Preparation of polyelectrolyte complex nanoparticles with tunable and narrow size distributions by template polymerization

Template polymerization (i.e., polymerization of monomers along a macromolecular template) provides a scalable method for preparing colloidal polyelectrolyte complexes (PECs) with narrow size distributions. To our knowledge, however, the formation of sub-50-nm PECs through template polymerization has generally required the use of block copolymers or involved covalent crosslinking. Here, we report a one-step synthesis of such PEC nanoparticles through a simple free-radical polymerization of an anionic monomer (acrylic acid) on a polycationic poly(allylamine) (PAH) template. The self-assembly of the resulting poly(acrylic acid) (PAA) with the PAH generated narrowly dispersed particles with average sizes ranging between roughly 20 and 400 nm, which could be readily tuned by adjusting the parent solution concentration. At particle-forming compositions, most of the PAH became incorporated into the PECs, thus indicating high particle yields. Once assembled, these particles remained stably dispersed throughout a monthlong stability experiment when stored at low ionic strengths. When stored in >= 40 mM NaCl solutions, however (unless the particles were prepared in an excess of PAH), the dispersions underwent at least partial agglomeration. Collectively, these findings show template polymerization to be an effective technique for generating nanoparticles (including those with sub-50-nm dimensions) with tunable, narrowly dispersed sizes and high yields.

Automated summary

Template polymerization is an effective technique for generating nanoparticles with tunable, narrowly dispersed sizes and high yields. In this study, sub-50-nm PEC nanoparticles were synthesized through one-step free-radical polymerization on a polycationic template. The resulting particles showed narrow size distributions and could be readily tuned by adjusting the parent solution concentration.