A controlled approach to iron oxide nanoparticles functionalization for magnetic polymer brushes.

In this article, we report a detailed study of surface modification of magnetite nanoparticles by means of three different grafting agents, functional for the preparation of magnetic polymer brushes. 3-Aminopropyltriethoxysilane (APTES), 3-chloropropyltriethoxysilane (CPTES), and 2-(4-chlorosulfonylphenyl)ethyltrichlorosilane (CTCS) were chosen as grafting models through which a wide range of polymer brushes can be obtained. By means of accurate thermogravimetric analysis a good control over the amount of immobilized molecules is achieved, and optimal operating conditions for each grafting agent are consequently determined. Graft densities ranging from approximately 4 to 7 molecules per nm(2) are obtained, depending on the conditions used. In addition, the surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) carried out with CTCS-coated nanoparticles is presented as an example of polymer brushes, leading to a well-defined and dense polymeric coating of around 0.6 PMMA chains per nm(2).

Self-assembled nanofibers of fluorescent zeolite L crystals and conjugated polymer.

Through this work, we present self-assembled structures which can be obtained by mixing surface modified dye loaded zeolite L crystals and cationic precursors of a conjugated polymer. The zeolite crystals are modified with anionic end groups which give the former a polyanionic character and allow a polyelectrolytic assembly. Microfluidic forces, introduced during the drying of a drop of water containing both polyelectrolytes casted on a clean glass substrate, and localized adsorption on the single zeolite crystal lead to the formation of micro- and nanofibers of highly ordered zeolite nanocrystals. As a result, the fibers display a very well polarized emission from the organic dye included into the nanochannels of the inorganic crystal. Playing on the relative concentrations of polycation and zeolites, and after thermal conversion of the polymer precursor, rigid and insoluble fibers with diameters ranging from less than 200 nm to a few micrometers are obtained.

Multilevel organization in hybrid thin films for optoelectronic applications.

In this work we report two simple approaches to prepare hybrid thin films displaying a high concentration of zeolite crystals that could be used as active layers in optoelectronic devices. In the first approach, in order to organize nanodimensional zeolite crystals of 40 nm diameter in an electroactive environment, we chemically modify their external surface and play on the hydrophilic/hydrophobic forces. We obtain inorganic nanocrystals that self-organize in honeycomb electroluminescent polymer structures obtained by breath figure formation. The different functionalizations of the zeolite surface result in different organizations inside the cavities of the polymeric structure. The second approach involving soft-litography techniques allows one to arrange single dye-loaded zeolite L crystals of 800 nm of length by mechanical loading into the nanocavities of a conjugated polymer. Both techniques result in the formation of thin hybrid films displaying three levels of organization: organization of the dye molecules inside the zeolite nanochannels, organization of the zeolite crystals inside the polymer cavities, and micro- or nanostructuration of the polymer.

The role of triphenylamine in the stabilization of highly efficient polyfluorene-based OLEDs: a model oligomers study.

In order to understand the factors responsible for the improved efficiency and stability of organic light-emitting diodes (OLEDs) based on poly(9,9-dioctylfluorene) (PFO) when triphenylamine (TPA) is introduced as lateral fluorene substituent, we synthetize mono-disperse fluorene-thiophene oligomers as model compounds. Their blends with different concentrations of the fluorenone containing oligomer are studied in order to verify if only a reduction of ketonic defect sites or also an impeded energy transfer (ET) towards such sites are responsible for the suppression of the green emission band. We show that the introduction of TPA groups leads specifically both to an antioxidant action and a reduced ET towards residual defect sites, thanks to the environmental micro-encapsulation role played by TPA units surrounding the polymer backbone. As a result, the performances and colour stability of a device fabricated with TPA-substituted PFO (PFTPA) are strongly improved with respect to standard PFO device prepared in the same conditions.

Nanophase separation in polystyrene-polyfluorene block copolymers thin films prepared through the breath figure procedure.

The amphiphilic block copolymer formed by a hydrophobic body of polystyrene and a hydrophilic head of poly[9,9-di(2-(2-tetrahydropyranyl-oxy)hexyl)fluorene-alt-9,9-dioctylfluorene] was synthesized, and its solution was used to create thin films with ordered pattern of holes, by means of the breath figure technique. These porous films, after a thermal treatment, were found to show ordered aggregates of the pi-conjugated blocks in the place of the cavities. This is probably due to a preorganization of the two different blocks of the copolymer occurring during the breath figure formation, which is driven by the condensation of water microdroplets on the polymer solution, and to a following phase segregation occurring during the thermal annealing. This approach is a promising tool to be employed for the organization of organic materials at the micro and nanoscale.