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International audience; A bidentate chiral dithiol (diBINAS) is utilised to bridge Au 25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by smallangle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed selfassembly of metal clusters.

International audience; Hypothesis: Langmuir-Blodgett (LB) technique allows the deposition of gold nanoparticles and nanoclusters (atomically precise nanoparticles below 2 nm in diameter) onto solid substrates with an unprecedented degree of control and high transfer ratios. Nanoclusters are expected to follow the crinkle folding mechanism, which promotes the formation of trilayers of nanoparticles but kinetically disfavors the formation of the fourth layer.Experiments: LB films of Au38(SC2H4Ph)24 nanocluster were prepared at a range of surface pressures in the bilayer/trilayer regime and their internal structure was analyzed with X-ray Reflectivity (XRR) and Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS). Bimodal atomic force microscopy (AFM) imaging was used to quantify the elastic modulus, which can be correlated with the topography at the same point on the surface.Findings: Nanocluster bilayers and trilayers exhibited the elastic moduli of ca. 1.2 GPa and 0.9 GPa respectively. Films transferred in the 20-25 mN/m surface pressure regime displayed a particular propensity to form highly vertically organized trilayers. Further compression resulted in disorganization of the layers. Crucially, the use of two cantilevers of contrasting stiffness for bimodal AFM measurements has demonstrated a new approach to quantify the mechanical properties of ultrathin films without the use of deconvolution algorithms to remove the substrate contribution.

International audience; The formation of dense protein interfacial layers at afree air−water interface is known to result from both diffusion andadvection. Furthermore, protein interactions in concentrated phasesare strongly dependent on their overall positive or negative net charge,which is controlled by the solution pH. As a consequence, aninteresting question is whether the presence of an advectionflow ofwater toward the interface during protein adsorption producesdifferent kinetics and interfacial structure of the adsorbed layer,depending on the net charge of the involved proteins and, possibly, onthe sign of this charge. Here we test a combination of the followingparameters using ovalbumin and lysozyme as model proteins: positiveor negative net charge and the presence or absence of advectionflow. The formation and the organization of the interfacial layers arestudied by neutron reflectivity and null-ellipsometry measurements. We show that the combined effect of a positive charge oflysozyme and ovalbumin and the presence of advectionflow does induce the formation of interfacial multilayers. Conversely,negatively charged ovalbumin forms monolayers, whether advectionflow is present or not. We show that an advection/diffusionmodel cannot correctly describe the adsorption kinetics of multilayers, even in the hypothesis of a concentration-dependent diffusioncoefficient as in colloidalfiltration, for instance. Still, it is clear that advection is a necessary condition for making multilayers througha mechanism that remains to be determined, which paves the way for future research.

International audience; Langmuir–Blodgett technique is utilized to deposit ultrathin films of Au$_{38}$(SC$_2$H$_4$Ph)$_{24}$ nanocluster onto solid surfaces such as mica and silicon. The morphologies of the films transferred at various surface pressures within the mono/bi/trilayer regime are studied by atomic force microscopy (AFM). The time spent on the water surface before the deposition has a decisive effect on the final ordering of nanoclusters within the network and is studied by fast AFM, X-ray reflectivity, and grazing-incidence wide-angle X-ray scattering.

Nanofilms of thickness of about two nanometers have been formed at the air-water interface using functionalized castor oil (ICO) with cross-linkable silylated groups. These hybrid films represent excellent candidates for replacing conventional polymeric materials in biomedical applications, but they need to be optimized in terms of biocompatibility which is highly related to protein adsorption. Neutron reflectivity has been used to study the adsorption of two model proteins, bovine serum albumin and lysozyme, at the silylated oil (ICO)-water interface in the absence and presence of salt at physiologic ionic strength and pH and at different protein concentrations. These measurements are compared to adsorption at the air-water interface. While salt enhances adsorption by a similar degree at the air-water and the oil-water interface, the impact of the oil film is significant, with adsorption at the oil-water interface three-to four-fold higher compared to the air-water interface. Under these conditions, the concentration profiles of the adsorbed layers for both proteins indicate multilayer adsorption: The thickness of the outer layer (oil-side) is close to the dimension of the minor axis of the protein molecule, ~ 30 {\AA}, suggesting a side-way orientation with the long axis parallel to the interface. The inner layer extends to 55-60 {\AA}. Interestingly, in all cases, the composition of oil film remains intact without significant protein penetration into the film. The optimal adsorption on these nanofilms, 1.7-2.0 mg$\bullet$m-2 , is comparable to the results obtained recently on thick solid cross-linked films using quartz crystal microbalance and atomic force microscopy, showing in particular that adsorption at these ICO film interfaces under standard physiological conditions is non-specific. These results furnish useful information towards the elaboration of vegetable oil-based nanofilms, in direct nanoscale applications or as precursor films in the fabrication of thicker macroscopic films for biomedical applications. 2, Comment: Langmuir, 2019

International audience; During evaporative drying of a colloidal dispersion, the structural behavior at the air–dispersion interface is of particular relevance to the understanding of the consolidation mechanism and the final structural and mechanical properties of the porous media. The drying interface constitutes the region of initial drying stress that, when accumulated over a critical thickness, leads to crack formation. This work presents an experimental study of top-down drying of colloidal silica dispersions with three different sizes (radius 5, 8, and 13 nm). Using specular neutron reflectivity, we focus on the structural evolution at the free drying front of the dispersion with a macroscopic drying surface and demonstrate the existence of a thick concentrated surface layer induced by heterogeneous evaporation. The reflectivity profile contains a strong structure peak due to scattering from particles in the interfacial region, from which the interparticle distance is deduced. A notable advantage of these measurements is the direct extraction of the corresponding dispersion concentration from the critical total reflection edge, providing a straightforward access to a structure-concentration relation during the drying process. The bulk reservoir of this experimental configuration renders it possible to verify the evaporation–diffusion balance to construct the surface layer and also to check reversibility of particle ordering. We follow the structural evolution of this surface layer from a sol to a soft wet-gel that is the precursor of a fragile skin and the onset of significant particle aggregation that precedes formation of the wet-crust. Separate complementary measurements on the structural evolution in the bulk dispersion are also carried out by small-angle neutron scattering, where the particle concentration is also extracted directly from the experimental curves. The two sets of data reveal similar structural evolution with concentration at the interface and in the bulk and an increase in the degree of ordering with the particle size.

International audience; Shrinkage cracks are observed in many materials, particularly in paintings where great interest lies in deducing quantitative information on the material with the aim of proposing authentication methods. We present experimental measurements on the crack opening induced by the drying of colloidal layers and compare these results to the case of a pictorial layer. We propose a simple model to predict the crack width as a function of the thickness of the drying layer, based on the balance between the drying stress buildup and the shear frictional stress with the substrate. Key parameters of the model include the mechanical properties that are measured experimentally using micro-indentation testing. A good agreement between theory and experimental data for both colloidal layers and the real painting is found. These results, by comparing the shrinkage cracks in model layers and in pictorial layers, validate the method based on the use of colloidal systems to simulate and to reproduce drying cracks in paintings.

International audience; The optical properties of a series of gold nanoparticles (D ≈ 2.3−8 nm) grafted with a stabilizing polymer with a wide range of chain lengths (Mw ≈ 6.5K−29.5K) have been studied quantitatively in different dielectric solvents. Mie−Drude dipolar theory was applied to model the localized surface plasmon resonance (SPR) peak position, as well as the peak width of the absorption spectra, using the dielectric function of gold. The modeled spectra yielded information on the dielectric function of the polymer shell, ϵs, from which the average polymer concentration in the shell was deduced. Combining information from optical modeling and structural properties obtained from small-angle neutron scattering (SANS) on the polymer shell thickness and from transmission electron microscopy (TEM) on the gold core size, the SPR peak shifts and their attenuated sensitivity to solvent refractive index were characterized. The SPR behaviors for all of the gold colloids with different core sizes and graft chain lengths were thus expressed as a function of the effective polymer volume fraction, p,of the composite nanoparticle. It was found that sensitivity to the solvent dielectric property decreased until, for p > 0.9 (corresponding to an effective shell thickness on the order of the core radius), the SPR mode was "frozen" in by the polymer shell and lost sensitivity to the solvent.

The relationship between the properties of surfactant monolayers at oil-water interfaces and the phase behaviour in bulk of mixtures of oil + water + surfactant is discussed. Such monolayer properties include the spontaneous curvature, c o the interfacial tension, I γ, the elasticity K (or rigidity) associated with the mean curvature, and the elasticity K associated with the Gaussian curvature. The model system chosen for investigation is the anionic surfactant AOT + aqueous NaCl + n-alkane at 20°C. In such systems, inversion of microemulsion type from oil-in-water (o/w) to water-in-oil (w/o) is possible with increasing electrolyte concentration. The tension, γ, passes through an ultralow minimum value at conditions corresponding to the formation of three phases. Using small angle neutron scattering, we have determined the structure of surfactant-rich third phases (c o ~ 0) formed with the different alkanes. Lamellar phases consisting of surfactant monolayers separated alternately by oil and water appear with short alkanes, whereas L 3 and bicontinuous phases form in systems containing longer alkanes. The bending elasticity K has been measured for planar monolayers at the oil-water interface by ellipsometry. K is independent of salt concentration but depends markedly on alkane chain length N, falling from ~ 1 k B T for N B T for N = 14. This is discussed in terms of the differing extents of oil penetration into the surfactant chains. Higher rigidities favouring lamellar phases and lower rigidities favouring bicontinuous microemulsions are in line with the theoretical predictions of de Gennes and Taupin. Estimates of the constant K have been obtained in droplet microemulsions (w/o) from a knowledge of their size, K and γ. The sign of the constant is in agreement with the geometry of the phases formed in three phase systems. Finally, the ideas and concepts developed in the oil-water systems described above are used to explain the wetting behaviour by alkanes of AOT monolayers at the air-water surface.

International audience; Mixed films formed by an insoluble polymer, poly(dimethylsiloxane) (PDMS), placed on the surface of aqueous solutions of two different soluble surfactants are studied by a variety of different methods: surface tension isotherms, ellipsometry complemented by the neutron reflectivity experiments presented in part 2, and direct observations of the surface via the Brewster angle microscope. A vertical separation into superimposing surfactant and polymer layers is exhibited, with mixing between the layers depending on the surfactant. On one but not the other of the surfactant solutions studied, a lateral separation of the polymer monolayer is also observed, into domains similar to those previously observed on pure water. The collapse of the monolayer into a three-dimensional state with increasing polymer concentration occurs more smoothly than on water.

We report measurements of the concentration profile of the submerged block of a diblock copolymer monolayer at the air surface of a selective solvent. The profile is found to contain a depletion layer near the surface (∼35 A), followed by a parabolic (or similar) decay which tails off smoothly away from the surface. The dependencies of the maximum dimension (h * ) of the profile on the surface density (σ) and the molecular weight (M) of the submerged block are found to be weaker than those predicted in the limit of strong stretching, but are in reasonably good agreement with numerical SCF calculations of Whitmore, et al. A sharp rise in the surface pressure (measured simultaneous with the reflectivity) is observed for each sample at high surface densities which is not predicted by the existing mean-field or scaling theories

Aromatic dithiol linkers were used to prepare aggregates of Au25(SR)18 clusters (SR: thiolate) via ligand exchange reactions. Fractions of different aggregate sizes were separated by size exclusion chromatography (SEC). The aggregates were characterized by UV-vis absorption spectroscopy, matrix assisted laser desorption ionization (MALDI) mass spectrometry, nuclear magnetic resonance (NMR) spectroscopy (including diffusion-ordered spectroscopy, DOSY) and small angle X-ray scattering (SAXS). At a 2 : 1 cluster : dithiol ratio, small aggregates (dimers, trimers) and also larger aggregates consisting of 10–20 Au25 clusters were formed, according to DOSY, besides unreacted (monomeric) Au25(SR)18. MALDI mass spectrometry shows signals consistent with dimers and trimers (doubly charged). The SAXS curves for the small aggregates can be well fitted by a pearl-necklace model. For the bigger aggregates the SAXS curves evidence a characteristic separation distance between the clusters within the aggregates, which is imposed by the length of the linker. The SAXS curves of these larger aggregates can be well fitted with a core–shell sphere model with a sticky hard-sphere structure factor, in agreement with closely packed aggregates. The absorption spectra of smaller aggregates resemble those of individual Au25(SR)18 clusters; however, and most importantly, the larger aggregates show completely different, less structured spectra with a new band emerging at 840 nm. We assign this drastic change in the absorption spectra and the new band to the electronic coupling between the clusters through the all aromatic linker. In accordance with this view, the aggregates formed with a linker containing methylene groups, thus breaking conjugation, do not show the band at 840 nm. By the addition of monothiols to the larger aggregates their size can be reduced through an “unlinking” reaction. This reaction also affects the band at 840 nm, which moves to higher energy when reducing the aggregate size, as would be expected within a particle in a box model. The electronic coupling between the clusters through the linker is the basis for future applications in nanoelectronics.

In this thesis, the objective is to control the polymer-grafted gold nanoparticles optical properties (SPR) by tuning the protecting polymer shell structural properties. Gold nanoparticles grafted with thermosensitive polymers with a large range of molecular masses and different degrees of hydrophobicity are synthesized by “grafting-to” technique. SANS is employed to characterize the protecting polymer shell structural properties. The absorption spectra are modeled using the Mie Dipolar theory. It is shown that the gold nanoparticle sensitivity to external solvent is progressively reduced with increasing polymer volume fraction of the nanocomposite until the SPR is frozen by the polymer shell. In this case, the SPR mode becomes insensitive to the dielectric properties of the solvent. SPR is also red-shifted (a color change occurs) by thermally inducing the collapse of the polymer shell. The temperature and the extent of the red-shift are controlled by the graft polymer hydrophobicity and salinity. An important part of this thesis is also dedicated to the polymer-protected gold nanoparticles behaviour at the air-water interface. The Langmuir balance technique is used to build interfacial layers whose interparticle distance is modulated by compression, polymer graft chain length and temperature. The interfacial layer structural properties are determined by studying both the polymer graft layer conformation and the gold core organization with neutron and X-ray reflectivities. These reflectivitity measurements also enable us to evaluate and ameliorate the surface layers stability for a better control of the interparticle distance that is important for optimizing the SPR of the surface layer., L’objectif de cette thèse est de contrôler les propriétés optiques des nanoparticules d’or greffées de polymère en modulant les propriétés structurales de la couche protectrice de polymères. Des nanoparticules greffées de polymères thermosensibles avec une large gamme de masse molaire et différents degrés d’hydrophobicité sont synthétisées par la méthode de « grafting-to ». La DNPA est utilisée pour caractériser les propriétés structurales de la couche protectrice de polymère. Les spectres d’absorption sont modélisés en utilisant la théorie de Mie. Nous démontrons que la sensibilité de la SPR à la propriété diélectrique du solvant diminue progressivement avec la fraction volumique de la couche de polymère jusqu’à devenir quasi-nulle; dans ce dernier cas de figure, la SPR est dite « gelée » par la couche de polymère. Un déplacement significatif de la bande de SPR vers le rouge est induit (un changement de couleur se produit) dû à une transition de collapse de la couche de polymère avec la température. La gamme de température pour induire ce déplacement dépend du degré d’hydrophobicité du polymère et de la salinité. Une partie important de cette thèse est également consacrée aux propriétés des nanoparticules d’or greffées de polymères à l’interface air-eau. La technique de Langmuir est utilisée pour former des films minces dont la distance entre particule est contrôlée par la compression, la longueur des chaînes du polymère greffé et la température. Les propriétés structurales des films minces sont étudiées en déterminant la conformation de la couche de polymère greffée et l’organisation du cœur de l’or par la réflectivité de neutron et de X, respectivement. Les mesures de réflectivité nous permettent également d’évaluer et d’améliorer la stabilité des films minces pour un meilleur control de la distance entre particule, aspect important pour l’optimisation de la SPR. Enfin, les propriétés optiques des nanoparticules d’or à l’interface sont mesurées par des mesures de transmission.