Structure of nanoparticles embedded in micellar polycrystals.

We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0 °C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to independently probe the structure of the nanoparticles and that of the polymer. We find that the nanoparticles do not perturb the crystalline order. In addition, a structure peak is measured for the silica nanoparticles dispersed in the polycrystalline samples. This implies that the samples are spatially heterogeneous and comprise, without macroscopic phase separation, silica-poor and silica-rich regions. We show that the nanoparticle concentration in the silica-rich regions is about 10-fold the average concentration. These regions are grain boundaries between crystallites, where nanoparticles concentrate, as shown by static light scattering and by light microscopy imaging of the samples. We show that the temperature rate at which the sample is prepared strongly influence the segregation of the nanoparticles in the grain-boundaries.

Responsivity of Fractal Nanoparticle Assemblies to Multiple Stimuli: Structural Insights on the Modulation of the Optical Properties.

Multi-responsive nanomaterials based on the self-limited assembly of plasmonic nanoparticles are of great interest due to their widespread employment in sensing applications. We present a thorough investigation of a hybrid nanomaterial based on the protein-mediated aggregation of gold nanoparticles at varying protein concentration, pH and temperature. By combining Small Angle X-ray Scattering with extinction spectroscopy, we are able to frame the morphological features of the formed fractal aggregates in a theoretical model based on patchy interactions. Based on this, we established the main factors that determine the assembly process and their strong correlation with the optical properties of the assemblies. Moreover, the calibration curves that we obtained for each parameter investigated based on the extinction spectra point out to the notable flexibility of this nanomaterial, enabling the selection of different working ranges with high sensitivity. Our study opens for the rational tuning of the morphology and the optical properties of plasmonic assemblies to design colorimetric sensors with improved performances.

Collective thermal diffusion of silica colloids studied by nonlinear optics.

We investigate the collective thermal diffusion of silica charged spheres in Sulpho-Rhodamine B/water solution at different concentrations by measuring time-dependent thermal and Soret lensings. We show a significant concentration-dependence of the thermal diffusion coefficient D(T), not previously reported. Moreover, the results clearly show that both mass diffusion and Soret coefficient are collective quantities being strongly dependent on the particles' packing fraction. Our Z-scan setup allows us to investigate the dynamics of the system at low wave vector, which addresses the influence of the interparticle interactions on the thermal diffusion of the colloids.

Assembly kinetics in binary mixtures of strongly attractive colloids.

The early stages of aggregation kinetics in a binary mixture of asymmetric colloids, aggregating irreversibly via biotin-streptavidin bonds, are experimentally and numerically studied. Experiments are performed by DLS methods, and data are analyzed in terms of a Smoluchowski-like coagulation equation. Focus is on the case of small (S) biotin-covered particles interacting with large (L) streptavidin-covered ones. The small particles act as linkers between the large ones. The dependence of S-L and L-L aggregation rate constants on the ratio between concentration of small and large particles is investigated, to detect the concentration at which aggregation of large particles is most effective.

Shocks in nonlocal media.

We investigate the formation of collisionless shocks along the spatial profile of a Gaussian laser beam propagating in nonlocal nonlinear media. For defocusing nonlinearity the shock survives the smoothing effect of the nonlocal response, though its dynamics is qualitatively affected by the latter, whereas for focusing nonlinearity it dominates over filamentation. The patterns observed in a thermal defocusing medium are interpreted in the framework of our theory.

Time-resolved dynamics of granular matter by random laser emission.

Because of the huge commercial importance of granular systems, the second-most used material in industry after water, intersecting the industry in multiple trades, like pharmacy and agriculture, fundamental research on grain-like materials has received an increasing amount of attention in the last decades. In photonics, the applications of granular materials have been only marginally investigated. We report the first phase-diagram of a granular as obtained by laser emission. The dynamics of vertically-oscillated granular in a liquid solution in a three-dimensional container is investigated by employing its random laser emission. The granular motion is function of the frequency and amplitude of the mechanical solicitation, we show how the laser emission allows to distinguish two phases in the granular and analyze its spectral distribution. This constitutes a fundamental step in the field of granulars and gives a clear evidence of the possible control on light-matter interaction achievable in grain-like system.

Time-dependent nonlinear optical susceptibility of an out-of-equilibrium soft material.

We investigate the time-dependent nonlinear optical absorption of a clay dispersion (Laponite) in an organic dye (rhodamine B) water solution displaying liquid-arrested state transition. Specifically, we determine the characteristic time tauD of the nonlinear susceptibility buildup due to the Soret effect. By comparing tauD with the relaxation time provided by standard dynamic light scattering measurements we report on the decoupling of the two collective diffusion times at the two very different length scales during the aging of the out-of-equilibrium system. With this demonstration experiment we also show the potentiality of nonlinear optics measurements in the study of the late stage of arrest in soft materials.

Laser beam filamentation in fractal aggregates.

We investigate filamentation of a cw laser beam in soft matter such as colloidal suspensions and fractal gels. The process, driven by electrostriction, is strongly affected by material properties, which are taken into account via the static structure factor, and have impact on the statistics of the light filaments.