Polymerization-Induced Hierarchical Self-Assembly: From Monomer to Complex Colloidal Molecules and Beyond.

Area of Science:

• Materials Science
• Polymer Chemistry
• Nanotechnology

Background:

• Nanoscale hierarchical designs inspired by natural biomaterials enhance material performance and applications.
• Block copolymer self-assembly offers a bottom-up strategy for synthesizing soft colloidal hierarchies.
• Polymerization-induced self-assembly (PISA) enables one-step polymer synthesis and in situ self-assembly, but aqueous PISA struggles with diverse morphologies.

Purpose of the Study:

• To develop a scalable method for fabricating diverse hierarchical polymer colloids via aqueous PISA.
• To overcome the limitations of current aqueous PISA methods in producing complex nanostructures.
• To demonstrate the synthesis of various colloidal morphologies including colloidal molecules (CMs).

Main Methods:

• Sequential one-pot aqueous PISA utilizing "host-guest" inclusion complexation of water-immiscible monomers with cyclodextrin.
• Synthesis of linear triblock terpolymers through sequential aqueous polymerization.
• Characterization of nanostructures using transmission electron microscopy (TEM) and atomic force microscopy-infrared spectroscopy (AFM-IR).

Main Results:

• Successfully synthesized linear triblock terpolymers that self-assemble into hierarchical nanostructures.
• Achieved diverse morphologies including AX-type colloidal molecules (CMs), core-shell-corona micelles, and raspberry-like nanoparticles.
• Revealed the influence of interfacial tensions and glass transition temperatures of core-forming blocks on morphology.

Conclusions:

• The developed method provides a scalable route for producing colloidal molecules and other hierarchical structures via aqueous PISA.
• This approach allows for the creation of complex nanostructures with tunable morphologies by varying block copolymer formulations.
• The findings enable the enrichment of morphology complexity and diverse functions of nano-objects.