A comparative study of the self-assembly of achiral and chiral hairy nanoparticles with polystyrene cores and poly(2-hydroxyethylmethacrylate) hairs

Abstract

Hairy nanoparticles with polystyrene cores (PS cores) and poly(2-hydroxyethylmethacrylate) (PHEMA) shells were synthesized by combining living anionic polymerization and atom transfer radical polymerization (ATRP). The structural characterization was carried out by FT-IR and NMR spectroscopy (¹H NMR, ¹³C NMR, APT ¹³C NMR and ¹H ¹³C HMQC). The thermal stability of the PS cores was not affected by grafting PHEMA on their surfaces. A differential scanning calorimetry (DSC) thermogram of the HNPs showed two distinct transition temperatures indicating microphase separation. Chiral HNPs were prepared by inducing chirality in the achiral HNPs by complexation with R- or S-mandelic acid. The circular dichroism (CD) spectroscopy of complexes of the HNPs/R- or S-mandelic acid indicated the formation of enantiomeric chiral structures. The self-assembled structures formed from the achiral HNPs show different surface morphologies, porous and zigzag, dependent on the solvents used. Blends of polystyrene functionalized with hydroxyl groups and PHEMA show different morphology and thermal properties compared with the core–shell HNP system. The chiral HNPs self-assembled into donut like structures or toroids with sizes in the range between 200 to 5000 nm. The study suggests that chirality can be utilized to develop interesting self-assembled structures.