New one-dimensional (1D) hybrid nanosystems are elaborated with metalated or metal free phthalocyanine molecules encapsulated into the hollow core of single-walled carbon nanotubes. The X-ray diffraction experiments coupled to simulation allow evidencing the 1D structural organization of the molecules inside the nanotubes. The angle between the molecule ring and the nanotube axis is close to 32° as determined from our density functional theory calculations. Confined molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. For comparison, noncovalent functionalization at the outer surface of the tube is also investigated. The vibrational properties of the molecules functionalized at the outer surface of tubes display important modifications. A significant curvature of the phthalocyanine is induced by the interaction with the tube walls, leading to change of the central atom position within the molecular ring, in good agreement with our first-principles calculations.

Poly(l-lactic acid) (PLLA) membranes containing pharmaceutically active ionic liquids (API-ILs) have been prepared by using a simple film casting from solvent evaporation method. Several sets of membranes were prepared from two different ionic liquids namely 1-methyl-3-butyl-imidazolium ibuprofenate (C4MImIbu) and lidocainium ibuprofenate (LidIbu) with different API-IL contents. Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Wide-Angle and Small-Angle X-ray Scattering (WAXS and SAXS) revealed the strong influence of both the IL nature and content on the morphology and the crystallinity of the resulting PLLA. At 20 weight%, LidIbu was shown to act as a plasticizer for PLLA and homogeneous membranes were obtained. In contrast, at the same IL content, phase separation occurred using C4MImIbu, resulting in the formation of porous PLLA. An increase of LidIbu content to 50 weight% results also in phase separation. 1H and 1H-13C CP-MAS NMR measurements evidenced the influence of different morphologies and crystallinities on IL mobility. C4MImIbu was found to be highly mobile whereas the mobility of LidIbu was content dependent. At low percent, low mobility was observed while at higher content, two populations with respectively high and low mobility were observed. These PLLA-IL membranes were further tested as drug delivery systems. In accordance with the morphology and mobility obtained, we demonstrated that release kinetics from PLLA membranes can be tuned by the nature and the content of API-ILs. Sustainable release kinetics were obtained with API-IL acting as a plasticizer while the fastest release was obtained with API-IL acting as a porogenic agent.

The transformation by hydrolysis/condensation of four new mesityl-(bis or tris)imidazolium-based alkoxysilane precursors into their corresponding bridged silsesquioxanes has been investigated. These precursors feature urea groups and either short or long alkylene chains, which are known to favor self-assembly. The most regular nanostructures were obtained by a combination of the tripodal precursors with C10H20 alkylene chains, as shown by powder X-ray diffraction (PXRD) analysis, independent of the reaction conditions.

Two model drugs of different physico-chemical and pharmaceutical properties (ibuprofen, acetaminophen) have been incorporated together or separately in silicabased microspheres using sol-gel and spray-drying processes. A variable amount of a neutral surfactant Brij-56 has also been added. The properties of the microspheres vary significantly depending on their composition. Three kinds of texture are identified: (1) silica containing spheroid nano-domains (formed by ibuprofen; diameters between 20 and 100 nm), (2) silica containing worm-like mesophases (formed by Brij-56 and both model drugs, typical correlation distances *6 nm), (3) silica intimately mixed with the drug (acetaminophen) without visible phase-separation. The kinetics of drug release in simulated intestinal fluid strongly depend on these textures. The association of ibuprofen and acetaminophen in a single type of microsphere and without surfactant favours a concomitant release. Possible mechanisms of materials' formation are discussed.

Photo-active molecules are confined into single-wall carbon nanotubes to create 1D hybrid systems with new and original opto-electronic properties. This work deals with the encapsulation of quaterthiophene derivative and phthalocyanine molecules. They display strong optical absorption in the visible range, respectively around 400 and 670 nm. Encapsulation efficiency is investigated through Transmission Electron Microscopy. The physical interactions are mainly investigated by optical spectroscopies. The Raman spectra of the oligothiophene hybrid systems exhibit a striking dependence with the excitation energy which is correlated to the optical absorption energy of the photo-active molecule. Close to the molecule resonance, the results suggest a significant photo-induced charge transfer between the photo-active molecules and the nanotubes. In addition, the resonance window of the confined molecules depends on the nanotube diameter. The Raman spectra of the phthalocyanine based systems depend on the optical resonance conditions of the encapsulated molecules and on the structural properties of the hybrid system.

NOBLE-METAL NANOPARTICLES; OXIDE HOLLOW SPHERES; HYDROTHERMAL CARBONIZATION; NITRIDE CATALYSTS; CARBONACEOUS MATERIALS; HYBRID MATERIALS; CO-MO; HYDRODESULFURIZATION; NANOSTRUCTURES; MICROSPHERES