Thermoresponsive Chiral Polymeric Microgels through In Situ Cross-Linking Polymerization of Thermally Aggregated Dendritic Phenylacetylenes

Fabrication of chiral microgels through in situ cross-linking polymerization of thermally aggregated chiral dendronized phenylacetylene (PA) macromonomers is reported. These macromonomers bear either ethoxyl- (more hydrophobic) or methoxyl-terminated (more hydrophilic) dendritic oligo(ethylene glycol)s (OEGs), affording tunable thermoresponsive properties with distinct cloud points (Tcps). Systematic optimization of polymerization parameters─including macromonomer hydrophilicity and concentration, temperature, stirring rate, and cross-linker loading─enables the convenient one-pot synthesis of cross-linked chiral microgels with uniform spherical morphology and stable helicity from the thermally aggregated monomeric mesoglobules. Notably, this surfactant-free strategy offers a significant advantage over conventional microgel preparation methods. Moreover, the approach is versatile and readily extendable to the one-pot fabrication of other nano-objects via polymerization from aggregated monomers.