Phenylalanine-Tethered pH-Responsive Poly(2-Hydroxyethyl Methacrylate)

A series of pH-responsive random copolymers comprised of 2-hydroxyethyl methacrylate (HEMA) and tert-butyl carbamate (Boc)-protected phenylalanine methacryloyloxyethyl ester (Boc-Phe-EMA) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization in N,N '-dimethylformamide (DMF) at 70 degrees C. The synthesized copolymers were comprehensively characterized using a combination of techniques, including H-1 NMR, FT-IR spectroscopy and size exclusion chromatography (SEC). Reactivity of each monomers towards controlled radical polymerization was evaluated by determining the reactivity ratios by virtue of extended Kelen-Tudos method at high conversions revealed the higher reactivity of non-modified HEMA (r(HEMA)=1.03) in contrast to Boc-Phe-EMA (r(Boc-Phe-EMA)=0.48). Furthermore, the expulsion of the Boc-groups resulted copolymers with ionizable pendant primary ammonium and hydroxyl groups. To understand the glass transition behaviours of homo- and co-polymers, differential scanning calorimetric (DSC) measurements were carried out. The effect of HEMA content on the pH-sensitivity of the copolymers in aqueous medium was investigated through turbidity measurements. Finally, the counteranion exchange from trifluoroacetate to chloride provided copolymers with enhanced water solubility and unaltered phase transition pH.

Automated summary

The pH-responsive random copolymers synthesized in this study showed high reactivity, with the removal of Boc groups resulting in copolymers with ionizable pendant groups. Differential scanning calorimetry and turbidity measurements were conducted to investigate the properties of the copolymers.