Marie-Paule Pileni

Solubilization by reverse micelles: Solute localization and structure perturbation

Abstract In the system AOT-isooctane-water, the reverse micelle radii, governed by the water content, vary upon addition of small amounts of compounds solubilized in the microemulsion. These small variations were measured by high-resolution small-angle X-ray scattering. Structural changes are related to the solubilization sites by means of simple geometrical models. Solutes situated at the interface decrease the water core radius; solutes located in the water core increase this radius.

Assemblies of Aligned Magnetotactic Bacteria and Extracted Magnetosomes: What Is the Main Factor Responsible for the Magnetic Anisotropy?

The origin of the magnetic anisotropy is explained in an assembly of aligned magnetic nanoparticles. For that, nanoparticles synthesized biologically by Magnetospirillum magneticum AMB-1 magnetotactic bacteria are used. For the first time, it is possible to differentiate between the two contributions arising from the alignment of the magnetosome easy axes and the strength of the magnetosome dipolar interactions. The magnetic anisotropy is shown to arise mainly from the dipolar interactions between the magnetosomes.

Crystallinity Dependence of the Plasmon Resonant Raman Scattering by Anisotropic Gold Nanocrystals

Au nanocrystals (NCs) with different crystalline structures and related morphologies are unselectively synthesized using an organometallic route. The acoustic vibrations of these NCs are studied by plasmon mediated low-frequency Raman scattering (LFRS). A splitting of the quadrupolar vibration mode is pointed out in the LFRS spectrum. Comparison of the measured frequencies with calculations and careful examination of the NCs morphologies by transmission electron microscopy ascertain this splitting as being an effect of crystallinity. The excitation dependence of the LFRS spectra is interpreted by the shape-selection of the NCs via plasmon-vibration coupling. These results give new insights into the crystallinity influence on both the vibrations of the NCs and their coupling with plasmons and demonstrate the relevance of elastic anisotropy in monodomain NCs.

A way to control the gold nanocrystals size: using seeds with different sizes and subjecting them to mild annealing.

We demonstrate that the sequence of reactants plays a key factor in the final size of Au nanocrystals. The growth mechanism markedly differs with seed size and/or internal crystallinity. Conversely to what could be expected when the multiple-twinned particle (MTP) seeds are rather large (3.5 nm) they control the nanocrystal growth. When the single domain seeds are very small (1.5 nm) the majority of nanocrystals produced are large icosahedral (85%) nanoparticles as predicted from a theoretical model.

Vibration dynamics of supra-crystals of Cobalt nano-crystals studied with femtosecond laser pulses

Using femtosecond laser pulses, we have observed in real time the coherent motion of nanocrystals self-assembled in a three-dimensional (3D) supra-crystal.

Ag Nanocrystals: 1. Effect of Ligands on Plasmonic Properties

Silver nanocrystals (NCs) stabilized using amine-terminated coating agents (oleylamine or dodecylamine), their size ranging between 2 and 12 nm in diameter, are synthesized by hot injection methods. Their dispersion in size is relatively low (typically below 10%) without the need for a postsynthesis size segregation process. The amine-terminated coating agents are replaced by thiol-terminated molecules (dodecanethiol or hexadecanethiol) by ligand exchange, allowing the formation of alkanethiol coated Ag colloids. All NCs with various surface coatings are dispersed in toluene. Regardless of the nature of the coating agent, the surface plasmon resonance (SPR) is red-shifted with decreasing the NC size. For a given size, the SPR peak of thiol-stabilized NCs is shifted to lower energies compared to that of amine-stabilized NCs. Furthermore, with thiol-stabilized Ag NCs, the position of the SPR peak was found to be sensitive to the length of the alkyl chains of the coating agent, whereas minor differences are detected for Ag NCs coated with amines terminated with differing alkyl chain lengths.

Negative supracrystals inducing a FCC-BCC transition in gold nanocrystal superlattices

The growth of nanocrystal superlattices of 5 nm single domain Au nanocrystals at an air-toluene interface induces formation of well-defined thin films (300–400 nm) with large coherence lengths. High-resolution electron microscopy showed that polyhedral holes (negative supracrystal) were formed on the nanocrystal superlattice surface. Formation of negative supracrystals is attributed to inclusion in the superlattice of organic molecules (dodecanethiol), which are present in concentrated zones at the air-toluene interface. The coexistence of two supracrystalline structures (bcc/fcc) is attributed to diffusion of dodecanethiol molecules resulting in a Bain deformation of the nanocrystal array.

Micellar effects on charge separation

Abstract Photoelectron transfer fron a zinc tetramethylpyridylporphyrin to mono- and di-alkylviologens has been studied in aqueous and in cetyltrimethylammonium chloride micellar solutions. For viologens having side chains with more than twelve (for monoalkylviologens) or eight (for dialkylviologens) carbon atoms, the back reaction between porphyrin cation and reduced viologen, formed in the bulk aqueous phase from the zinc porphyrin triplet state, is strongly retarded. From kinetic studies and NMR experiments, the strong delay of the back reaction is attributed to trapping of reduced viologen in the micellar core.

Crystal polymorphism: dependence of oxygen diffusion through 2D ordered Co nanocrystals

8 nm Co nanoparticles with various crystalline structures called polymorphs were produced using different synthetic procedures, such as using reverse micelles, the thermal decomposition of organometallics approach or the hot injection process. These 8 nm Co nanoparticles differing by their crystalline structures are exposed to oxygen at elevated temperature. The fcc Co polycrystalline nanoparticles produce either Co-CoO yolk-shell or CoO hollow structures whereas amorphous Co nanoparticles produce Co-CoO core-shell nanoparticles. Furthermore, single domains with either hcp or ε crystalline structure behave differently upon oxygen diffusion. Co-CoO nanoparticles were produced from the hcp phase while CoO hollow nanoparticles were the product for ε-phase Co nanocrystals.

How nanocrystallinity and order define the magnetic properties of ε-Co supracrystals

Single domain cubic ε-Co nanocrystals are synthesized via a high-temperature thermal decomposition of cobalt carbonyl in the presence of oleic acid and trioctylphosphane oxide (TOPO). The ε-Co nanocrystals are characterized by a low size distribution (σ < 7%) and the average diameter is tuned from 7 nm to 9 nm by tailoring the molar ratio of the surfactants oleic acid and TOPO. Moreover, we have demonstrated the self-assembly of ε-Co nanocrystals in highly ordered three-dimensional (3D) face-centered cubic (fcc) structures called supracrystals. The layer-by-layer organization of these building blocks is achieved through solvent evaporation. Simultaneously, we produce. with the same ε-Co nanocrystals, disordered (amorphous) films. We demonstrate the presence of large interparticle magnetic interactions in the supracrystals by comparing their magnetic properties with the diluted samples. Then, by a detailed comparison of their collective magnetic properties with partially disordered films, the significant differences due to the change in anisotropy and distribution of dipolar interaction energies in the two systems are presented. This is attributed to the orientational and spatial ordering of single domain ε-Co nanocrystals markedly changing between ordered and disordered assemblies. The thermal evolution of the magnetization in ZFC/FC procedure presents three characteristic temperatures representing the blocking, the irreversibility and the maximum of Zeeman coupling temperatures. They are all affected by the presence of the order in supracrystals and they present different evolution trends as a function of nanoparticles size. While the variations of reduced remanent magnetizations in both condensed series are in good agreement with the previous theoretical calculations, the coercive fields present opposite evolutions.