Benjamin Abécassis

Colloidal motility and pattern formation under rectified diffusiophoresis.

In this Letter, we characterize experimentally the diffusiophoretic motion of colloids and lambda-DNA toward higher concentration of solutes, using microfluidic technology to build spatially and temporally controlled concentration gradients. We then demonstrate that segregation and spatial patterning of the particles can be achieved from temporal variations of the solute concentration profile. This segregation takes the form of a strong trapping potential, stemming from an osmotically induced rectification mechanism of the solute time-dependent variations. Depending on the spatial and temporal symmetry of the solute signal, localization patterns with various shapes can be achieved. These results highlight the role of solute contrasts in out-of-equilibrium processes occurring in soft matter.

Self-Assembly of CdSe Nanoplatelets into Giant Micrometer-Scale Needles Emitting Polarized Light

We report on the self-assembly of colloidal CdSe nanoplatelets into micrometers long anisotropic needle-like superparticles (SPs), which are formed in solution upon addition of an antisolvent to a stable colloidal dispersion. Optical fluorescence microscopy, transmission electron microscopy, and small-angle X-ray scattering provide detailed structural characterization and show that each particle is composed of 10(6) nanoplatelets organized in highly aligned columns. Within the SPs, the nanoplatelets are stacked on each other to maximize the contact surface between the ligands. When deposited on a substrate, the planes of the platelets are oriented perpendicularly to its surface and the SPs exhibit polarized emission properties.

Influence of Monomer Feeding on a Fast Gold Nanoparticles Synthesis: Time-Resolved XANES and SAXS Experiments

A comprehensive study of the mechanism of gold nanoparticle formation has been conducted using third-generation synchrotrons. The particles were obained by reduction of AuCl(3) by BH(4)(-) in toluene. Gold oxidation state was monitored by X-ray absorption near edge spectroscopy (XANES), while the size and concentration of the nanoparticles were assessed by small-angle X-ray scattering (SAXS). A time-resolution of 100 ms has been achieved for a total formation time of a few seconds. The change with time of the total amount of Au(0) present in the solution is obtained by XANES. The change of the amount of Au(0) inside the nanoparticles is obtained from the SAXS signal. The comparison between these two quantities shows that a measurable amount of Au(0) exists transiently as monomers (or very small entities) in solution and this quantity is linked to an observed burst of nucleation of nanoparticles. The reduction kinetics is strongly influenced by the presence of ligands and a change in temperature. A model coupling the observed reduction kinetics and nucleation and growth laws is able to recover the final size and number densities of the explored experimental conditions.

Osmotic manipulation of particles for microfluidic applications

Diffusiophoresis, i.e. the movement of macromolecules along a molecular gradient, is shown to be an efficient means to drive particles in microchannels. By using a generic microfluidic setup, we assess the displacement of silica particles under a controlled salt gradient and provide experimental evidence for a strongly enhanced migration process, the amplitude of which depends on the nature of the salt. A theoretical description shows quantitative agreement with the observed experimental features. Furthermore, we describe a set of microfluidic operations such as separation, sorting or focusing of a colloidal assembly which can be efficiently performed using diffusiophoresis.

Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles

The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In a strongly dissociating solvent, a discrete metallomacrocycle, described as a molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and molecular modeling. In a less dissociating solvent, the primary supramolecular structure, combining negatively charged POMs and cationic metal linkers, further self-assemble through intermolecular electrostatic interactions in a reversible process. The resulting hierarchical assemblies are dense monodisperse nanoparticles composed of ca. 50 POMs that were characterized by SAXS and transmission electron microscopy (TEM). This multiscale organized system directed by metal coordination and electrostatic interactions constitutes a promising step for the future design of POM self-assemblies with controllable structure-directing factors.

Phonon Line Emission Revealed by Self-Assembly of Colloidal Nanoplatelets

We show that colloidal nanoplatelets can self-assemble to form a 1D superlattice. When self-assembled, an additional emission line appears in the photoluminescence spectrum at low temperatures. This emission line is a collective effect, greatly enhanced when the NPLs are self-assembled. It is attributed to the longitudinal optical (LO) phonon replica of the band-edge exciton, and its presence in self-assembled nanoplatelets is explained using a model based on an efficient photons reabsorption between neighboring nanoplatelets. The presence of phonon replica at low temperatures in ensemble measurements suggests the possibility to design a laser, based on self-assembled nanoplatelets.

Gold nanoparticle synthesis in worm-like catanionic micelles: microstructure conservation and temperature induced recovery

Spherical gold nanoparticles are synthesized in worm-like catanionic reverse micelles, demonstrating the absence of shape templating except when the growth of the particles is slow. In situ time resolved SAXS measurements show that the microstructure of the microemulsion is conserved during the whole reaction. The liquid–liquid phase transition of the catanionic microemulsion induced by a gentle cooling is used to recover and purify the nanoparticles in a simple manner.

Self-assembling properties of malonamide extractants used in separation processes

A review of the four microstructures present in oil phases of malonamide extractants used for nuclear fuel reprocessing is presented in relation with the extraction properties and the third phase formation. Due to their surface active properties, extractants can be considered as a weak surfactants and are organised into reverse micelles interacting through an attractive potential. The Van der Waals attractions between the cores of reverse micelles are the key parameters for understanding “third phase” formation. Extractant solutions are similar to reverse microemulsions and the stability rules known in the field of microemulsions can be applied. In some cases, micelles are transformed into a regular molecular solution by modest heating. Apart from micellar and regular solutions, two new modes of association of extractant molecules have been identified. Networks of H-bounds are obtained when “modifiers” such as octanol are added by formulators in order to improve stability range. Microphase separation in a more crystalline phase may be obtained by increasing extractant and/or ion concentrations.

Real-Time in Situ Probing of High-Temperature Quantum Dots Solution Synthesis

Understanding the formation mechanism of colloidal nanocrystals is of paramount importance in order to design new nanostructures and synthesize them in a predictive fashion. However, reliable data on the pathways leading from molecular precursors to nanocrystals are not available yet. We used synchrotron-based time-resolved in situ small and wide-angle X-ray scattering to experimentally monitor the formation of CdSe quantum dots synthesized in solution through the heating up of precursors in octadecene at 240 °C. Our experiment yields a complete movie of the structure of the solution from the self-assembly of the precursors to the formation of the quantum dots. We show that the initial cadmium precursor lamellar structure melts into small micelles at 100 °C and that the first CdSe nuclei appear at 218.7 °C. The size distributions and concentration in nanocrystals are measured in a quantitative fashion as a function of time. We show that a short nucleation burst lasting 30 s is followed by a slow decrease of nanoparticle concentration. The rate-limiting process of the quantum dot formation is found to be the thermal activation of selenium.

Stacking and Colloidal Stability of CdSe Nanoplatelets

Colloidal CdSe nanoplatelets with monolayer control over their thickness can now be synthesized in solution and display interesting optical properties. From a fundamental point of view, the self-assembly of CdSe nanoplatelets can impact their optical properties through short-range interactions, and achieving control over their dispersion state in solution is of major relevance. The related issue of colloidal stability is important from an applicative standpoint in the perspective of the processing of these materials. Using UV-vis spectroscopy, we assess the colloidal stability of dispersions of CdSe nanoplatelets at different nanoparticle and ligand (oleic acid) concentrations. We unravel an optimum in oleic acid concentration for colloidal stability and show that even moderately concentrated dispersions flocculate on a time scale ranging from minutes to hours. Small-angle X-ray scattering shows that the precipitation proceeds through a face-to-face stacking of the nanoplatelets due to long-ranged van der Waals attraction. To address this issue, we coated the platelets with a carboxylic acid-terminated polystyrene, thus achieving colloidal stability while retaining the optical properties of the platelets.