Unimolecular micelles and electrostatic nanoassemblies stemming from hyperbranched polyethyleneimine

Full text: Hyperbranched polyethyleneimine (HPEI) was used as a building block to construct different self-assembled soft nanomaterials. This was accomplished via covalent linkage of carboxylic acids (CA) of different chain lengths to terminal amino groups of HPEI, thus leading to the formation of reverse unimolecular micelles constituted of a hydrophilic core and a hydrophobic shell. On the other hand, acid base interactions in organic solvents between CAs and peripheral amino groups of HPEI also facilitated the formation of electrostatic assemblies with reverse micellar properties. In this work we describe the formation of both structures as well as their characterization using diverse techniques including SAXS, NMR, IR, and fluorescence spectroscopy, among others. Unimolecular micelles were synthesized through the reaction of HPEI (Mn= 10 KDa) and acyl chlorides with different chain lengths (C8, C10, C12, C14, C16, C18). Depending on the chain length, the solvent and the temperature, a broad variety of supra macromolecular assemblies can be observed by SAXS measurements, including structured aggregation, and gelation. Hyperbranched electrostatic assemblies were simply produced by mixing HPEI with selected carboxylic acids (C8, C10, C12, C14, C16, C18) in an appropriate solvent, which dissolves the CA, or both reactants, i.e. chloroform, toluene or THF. The formation of the assemblies was corroborated using FT-IR by monitoring the appearance of the carboxylate bands. SAXS experiments of electrostatically assembled micelles showed globular, core-shell structures, whose characteristics are similar, in many cases, to their covalent counterparts prepared using the same chain length CA shells. (author)