Formation of Molecular Bundles from Self-Assembly of Symmetrical Poly(oxyalkylene)−Diamido Acids

Abstract

Sodium salts of poly(oxypropylene)-trimellitic amido acid (POP-amido acid), prepared from the reaction of POP-diamines and trimellitic anhydride, were found to self-assemble into orderly molecular bundles. The POP-amido acid has a symmetrical structure consisting of a hydrophobic POP middle block (2000 g/mol) and four symmetrical carboxyl end groups. By dissolving in water and evaporating on a polyether sulfone film, the POP-amido acid molecules self-assembled into a unique array with average dimensions of 7-13 nm in width, 2-5 nm in height, and 20-50 nm in length, observed by atomic force microscope. Varied morphologies were also observed when varying the pH, solvents, evaporating rate, concentration, and substrate surface. Unlike the common surfactants of single head-to-tail structure and the naturally occurring phospholipids of one head and two tails, the synthesized POP derivative is a symmetrical structure of four hydrophilic heads and one long hydrophobic block. Through the complementary noncovalent bonding forces, the molecules tend to align into molecular bundles or loops as the primary structure. The formation of different morphologies is controlled by the intermolecular forces including hydrogen bonding, aromatic pi-pi stacking, ionic charge, and hydrophobic interaction, in a concerted manner.