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Near-Infrared-Emitting Lanthanide(III)/Gallium(III) Metallacrowns with Appended Coumarins: Tuning the Sensitizer–Emitter Distance through the Linker
International audienceNear-infrared (NIR)-emitting trivalent lanthanides (LnIII) are attractive for applications such as biological imaging and telecommunications. However, their sensitization remains challenging, particularly at excitation wavelengths corresponding to low energies. To address this challenge, a new coumarin-bearing isophthalate-based bridging ligand (C-ip2–), in which the coumarin sensitizer is directly attached to the bridge, was synthesized. In the corresponding [Ln2Ga8(shi)8(C-ip)4]2– metallacrowns (MCs), the sensitization of the NIR-emitting NdIII, ErIII, and YbIII cations was achieved upon excitation of appended coumarins in the visible range (λexc = 435 nm). Compared to the previous generation of [Ln2Ga8(shi)8(C-mip)4]2– MCs, the coumarin antennas are about 5 Å closer to the LnIII emissive centers in this new series of [Ln2Ga8(shi)8(C-ip)4]2– MCs, resulting in an increase in the Q values by factors of 6.2, 9.4, and 2.7 for NdIII, ErIII, and YbIII analogues, respectively. This allows the detection of their NIR emissions through tissue-mimicking phantoms of 1 mm thickness, validating the potential of this design for NIR imaging applications
On the Formation of PAHs from the Oxidation of Ethylene in a JSR
International audienceThe oxidation of ethylene was performed in a jet-stirred reactor at 1 bar and high-temperature under fuel-rich conditions. The reacting mixtures were sampled and analyzed using gas chromatography, mass spectrometry, and high-pressure liquid chromatography. Polyaromatic hydrocarbons were measured. The experiments were simulated using several detailed kinetic reaction mechanisms, indicating that improvements are needed
Lanthanide Compounds for Biological Imaging: Dual-mode Near-infrared Optical and Photoacoustic Imaging Agents with Low Energy Excitation Wavelengths
International audienceMedical and biological diagnostics are in great needs of non-invasive imaging approaches with responses in real-time using small footprints instruments. Photoacoustic (PA) and near-infrared (NIR) luminescence are imaging techniques that can uniquely address these requirements. They take advantage of the NIR light operating in the biological transparency window as excitation source. The creation of dual-mode imaging agents allows to combine the advantages of the two techniques: high sensitivity and high resolution of the NIR luminescence imaging with high signal detection depth of the PA imaging. Lanthanide complexes formed with NIR-absorbing chromophores are promising candidates for the creation of such dual-mode agents. Lanthanide ions possess unique luminescence properties which makes them excellent candidates for the luminescence imaging. However, they have small values of molar extinction coefficients that will directly limit the number of photons they can emit. To achieve our goal, we have used organic chromophores to absorb a large amount of excitation light and sensitize the luminescent lanthanide ions with the collected energy. In complement, organic chromophores can generate photoacoustic signals by dissipating the part of the excitation energy that results in non-radiative processes. The presence of both the NIR-emitting lanthanide ion and the organic chromophore in the complex allows using the same molecule for the creation of new dual-mode imaging agents. In this work, we present new dual-mode photoacoustic and NIR luminescence imaging agents that are based on lanthanide complexes bearing NIR-absorbing chromophores. We will also present the results of the evaluations of the performances of these new PA and NIR imaging agents for non-invasive detection in biological systems using phantom models
Decoupling individual host response and immune cell engager cytotoxic potency
International audienceImmune cell engagers are molecular agents, usually antibody-based constructs, engineered to recruit immune cells against cancer cells and kill them. They represent a versatile and powerful tool for cancer immunotherapy. Despite the multiplication of new engagers tested and accepted in the clinics, how molecular and cellular parameters influence their action is poorly understood. In particular, disentangling the respective role of host immune cells and engager biophysical characteristics is needed to improve their design and efficiency. Focusing here on harnessing antibody dependent Natural Killer cell cytotoxicity, we measure the efficiency of 6 original bispecific antibodies (bsAb), associating an anti-HER2 nanobody and an anti-CD16 nanobody. In vitro cytotoxicity data using primary human NK cells on different target cell lines exposing different antigen densities were collected, exhibiting a wide range of bsAb dose response. In order to rationalize our observations, we introduce a simple multiscale model, postulating that the density of bsAb bridging the two cells is the main parameter triggering the cytotoxic response. We introduce two new microscopic parameters: the surface cooperativity describing bsAb affinity at the bridging step and the threshold of bridge density determining the donor-dependent response. Both parameters permit to rank Abs and donors and to predict bsAb potency as a function of antibodies bulk affinities and receptor surface densities on cells. Our approach thus provides a general way to decouple donor response from immune engagers characteristics, rationalizing the landscape of molecule design
Optimization of Textural and Structural Properties of Carbon Materials for Sodium Dual-Ion Battery Electrodes
International audienceSodium dual-ion batteries combine economic and environmental benefits by using carbon materials in both electrodes and sodium compounds in the electrolyte. Among other factors, their successful implementation for energy storage relies on optimization of the properties of the carbon electrode materials. To this end, carbon materials with a wide range of textural and structural properties were prepared by simply heat treating a single porous carbon in the absence or presence of a low-cost highly effective iron-based catalyst. These materials were investigated as anode or cathode in the sodium dual-ion batteries by prolonged galvanostatic cycling. The optimal textural and structural properties for carbon materials to achieve the best performance as electrodes in sodium dual-ion batteries were identified as having a high degree of graphitic structural order combined with minimal microporosity in the cathode and a non-graphitic structure with a layer spacing of around 0.37 nm and moderate microporosity in the anode
Simulations Euler-Euler du transport et de la rétention des colloïdes à l'échelle du pore
International audienceNon-aqueous liquids (NAPLs) are water-immiscible pollutants that can disperse and release significant amounts of toxic compounds into underground water resources. Numerous methods have been developed to remove these pollutants from aquifers, but NAPL droplets remain trapped by capillary forces in the porous matrix even after depollution. The aim of our research is to explore the potential of colloids (e.g. nanoparticles, bacteria) to remobilize immiscible pollutant droplets. Our final objective is to develop a multiphase model at the pore scale that includes colloidal interactions with the solid phase, the aqueous phase, and the NAPL. Euler-Lagrange models allow an accurate description of colloidal particle interactions (e.g. transport and retention) but remains very time-and resource-intensive. In this work, we are developing Euler-Euler approaches based on OpenFOAM's multiphaseEuler module to represent particles as a dispersed phase in water. The use of this model in the context of the remediation of polluted porous media is currently under development. Our package includes new viscosity models and plastic behavior, as well as poromechanic properties to account for the compressibility threshold of clogged particles. Aggregation forces in between particles and between particles and grains are also considered. To this end, we are using DLVO theory, which characterizes the forces exerted between two charged surfaces separated by a liquid. We present preliminary results such as : i) comparisons with Euler-Lagrange simulations for very diluted suspension, ii) response to fluid stresses and its compressibility, and iii) study of the impact of particle aggregation in the context of porous media.Les liquides non aqueux (NAPL) sont des polluants non miscibles à l'eau qui peuvent se disperser et libérer des quantités importantes de composés toxiques dans les ressources en eau souterraines. De nombreuses méthodes ont été mises au point pour éliminer ces polluants des aquifères, mais des gouttelettes de NAPL restent piégées par les forces capillaires dans la matrice poreuse, même après dépollution. Notre recherche vise à explorer le potentiel des colloïdes (par exemple, les nanoparticules, les bactéries) pour remobiliser les gouttelettes de polluants non miscibles. Notre objectif final est de développer un modèle multiphasique à l'échelle des pores qui inclut les interactions colloïdales avec la phase solide, la phase aqueuse et les NAPL. Les modèles Euler-Lagrange permettent une description précise des interactions entre les particules colloïdales (par exemple, le transport et la rétention), mais restent très gourmands en temps et en ressources. Dans le cadre de ces travaux, nous développons des approches Euler-Euler basées sur le module multiphaseEuler d'OpenFOAM afin de représenter les particules comme une phase dispersée dans l'eau. L'utilisation de ce modèle dans le contexte de la remédiation des milieux poreux pollués est actuellement en cours de développement. Notre package comprend de nouveaux modèles de viscosité et de comportement plastique, ainsi que des propriétés poromécaniques permettant de prendre en compte le seuil de compressibilité des particules obstruées. Les forces d'agrégation entre les particules et entre les particules et les grains sont également prises en compte. À cette fin, nous utilisons la théorie DLVO, qui caractérise les forces exercées entre deux surfaces chargées séparées par un liquide. Nous présentons des résultats préliminaires tels que : i) des comparaisons avec des simulations Euler-Lagrange pour une suspension très diluée, ii) la réponse aux contraintes fluides et sa compressibilité, et iii) l'étude de l'impact de l'agrégation des particules dans le contexte des milieux poreux
La parure grecque au goût des Carthaginois ? Essai de contribution de l’iconographie monétaire à l’étude du goût punique (IVe-IIe s. av. n. è.)
International audienceLe passage bien connu du Poenulus de Plaute dans lequel Hannon et ses esclaves sont moqués par Milphion en raison de leur vêtement et de leurs bijoux - en l'occurrence des anneaux portés aux oreilles -montre bien l'importance que pouvaient revêtir ces éléments dans la définition des identités chez les Anciens. Les Carthaginois semblent avoir eu un goût particulier en la matière puisqu'on leur prête aussi la pratique, singulière dans l'Antiquité, qui consistait à porter un anneau au nez, le nezem. S'il ne fait pas de doute qu'il présente des spécificités, ce goût punique en matière de parure peut-il être précisé ? Le sujet n'a été qu'assez peu abordé, et jamais sous l'angle particulier qui réunit les différentes contributions de cet ouvrage. Le terme de goût est entendu ici dans une acception large, comme un ensemble de préférences d'ordre esthétique, qui sont partagées au sein d'un groupe dont il s'agira de préciser les contours et les attitudes. Ce prisme offre la possibilité d'étudier la parure portée et représentée par les Carthaginois à la fois comme un ensemble de bijoux appartenant à la culture punique ou empruntés à d'autres cultures, mais aussi plus largement comme le support de stratégies particulières constitutives d'une partie de l'identité punique. Une partie seulement, et à plusieurs titres, puisque la documentation utilisée nous amènera à nous intéresser essentiellement à l'aristocratie carthaginoise dans son rapport avec le monde grec et ses influences entre le milieu du iv e et le milieu du ii e siècle av. n. è. C'est en effet à partir de l'étude de l'iconographie monétaire que la question sera abordée ici. La démarche peut sembler périlleuse tant la monnaie, objet dont la production est par essence très normée et contrôlée, n'apparaît pas spontanément comme une source propice à nourrir la réflexion sur le goût. Le renouveau historiographique des études phénico-puniques, qui a bien mis en évidence la diversité des identités au sein de cette large aire culturelle, appelle par ailleurs à la prudence face à la tentation de définir « un » goût punique qui serait commun à l'échelle de la Méditerranée occidentale. Comment, dans cette configuration particulière à plusieurs égards, les choix relatifs à la typologie monétaire, qui reposent avant tout sur des impératifs politiques ainsi que sur la destination des monnaies, pourraient-ils être le reflet de préférences esthétiques et de pratiques spécifiques d'une partie des Carthaginois ? C'est pour tenter de répondre à cette question qu'a été mené le travail exploratoire présenté ici
Evaluation of carbon quantification by LIBS in hardened steels: impact of matrix effects induced by hardening heat treatments
International audienc
Discovery and chemical biology of CDK8 inhibitors reveals insights for kinase inhibitor development
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