Nanoparticles from polylactide and polyether block copolymers: formation, properties, encapsulation, and release of pyrene--fluorescent model of hydrophobic drug.

Polylactide-b-polyglycidol-b-poly(ethylene oxide) terpolymers and their derivatives with carboxyl and 4-(phenylazo)phenyl labels in polyglycidol blocks were used for formation of nanoparticles. Nanoparticles were produced by self assembly of terpolymer macromolecules in water above the critical aggregation concentration and by dialysis of terpolymer solutions in 1,4-dioxane against water. For terpolymers with 4-(phenylazo)phenyl labels critical aggregation concentrations increased after irradiation with UV light (300 < lambda < 400 nm) inducing conformational change of the label from trans- to cis-conformation. Diameters of nanoparticles obtained by self-assembly of macromolecules ranged from 20 to 44 nm. Dialysis yielded nanoparticles with bimodal diameter distribution. One fraction had diameters below 35 nm and diameters of the second fraction were in a range from 350 to 2300 nm, depending on terpolymer structure. Mixtures of terpolymers with poly(L,L-lactide) and poly(D,D-lactide) blocks yielded nanoparticles with diameters from 350 to 440 nm. Pyrene was incorporated into nanoparticles by partition between solution and nanoparticles or directly during particle formation by dialysis. Monitoring of pyrene release from nanoparticles suggests that a fraction of this compound was entrapped into the polylactide core whereas the remaining one was located in the polyether rich shell. The release from shells is faster for nanoparticles made from copolymers with carboxyl labels in polyglycidol blocks.

Nanostructured hybrid materials from aqueous polymer dispersions.

Organic-inorganic (O-I) hybrids with well-defined morphology and structure controlled at the nanometric scale represent a very interesting class of materials both for their use as biomimetic composites and because of their potential use in a wide range of technologically advanced as well as more conventional application fields. Their unique features can be exploited or their role envisaged as components of electronic and optoelectronic devices, in controlled release and bioencapsulation, as active substrates for chromatographic separation and catalysis, as nanofillers for composite films in packaging and coating, in nanowriting and nanolithography, etc. A synergistic combination or totally new properties with respect to the two components of the hybrid can arise from nanostructuration, achieved by surface modification of nanostructures, self-assembling or simply heterophase dispersion. In fact, owing to the extremely large total surface area associated with the resulting morphologies, the interfacial interactions can deeply modify the bulk properties of each component. A wide range of starting materials and of production processes have been studied in recent years for the controlled synthesis and characterization of hybrid nanostructures, from nanoparticle or lamellar dispersions to mesoporous materials obtained from templating nanoparticle dispersions in a continuous, e.g. ceramic precursor, matrix. This review is aimed at giving some basic definitions of what is intended as a hybrid (O-I) material and what are the main synthetic routes available. The various methods for preparing hybrid nanostructures and, among them, inorganic-organic or O-I core-shell nanoparticles, are critically analyzed and classified based on the reaction medium (aqueous, non-aqueous), and on the role it plays in directing the final morphology. Particular attention is devoted to aqueous systems and water-borne dispersions which, in addition to being environmentally more acceptable or even a mandatory choice for any future development of large output applications (e.g. in paint, ink and coating industry), can provide the thermodynamic drive for self-assembling of amphiphilics, adsorption onto colloidal particles or partitioning of the hybrid's precursors between dispersed nanosized reaction loci, as in emulsion or miniemulsion free-radical polymerization. While nanoencapsulation and self-assembling processes are already exploited as commercially viable fabrication methods, a newly developed technique based on two-stage sol-gel and free-radical emulsion polymerization is described, which can grant a versatile synthetic approach to hybrid O-I nanoparticles with tailor-made composition of both the organic core and the silica or organosilica shell, and good control on morphology, size and heterophase structure in the 50-500 nm range. Styrene or acrylate homo- and copolymer core latex particles need to be modified with a reactive comonomer, such as trimethoxysilylpropyl methacrylate, to achieve efficient interfacial coupling with the inorganic shell. Accurate control over pH and process conditions is required to avoid latex coagulation or, in case of organic particles with uniform composition, incipient intraparticle crosslinking.