Hybrasurfs-A New Class of Hyperbranched Surfactants

A hyperbranched (HB) polyester carrying peripheral allyl groups was prepared by melt-condensation of a suitably designed AB₂ monomer bearing two allyl ester groups and one hydroxyl group. The periphery of the hyperbranched polymer was co-clicked with two different organic thiols, namely, hexadecane thiol and 3-mercaptopropionic acid, using the thiol-ene reaction. Three different samples with varying mole fractions of the hydrophilic carboxylic acid groups were prepared; the conformational adaptability of the hyperbranched polymer backbone permitted these amphiphilic systems to form Janus structures that exhibit surfactant-like properties and, therefore, we have termed them hybrasurfs. These polymers behave like clusters of surfactants that have been stitched at the waist by the HB polymer backbone; the Langmuir isotherms revealed the formation of a monolayer, and in two of the samples having higher mole fractions of hexadecyl segments a weak inflection in the isotherm is seen. This suggests a densification, typically implying the crystallization of the alkyl segment at the air-water interface. The monolayers were transferred onto a substrate, and their heights were estimated using atomic force microscopy; the values thus obtained were in reasonable agreement with the expected value. The water contact angles of the substrates bearing the transferred monolayers of the three different samples (transferred at two different points along the isotherm) were measured; it was seen that the sample carrying the highest mole fraction of hexadecyl chains exhibited a significantly larger contact angle when compared to that of the other two samples. Interestingly, these hybrasurfs also formed vesicles in water and were shown to encapsulate water-soluble dyes, such as Eosin Y. Thus, this class of readily accessible amphiphilic HB polymers that behave as a cluster of surfactants opens some interesting possibilities for further exploration.