Temperature- and pH-dependent aggregation behavior of hydrophilic dual-sensitive poly(2-oxazoline)s block copolymers as latent amphiphilic macromolecules

A variety of hydrophilic diblock and triblock copolymers of AB and ABA type with temperature-sensitive poly(2-isopropyl-2-oxazoline) blocks and pH-sensitive poly(2-carboxyethyl-2-oxazoline) blocks have been synthesized. The temperature- and pH-induced reversible phase transition renders the block copolymers as amphiphilic macro-molecules and allows for defined aggregation through self-assembly following the packing parameter of amphiphilic macromolecules. Size, structure and arrangement of the individual block copolymer segments define the temperature and pH values of the transitions as well as the nature of the formed aggregates. DLS measurements were used to determine the transition temperatures at selected pH values in aqueous solution whereas AFM was used to visualize and characterize the formed aggregates adsorbed on Si wafer surfaces. In the case of vesicles formed by the diblock and triblock copolymers, double and mono-layer membranes could be verified. The tendency of different states of organization of poly(2-isopropyl-2-oxazoline) blocks from crystalline to amorphous is assumed to be the cause for the different box-like structures determined on Si wafer surfaces. (C) 2016 Elsevier Ltd. All rights reserved.