GANDALF aims at modifying the surface of positive electrodes (LiFexMn1-xPO4 (LFMP) and LiNi0.5Mn1.5O4 (LNMO)) of Li-ion devices by a novel atomic layer fluorination process, improving their inertness towards their electrolytic environment, augmenting their performances as high-voltage systems, and validating their use as real-life size SAFT prototypes. Through a PhD funded by the RS2E, we could study our novel atomic layer fluorination process, so-called ALF, on TiO2, Li4Ti5O12 (LTO), LiCoO2 (LCO), and Li(Ni0.80Co0.15Al0.05)O2 (NCA). For each system, we demonstrate that ALF-electrodes display improved cyclability, polarization, and cycle life. Electrochemical operando FTIR measurements show that ALF-NCA is relatively inert towards its electrolyte, as compared to pristine NCA. Encouraged by the ANR, we were advised to build this project as PRCE in order to reach the industrial validation.

The Electrophylle project seeks to characterize a fundamental process involved in the initial transformation of light energy in the reaction center of Photosystem II that initiates photosynthesis in plants and algae. Electrophylle will create a synergy around a new gas phase experimental method applied to chlorophyll systems, a condensed phase approach and their theoretical modeling. Photosystem II (PSII) plays a central role during photosynthesis: indeed, solar energy collected by the antennae is transferred to PSII where the initial charge separation takes place, leading after subsequent steps to a negative charge production and water splitting into dioxygen+ protons. This charge separation is the initial and limiting step to the production of energy and dioxygen, the sources of life. Its quantum efficiency is close to unity and remains unexplained unless one accepts an hypothesis involving a resonant effect and is produced by natural evolutive adaptation. Indeed, the core of the PSII reaction center consists of a set of 12 chlorophyll-related molecules undergoing excitonic coupling, which can be reduced to a working ensemble of only 4 molecules. 2D time-domain spectroscopy measurements indicate the crucial influence in the efficiency of the charge separation mechanism, of resonances between chlorophyll vibration frequencies and the energy gaps separating neutral from ionic pairs. The resulting model reproduces the initial charge separation dynamics in this reaction center based however on fragmentary spectroscopic data. The electronic and vibrational structure of the elements in the core of the PSII reaction center, the chlorophylls, their excitonic pairs are insufficiently known to validate the essential hypothesis of a vibration energy gap resonance that will establish a new model. This can only be achieved by measurements in the gas phase or cryogenic solutions or as in the Electrophylle project, by a combination of both with quantum chemistry calculations. We propose to determine by resonant electron photodetachment spectroscopy, the vibrational and electronic structure of neutral chlorophyll and chlorophyll dimers cooled at 10K and electron tagged. Gas phase spectroscopy of biomolecules has the unique advantage of allowing access to the structure of biomolecules in the absence of medium interactions and being directly comparable to the results of quantum computations. On the other hand, we will achieve microsolvation of chlorophylls by single molecular bonds to bring them into dimers akin to those of the reaction center. This step is essential since it allows tuning their electronic levels into resonance with chlorophyll vibrations that drive charge separation with maximum efficiency. These gas phase measurements will be combined with fluorescence line narrowing (FLN) spectroscopy that addresses the interacting dimers in the protein environment. This will give access to a complete picture of the interaction landscape in chlorophyll dimers in several conditions, from free to assembled into special pairs. Specific quantum calculations will characterize the electronic and vibrational structure of these systems. This will yield energy level positions for chlorophylls and pairs in ground and first electronically excited states, together with a landscape of the interactions within chlorophyll pairs between neutral and ionic states. This project is designed to characterize a fundamental process related to energy transformation –photosynthesis- by a synergy between a new experimental method as applied to a complex system, the reaction center of Photosytem II, theoretical modelling and condensed phase spectroscopy. The precise modeling and understanding of such a fundamental process could help boosting the efficiency of artificial molecular photocatalysts, the electronic properties of which could be tuned to improve their ability of performing ultrafast (10-12 s) charge separation with high quantum yield.

BARRIER is a proof of concept project with multidisciplinary expertise for demonstrating, from the laboratory to a pilot process, that selected bacteria can protect microalgae when growing in various waters including produced water, seawater or wastewaters containing toxic compounds, providing higher algal resilience, productivity and bioremediation efficiency in saline wastewater treatments. Saline wastewater is a stubborn pollution source representing one of the most serious environmental problems occurring on land formations and in water reservoirs. In BARRIER project, natural microalgae and associated bacteria will be selected on organic and metallic toxic compounds. Microalgae-bacteria assemblages will be built, optimized through modeling and tested in large-scale mass culture processes using industrial wastewaters. Microalgae are promising organisms for producing a wide range of commodities (biofuel, bioplastics, …) including recycling and valuation of liquid and gaseous effluents. However, this is hindered by the difficulty to grow microalgae in contaminated waters, where various toxic may reduce their growth, and can even contribute to dramatic crash of the culture. Recent advances have shown that, when associated with a specific cluster of bacterial species, the resilience of assemblage can be significantly stronger than the microalgae alone. Microalgae-bacteria consortia are shaped by complex interactions. Microalgae stimulate bacterial growth by the release of carbon exudates, whereas bacteria supply algae with vitamins and nutrients. Although the microalgae-bacteria relationships through metabolite exchanges are well studied, little is known however regarding the impact of chemical contaminants on the interactions between both microalgae and bacteria. Further experimental studies are required to understand the algae-bacteria interactions in the context of chemical pollution pressure in order to propose innovative strategies for improving the resilience of microalgae assemblage in contaminated effluents. Four objectives in BARRIER project: • To evidence the role of bacteria in the protection of microalgae against contamination, by analyzing physiological responses of microalgae under controlled exposure to toxic chemicals. • To characterize the fate of toxic chemicals and organic matrix during the biodegradation/immobilization processes. • To model and predict the role of interactions between microalgae and associated bacteria when exposed to combined toxic chemicals. • To demonstrate in realistic outdoor pilot conditions that a selected microalgae-bacteria association provides a better resilience of the mass culture process and thus increases the yearly microalgal productivity and bioremediation processing in saline wastewaters with toxic contaminants. BARRIER will perform complementary laboratory experiments in controlled and outdoor conditions with an upscaling approach using cultures of microalgae species and bacteria isolated from a contaminated environment. BARRIER proposes a multidisciplinary approach relying on a consortium associating five academic laboratories and one industrial company developing bioremediation strategies, in order to obtain competencies in microbial ecology, ecotoxicology, organic and inorganic chemistry, molecular biology, modeling and process engineering and microalgae cultivation on oil and gas wastewater. BARRIER will allow a better understanding of the interactions between microalgae and bacteria. The methodological approach will help in characterizing the role of the bacteria in the protection of microalgae against chemical contamination. Lastly, BARRIER will propose innovative approaches with the manipulation of algae-bacteria consortia to use the effective algae-bacteria interactions, approaches that will be tested in realistic outdoor conditions with the support facilities and competences of the industrial Partner.

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.