Emulsion radical polymerization processes have created considerable wealth in many industrial sectors, including coatings, adhesives, paints, additives for textiles and paper… Traditionally, waterborne polymer dispersions are produced in stirred tank reactors by the thermally-activated free-radical polymerization of a starting monomer emulsion. The objective of this project is to exploit UV radiation to promote the formation of high solid contents polymer latexes. The breakthrough is to generate highly concentrated dispersions of monomer nanodroplets (< 100 nm), that are subsequently photopolymerized in a specially designed photochemical reactor to produce polymer nanoparticles. Replacing a thermal process by a photochemical one has several advantages: (i) UV irradiation can induce very high rates of initiation that directly affect the overall rate of polymerization. In fact, the radical generation is known to be controlled by the incident photon flux and by the absorption conditions of the reaction system inside the photochemical reactor. Remaining within the nanometric (submicrometric) size range, the ratio of light absorption vs. scattering will be optimized in order to work under best conditions as far as light penetration is concerned. (ii) Photopolymerization will favour the implementation of continuous processes replacing the production limiting semi-batch operations used nowadays in industry. (iii) Photochemically initiated radical polymerizations are generally temperature independent and bear a much higher potential of application due to defined solubility, emulsion stabilization and controlled polymerization kinetics. (iv) A photochemical technology also complies with impeding European directives on solvent emissions and energy reductions. A viable emulsion photopolymerization process can thus impart a wide range of attractive advantages of process intensification, but there is currently no mature technology in this field. To achieve this objective, the PHOTOEMULSION project will integrate contributions from two academic laboratories and an industrial partner: the Laboratoire de Photochimie et d'Ingénierie Macromoléculaires (LPIM, Université of Haute Alsace, Mulhouse), the Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP, Université Paul Sabatier, Toulouse III) and the MÄDER group. The LPIM (ex-Department of Phochemistry) is internationally recognized in the development of radiation-curing technology while the IMRCP has a complementary expertise in the domains of photochemical technology and engineering. A major change from the initial project submitted in 2010 is the involvement of MÄDER, responsible for planning and upscaling process innovations. MÄDER has a well-established activity in the sector of industrial and decorative coatings, and has been a pioneer company in the design and use of water-based paints and bio-sourced resins/monomers. As a result of the project, an innovative photopolymerization process in water will be introduced and applied in the highly technical market segment of bio-sourced latexes.

The main objective of the project is to determine the life-cycle of micro- and nano-plastics (MNP) in the watershed area, to understand their fragmentation pattern and to investigate the first impact of the whole size distribution of plastics litter. In the sampling campaign in the North Atlantic Ocean - NOA (Expedition 7th Continent) realized in 2014 and 2015, we were the first to develop an analytical strategy for demonstrating the presence of nanoscale (colloidal) plastics mainly made of polyethylene in the NOA for the first time. Based on these unprecedented results, several questions raise: What are the mechanisms of nano-plastics formation? Are the nanoplastics formed in the ocean or before in the watershed area? Where the other plastics at the micro and nanoscale are located? We found only PE and PS trace at the micro and nanoscale in the NOA. Where are the other polymers? Where do the Nano-plastics come from in the coastal zone? Rapidly, based on recent expedition and missions, we identified the watershed area as the principal zone susceptible to play a key role in the MNP environmental fate and impact. For these reasons and due to the total absence of available data in literature, we decided to focus the PEPSEA proposal on this novel consideration. From all the watershed areas and based on our previous mission and investigation in Guadeloupe (French Caribbean Island), we focused PEPSEA project on the Mangrove swamp system. Mangroves are present along a high fraction of tropical and subtropical coastlines. These systems play a crucial ecological role providing shelters and food resources for many species. Mangroves are also directly endangered by human activities. Plastics are susceptible to be captured in this environment due to the structure of Mangrove tree roots physically reducing circulation of water. In Guadeloupe, two Mangrove swamps were identified, the first one directly exposed to the landfill of the island (Décharge de la Gabarre) and the second one located at Le Moule, on the east coast of the island, which is directly influenced by the current from both the NOA and the gyre. These two systems offer the opportunity to directly monitor the impact of the MNPs waste on the Mangrove system and also discriminate the influence of terrestrial activities on the incoming MNPs compared to the flux of MNPs from the principal oceanic gyre. This study is complementary to existing project working on the presence and environmental fate of MNPs in the oceanic system. PEPSEA is an interdisciplinary research project on the plastic debris in the watershed area. It involves the participation of five different partners in the consortium that successfully work together in trust on the plastic presence and contamination thematic since 2014. Compare to all the major projects funded these last year through the principal governmental national agency and focusing on Plastic debris in environmental system, we propose a totally novel approach based on our expertise and our recent expeditions.

Cells are constantly exposed to mechanical stimuli that provide important signals which, combined with others from the cellular microenvironment, regulate a plethora of functions at molecular, cellular, and tissue levels. A typical example is the cardiac muscle, the failure of which remains a central health and societal issue. Approaches making it possible to address cell mechanobiology on different spatial and temporal scales within an integrated biological system are still lacking, although this would be of tremendous importance to tackle a great number of various biological processes linked to illnesses such as heart ischemia. OPTO-MECHA-3D is an ingenious new technology to conceptualize cell mechanobiological approaches in 3D ex vivo tissue models. In this project, we aim to develop a dedicated multiscale and multifunctional imaging platform capable of dealing with such 3D models, as well as both interacting with and perturbing them mechanically in a spatially resolved and well-defined fashion. A successful demonstration of the potential of our technology with ex vivo cardiac tissue would represent a major milestone for the future of biomedical research, since OPTO-MECHA-3D has the potential of becoming the standard for studying, not just cardiac function, but various cell mechano-physiological processes that are of interest in many biological fields. The central idea of the project is to associate an intelligent sample holder based on hydrogels that will produce the mechanical stimulus into a light sheet fluorescence microscopy (LSFM) setup that will give access to the response of the cardiac tissue to the stimulus For this, OPTO-MECHA-3D will bond 5 academic teams and an industrial partner: ITAV (CNRS laboratory, specialist of light sheet fluorescence microscopy), I2MC (INSERM unit, specialized in cardiovascular diseases), IMRCP (CNRS unit, expertise in hydrogel synthesis and photoresponsive systems), ICFO in Spain (specialist of photonic microscopy) and FHNW in Switzerland (expertise in laser development). The last partner is Kaivogen Inc, a finnish company specialized in up-converting nanoparticles, which will be incorporated in the hydrogels. This consortium enables to join together the different disciplines which are essential for the carrying out of the work, but the ANR funding would enable the consortium to get more optimized (possibly by addition of one or 2 new partners), answering critical comments from two former proposal submissions in 2016 and 2017.

Interest in the use of nanostructured materials in medicine and diagnostics has grown rapidly in recent years. The dimension of so-called nanomedicine results in new medical effects and requires novel, scientifically demanding chemistry. Thus, drug delivery systems with controllable size and shape in the nm range are needed to deliver bioactive agents and drugs for specific pathological and pharmacological purposes with improved bioavailability and pharmacokinetics. Among them organic-inorganic nanoparticles, which show great potential for imaging and diagnosis as well as for clinical therapeutics, have started to gain large interest. In order to develop new high sensitivity contrast agents while minimizing synthetic complexity, we plan to use hybrid polyion complexes obtained from complexation between metal ions and anionic block copolymers. Their formation is mainly driven by electrostatic interactions and entropy gain from the release of counter-ions. Relaxivity properties and high stability in biological medium obtained from preliminary experiments have shown the great potential of these systems. Hence the main objective of this project is to develop new highly stable and versatile medical imaging nano-objects easily generated by the complexation of double hydrophilic block copolymers in presence of metal ions. Incorporation of different family of ions or polymers within these objects will enable to extent the proposed strategy to multimodal imaging (PET, MRI…) and will also enable to target specific probe.

One of the most important scientific and industrial challenges in polymer chemistry is the synthesis of materials with well-defined composition and macromolecular architectures, which are in principle accessible by living polymerization methods. The recent development of controlled radical polymerization (CRP) has greatly expanded the scope of monomers that can be incorporated in well-defined macromolecular architectures but there are still important bottlenecks. CRP functions through dynamic equilibrium between growing active chains and latent chains bonded to a moderating agent, the nature of which is adapted to the monomer being polymerized (i.e. to the reactivity of the associated radical). Thus, monomers with very different reactivity (More Activated Monomers or MAMs on one side, Less Activated Monomers or LAMs on the other) cannot be controlled with the same moderating agent. This limits the possibility of making block PMAM-b-PLAM architectures of interest for multiple innovative applications, by sequential addition. Among the various CRP strategies, reversible addition-fragmentation chain-transfer (RAFT) polymerization is the most versatile and promising for industrial implementation. The present project proposes to remove this bottleneck by developing switchable RAFT agents that can function in two forms, one suitable for LAMs and the other one for MAMs, by development of a new type of RAFT agent based on trivalent phosphorus and a switch controlled by chemical modification at the P atom by either PV/PIII conversion, by coordination chemistry or by a redox process on the incorporated metal. It is implemented by the joint efforts of the P3R team, a world leader in RAFT polymerization of LAMs with strong industrial experience, and the LCAC team, which brings expertise in functionalized P ligands and coordination chemistry, including the application of metal complexes in a range of CRP processes. The project is divided into 4 scientific tasks. Task 1 is the synthesis of several new tunable RAFT agents that can be switched to a different form, one form being suitable to control MAMs and the other form being able to control LAMs. In Task 2, the controlling ability of these new RAFT agents will be tested to assess the monomer compatibility for each pair of partners that are related to each other by a chemical switch. Task 3 will optimize the switching phase by investigating the chemical change on the chain-end for the single-block polymers developed in Task 2. Finally, in Task 4 a variety of new block copolymers will be synthesized by sequential addition, the RAFT agent will be removed from the chain end, and the polymers will be purified. A further aim of Task 4 is to develop protocols for sequential monomer addition (with switch) in aqueous media. Finally, an ultimate challenge of this project will be to access block copolymers containing one ethylene-rich block. These investigations will lead to the development of previously inaccessible added-value polymers by simplified protocols that only require the use of a single, easily switchable, RAFT agent.