Protactinium, a radioelement with unknown chemistry, is a key element : first actinide for which the 5f orbitals can be involved in chemical bonding, it is also naturally ocurring in envrionment, in the nuclear fuel cycle and also appear in the synthesis of innovative isotopes for medicine. Understanding the chemical behaviour of Pa in these compartments constitutes a great challenge especially since the basic chemistry of this element remains quite blurred ! In this project, we propose to switch to a new paradigm: "predict then experiment". Two main types of properties will be scrutinized, reactivity in terms of equilibrium constants between a set of ligands and protactinium(IV/V) and spectroscopy of protactium compounds. After an extensive methodological study and state-of-the-art theoretical predictions, we will set up prime electromigration, solvent extraction and spectroscopy (high-resolution XANES and laser spectrofluorimetry) experiments aiming at validating/improving the theoretical models and revealing this rare chemistry.

Like terahertz wave few years ago, the spectral domain of long infrared between 20 and 40 µm is still not so much investigated, mainly in the reason of the absence of source and materials available. However some projects like SOFIA (``Stratospheric Observatory For Infrared Astronomy'') developed at NASA, have demonstrated that measurements in this wavelength range can provide important informations inaccessible at lower wavelength. As an example, essential data have been obtained concerning comet leg by taking advantage of a higher ratio between wavelength and dust grain size that decreases the diffusion. We note also that the coming of quantum cascade laser operating near room temperature at wavelength beyond 20 µm is going to facilitate the development of applications in this spectral range. Globally, apart from diamond, there is only a few of transparent materials in long infrared, excepting maybe glasses containing tellurium and germanium. Therefore optical systems working in this spectral range are constrained to used reflective optics that gives unwanted complexity and size. The improvement of such system through the use of transmissive optics needs the production of new materials possessing adapted physical properties: transparency, sensitivity to environment (water, temperature, ...) and so on. The objective of this project is the realization of glasses transparent in the partialy transmitting atmospheric window located in the long infrared between 24 and 30 µm, even up to 40 µm. The main component will be tellurium that is well known to produce glasses transparent beyond 20 µm, associated with heavy atoms to lower the vibrationnal frequency of inter-atomic bond. Moreover, our previous results tend to indicate that the dimensionality of the atomic structure is an important criterion to obtain transparency window at long wavelength. This aspect will be integrated in the design of the glass composition. The glass synthesis will be done by two different routes: conventional melt and quench technique in sealed tube and mecano-synthesys associated with compaction by hot pressing or Spark plasma sintering (SPS). This new way represents a innovative aspect because it should be possible to extend the vitreous domain. Several stoechiometry will be evaluated in order to proceed to comparative analysis of the properties. The strategy developed to reach the goal of the project, is centered around the understanding of the structure of the glass network. Several technique will be used: Raman and Mössbauer spectroscopies, terahertz spectroscopy (in transmission and/or reflection geometry), neutron diffraction, high energy X-ray diffraction. The results will be completed and interpreted by ab initio calculations according to density functional theory (DFT), Empirical Potential Structure Refinement (EPSR) and Reverse Monte-Carlo (RMC). The evaluation of macroscopic properties of transmission, refractive index, etc ... will be confronted to structural studies in order to orient the stoechiometry of new synthesis.

The aim of the project is to synthesize new 1,1,4,4-tetracyanobutadienes (TCBDs) from ynamides possessing the "aggregation induced emission" (AIE) property. The synthetic pathway towards this kind of compounds, which has recently been developed by the team of the scientific coordinator, consists in a sequence of [2+2]cycloaddition followed by a [2+2]retroelectrocyclization between tetracyanoethylene and ynamides. This method is tolerant to many functional groups and generally leads to TCBDs in high yields. Compounds that have the AIE property exhibit fluorescence in the solid state (potentially as nano-aggregates dispersed in a liquid) but not in solution. This property comes from the restriction of the internal molecular movements (rotation, vibration) that allows for the radiative deactivation of the excited state, which is impossible when the molecule possesses "too many" degrees of freedom (non-radiative deactivation in this case). TCBDs that do not come from ynamides are generally not fluorescent at room temperature, neither in the solid state nor in solution. Consequently, this project would raise a new family of compounds having this remarkable property. Moreover, the emission maximum of the AIEgen TCBDs recently synthesized in our laboratory is located beyond 600 nm, which allow for biological applications since it does not compete with the natural autofluorescence that is encountered in living organisms. Once the best emitters identified and characterized, two potential applications will be studied in order to take advantage of the restoration of the fluorescence of the TCBDs in strained medium. First, they will be made water-soluble in order to incorporate them into artificial membranes formed with a Langmuir trough, which would thus allow for their visualization by fluorescence. Given that the emission maximum of our TCBDs is very sensitive to the surrounding medium, one can imagine that this maximum could also be sensitive to the pressure applied to the membrane. In this case, it would constitute one of the first pressure sensors at the molecular level. Finally, these TCBDs will be linked to substrates specific of some proteins such as sugar derivatives, which could allow for their specific visualization in vitro. Whether it be for working on membranes or be it on proteins, TCBDs could be linked to water-soluble groups by "click" chemistry from a common propargylic synthon for the these two applications.

The objective of this project is to develop multispectral molded optics operating simultaneously in the visible/short wave infrared (SWIR) and far infrared between 8-12 µm. These optics will allow the fusion of images taken in these two complementary spectral bands with the same optic, leading to a simplification of design and fabrication as well as important decrease of cost and weight. Imaging in visible/SWIR and in far infrared has many applications still in rapid growth. The fusion of the two complementary images will lead to many new applications both in commercial and defense fields. As an example, for car driving assistance, visible/SWIR image is better for reading road indications and for detecting the presence of ice on the road. Thermal image is much better for seeing further and pedestrians in foggy condition and during the night. For defense applications, it is, for example, easier to move in the dark with intensified SWIR image and thermal imaging is indispensible to detect hidden hot target. There are many optics operating either in the visible/SWIR region or in the far infrared region. Only two materials, known since long time, ZnS and ZnSe, can be considered for producing multispectral optics even they cover only partially these two spectral bands. These materials are fabricated with the long and expensive chemical vapor deposition (CVD). They are polycrystalline materials and consequently, no molded optic is possible. The only way to produce complex asphero-diffractive optics, indispensable with these materials, is to use the expensive single point diamond tuning. In this project, we propose to - develop some new glasses transparent from visible to far infrared up to 12 µm. - develop a molding process for fabricating multispectral optics - develop large band antireflection coating - study some potential applications with the multispectral optics. One commercial application and one defense application will be proposed. The originality and novelty of this project are associated with the following - Completely new glasses transparent from visible to far infrared will be developed. The base compositions are protected by a CNRS patent which has been extended to most industrialized countries. - The first molded multispectral optic will be developed - A system with fused visible/SWIR image and thermal image will be proposed with the same entrance optic, leading to simplified design and fabrication. This should be considered as breaking technological innovation. This consortium is composed of an academic laboratory and an industrial partner well recognized in their field of expertises, with a long term relationship of successful cooperations. These cooperations have, for example, allowed the industrialization of molded infrared optics which are installed in the BMW cars for driving assistance and also in the infrared cameras of the World most important manufacturer.

The application of manufactured nanomaterials (MNMs) in food and packaging industries is expected to increase considerably in the near future, and the evaluation of the safety of MNMs present in foodstuff is thus a major concern in Europe and worldwide. Although some consumer food products contain MNMs (additives or contaminants from packaging), little is known concerning the toxicity of these MNMs following ingestion. Moreover, their size, morphology and state of agglomeration together with physiological modifications (e.g. digestion) are likely to play a considerable role in the uptake and toxicity of these materials to humans. Although numerous in vitro studies have begun to shed light on mechanistic effects, very little data is available concerning the toxic effects of MNMs following oral exposure in vivo. Nevertheless, results from in vivo experiments are the main data useful for risk evaluation. However, due to the vast quantity of different MNMs and the variability of their physic-chemical properties together with the inherent limitations of animal experimentation, the toxic effects in vivo cannot be investigated for each MNM. Therefore it is clearly necessary to establish key guidelines in the classification of MNMs according to their potential adverse effects Among the properties of MNMs, the solubilisation capacity is likely an important determinant of nanomaterial uptake and the initiation of specific pathways of toxicity. In the SolNanoTox project, representatives of two different classes of MNMs will be investigated: titanium dioxide as an example for insoluble species due to its stability in water and aluminium representing the soluble category. Moreover, several reports in the literature suggest that aluminium and titanium oxide nanomaterials target different organs following oral exposure. It is hypothesized that aluminum nanoparticles form aluminum ions, either before or during the uptake in the intestine, whilst titanium dioxide nanoparticles may cross the intestine as intact nanoparticles. This difference in behaviour could then explain the different target organs and toxicity for the two MNMs. In this project, we plan to test this hypothesis by using an innovative combination of modern analytical methods for nanomaterials in tissues and single cells. The characterization of Al and TiO2 nanomaterials will be performed in solution, as well as in cell and tissue. The interaction of lipids, proteins, cell media and intestinal mucus on the characterization parameters of the MNMs will be also addressed. To explore the different solubility in physiological matrices and its influence on the potential uptake mechanisms, the project combines integrative in vitro and in vivo approaches to compare the fate, cytogenotoxic and toxicogenomic effects of the two selected MNMs. Firstly, the oral uptake and fate of MNMs in intestine and liver will be investigated in vivo after short-term oral treatment of rodents and compared to in vitro data obtained in human intestinal and hepatic cell models. Moreover, various toxic effects (genotoxicity, apoptosis, inflammation, proliferation,...) will be studied in vivo and compared the responses observed in in vitro models. In addition, to gain precise information concerning the molecular mechanisms of response following MNM treatment in vivo and in vitro, this project will employ transcriptomic and proteomic approaches. The integrative and multidisciplinary studies outlined in this project will permit to identify determining factors of MNMs driving their uptake, distribution and mechanisms of action. The combined expertise of accomplished research groups in the areas of MNM characterization and analytical analysis, uptake, in vitro and in vivo cytotoxicity and genotoxicity involved in this ambitious project will solve some critical questions raised for MNMs health impacts.