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1. Mapping the race between crop phenology and climate risks for wheat in France under climate change

Author

Renan Le Roux, Carina Furusho-Percot, Jean-Charles Deswarte, Marie-Odile Bancal, Karine Chenu, Nathalie de Noblet-Ducoudré, Iñaki García de Cortázar-Atauri, Alexis Durand, Burak Bulut, Olivier Maury, Jérémie Décome, and Marie Launay

Subjects
Medicine, Science
Abstract

Abstract Climate change threatens food security by affecting the productivity of major cereal crops. To date, agroclimatic risk projections through indicators have focused on expected hazards exposure during the crop’s current vulnerable seasons, without considering the non-stationarity of their phenology under evolving climatic conditions. We propose a new method for spatially classifying agroclimatic risks for wheat, combining high-resolution climatic data with a wheat’s phenological model. The method is implemented for French wheat involving three GCM-RCM model pairs and two emission scenarios. We found that the precocity of phenological stages allows wheat to avoid periods of water deficit in the near future. Nevertheless, in the coming decades the emergence of heat stress and increasing water deficit will deteriorate wheat cultivation over the French territory. Projections show the appearance of combined risks of heat and water deficit up to 4 years per decade under the RCP 8.5 scenario. The proposed method provides a deep level of information that enables regional adaptation strategies: the nature of the risk, its temporal and spatial occurrence, and its potential combination with other risks. It’s a first step towards identifying potential sites for breeding crop varieties to increase the resilience of agricultural systems.

Published
2024
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2. The Past and Future of the Fisheries and Marine Ecosystem Model Intercomparison Project

Author

Camilla Novaglio, Andrea Bryndum‐Buchholz, Derek P. Tittensor, Tyler D. Eddy, Heike K. Lotze, Cheryl S. Harrison, Ryan F. Heneghan, Olivier Maury, Kelly Ortega‐Cisneros, Colleen M. Petrik, Kelsey E. Roberts, and Julia L. Blanchard

Subjects
skill assessment, ensemble modeling, socio‐economic scenarios, food security, biodiversity, fishmip, Environmental sciences, GE1-350, Ecology, QH540-549.5
Abstract

Abstract Climate change is increasingly affecting the world's ocean ecosystems, necessitating urgent guidance on adaptation strategies to limit or prevent catastrophic impacts. The Fisheries and Marine Ecosystem Model Intercomparison Project (FishMIP) is a network and framework that provides standardised ensemble projections of the impacts of climate change and fisheries on ocean life and the benefits that it provides to people. Since its official launch in 2013 as a small, self‐organized project within the larger Inter‐Sectoral Impact Model Intercomparison Project, the FishMIP community has grown substantially and contributed to key international policy processes, such as the Intergovernmental Panel on Climate Change Assessment Report, and the Intergovernmental Science‐Policy Platform on Biodiversity and Ecosystem Services Global Biodiversity Assessment. While not without challenges, particularly around comparing heterogeneous ecosystem models, integrating fisheries scenarios, and standardising regional‐scale ecosystem models, FishMIP outputs are now being used across a variety of applications (e.g., climate change targets, fisheries management, marine conservation, Sustainable Development Goals). Over the next decade, FishMIP will focus on improving ecosystem model ensembles to provide more robust and policy‐relevant projections for different regions of the world under multiple climate and societal change scenarios, and continue to be open to a broad spectrum of marine ecosystem models and modelers. FishMIP also intends to enhance leadership diversity and capacity‐building to improve representation of early‐ and mid‐career researchers from under‐represented countries and ocean regions. As we look ahead, FishMIP aims to continue enhancing our understanding of how marine life and its contributions to people may change over the coming century at both global and regional scales.

Published
2024
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3. 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, and Stéphan Guy

Subjects
Science
Abstract

The authors present an artifact-free circularly polarized luminescence spectrophotometer using a single camera and two polarization encoding paths. The spectra are measured in a few seconds without the need of calibration by inverting the role of the paths.

Published
2023
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4. Applying ensemble ecosystem model projections to future-proof marine conservation planning in the Northwest Atlantic Ocean

Author

Andrea Bryndum-Buchholz, Julia L. Blanchard, Marta Coll, Hubert Du Pontavice, Jason D. Everett, Jerome Guiet, Ryan F. Heneghan, Olivier Maury, Camilla Novaglio, Juliano Palacios-Abrantes, Colleen M. Petrik, Derek P. Tittensor, and Heike K. Lotze

Subjects
climate change impacts, ensemble modelling, marine biomass projections, MPAs, OECMs, Atlantic Canada, Education, Science
Abstract

Climate change is altering marine ecosystems across the globe and is projected to do so for centuries to come. Marine conservation agencies can use short- and long-term projections of species-specific or ecosystem-level climate responses to inform marine conservation planning. Yet, integration of climate change adaptation, mitigation, and resilience into marine conservation planning is limited. We analysed future trajectories of climate change impacts on total consumer biomass and six key physical and biogeochemical drivers across the Northwest Atlantic Ocean to evaluate the consequences for Marine Protected Areas (MPAs) and Other Effective area-based Conservation Measures (OECMs) in Atlantic Canada. We identified climate change hotspots and refugia, where the environmental drivers are projected to change most or remain close to their current state, respectively, by mid- and end-century. We used standardized outputs from the Fisheries and Marine Ecosystem Model Intercomparison Project and the 6th Coupled Model Intercomparison Project. Our analysis revealed that, currently, no existing marine conservation areas in Atlantic Canada overlap with identified climate refugia. Most (75%) established MPAs and more than one-third (39%) of the established OECMs lie within cumulative climate hotspots. Our results provide important long-term context for adaptation and future-proofing spatial marine conservation planning in Canada and the Northwest Atlantic region.

Published
2023
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5. 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, and Clément Cabanetos

Subjects
Chemistry, QD1-999
Abstract

Site-selective thionation is a powerful strategy to access heavyatom-free small-molecule photosensitizers for photodynamic therapy. Here, a series of sulfur-substituted benzothioxanthene chromophores is synthesized and the sequential insertion of sulfur atoms is shown to result in strong and concomitant optimization of both light absorption and therapeutic activity.

Published
2022
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6. 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, and Jacques-Philippe Colletier

Subjects
Science
Abstract

An environmentally safe means of mosquito control is the application of Bacillus thuringiensis israelensis, which produces a cocktail of four naturally crystalline proteins exclusively toxic to mosquito. Here the authors report the atomic-resolution structures of Bti Cry11Aa and related Btj Cry11Ba solved de novo through Serial Femtosecond Crystallography on naturally-occurring nanocrystals.

Published
2022
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7. Potential impacts of climate change on agriculture and fisheries production in 72 tropical coastal communities

Author

Joshua E. Cinner, Iain R. Caldwell, Lauric Thiault, John Ben, Julia L. Blanchard, Marta Coll, Amy Diedrich, Tyler D. Eddy, Jason D. Everett, Christian Folberth, Didier Gascuel, Jerome Guiet, Georgina G. Gurney, Ryan F. Heneghan, Jonas Jägermeyr, Narriman Jiddawi, Rachael Lahari, John Kuange, Wenfeng Liu, Olivier Maury, Christoph Müller, Camilla Novaglio, Juliano Palacios-Abrantes, Colleen M. Petrik, Ando Rabearisoa, Derek P. Tittensor, Andrew Wamukota, and Richard Pollnac

Subjects
Science
Abstract

Responses of agriculture and fisheries to climate change are interlinked, yet rarely studied together. Here, the authors analyse more than 3000 households from 5 tropical countries and forecast mid-century climate change impacts, finding that communities with higher fishery dependence and lower socioeconomic status communities face greater losses.

Published
2022
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8. Trophic amplification: A model intercomparison of climate driven changes in marine food webs.

Author

Vianney Guibourd de Luzinais, Hubert du Pontavice, Gabriel Reygondeau, Nicolas Barrier, Julia L Blanchard, Virginie Bornarel, Matthias Büchner, William W L Cheung, Tyler D Eddy, Jason D Everett, Jerome Guiet, Cheryl S Harrison, Olivier Maury, Camilla Novaglio, Colleen M Petrik, Jeroen Steenbeek, Derek P Tittensor, and Didier Gascuel

Subjects
Medicine, Science
Abstract

Marine animal biomass is expected to decrease in the 21st century due to climate driven changes in ocean environmental conditions. Previous studies suggest that the magnitude of the decline in primary production on apex predators could be amplified through the trophodynamics of marine food webs, leading to larger decreases in the biomass of predators relative to the decrease in primary production, a mechanism called trophic amplification. We compared relative changes in producer and consumer biomass or production in the global ocean to assess the extent of trophic amplification. We used simulations from nine marine ecosystem models (MEMs) from the Fisheries and Marine Ecosystem Models Intercomparison Project forced by two Earth System Models under the high greenhouse gas emissions Shared Socioeconomic Pathways (SSP5-8.5) and a scenario of no fishing. Globally, total consumer biomass is projected to decrease by 16.7 ± 9.5% more than net primary production (NPP) by 2090-2099 relative to 1995-2014, with substantial variations among MEMs and regions. Total consumer biomass is projected to decrease almost everywhere in the ocean (80% of the world's oceans) in the model ensemble. In 40% of the world's oceans, consumer biomass was projected to decrease more than NPP. Additionally, in another 36% of the world's oceans consumer biomass is expected to decrease even as projected NPP increases. By analysing the biomass response within food webs in available MEMs, we found that model parameters and structures contributed to more complex responses than a consistent amplification of climate impacts of higher trophic levels. Our study provides additional insights into the ecological mechanisms that will impact marine ecosystems, thereby informing model and scenario development.

Published
2023
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9. Differing marine animal biomass shifts under 21st century climate change between Canada’s three oceans

Author

Andrea Bryndum-Buchholz, Faelan Prentice, Derek P. Tittensor, Julia L. Blanchard, William W.L. Cheung, Villy Christensen, Eric D. Galbraith, Olivier Maury, and Heike K. Lotze

Subjects
climate change, ensemble modeling, marine ecosystem models, canada exclusive economic zone, fish-mip, projection uncertainty, Education, Science
Abstract

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

Published
2020
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10. Movement Shapes the Structure of Fish Communities Along a Cross-Shore Section in the California Current

Author

Jérôme Guiet, Daniele Bianchi, Olivier Maury, Nicolas Barrier, and Fayçal Kessouri

Subjects
California Current, size spectrum, community composition, swimming, marine ecosystem model, pelagic fish, Science, General. Including nature conservation, geographical distribution, QH1-199.5
Abstract

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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11. Climate Change-Induced Emergence of Novel Biogeochemical Provinces

Author

Gabriel Reygondeau, William W. L. Cheung, Colette C. C. Wabnitz, Vicky W. Y. Lam, Thomas Frölicher, and Olivier Maury

Subjects
physical oceanography, marine biogeography, pelagic environment, novel ocean climate, environmental niche model, Science, General. Including nature conservation, geographical distribution, QH1-199.5
Abstract

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

Published
2020
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12. Data on spatio-temporal representation of mineral N fertilization and manure N application as well as ammonia volatilization in French regions for the crop year 2005/06

Author

Sophie Génermont, Maharavo Marie Julie Ramanantenasoa, Karine Dufosse, Olivier Maury, Catherine Mignolet, and Jean-Marc Gilliot

Subjects
Computer applications to medicine. Medical informatics, R858-859.7, Science (General), Q1-390
Abstract

The data presented in this article are related to the research article entitled “A new framework to estimate spatio-temporal ammonia emissions due to Nitrogen fertilization in France” (Ramanantenasoa et al., 2018) but are given with more details at a regional scale (NUTS2) in the objective to get them available for other research or applied studies. They concerns (i) the data implemented in the CADASTRE_NH3 framework and (ii) the data obtained using it, for crop year 2005/06. For the source data, the article focusses on the N fertilization practice management description, as this dataset is the most difficult to collect and to analyze in the objective of realistically representing the spatial and temporal variabilities needed in the framework.

Published
2018
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14. Redox-Modulations of Photophysical and Single-molecule Magnet Properties in Ytterbium Complexes Involving Extended-TTF Triads

Author

Bertrand Lefeuvre, Jessica Flores Gonzalez, Frédéric Gendron, Vincent Dorcet, François Riobé, Vladimir Cherkasov, Olivier Maury, Boris Le Guennic, Olivier Cador, Viacheslav Kuropatov, and Fabrice Pointillart

Subjects
ytterbium, extended-tetrathiafulvalene, electro-activity, single-molecule magnet, luminescence, Organic chemistry, QD241-441
Abstract

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

Published
2020
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15. Monitoring the Production of High Diffraction-Quality Crystals of Two Enzymes in Real Time Using In Situ Dynamic Light Scattering

Author

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

Subjects
enzyme, crystallization, dynamic light scattering, nucleation, nucleant, tb-xo4 crystallophore, microcrystals, nanocrystals, x-ray diffraction, xtalcontroller, Crystallography, QD901-999
Abstract

The reproducible preparation of well-diffracting crystals is a prerequisite for every structural study based on crystallography. An instrument called XtalController has recently been designed that allows the monitoring of crystallization assays using dynamic light scattering and microscopy, and integrates piezo pumps to alter the composition of the mother liquor during the experiment. We have applied this technology to study the crystallization of two enzymes, the CCA-adding enzyme of the psychrophilic bacterium Planococcus halocryophilus, and the lysozyme from hen egg white in the presence of a synthetic chemical nucleant. We were able to (i) detect early nucleation events and (ii) drive the crystallization system (through cycles of dissolution/crystallization) toward growth conditions yielding crystals with excellent diffraction properties. This technology opens a way to the rational production of samples for crystallography, ranging from nanocrystals for electron diffraction, microcrystals for serial or conventional X-ray diffraction, to larger crystals for neutron diffraction.

Published
2020
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16. Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio)-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand

Author

Fabrice Pointillart, Saskia Speed, Bertrand Lefeuvre, François Riobé, Stéphane Golhen, Boris Le Guennic, Olivier Cador, Olivier Maury, and Lahcène Ouahab

Subjects
lanthanides, tetrathiafulvalene, magnetism, photo-physics, TD-DFT calculations, Inorganic chemistry, QD146-197
Abstract

The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L) and the metallo-precursors Ln(hfac)3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac)6(L)]·(CH2Cl2)·(C6H14)0.5 (LnIII = DyIII (1) and YbIII (2)). The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF) core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital)→LUMO (Lowest Unoccupied Molecular Orbital) Intra-Ligand Charge Transfer (ILCT) transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties.

Published
2015
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17. Tricaesium tris(pyridine-2,6-dicarboxylato-κ3O2,N,O6)lutetium(III) octahydrate

Author

Olivier Maury, Philippe Rabiller, Anthony D'Aléo, Flavien Aubert, and Vincent Legrand

Subjects
Crystallography, QD901-999
Abstract

Colourless block crystals of the title compound, Cs3[Lu(dipic)3]·8H2O [dipic is dipicolinate or pyridine-2,6-dicarboxylate, C7H3NO4] were synthesized by slow evaporation of the solvent. The crystal structure of this LuIII-complex, isostructural with the DyIII and EuIII complexes, was determined from a crystal twinned by inversion and consists of discrete [Lu(dipic)3]3− anions, Cs+ cations and water molecules involving hydrogen bonding. The Lu atom lies on a twofold rotation axis and is coordinated by six O atoms and three N atoms of three dipicolinate ligands. One Cs atom is also on a twofold axis. The unit cell can be regarded as successive layers along the crystallographic c-axis formed by [Lu(dipic)3]3− anionic planes and [Cs+, H2O] cationic planes. In the crystal structure, although the H atoms attached to water molecules could not be located, short O—O contacts clearly indicate the occurrence of an intricate hydrogen-bonded network through contacts with other water molecules, Cs cations or with the O atoms of the dipicolinate ligands.

Published
2008
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18. Le début du ive s. av. J.-C. dans l’espace culturel sénonais : les habitats de Bois d’Echalas à Ville-Saint-Jacques et de Beauchamp à Varennes-sur-Seine (Seine-et-Marne) dans le contexte de l’interfluve Seine-Yonne

Author

Jean-Marc Séguier, Ginette Auxiette, Benoît Clavel, Olivier Maury, and Sylvie Rimbault

Subjects
array of silos, ceramics, early La Tène, Seine-Yonne confluence, settlement, territory, Archaeology, CC1-960
Abstract

The study of two settlements of the beginning of the 4th century BC near the confluence of the Seine and the Yonne enables us to define the movable culture of this part of the Paris basin during La Tène B1a, notably because of the association of an important series of local and imported ceramics and significant metal articles. The analysis of the structures of conservation and of furniture lead to the establishment of a hierachy of settlements. That of Ville-Saint-Jacques, Bois d’Echalas, occupied a prominent place in the social system set up in the region in question, whereas that of Varennes-sur-Seine, Beauchamp, proved to be of a lower level. Beyond the comparison between the two sites, what is presented is a socio-economic lecture on territorial organisation.

Published
2008

20. JEAI-MOCAs: A multi-institutional initiative to build marine research capacity in Mozambique

Author

Issufo Halo, Bjorn Backeberg, Atanasio Brito, Charine Collins, Obadias Cossa, Francisco Gemo, Yonss Jose, Benjamin Loveday, Bernardino Malauene, Francis Marsac, Clousa Maueua, Olivier Maury, Alberto Mavume, Fialho Nehama, Pierrick Penven, Stephane Pous, Chris Reason, Mike Roberts, and Frank Shillington

Subjects
biogeochemistry, ocean eddies, tropical cyclones, ocean models, tides, Science, Science (General), Q1-390, Social Sciences, Social sciences (General), H1-99
Published
2013
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26. 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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27. 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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28. 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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29. 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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31. 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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32. 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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33. 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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34. 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

35. 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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36. 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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37. 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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38. 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

39. '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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40. 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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41. 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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44. 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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45. 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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47. 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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49. 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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50. 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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