To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons.

Hydrophobic “pockets” in aqueous microgels act as a spectroscopic and kinetic probe sensing the microenvironment inside the particles.

In this work a series of aliphatic biodegradable poly(ester amide amide) polymers was synthesized by melt polycondensation of a tailor-made amide-containing monomer based on 1,4-diaminobutane and ε-caprolactone and different dicarboxylic acid methyl esters with even number of methylene groups. The synthesized polymers were characterized by 1 H NMR, FT-IR spectroscopy, GPC, SAXS and WAXS. DSC results show that the melting point is located at about 150°C for all polymers. X-ray scattering experiments in small and wide angles reveal formation of crystals with extended-chain conformation resulting in strict periodicity of electron density along the main chain. TGA data indicates the high thermal stability of polymers to temperatures above 350°C, which are much above the melting point. The obtained characteristics of the newly synthesized PEAAs can open new perspectives for melt processing to fabricate films, highly oriented fibers and injection-molded parts with good thermal stability and mechanical performance.