The scientific interest for h-BN material is growing every year due to its potential use in various domains such as microelectronic. The presented project aims to develop and study a new atomic layer deposition (ALD) approach for boron nitride very thin films. Indeed, the few existing ALD processes being mostly based on ammonia and/or halide precursors, new ALD approach using alternative precursors is proposed to avoid corrosive and/or irritant reactant and by-product as well as to improve the film quality especially in term of crystallinity. Regarding an eventual industrial application, low energy consumption and environmentally friendly process is sought after. The polymer derived ceramics route will thus be transposed to ALD. No process combining these two synthetic routes has been reported up to now. Elaboration of well crystallized h-BN ultra-thin films is motivated among others by further study of BN/graphene heterostructures, which are highly promising in microelectronics.

This project targets the synthesis of lanthanide(III) complexes with redox-sensitive ligands for monitoring of the redox status. A major downstream application is the non-invasive preclinical and biomedical imaging. We hypothesize that a change in the redox state of the ligand will influence both the lanthanide-based luminescence and the relaxation times (coordinated water molecules) for magnetic resonance imaging (MRI). Thus, the ligand will be the probe of the redox-status and the lanthanide will be the reporter. Polydentate ligands appended by pro-phenoxyl, pro-iminosemiquinonate and nitronyl nitroxide units will be prepared and chelated to a series of lanthanide ions: TbIII, EuIII for luminescence detection in the visible region, NdIII and YbIII for a luminescence in the NIR region and GdIII for application as contrast agents. The stability constants of the complexes will be determined and structural characterizations will be conducted. With the aim of improving the solubility and targeting the ligands will be appended by cell penetrating peptides or integrin recognition peptides. The operating potentials of the probes will be next investigated by electrochemical techniques (cyclic voltammetry, electrolysis). The complexes under their different redox states (radical or not) will be prepared both electrochemically and in vitro with biologically relevant reactants, and characterized by luminescence and relaxometric techniques. Having established that the oxidation state of the complexes could be monitored by luminescence and relaxivity, biological studies will be undertaken. They include MTT assays in order to ensure that the probes are non-toxic. Further in cellulo luminescence measurements (2D/3Dfluorescence microscopy) and relaxivity studies will be conducted on cells under various redox status (oxidative stress or hypoxia) for assessing the sensitivity of the probes. Finally, a thorough investigation of the magnetic coupling between the ligand radical and the lanthanide ions will give us major insight onto the operating mode of the complexes.

Singlet oxygen, an excited state of molecular oxygen is a highly reactive species, relevant for an array of applications, ranging from sustainable oxidation catalysis to photodynamic therapy (PDT). The development of tailored materials capable of precisely controlling the generation and manipulation of singlet oxygen is paramount for advancing these applications. PDT, in particular, serves as a compelling example highlighting the importance of controlled singlet oxygen management. It relies on the interplay between a photosensitizer (PS), light, and ground state oxygen (3O2), producing highly reactive oxygen species such as the cytotoxic singlet oxygen (1O2) that is used to destroy cancer and microbial pathogens. Currently PDT faces two key limitations: the control of oxygen supply and limited light penetration inside the tissues. MOFSONG project addresses these limitations by proposing innovative materials capable of decoupling the light irradiation and the 1O2 release steps. The proposed approach involves the design and synthesis of porous Metal Organic Frameworks (MOFs) combining two types of organic linkers: arenes and porphyrins in a single porous structure. Porphyrins are excellent PSs capable of generating 1O2, and arenes are aromatic molecules capable of trapping this 1O2 in their structure upon a cycloaddition reaction and endoperoxide (EPO) formation, while porosity favors the concentration and fast diffusion of oxygen species. Thus, MOFs containing EPO can be generated by illumination at the optimum porphyrin excitation wavelength and stored at low temperature until being used to controllably release 1O2 in a desired environment upon heating. The project objectives involve the synthesis of molecular building units, the development of porous materials assisted by the design of experiments and robotic synthesis, comprehensive structural and spectroscopic investigations and the study of 1O2 dynamics. The success of the project is assured through an interdisciplinary consortium of five research partners providing all the necessary expertise and state of the art facilities.

With proven effects on the environment and health, synthetic polymer microparticles usually called microplastics (MPs) can accumulate in the food chain, release toxic substances or serve as vectors for other contaminants and pathogens. Urban areas are major sources and pathways for the transfer of MPs to water bodies. Their transfer to the natural environment involves complex transport processes through runoff and stormwater management systems. A better control and understanding of transport mechanisms and the estimation of MPs flows in urban water management structures during wet weather periods are crucial to better master their fate and to guide public policies on the management of urban wet weather discharges (UWWD) and reduction of these particle flows. Due to their central role in the management of UWWD, spilled flows from Combined Sewer Overflow structures (CSOs) are the main source of MPs in rivers. Installed in combined sewer networks, CSOs (more than 400 in the metropole of Lyon, France) make it possible to reduce the hydraulic load in wastewater treatment plants, by diverting the exceeding volumes without treatment into the surface waters during heavy rainfall events (expected to increase due to urbanization and climate change). The behavior of MPs during their transfer through CSOs must therefore be characterized: by means of a better understanding of the key mechanisms of interaction of the latter with other constituents conveyed in runoff and stormwater as well as involved hydrodynamic variables. This is the major challenge to be faced by the TRANSPLAST consortium focusing on the following goals (i) to develop an in situ sampling methodology on CSOs in urban areas leading to quantify the related MPs contribution to the contamination of receiving water bodies – for this purpose, an original combination of three analytical approaches is proposed, (ii) to identify and capture the interactions between MPs and the organic or inorganic fractions of the liquid and solid phases, (iii) to simulate the transport mechanisms of these particles and, (iv) to evaluate innovative trapping solutions to control MPs rejected by CSOs. To achieve these objectives, the project is organized into 5 tasks. The first task will be dedicated to qualify and quantify the flows of MPs in a dozen of CSOs located on the territory of the metropolis of Lyon, selected for their representativeness of multiple urban contexts. The hydrodynamic characteristics will be detailed on two CSOs equipped with monitoring devices and systems (Task 1). The investigation of the MPs behavior in CSOs requires to track properly MPs in order to ease their quantification in complex matrices. The development and use of MPs doped with rare metals (D-MPs) (Task 2) will allow their traceability, the understanding of their interactions with the solid and liquid phases of urban effluents and the consequences on their settling velocities (Task 3). These experimental laboratory investigations will be combined with experiments on small scale physical models of CSOs, in order to estimate the fraction of MPs transferred from the network to the natural environment and to improve their interception rate via original trapping structures (Task 4). Numerical models of MPs’ transport will be developed and validated against experimental data taking into account the interactions with particulate and dissolved matter as well as the geometry of the CSOs studied (Task 5). These validated models will be used to simulate multiphase flows in new structures with various hydrodynamic configurations in order to optimize their MPs’ trapping efficiency (Tasks 4 & 5). This program associates 5 public laboratories (DEEP, IMP, LMFA, LEHNA, LMI) and the results will bring new insights and strategies for practitioners and water authorities to better manage CSOs releases through MPs quantification methods and interception technologies.

2D materials exhibit promising properties for key European industrial areas including high-speed computing and communication technologies. However, mainly focused on crystalline materials, these applications are currently limited by the lack of direct and reproducible low cost-synthesis methods, due to high temperature growth. Recently, structurally disordered 2D materials, produced at much lower temperatures, have been shown to manifest a large degree of uniformity over large areas, and performant properties for device applications. Amorphous boron nitride (aBN) is found to exhibit ultra-low dielectric-constant, and excellent field emission performance, being suitable for interconnects technologies and high performance electronics, such as flexible dielectric devices or conductive bridging RAM. MINERVA aims to grow aBN thin films over large area on various substrates, and evaluate their properties as coatings for thermal, electronic and spintronic applications. Particular attention will be paid to achieve nanoscale control of the amorphicity, thickness of the films as well as doping rate and substrate interaction. The relationship between processing and atomic structure will be studied by an appropriate combination of analytical techniques. Modelling to understand the structures and properties of the materials will support and validate the experiments at every stage. The expected physical properties of such deposited layers, coupled with the versatility and adaptability in materials processing, as well as the large-area and uniform coverage at low temperature, should allow their integration as electronic components in ultimate nanoelectronic systems. More concretely, the added value of large scale aBN will be studied for resistive switching devices, magnetic tunnel junctions and spin injection tunnel barriers. The possible dependence of aBN electronic properties in contact to ferromagnetic electrodes will be explored in detail, predicting the possible fruitful potential of spin manipulation by proximity effect at the hybridized aBN/ferromagnet interface. This is expected to generate new scientific knowledge of charge and spin transport across novel 2D hybrid junctions. In addition, these newly tuned aBN materials, on which no studies have yet been conducted within the Graphene Flagship, will be added to the Samples and Materials Database as standard references. MINERVA brings together complementary expertises and is characterized by a high level of interaction between partners. UCBL will coordinate MINERVA and synthesize controlled aBN samples. ICN2 and UU will respectively perform measurements of thermal conductivity and charge and spin transport. UCLouvain and ICN2 will simulate spin-dependent transport throughout aBN films and investigate the coupling between aBN electronic properties and ferromagnetic materials. MINERVA will bring new materials and technological devices to the Flagship consortium, thereby supporting its industrial objectives.