pH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.