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.

The NanoSCAPE project aims to develop a new analytical methodology based on the use of nanoparticles and spectrometry techniques for the very high sensitive detection of bacteria and pathogens. The use of spectrometrically revealed nanoparticles will allow the direct detection of bacteria with extremely low detection limits, of the order of 0.1 bacteria/ml in biological fluids (e.g. blood, urine, synovial fluid). Furthermore, this approach will allow the highly selective detection and counting of up to 30 strains of target bacteria and pathogens simultaneously and in just a few minutes. As part of the NanoSCAPE project, we will carry out a proof of concept on 10 different strains of bacteria. This new approach could be complementary or even alternative to indirect diagnostic methods such as those based on antibody detection (ELISA, Western blot), or PCR. An application for the direct detection of Borrelia involved in Lyme disease, which is considered difficult to diagnose, will be developed using blood, urine or synovial fluid samples. Through a diagnostic programme on nearly 450 patients (including controls) at different stages of the disease, we will evaluate the NanoSCAPE analytical approach in terms of efficiency, selectivity and ease of implementation on the different biological fluids mentioned above. The results will be systematically compared to existing tests and will allow us to decide on the relevance of proposing new tests based on the methodology developed in the project. Given the wide range of scientific and technological fields involved (analytical chemistry, physical chemistry of nanoparticles, immunology, medicine), we have set up a consortium of 3 public research laboratories (including a university hospital), each of which is an expert in a key discipline, a private company that is a leader in the development of antibodies and a hospital that is recognised as a centre of competence for Lyme disease. A significant part of the project will be devoted to technological (patents with the support of a regional SATT) and scientific (conferences, peer-reviewed articles) development. As such, it is not possible to give more strategic, technical and scientific information on the NanoSCAPE project in this summary. In addition, after having carried out the main actions of technological valorisation, we will boost the interactions towards the general public through several conferences, interventions in high schools/colleges, diffusion on social networks and creation of a comic strip. We will also subcontract an expert organisation in the field of scientific popularisation to ensure not only the quality and content of the media (videos, comic strip) but also high visibility (several million views per week). An association (at least) on Lyme disease will also serve as a relay for the dissemination of the project's progress to the general public. We will also rely on the actions of a competitiveness cluster to help us disseminate our advances to the industrial world. The NANOScape project will thus make it possible to develop a novel, extremely sensitive and rapid approach for the simultaneous detection of bacteria and pathogens in biological fluids, with applications that will ultimately go beyond the detection of Lyme disease.

BioInspired Oleophobic Self-Cleaning surfaces for Automotive indoor environment The fast development of new types of mobility based on car sharing, with frequent change of drivers and occupants of the vehicle, reinforces the need for the development of innovative automotive interior materials surfaces with anti-fouling and self-cleaning properties, especially against oily deposits. Based on bioinspired models of superoleophobic surface texture and composition, from natural species such as springtails, the BIOSCA project gathers two research laboratories specialized in bio-inspired surface functionalization, and two major actors of the automotive industry. It combines 1) the preparation and structuration at the nano and micro levels of polymer surfaces, 2) their chemical functionalization to achieve low surface energy, 3) the evaluation of performances on automotive interior materials samples and process industrialization. This applied research project relies on complementary scientific expertises of the academic partners. One research laboratory has developed an expertise to create polymer films exhibiting topographical features such as hierarchical organization and re-entrant roughness or porosity relevant for superoleophobicity. This topography can be achieved by the “breath figure” (BF) process leading to honeycomb films in close-packed hexagonal arrays after fast drying of a polymer solution under a humid air-flow. It can also combine nanoscale self-assembly of diblock copolymers. Another research laboratory, coordinator of the project, is one of the world leaders in the preparation of bioinspired superhydrophobic/suoeroleophobic surfaces thanks to a molecular conception developed from the deposition of polymers to their nanostructural and chemical surface functionalization using electrochemical and plasma-assisted treatments. The industrial partners will select car interior parts of interest for anti-fouling and self-cleaning treatment, and will prepare samples of car interior materials, possibly painted or film-coated. After their surface treatment by the academic partners theses samples will undergo a series of standardized tests to validate and quantify the performance of the process, including its durability after ageing. They will also analyze the technical and economical feasibility of industrializing the process, with environment compliance criteria and cost targets. Possible extension to other car parts and to other industrial sectors will also be examined.