Synthetic polymers have found applications in many areas, ranging from most “basic” ones such as packaging to high-tech fields such as energy storage, aeronautics or biomedicine. The need of complex and precise architectures with specific monomer composition and enchainment requires living or controlled polymerization techniques, and several breakthroughs have already been achieved in that direction. Block or segmented copolymers combining biodegradable polyester or polycarbonate segments, made by ring-opening polymerization (ROP) of bio-based lactones or by ring-opening co-polymerization (ROcoP) of epoxides and CO2, respectively, and poly(vinyl monomer) segments, made by controlled radical polymerization (CRP), are of particular interest for biomedical applications. These polymeric structures are not attainable using a single polymerization technique and have so far been assembled by either: 1) preparing different blocks and covalently linking them together via various strategies (e.g. “Click” chemistry), or 2) growing the different chains at each end of a specific linker with adequate end groups using the appropriate method. These approaches require several catalytic systems or multi-steps syntheses, and access to multi-block copolymers may become very difficult. Moreover, statistical copolymers do not seem accessible following these strategies. The present proposal aims at using coordination and organometallic chemistry to overpass this limitation by the development of compounds that would mediate both organometallic-mediated radical polymerization (OMRP) of vinyl monomers and RO(co)P of cyclic esters/carbonates or epoxides and CO2, and switch from one mechanism to the other either randomly or “on demand”. The choice of these two polymerization techniques to access such partially unprecedented polymeric architectures is based on a carefully analysis of their mechanisms. The OMRP mechanism involves reversible trapping of a radical active species (propagating chain) by a metal complex to form an organometallic dormant species. The propagation step in a coordination-insertion RO(co)P mechanism is based on the activation of the monomer by the metal center, followed by the attack of the nucleophile ligand linked to the metal (growing polymer chain). Indeed, both mechanisms make use of similar species of type [(L)Mt-polymer], the dormant species of OMRP having a Mt-C bond and the propagating species of RO(co)P having a Mt-O bond. Therefore, the key to succeed in our highly ambitious project is to develop compounds with a homolytically weak Mt-O bond, able at the same time to generate oxygen-based radicals to initiate OMRP and to activate a cyclic ester/carbonate/epoxide monomers to initiate and sustain RO(co)P. If this reactivity is achieved, the polymerization mechanism switch may be established sequentially, by successive additions of monomers to form block copolymers of the type polyester/polycarbonate-b-poly(vinyl monomer), or randomly on a pool of various monomers (one-pot reaction) to produce statistical polyesters/polycarbonate-co-poly(vinyl monomer) copolymers. Cobalt(III) and iron(III) alkoxide complexes have been identified as the best candidates for this purpose, because of their well-established or promising performances in both techniques. However, none of the known complexes have so far been applied to both OMRP and ROP. The present consortium possesses all the required know-how in coordination and organometallic chemistry and in OMRP and RO(co)P processes to achieve the challenging objectives of this proposal and to access novel bio-based high-performance materials.

CO2 capture and utilization (CCU) will play a prominent role in the restructuring of the energy sector and the fight against global warming. The conversion of carbon dioxide into methane is a practical way of recycling CO2 and storing energy at off-peak conditions when H2 can be produced cheaply. This project aims at determining the optimal properties of sorbent-catalysts used for the sequential trapping and methanation of carbon dioxide under isothermal conditions. The project will investigate promising metal-oxide combinations to allow both strong CO2 adsorption and CO2 hydrogenation with H2 on the same material. The consortium involves experts in catalyst synthesis, characterization and testing, as well as modelers, to be able to develop structure-activity relationships that will help develop better systems. The objectives are to understand the limiting factors of CO2 sorption and methane production. The structural evolution and ageing of the materials under continued cycling under CO2/H2O/O2 and H2 atmospheres will also be of strong importance. The project aims at proposing adequate and cheap formulations based mostly on cheap and widely available metals and oxides as well as the range of conditions of use for practical applications.

CO2 photoreduction with water is an attractive photosynthesis-like reaction which could lead to the direct, selective, on-site recycling of CO2 industrial emission sources into synthetic natural gas (methane), provided that the reaction can be carried out selectively and in the continuous flow, gas phase. However, the competing reduction of water severely inhibits viability of this still hypothetic process. Metal oxide semi-conductor (MOS)-based photocatalysts in particular are inherently limited by both a low selectivity and by their poor stability with time-on-stream, which hinders application of these materials. Recently it was found that illumination of Au nanoparticles (NPs) in contact with a flowing mixture of CO2 and water vapor yielded methane selectively and steadily over extended period of times. This reaction was attributed to absorption of light by Au NPs in the visible range via their localized surface plasmon resonance . These promising plasmonic materials could be an interesting alternative to MOS for large scale recycling of CO2 into methane. However they so far exhibit a low activity and will thus need to be optimized. One major hurdle towards that goal is that no consensual description of the underlying mechanism has been reached to date, making any potential development of the field dependent on inefficient, time-consuming, trial and error strategies. In particular, the nature of the energy transfer controlling light-to-chemical conversion in the plasmon-induced reaction is highly debated. Both hot carriers and heat are generated in the process at very short time interval. Distinguishing their respective role in the process is a challenge. TOGETHER-FOR-CO2 has the ambition to undertake a paradigm shift in the optimization of plasmonic catalysts and set-up a rational mechanistic-based optimization approach to plasmonic catalyst design, in order to take the development of the plasmon-induced continuous flow, gas phase CO2-to-CH4 reduction with water to the next level. In order to achieve that, TOGETHER-FOR-CO2 intends to understand the roles of both hot carriers and heat in the plasmon-induced reaction. TOGETHER-FOR-CO2 will use the fact that both phenomena are dependent on the intrinsic properties of the metals and on the geometric characteristics of plasmonic NPs assemblies to undertake a systematic, experimental, material-based study aimed at unraveling the respective roles of hot carriers and heat in the plasmon-induced CO2-to-CH4 reduction with water. Assuming that both phenomena likely contribute to the plasmon-induced catalytic performance, TOGETHER-FOR-CO2 will further optimize their synergy to boost plasmon-induced methane production rates. This requires (1) smart control of plasmonic substrates configuration to allow fine tuning of the hot carriers vs. heat phenomena (2) design of a unique photoreactor to evaluate plasmon-induced catalytic performances under strict temperature control (3) in-depth characterization and simulations of optical and photothermal properties. Hence, by combining expertise in (nano)material synthesis, (photo)catalysis and thermoplasmonics, the TOGETHER-FOR-CO2 team will (1) synthesize a large variety of 2D plasmonic substrates with well-defined configurations using well-controlled organometallic routes applicable to metal, alloy and oxide NP synthesis (2) implement a pioneering combination of temperature metrologies, including nanothermometry with lanthanide particles, to accurately measure the temperature of the working substrate (3) use photothermal characterization and simulation to validate the initial assumptions, (4) evaluate the impact of structural parameters of the plasmonic substrate and of temperature on the plasmon-induced catalytic performances, and ultimately (5) optimize plasmonic catalysts on the basis of structure-activity relationships, with special focus on combining high activity with both full selectivity towards methane and long-term stability.

The Atg8/LC3/GABARAP family of ubiquitin-like proteins is a main player of the macroautophagy pathway, a stress-resistance process that maintains cellular homeostasis by promoting the degradation of cytoplasmic components and organelles within lysosomes. Atg8s are addressed to double membrane vesicles termed autophagosomes (AP), participating to the initiation, cargo recognition/engulfment, and vesicle closure. In addition, Atg8s also function in autophagy unrelated pathways, either conjugated to single-membrane vesicles (CASM) or independently of membrane anchorage. However, the molecular mechanisms and the regulations underlying the multiple roles of Atg8s are not well understood. The Janus consortium federate partners working on Autophagy, Proteostasis and Stress, and complementary expertise on cellular biology, genetics, proteomics and big data analyses. The Janus project explores the two faces of LC3/GABARAP functions within the cell and aims to characterize the molecular mechanisms allowing "spatio-temporal functionality" in autophagy-related and unrelated processes. Janus will describe and quantify the variability and versatility of LC3/GABARAP functions. It takes advantage of C. elegans for in vivo studies of several autophagy processes, but also CASM processes and developmental functions. This tiny animal with multiple tissues but with only two LC3/GABARAP proteins (six in humans) will foster the exploration of their specific roles and the elaboration of a functional model for LC3/GABARAP repertoire. The novelty and ambition of Janus is to obtain a detailed and comprehensive view of Atg8s functions and to better understand how they participate to stress sensing and homeostasis through autophagy-related and unrelated processes.

The project "FENMAG" relates to the current need to develop new nanomaterials for the production of permanent magnets of high power and with a reduced ecological footprint throughout their life cycle. The issue of permanent magnets has become strategic again this last decade. Magnets are made up of magnetic materials called "hard", that is to say with strong spontaneous magnetization and strong anisotropy, capable of storing strong magnetic energies per unit of mass and volume, and thus reducing the quantities of necessary materials for the intended applications. To date, medium and high performance magnets require rare earth-based materials such as SmCo or NdFeB. The latter must be doped with dysprosium at prohibitive cost to maintain their performance level up to 100-150 ° C. With the development of electrification systems, the production of electricity from renewable energies (wind, maritime), hybrid vehicles, the need in terms of volume is growing very rapidly. Military applications, with the increase in on-board electrical power, the increase in the number of electrically controlled components do not escape this trend. However, rare earth resources are limited, expensive and have become a virtual monopoly of China. To reduce this dependency, it is necessary to produce new magnetic phases with increased performances, and to implement alternatives to the use of rare earths. To meet this fundamental need, the FENMAG project aims to produce iron-nitride magnetic single-domain nanoparticles (a '' - Fe16N2 phase) that could be integrated as new bricks in permanent magnets. The targeted phase a '' - Fe16N2 has serious advantages in view of the desired properties: - a spontaneous magnetization superior to that of massive Fe. - the strongest anisotropy for a material not comprising heavy metal, noble metal or rare earth. - the absence of a risk of diffuse pollution in the event of dissemination, and of non-recycling. - the lowest cost in terms of the elements that compose it. - a theoretical stored energy potential of 135 MGOe, superior to the best materials doped with rare earths (60 MGOe) To carry out this ambitious project, FENMAG associates 3 Toulouse laboratories that have complementary expertise in nanomaterials science: the LCC for the chemical synthesis of perfectly calibrated metallic and magnetic nanoparticles, the CEMES for the study of the chemical and structural order and the SPS (spark plasma sintering) sintering processes, and the LPCNO for the study of the magnetic properties of nanoparticles. The objectives of the project are: - to develop a new, unambiguous and reproducible chemical synthesis pathway of nanoparticles models of iron nitride '' - Fe16N2 (composition, chemical and atomic order controlled) - Shape these nanoparticles to make a small magnet based on iron nitride a '' - Fe16N2 (mass 1g). - Qualify this phase for the manufacture of magnets, potentially in the intermediate zone between rare earth magnets and ferrites. - lay the groundwork for a scale-up of the production of these nanoparticles and facilitate the production of small magnets. The process will involve a SME company for the scale-up phase.