry Kirkwood, Romain Letrun, Alexander Batyuk, Irina Snigireva, Daphna Fenel, Robin Schubert, Ethan J. Canfield, Mario M. Alba, Frédéric Laporte, Laurence Després, Maria Bacia, Amandine Roux, Christian Chapelle, François Riobé, Olivier Maury, Wai Li Ling, Sébastien Boutet, Adrian Mancuso, Irina Gutsche, Eric Girard, Thomas R. M. Barends, Jean-Luc Pellequer, Hyun-Woo Park, Arthur D. Laganowsky, Jose Rodriguez, Manfred Burghammer, Robert L. Shoeman, R. Bruce Doak, Martin Weik, Nicholas K. Sauter, Brian Federici, Duilio Cascio, Ilme Schlichting, and Jacques-Philippe Colletier

Abstract

Cry11Aa and Cry11Ba are the two most potent toxins produced by mosquitocidal Bacillus thuringiensis subsp. israelensis and jegathesan, respectively. The toxins naturally crystallize within the host; however, the crystals are too small for structure determination at synchrotron sources. Therefore, we applied serial femtosecond crystallography at X-ray free electron lasers to in vivo-grown nanocrystals of these toxins. The structure of Cry11Aa was determined de novo using the single-wavelength anomalous dispersion method, which in turn enabled the determination of the Cry11Ba structure by molecular replacement. The two structures reveal a new pattern for in vivo crystallization of Cry toxins, whereby each of their three domains packs with a symmetrically identical domain, and a cleavable crystal packing motif is located within the protoxin rather than at the termini. The diversity of in vivo crystallization patterns suggests explanations for their varied levels of toxicity and rational approaches to improve these toxins for mosquito control.

Published
2021
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23. 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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24. 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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25. 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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26. Investigation of the K

Author

Pablo, Simón Marqués, José María, Andrés Castán, Laura Abad, Galan, Magali, Allain, Olivier, Maury, Tangui, Le Bahers, Philippe, Blanchard, and Clément, Cabanetos

Subjects
Nitriles, Catalysis, Palladium, Hydrogen
Abstract

The pallado-catalyzed cyanation of benzothioxanthene imide (

Published
2021

27. Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral Yb

Author

Bertrand, Lefeuvre, Carlo Andrea, Mattei, Jessica Flores, Gonzalez, Frédéric, Gendron, Vincent, Dorcet, François, Riobé, Claudia, Lalli, Boris, Le Guennic, Olivier, Cador, Olivier, Maury, Stéphan, Guy, Amina, Bensalah-Ledoux, Bruno, Baguenard, and Fabrice, Pointillart

Abstract

A field-induced chiral Yb

Published
2021

28. 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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29. Design of Polyazamacrocyclic Gd3+ Theranostic Agent Combining MRI and Two-Photon PDT

Author

Laura Abad Galan, Nadège Hamon, Christophe Nguyen, Enikő Molnár, János Kiss, Jonathan Mendy, Kamel Hadj-Kaddour, Mélanie Onofre, György Trencsényi, Cyrille Monnereau, Maryline Beyler, Gyula Tircso, Magali Gary-Bobo, Olivier MAURY, Raphael Tripier, RENARD, NICOLAS, 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), Université de Debrecen [Hungary], 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
theranostic applications, lanthanide, [CHIM.ORGA]Chemical Sciences/Organic chemistry, photodynamic therapy platform, [CHIM.ORGA] Chemical Sciences/Organic chemistry, azamacrocyclic complex, tacn framework, [CHIM] Chemical Sciences, [CHIM.RADIO] Chemical Sciences/Radiochemistry, [CHIM]Chemical Sciences, [CHIM.RADIO]Chemical Sciences/Radiochemistry, gadolinium contrast agents, Biphotonic excitation, pyclen-based lanthanide chelators
Abstract

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 sec. Finally, its relaxivity was measured in a DMSO/H2O solvents mixture with r1p = 11.21 and r2p = 24.60 mM-1s -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
2020
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30. An iron cycle cascade governs the response of equatorial Pacific ecosystems to climate change

Author

Alessandro, Tagliabue, Nicolas, Barrier, Hubert, Du Pontavice, Lester, Kwiatkowski, Olivier, Aumont, Laurent, Bopp, William W L, Cheung, Didier, Gascuel, and Olivier, Maury

Subjects
Climate Change, Iron, Fisheries, Animals, Biomass, Ecosystem
Abstract

Earth System Models project that global climate change will reduce ocean net primary production (NPP), upper trophic level biota biomass and potential fisheries catches in the future, especially in the eastern equatorial Pacific. However, projections from Earth System Models are undermined by poorly constrained assumptions regarding the biological cycling of iron, which is the main limiting resource for NPP over large parts of the ocean. In this study, we show that the climate change trends in NPP and the biomass of upper trophic levels are strongly affected by modifying assumptions associated with phytoplankton iron uptake. Using a suite of model experiments, we find 21st century climate change impacts on regional NPP range from -12.3% to +2.4% under a high emissions climate change scenario. This wide range arises from variations in the efficiency of iron retention in the upper ocean in the eastern equatorial Pacific across different scenarios of biological iron uptake, which affect the strength of regional iron limitation. Those scenarios where nitrogen limitation replaced iron limitation showed the largest projected NPP declines, while those where iron limitation was more resilient displayed little future change. All model scenarios have similar skill in reproducing past inter-annual variations in regional ocean NPP, largely due to limited change in the historical period. Ultimately, projections of end of century upper trophic level biomass change are altered by 50%-80% across all plausible scenarios. Overall, we find that uncertainties in the biological iron cycle cascade through open ocean pelagic ecosystems, from plankton to fish, affecting their evolution under climate change. This highlights additional challenges to developing effective conservation and fisheries management policies under climate change.

Published
2020

31. Pyclen-Based Ln(III) Complexes as Highly Luminescent Bioprobes for

Author

Nadège, Hamon, Amandine, Roux, Maryline, Beyler, Jean-Christophe, Mulatier, Chantal, Andraud, Christophe, Nguyen, Marie, Maynadier, Nadir, Bettache, Alain, Duperray, Alexei, Grichine, Sophie, Brasselet, Magali, Gary-Bobo, Olivier, Maury, and Raphaël, Tripier

Subjects
Photons, Luminescent Agents, Molecular Structure, Coordination Complexes, Optical Imaging, MCF-7 Cells, Animals, Humans, Ligands, Azabicyclo Compounds, Lanthanoid Series Elements, Zebrafish
Abstract

In addition to the already described ligand

Published
2020

32. Impacts of Ion-Pairing Effects on Linear and Nonlinear Photophysical Properties of Polymethines Dyes

Author

Simon Pascal, San-Hui Chi, Joseph W. Perry, Chantal Andraud, and Olivier MAURY

Abstract

Ion-pairing between cationic heptamethine and small bromine anion in a non-dissociating solvent results in a symmetry breaking towards a dipolar type chromophore, a transition that is never observed in presence of a bulky B(C6F5)4 anion. For the first time, the effects of ion-pairing on the linear and nonlinear photophysical properties is investigated and reveals significant discrepancies between cyanine and dipolar states.

Published
2020
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33. Pyclen Based Ln(III) Complexes as Highly Luminescent Bioprobes for in Vitro and in Vivo 1P and 2P Bioimaging Applications

Author

Nadège Hamon, Amandine Roux, Maryline Beyler, Jean-Christophe Mulatier, Chantal Andraud, Christophe Nguyen, Marie Maynadier, Nadir Bettache, Alain Duperray, Alexei Grichine, Sophie Brasselet, Magali Gary-Bobo, Olivier MAURY, and Raphael Tripier

Abstract

Two pyclen based lanthanide chelators, L4b and L4c, bearing two specific picolinate 2P antennas (tailor-made for each targeted metal) and one acetate arm arranged in a dissymmetrical manner, have been synthesized to form, with the already described ligand L4a, a complete family of lanthanide luminescent bioprobes: [EuL4a], [SmL4a], [YbL4b], [TbL4c] and [DyL4c]. Additionally, 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 arm. 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 2P-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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34. Efficient Luminescence Control in a Dithienylethene Functionalized Cyclen Macrocyclic Complex

Author

François Riobé, Hassan Al Sabea, Nadège Hamon, Lucie Norel, Olivier Maury, Raphaël Tripier, Olivier Galangau, and Stéphane Rigaut

Subjects
Ytterbium, chemistry.chemical_compound, Photochromism, Materials science, Photoluminescence, Cyclen, chemistry, Ligand, chemistry.chemical_element, Yttrium, Photochemistry, Europium, Luminescence
Abstract

We report the synthesis of an original ligand scaffold based on a dimethyl-cyclen platform Medo2pa with two dithienylethene units attached to each picolinate arms and the corresponding yttrium(III), europium(III) and ytterbium(III) complexes. All three complexes show reversible photochromism with high photo-conversions. Photoluminescence experiments demonstrate that this design is versatile and adapted for both europium and ytterbium emission switching when measured in frozen organic glasses at 77 K.

Published
2020
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35. Regioselective Mono and Homo/hetero Dihalogenation of the Benzothioxanthene Monoimide

Author

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

Subjects
Chemistry, Halogenation, Regioselectivity, Combinatorial chemistry
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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36. 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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38. 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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39. 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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40. 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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41. Protein crystallization assisted by the crystallophore

Author

Eric Girard, Zaynab Alsalman, Adeline Robin, Sylvain Engilberge, Amandine Roux, François Riobé, and Olivier Maury

Subjects
Inorganic Chemistry, Structural Biology, General Materials Science, Physical and Theoretical Chemistry, Condensed Matter Physics, Biochemistry
Published
2021
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42. Monitoring the crystallization of two enzymes in real time by dynamic light scattering

Author

Kévin Rollet, Raphaël de Wijn, Sylvain Engilberge, Alastair G. McEwen, Oliver Hennig, Heike Betet, Mario Mörl, François Riobé, Olivier Maury, E. Girard, Philippe Bénas, Bernard Lorber, and Claude Sauter

Subjects
Inorganic Chemistry, Structural Biology, General Materials Science, Physical and Theoretical Chemistry, Condensed Matter Physics, Biochemistry
Published
2021
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43. 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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44. 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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45. 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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46. 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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47. Crystallophore: a versatile lanthanide complex for protein crystallography combining nucleating effects, phasing properties, and luminescence

Author

Louise Lassalle, Sebastiano Di Pietro, François Riobé, Nicolas Coquelle, Delphine Pitrat, Dominique Madern, Eric Girard, Charles-Adrien Arnaud, Sylvain Engilberge, Olivier Maury, Jean-Christophe Mulatier, Cécile Breyton, Institut de biologie structurale (IBS - UMR 5075 ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Chimie - 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), 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), 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
0301 basic medicine, Lanthanide, Chemistry, Chemistry (all), chemistry.chemical_element, Terbium, General Chemistry, Phase problem, law.invention, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 03 medical and health sciences, Crystallography, 030104 developmental biology, law, Atom, X-ray crystallography, Crystallization, Luminescence, ComputingMilieux_MISCELLANEOUS, Macromolecule
Abstract

Macromolecular crystallography suffers from two major issues: getting well-diffracting crystals and solving the phase problem inherent to large macromolecules. Here, we describe the first example of a lanthanide complex family named “crystallophore” (Xo4), which contributes to tackling both bottlenecks. This terbium complex, Tb–Xo4, is an appealing agent for biocrystallography, combining the exceptional phasing power of the Tb(III) heavy atom with powerful nucleating properties, providing ready-to-use crystals for structure determination. Furthermore, protein/Tb–Xo4 co-crystals can be easily detected and discriminated from other crystalline by-products using luminescence. We demonstrate the potential of this additive for the crystallisation and structure determination of eight proteins, two of whose structures were unknown.

Published
2017
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49. 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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50. 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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