We report on the synthesis of a series of second-generation hyperbranched polyesters with a variable composition of alkyl-terminated groups. We observed that the chemical modification of the hyperbranched cores by substituting a controlled fraction of the terminal hydroxyl groups with hydrophobic alkyl chains is an effective method for a controlling amphiphilic balance of hyperbranched cores with a degree of branching of 50%. Even for imperfect cores, the chemical reaction of hydroxyl groups alkyl tails was very efficient. In fact, the number of attached alkyl tails was fairly close to the theoretical value based on the assumption that all targeted hydroxyl groups were available for the reaction despite their different interior/exterior location. Detailed microstructural analysis of the structure revealed that organized monolayers could be formed at the air-water interface if the number of alkyl tails was higher than two per core. Similar to regular dendrimers, the alkyl tails of hyperbranched molecules at high surface pressure form intramonolayer ordering of the quasi-hexagonal type. However, higher defectness and irregularities of the hyperbranched cores are responsible for poor intralayer ordering of alkyl tails in comparison with regular dendrimers. At high surface pressure, the alkyl tails became arranged in an up-right orientation. The highly water-swollen state of the hyperbranched cores of prolate shape and the partially submerged and standing-off alkyl tails is a characteristic of hyperbranched molecules with fewer alkyl chains in condensed monolayer state at the air-water interface. The core structure is transformed into the oblate, flattened state with preservation of standing-off orientation of the alkyl tails for hyperbranched molecules with crowded outer shells.

This study probes the behavior of two series of organic-functionalized core-shell silsesquioxane (POSS-M)p-(x/y) derivatives with various hydrophobic-hydrophilic terminal group compositions in the bulk state and within mono- and multilayered films at the air-water interface and on solid surface. POSS-M refers to mixed silsesquioxane cores, in contrast to the geometrically specific POSS compounds. It is composed of polyhedra, incompletely condensed polyhedra, ladder-type structures, linear structures, and all the possible combinations thereof and attracts great interest because of its facile preparation, low polydispersity, high yield, and low cost. The two series of (POSS-M)p-(x/y) molecules are different in hydrophobic-hydrophilic balance of their terminal groups, with x and y respectively referring to the molar percent of -OCONH-C(18)H(37) tails and -OH for p = 1 and the percent of -OCONH-C(18)H(37) tails and -OCO-C(6)H(4)COOH terminal groups for p = 2. In the bulk state, the presence of aromatic rings in (POSS-M)2-(x/y) series resulted in a lower symmetry crystal structure than the (POSS-M)1-(x/y) series. Moreover, the (POSS-M)p-(x/y) molecules that contain a sufficient amount of -OCONH-C(18)H(37) tails exhibit double endothermic transition, which attributed to the melting of alkyl chains followed by the melting of the unit cells of (POSS-M) cores. The surface morphologies for the various hydrophobic-hydrophilic combinations at surface pressure p = 0.5 mN/m are similar to that observed for the classical amphiphilic star polymers. However, at higher surface pressure (p > or = 5 mN/m), the POSS-M compounds with lower content of hydrophilic groups form a uniform monolayer.