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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. High trophic level feedbacks on global ocean carbon uptake and marine ecosystem dynamics under climate change

Author

Léonard Dupont, Priscilla Le Mézo, Olivier Aumont, Laurent Bopp, Corentin Clerc, Christian Ethé, Olivier Maury, Laboratoire de Météorologie Dynamique (UMR 8539) (LMD), Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-École des Ponts ParisTech (ENPC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département des Géosciences - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), 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)), 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)), 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), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), and 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)

Subjects
Global and Planetary Change, climate change, Ecology, [SDE.MCG]Environmental Sciences/Global Changes, high trophic levels, Earth System Model, Environmental Chemistry, trophic cascades, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, General Environmental Science, feedbacks
Abstract

Despite recurrent emphasis on their ecological and economic roles, the importance of high-trophic levels on ocean carbon dynamics, through passive (fecal pellet production, carcasses) and active (vertical migration) processes, is still largely unexplored, notably under climate change scenarios. Additionally, high trophic levels impact the ecosystem dynamics through top-down effects on lower trophic levels, which might change under anthropogenic influence. Here we compare two simulations of a global biogeochemical-ecosystem model with and without feedbacks from large marine animals. We show that these large marine animals affect the evolution of low-trophic level biomasses, hence net primary production and most certainly ecosystem equilibrium, but seem to have little influence on the 21st century anthropogenic carbon uptake under the RCP8.5 scenario. These results provide new insights regarding the expectations for trophic amplification of climate change through the marine trophic chain and regarding the necessity to explicitly represent marine animals in Earth System Models.

Published
2023
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9. 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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10. Distributive Nd-to-Yb energy transfer within pure [YbNdYb] heterometallic molecules

Author

Diamantoula Maniaki, Annika Sickinger, Leoní A. Barrios Moreno, David Aguilà, Olivier Roubeau, Nicholas S. Settineri, Yannick Guyot, François Riobé, Olivier Maury, Laura Abad Galán, Guillem Aromí, Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Generalitat de Catalunya, Department of Energy (US), and European Commission

Subjects
Inorganic Chemistry, Physical and Theoretical Chemistry
Abstract

Facile access to site-selective hetero-lanthanide molecules will open new avenues in the search of novel photophysical phenomena based on Ln-to-Ln′ energy transfer (ET). This challenge demands strategies to segregate efficiently different Ln metal ions among different positions in a molecule. We report here the one-step synthesis and structure of a pure [YbNdYb] (1) coordination complex featuring short Yb···Nd distances, ideal to investigate a potential distributive (i.e., from one donor to two acceptors) intramolecular ET from one Nd3+ ion to two Yb3+ centers within a well-characterized molecule. The difference in ionic radius is the mechanism allowing to allocate selectively both types of metal ion within the molecular structure, exploited with the simultaneous use of two β-diketone-type ligands. To assist the photophysical investigation of this heterometallic species, the analogues [YbLaYb] (2) and [LuNdLu] (3) have also been prepared. Sensitization of Yb3+ and Nd3+ in the last two complexes, respectively, was observed, with remarkably long decay times, facilitating the determination of the Nd-to-Yb ET within the [YbNdYb] composite. This ET was demonstrated by comparing the emission of iso-absorbant solutions of 1, 2, and 3 and through lifetime determinations in solution and solid state. The comparatively high efficiency of this process corroborates the facilitating effect of having two acceptors for the nonradiative decay of Nd3+ created within the [YbNdYb] molecule., The authors thank the Spanish AEI for grants PGC2018-098630-B-I00 (G.A. and D.A.), PID2020-118329RB-I00 (O.R.), and the Generalitat de Catalunya for an FI-SDUR Grant (2020-FISDU-00492, D.M.), and the ICREA Academia 2018 Prize (G.A.), as well as the Advanced Light Source, which is a DOE Office of Science User Facility operating under contract no. DE-AC02-05CH11231. This work used resources of the ALBA synchrotron through access to beamline 13-XALOC. This study was also supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat de Catalunya.

Published
2023

11. Transmission des prix entre les marchés de l'énergie et du poisson : est-ce que les cours du pétrole représentent de bons prédicteurs des prix du thon ?

Author

Patrice Guillotreau, Frédéric Lantz, Lesya Nadzon, Jonathan Rault, 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), IFP Energies nouvelles (IFPEN), IFP School, LINDE GAS Benelux, ANR, and ANR-17-CE32-0008,CIGOEF,Impacts des changements climatiques sur les écosystèmes et les pêcheries océaniques globaux.(2017)

Subjects
oil prices, Economics and Econometrics, Cointegration, [QFIN]Quantitative Finance [q-fin], regime shift, JEL: Q - Agricultural and Natural Resource Economics • Environmental and Ecological Economics/Q.Q4 - Energy/Q.Q4.Q41 - Demand and Supply • Prices, Geography, Planning and Development, Management, Monitoring, Policy and Law, tuna markets, JEL: Q - Agricultural and Natural Resource Economics • Environmental and Ecological Economics/Q.Q2 - Renewable Resources and Conservation/Q.Q2.Q21 - Demand and Supply • Prices, Oceanography, [SHS]Humanities and Social Sciences, structural breaks, JEL: Q - Agricultural and Natural Resource Economics • Environmental and Ecological Economics/Q.Q2 - Renewable Resources and Conservation/Q.Q2.Q22 - Fishery • Aquaculture
Abstract

International audience; Because most food processes are fossil fuel-based, many food markets are more or less connected to the oil market. Fishing technology in the high seas being energy-intensive, higher oil prices should affect the fish markets. This research looks at price transmission between Marine Diesel Oil and a global fishery commodity, frozen Skipjack tuna (Katsuwonus pelamis) through a time series analysis combining four different methods to look for possible structural breaks and regime shifts in the relationship (Bai-Perron, Lavielle, Gregory-Hansen, Markov-switching). Our results prove that the long-run equilibrium between both prices is weakening after the turn of the 2010s. Explaining the drivers of change is of great interest for short-term forecast but also to build long-term scenarios where both supply and demand variables are likely to affect tuna markets.; Puisque la plupart des filières agro-alimentaires reposent sur des énergies fossiles, de nombreux marchés alimentaires sont plus ou moins connectés au marché du pétrole. La technologie des pêcheries hauturières étant elle-même intensive en énergie, un prix plus élevé du pétrole devrait se refléter dans le prix du poisson. Cette recherche s'intéresse à la transmission des prix entre le diesel marin et un produit de la pêche global, le listao (Katsuwonus pelamis) congelé, via une analyse de séries temporelles croisant quatre méthodes différentes pour repérer des changements structurels et de régime dans la relation de prix (Bai-Perron, Lavielle, Gregory-Hansen, Markov-switching). Nos résultats montrent que l'équilibre de long terme s'atténue au tournant des années 2010. Expliquer les facteurs de ce changement représente certes un enjeu important pour des prévisions de court-terme, mais permet également de bâtir des scénarios de long-terme où les variables d'offre et de demande sont susceptibles de perturber conjointement les marchés thoniers.

Published
2023
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12. Circularly polarized luminescence in the one-dimensional assembly of binaphtyl-based Yb( iii ) single-molecule magnets

Author

Carlo Andrea Mattei, Vincent Montigaud, Bertrand Lefeuvre, Vincent Dorcet, Gilles Argouarch, Olivier Cador, Boris Le Guennic, Olivier Maury, Claudia Lalli, Yannick Guyot, Stéphan Guy, Cyprien Gindre, Amina Bensalah-Ledoux, François Riobé, Bruno Baguenard, 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), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by CNRS, Université de Rennes, the European Research Council through the ERC-CoG 725184 MULTIPROSMM (project no. 725184) and the Agence Nationale de la Recherche (SMMCPL ANR-19-CE29-0012-02)., 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
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry
Abstract

Lanthanide ions have attracted great interest owing to their optical and magnetic properties. Single-molecule magnet (SMM) behavior has been a fascinating science for thirty years. Moreover, chiral lanthanide complexes allow the observation of remarkable circularly polarized luminescence (CPL). However, the combination of both SMM and CPL behaviors in a single molecular system is very rare and deserves attention in the design of multifunctional materials. Four chiral one-dimensional coordination compounds involving 1,1′-Bi-2-naphtol (BINOL)-derived bisphosphate ligands and the Yb(III) centre were synthesized and characterized by powder and single-crystal X-ray diffraction. All the Yb(III)-based polymers displayed field-induced SMM behavior with magnetic relaxation occurring by applying Raman processes and near infrared CPL in the solid state.

Published
2023
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13. 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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14. 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

15. '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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16. 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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17. 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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18. Global decline of pelagic fauna in a warmer ocean

Author

Alejandro Ariza, Matthieu Lengaigne, Christophe Menkes, Anne Lebourges-Dhaussy, Aurore Receveur, Thomas Gorgues, Jérémie Habasque, Mariano Gutiérrez, Olivier Maury, Arnaud Bertrand, 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), Ecologie marine tropicale des océans Pacifique et Indien (ENTROPIE [Nouvelle-Calédonie]), Institut de Recherche pour le Développement (IRD [Nouvelle-Calédonie])-Ifremer - Nouvelle-Calédonie, Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de la Nouvelle-Calédonie (UNC), Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre for the Synthesis and Analysis of Biodiversity (CESAB), Institut Bouisson Bertrand, Montpellier, France, Laboratoire d'Océanographie Physique et Spatiale (LOPS), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS), and Instituto Humboldt de Investigación Marina

Subjects
[SDU.OCEAN]Sciences of the Universe [physics]/Ocean, Atmosphere, [SDE.MCG]Environmental Sciences/Global Changes, Environmental Science (miscellaneous), [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Social Sciences (miscellaneous)
Abstract

International audience; Pelagic fauna is expected to be impacted under climate change according to ecosystem simulations. However, the direction and magnitude of the impact is still uncertain and still not corroborated by observational-based statistical studies. Here we compile a global underwater sonar database and 20 ocean climate projections to predict the future distribution of sound-scattering fauna around the world's oceans. We show that global pelagic fauna will be seriously compromised by the end of the 21 st century, if we continue under the current greenhouse emission scenario. Low and mid latitudes are expected to lose from 3 to 22% of animal biomass due to the expansion of low-productive systems, while higher latitudes would be populated by present-day temperate fauna, supporting conclusions drawn from ecosystem simulations. We further show that strong-mitigation measures to contain global warming below 2°C would reduce these impacts to less than half.

Published
2022
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19. 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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20. 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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21. 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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22. NIR-to-NIR two-photon bio-imaging using very bright tailored amino-heptamethines dyes

Author

Simon Pascal, San-Hui Chi, Alexei Grichine, Veronique Martel-Frachet, Joseph W. Perry, Olivier Maury, Chantal Andraud, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Georgia Institute of Technology [Atlanta], Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), and 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)

Subjects
Near-infrared, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, General Chemical Engineering, technology, industry, and agriculture, [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, Polymethine, Two-photon absorption, Bio-imaging, [SDV.IB]Life Sciences [q-bio]/Bioengineering, equipment and supplies, Fluorescence
Abstract

International audience; Amino-heptamethines are highly conjugated cationic dyes featuring electronic absorption in the red region and strong nearinfrared (NIR) fluorescence. Unlike their parent chloro-heptamethine cyanines, the substitution of the central position of their polymethine skeleton with an amine confers them a high Stokes shift. This work reports the synthesis of aminoheptamethines and the investigation of their optical properties, including two-photon absorption in the NIR and shortwave infrared (SWIR) ranges, which has been overlooked for such chromophores so far. Their structures were tailored, introducing selected substitutuents on the indolenine moieties to modulate their hydrophobic/hydrophilic balance and investigate their potential as NIR-to-NIR two-photon probes for the bio-imaging of living cells.

Published
2022
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23. 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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24. 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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25. 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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26. 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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27. 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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28. Femtosecond Spectroscopy and Nonlinear Optical Properties of aza-BODIPY Derivatives in Solution

Author

Hao‐Jung Chang, Mykhailo V. Bondar, Natalia Munera, Sylvain David, Olivier Maury, Gerard Berginc, Boris Le Guennic, Denis Jacquemin, Chantal Andraud, David J. Hagan, Eric W. Van Stryland, University of Central Florida [Orlando] (UCF), National Academy of Sciences of Ukraine (NASU), 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), Thales LAS France, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Army Research Laboratory. Grant Number: W911NF-15-2-0090, National Academy of Sciences of Ukraine. Grant Number: VC/188, and V-204, and Thales Group

Subjects
Boron Compounds, Porphobilinogen, Spectrum Analysis, Organic Chemistry, TD-DFT calculations, aza-boron dipyrromethene derivatives, [CHIM]Chemical Sciences, two-photon absorption, General Chemistry, femtosecond transient absorption pump-probe spectroscopy, Catalysis, Boron, Fluorescent Dyes
Abstract

International audience; The fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives (1-4) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two-photon absorption (2PA) and excited-state absorption (ESA) cross-sections were obtained for 1-4 in dichloromethane using femtosecond Z-scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum-chemical TD-DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross-sections ∼2000 GM), and large ESA cross-sections ∼10(-20) m(2) of these new aza-BODIPY derivatives 1-4 along with their measured high photostability reveal their potential for photonic applications in general and optical limiting in particular.

Published
2022
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29. Movement Shapes the Structure of Fish Communities Along a Cross-Shore Section in the California Current

Author

Nicolas Barrier, Daniele Bianchi, Jérôme Guiet, Fayçal Kessouri, Olivier Maury, Department of Atmospheric and Oceanic Sciences [Los Angeles] (AOS), University of California [Los Angeles] (UCLA), University of California (UC)-University of California (UC), MARine Biodiversity Exploitation and Conservation (UMR MARBEC), and 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)

Subjects
marine fisheries, Science, current system, size spectrum, ecosystem model, Ocean Engineering, Aquatic Science, QH1-199.5, Oceanography, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, pelagic fish, Ecosystem model, trophic transfer, 14. Life underwater, community composition, swimming, climate, Water Science and Technology, Trophic level, Shore, Global and Planetary Change, geography, Biomass (ecology), geography.geographical_feature_category, marine ecosystem model, Ocean current, General. Including nature conservation, geographical distribution, Pelagic zone, mesoscale, pelagic communities, size-spectrum, Food web, California Current, mesopelagic fishes, 13. Climate action, Upwelling, Environmental science, to-end model, [SDE.BE]Environmental Sciences/Biodiversity and Ecology
Abstract

Place: Lausanne Publisher: Frontiers Media Sa WOS:000760695700001; International audience; Pelagic fish communities are shaped by bottom-up and top-down processes, transport by currents, and active swimming. However, the interaction of these processes remains poorly understood. Here, we use a regional implementation of the APex ECOSystem Model (APECOSM), a mechanistic model of the pelagic food web, to investigate these processes in the California Current, a highly productive upwelling system characterized by vigorous mesoscale circulation. The model is coupled with an eddy-resolving representation of ocean currents and lower trophic levels, and is tuned to reproduce observed fish biomass from fisheries independent trawls. Several emergent properties of the model compare realistically with observations. First, the epipelagic community accounts for one order of magnitude less biomass than the vertically migratory community, and is composed by smaller species. Second, the abundance of small fish decreases from the coast to the open ocean, while the abundance of large fish remains relatively uniform. This in turn leads to flattening of biomass size-spectra away from the coast for both communities. Third, the model reproduces a cross-shore succession of small to large sizes moving offshore, consistent with observations of species occurrence. These cross-shore variations emerge in the model from a combination of: (1) passive offshore advection by the mean current, (2) active swimming toward coastal productive regions to counterbalance this transport, and (3) mesoscale heterogeneity that reduces the ability of organisms to return to coastal waters. Our results highlight the importance of passive and active movement in structuring the pelagic food web, and suggest that a representation of these processes can help to improve the realism in simulations with marine ecosystem models.

Published
2022
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30. Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based 'N(2)O(2)' Complexes as Efficient NIR-Fluorophores

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, Ewen Bodio, 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 de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), ANR-16-CE07-0020,SPID,Sondes intelligentes pour le suivi de complexes métalliques à visée thérapeutique(2016), ANR-18-CE18-0012,WazaBY,Développement de plateformes aza-BODIPY pour la construction d'agents multimodaux et de sondes thérapeutiques traçables(2018), and ANR-21-CE07-0025,MAP,sondes multimodales Metal-AzadiPy (MAP): ou comment trouver votre chemin in vivo(2021)

Subjects
Inorganic Chemistry, AzaBODIPY, NIRprobe, group 13, AzaAlDIPY, AzaGaDIPY, Gallium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, fluorescence, Physical and Theoretical Chemistry, azadipyrrin, Aluminum
Abstract

International audience; 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
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31. Tris‐dipicolinate lanthanide complexes: influence of the second hydration sphere on the solid‐state luminescence properties

Author

Jeremy Salaam, Isis N'Dala‐Louika, Cristina Balogh, Iurii Suleimanov, Guillaume Pilet, Laurent Veyre, Clément Camp, Chloé Thieuleux, François Riobé, Olivier Maury, 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), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire des Multimatériaux et Interfaces (LMI)

Subjects
Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; A series of tris-dipicolinate europium complexes featuring different complexes has been prepared, and their photophysical study has been performed in the solid state highlighting the crucial role of second sphere water molecules. The non-radiative deactivation constant (k nr ) varies significantly with the number of interstitial water molecules and their distance to the europium emitting center. The complex (NBu 4 ) 3 [Eu(DPA) 3 ], featuring the most lipophilic cation, exhibits excellent solubility and remarkable photophysical properties in aprotic solvents

Published
2022
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32. Site-selected thionated benzothioxanthene chromophores as heavy-atom-free small-molecule photosensitizers for photodynamic therapy

Author

Marco Deiana, Pierre Josse, Clément Dalinot, Artem Osmolovskyi, Pablo Simón Marqués, José María Andrés Castán, Laura Abad Galán, Magali Allain, Lhoussain Khrouz, Olivier Maury, Tangui Le Bahers, Philippe Blanchard, Sylvie Dabos-Seignon, Cyrille Monnereau, Nasim Sabouri, Clément Cabanetos, 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
[SDV]Life Sciences [q-bio], Materials Chemistry, Biophysics, Environmental Chemistry, [CHIM]Chemical Sciences, General Chemistry, Biochemistry, Biofysik
Abstract

Photodynamic therapy is a clinically approved anticancer modality that employs a light-activated agent (photosensitizer) to generate cytotoxic reactive oxygen species (ROS). There is therefore a growing interest for developing innovative photosensitizing agents with enhanced phototherapeutic performances. Herein, we report on a rational design synthetic procedure that converts the ultrabright benzothioxanthene imide (BTI) dye into three heavy-atom-free thionated compounds featuring close-to-unit singlet oxygen quantum yields. In contrast to the BTI, these thionated analogs display an almost fully quenched fluorescence emission, in agreement with the formation of highly populated triplet states. Indeed, the sequential thionation on the BTI scaffold induces torsion of its skeleton reducing the singlet-triplet energy gaps and enhancing the spin-orbit coupling. These potential PSs show potent cancer-cell ablation under light irradiation while remaining non-toxic under dark condition owing to a photo-cytotoxic mechanism that we believe simultaneously involves singlet oxygen and superoxide species, which could be both characterized in vitro. Our study demonstrates that this simple site-selected thionated platform is an effective strategy to convert conventional carbonyl-containing fluorophores into phototherapeutic agents for anticancer PDT. We acknowledge the Biochemical Imaging Center at Umeå University and the National Microscopy Infrastructure, NMI (VR-RFI 2019-00217) for providing assistance in microscopy.

Published
2022
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33. 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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34. Disentangling diverse responses to climate change among global marine ecosystem models

Author

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

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

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

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

Author

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

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

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

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

Author

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

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

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

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

Author

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

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

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

Published
2021
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38. 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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39. 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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40. 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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41. Investigation of the K 4 [Fe(CN) 6 ]-Mediated Mono- and Bis-Palladium-Catalyzed Cyanation of the Benzothioxanthene Core

Author

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

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

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

Published
2021
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42. 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

43. Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral YbIII-Single-Molecule Magnet

Author

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

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

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

Published
2021
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44. 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

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

Author

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

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

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

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

Author

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

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

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

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

Author

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

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

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

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

Author

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

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

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

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

Author

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

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

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

Published
2021
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50. 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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