Self-assembly of positively charged polymer patchy micelles in organic solutions and the reversible ultrasound responsivity of the assemblies

Abstract

Self-assembly of asymmetric structures has been attractive for applications in the fabrication of hierarchical structures. However, the role of the electrostatic interaction in the self-assembly of charged asymmetric particles in organic solvents has not been fully understood. In this research, self-assembly of positively charged patchy micelles in organic solutions and the reversible ultrasound responsivity of the assemblies are studied. Surface micelles (s-micelles) with cross-linked/quaternized poly(2-(dimethylamino)ethyl methacrylate) (q-PDMAEMA) cores and poly(oligo(ethylene glycol) monomethyl ether methacrylate) (POEGMA) coronae were prepared on the surfaces of silica particles. Positively charged patchy micelles were synthesized upon cleavage of the s-micelles. In THF, the patchy micelles self-assemble into vesicles with positively charged q-PDMAEMA in the walls and POEGMA in the coronae. The average size of the vesicles is dependent on POEGMA chain length. The repelling electrostatic interaction between the positively charged q-PDMAEMA patches in the walls is unfavorable for the achievement of low free energy of the assemblies, but it is energetically favorable for the vesicles to overcome energy barriers in the dissociation of the structures under ultrasound irradiation. The vesicle structures present reversible ultrasound responsivity. Under sonication the vesicles formed by patchy micelles dissociate into transient nanostructures, including aggregates and isolated patchy micelles. When the ultrasound is switched off, the transient nanostructures self-assemble into vesicles. By contrast, crosslinked vesicles do not show ultrasound responsivity. This research provides a new approach to the fabrication of responsive assemblies based on asymmetric structures, and the assemblies could find potential applications in medicine and bioengineering.