Nanomaterials, nanoparticles and other engineered nanoscale constructs (ENCs) hold great promise for medical, technological and economical benefits. However, knowledge about the toxicity and environmental impact of ENCs is typically missing. Prior to any thorough study at the nanobiointerface, an exhaustive physico-chemical characterization of ENCs is of high relevance since these features can be correlated to their biological and toxicological responses. A wide variety of analytical tools exists in order to investigate the nanometrology of ENCs but no single method that can be considered complete and satisfactory. In this context, requirements for developing a new nanometrology instrument include flexibility, robustness, accuracy/reliability, multi-parameters measurability, rapid measurement as well as low cost. The PONAME project aims at developing such a new analytical tool coupling mass spectrometry and laser spectroscopy for polyscopic nanometrology. The instrument may be described according to three analytical units as followed: i) Charge detection mass spectrometry (CD-MS) will allow, in a single event approach, the direct determination of a true and accurate mass/size distribution. In addition, study of the mass/charge relationship in these megadalton weigthed objects (ENCs, (bio)macromolecules) will be of interest in a fundamental point of view by correlating the maximum charge at a given mass to the Rayleigh limit. ii) Laser induced photo-dissociation on single trapped megadalton ion will be carry out. This unique experiment is expected to provide relevant information on the structure, the morphology and/or surface properties of the trapped macroion of selected mass and charge. iii) Fluorescence spectroscopy in the gas phase on single trapped macroion will also be performed. We will thus be able to determine the intrinsic optical properties of a megadalton object relatively to its mass/size, charge and structure/morphology. Such a fine analysis might solve partially contradictory results described in the literature on hybrid nanoobjects such as Au@chromophore ranging from full quenching to dramatic increase of the fluorescence. The PONAME project appears particularly ambitious and relevant in the current context of nanotechnology. The developed instrument is expected to be highly robust and flexible towards the variability in the nature and composition of sampled objects.

The Dynachir project addresses the fundamental question of the birth of homochirality in molecular systems. This will be achieved with an innovative approach using nonlinear optical techniques in the frequency and time domain to investigate symmetry breaking in films of chiral and achiral molecules. The consortium is constituted by four partners and managed by E. Benichou (LASIM, UCB Lyon 1). The project first entails the fabrication by Pulsed Laser Deposition (PLD) of binaphthols and helicenes films, two chiral compounds. Monolayer and multilayer films of these compounds are known to remain isotropic and preserve the chiral properties of the initial molecules. Films of different enantiomeric ratio will thus be prepared and their stability towards segregation into domains investigated. In parallel, chiral films of achiral organic molecular compounds formed at the air-water interface in a Langmuir trough by lateral compression and subsequently transferred onto solid glass substrates will also be prepared. These films are known to segregate into enantiomerically pure microscopic domains. Access to the chiral and achiral compounds will be granted through close collaborations outside the consortium with ENS Lyon and the ICCAS in Beijing (China). The samples have already been realized and are therefore known to be available. In the frequency domain, Circular Dichroism Second Harmonic and Sum Frequency Generation (CD-SHG and CD-SFG) will be used to study the segregation process using a microscopic geometry adapted to the size of the domains. CD-SHG and CD-SFG are known to be two powerful techniques to observe chirality since the susceptibility tensor elements associated with this process can be isolated with specific polarization configurations. CD-SFG further supports a vibrational analysis specific to the molecular compounds when one of the exciting photons is tuned over a vibrational resonance. In the time domain, time-resolved CD spectroscopy will be conducted for films of varying enantiomeric ratio. It is indeed known that in the excited state, binaphthols have weaker chiral properties than in their fundamental state owing to a spatial intramolecular re-orientation. Hence, time-resolving the relaxation process will give a hint on how chirality appears over the course of time and how it can be imprinted on the environment. Such an experiment will be performed for one enantiomer diluted into a film enriched in the other enantiomeric form. Finally, the current models available will be confronted to the experimental results and refined to correctly account for the observations.

The ILLA project gathers three complementary teams to study in synergy liquid/liquid "LL" interfaces involved in the assisted ion extraction from water to an organic "oil" phase. This biphasic process is the basis of hydrometallurgical applications of outmost importance such as metal ion extraction or recycling. By coupling specific surface experiments and molecular simulations, we investigate the characteristics of relevant LL interfaces (size, polarity, dynamics, local intermiscibility of liquids), and the concentration and ordering of "adsorbed" species (extractants, complexes, …), following four well defined and parallel tasks. The aim is to obtain detailed molecular insights into interfacial events involved in the transfer of metallic cations (e.g. Ln3+ lanthanides) from an aqueous to an oil phase upon complexation with extractant molecules (e.g. lipophilic diamides). ILLA is a fundamental project combining for the first time synthesis of a "reporter" extractant, non linear optics spectroscopy (SHG) coupled with surface tension measurements, and simulations (molecular dynamics) on the same systems. Beyond studies on "static" planar and curved interfaces (e.g. aqueous interfaces with lanthanide salts, or extractants alone), we plan to investigate LL interfaces "in action", i.e. to follow the kinetics and spectroscopic signature of the multistep extraction processes. These studies involve experimental and theoretical developments. The results should serve as a basis for further understanding the extraction mechanism, to improve the efficiency and kinetics of existing processes, and to develop new ones. The methodological developments (e.g. "prediction" and interpretation of SHG signature, experimental set ups) will also allow to study other liquid interfaces (e.g. in phase transfer catalytic systems).

The mechanism of boundary lubrication of articulating cartilage, which leads to exceptionally low friction coefficients, is still poorly understood. The extreme lubricant properties of the articulating cartilages are even more surprising if one realizes that cartilage is rough and the joint filled with a complex synovial fluid. Using a biotribometer mimicking the articular contact, two partners in this project (LPMCN and LaMCoS) have shown that the stacking of phospholipid bilayers is a serious candidate for explaining these exceptional properties. Friction coefficients close to the ones of joints were measured with surfaces covered with supported phospholipid bilayers (SPB) in the gel state (DPPC). Values were larger in the presence of fluid bilayers (DOPC), due to bilayer degradation under mechanical stress during sliding. The general objective of the BioLub project is to understand better the lubricant role of phospholipid bilayers from complementary theoretical, numerical and experimental approaches. The consortium is highly pluridisciplinary as it associates laboratories from condensed, bio-, nano- and soft matter physics (LPMCN), but also nano- and molecular physics (LASIM), biomaterials and tribology (LaMCoS). On the experimental side, SPB will be used and deposited on different substrates, in presence of various buffers in order to understand the biolubrication of healthy joints (influence of lipid phase and ions): smooth model substrates, rough substrates, substrates separated with a vesicular solution with or without biopolymers. A second biotribometer will be developed during the project in order to detect small changes in friction coefficients by these parameters. Complementary experiments at a molecular scale will be performed: FRAP (Fluorescence Recovery After PhotoBleaching) to measure the diffusion of lipids in SPB, in particular in presence of roughness, ions or biopolymers, and AFM (Atomic Force Microscopy) in both imaging and force spectroscopy modes, to measure the bilayer structure, in particular on rough or patterned substrates. The dynamics of fluid membranes in the complex structure of synovial joints are intrinsically a multiscale phenomenon. In order to interpret the experimental results at different scales, theoretical modeling is essential, but it requires a full hierarchy of models, ranging from molecular dynamics at small scale to continuum theories at large scales. These models will be calibrated using experimental results. Mainly three approaches will be used in this project. At small scale molecular dynamics will be used to investigate the internal structure of the membranes, their phase behavior and their friction properties for various lipid molecules (DPPC, DMPC, DOPC). But these approaches (all-atoms models) are restricted to nanometric scales and coarse-grained molecular dynamics will be used to describe the larger scale behavior, including hydrodynamic flows. A continuum description at the largest scales will be used as well to investigate the hydrodynamic instabilities and the collective behavior of membranes or vesicles in a flow, based on analytical approaches or on numerical techniques such as the Boundary Integral formulation. Each model will benefit from the data of smaller scale models, and a wide variety of physical phenomena such as phase transitions, equilibrium and non-equilibrium fluctuations as well as destabilization or topological changes will be investigated and compared to experimental findings.