No abstract

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.

This paper describes the use of glass and mesoporous silica microspheres (typically 1-50 µm) as supports for biomimetic lipid bilayer membrane architectures for use in biotechnological applications. We present methods and characterization of lipid bilayer membranes supported on commercially available glass beads and mesoporous silica beads formed by an aerosol process that takes advantage of self-assembly of surfactant template phases in sol-gel synthesis. Methods for controlling the concentration of fluorescent lipids, ligands, receptors, and transmembrane proteins in the bead-supported bilayer assemblies are discussed, along with methods for measuring the concentration of these species using flow cytometry. Diffusion of molecular species both within the lipid bilayer and within the mesoporous bead structure is probed using fluorescence recovery after photobleaching. Flow cytometry and confocal fluorescence microscopy are used to examine dye uptake of the porous beads and the stability of the encapsulating lipid bilayer membranes to proton and fluorophore leakage. The studies presented herein form the basis for the use of several new types of biomimetic bead-supported bilayer architectures in a variety of biotechnological applications including microimmunoassays and fluorescence-based high-throughput screening of biochemical recognition and protein function.

ZnS:Cu nanocrystals were synthesized in polymeric networks. X-ray photoemission spectroscopy and atomic absorption data show that the Zn and Cu ion mass contents were about 8.2% and 0.12%, respectively. The particle size of ZnS:Cu nanocrystals was about 3.0 nm, measured by UV-vis spectrum. Due to the quantum size effects, the band gap energy of ZnS nanocrystals was about 4.2 eV. Compared with the photoluminescence of ZnS which peaks at 390 nm, the photoemission of ZnS:Cu/polymer thin films was peaking at 415 nm because of Cu acting as luminescent centers. The ZnS:Cu/polymer was also used to fabricate light-emitting diode (LED), as the emitting layer of LED, the blue light of electroluminescence was observed at room temperature, and its turn-on voltage was less than 4 V.

Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.