Straightforward solid-phase-supported synthesis routes were presented to obtain novel oligopeptide-based reversible addition fragmentation transfer (RAFT) agents. These approaches include the coupling of a functional RAFT agent to a resin-bound peptide and the functionality switch of an oligopeptide ATRP macroinitiator into an oligopeptide transfer agent. The solid-phase-supported methods allowed easy purification of the transfer agents, making difficult column purification steps unnecessary. Well-defined conjugates comprising sequence-defined peptides and synthetic polymers could be accessed by applying RAFT polymerization techniques in combination with the peptide macrotransfer agents. Polymerization reactions of n-butyl acrylate were performed in solution, yielding peptide-polymer conjugates with controllable molecular weight and low polydispersities of around 1.1. The peptide-polymer conjugates were characterized using 1 H NMR spectroscopy and size exclusion chromatography (SEC), while the incorporation of the oligopeptide into the synthetic polymer and the preservation of the chirality were shown by circular dichroism (CD) spectroscopy.

BackgroundCurrent methods of removing organic pollutants from water are becoming ineffective as the world population increases. In this study, a series of biorenewable triblock copolymers with hydrophobic poly(ε-caprolactone) block and hydrophilic poly(l-lactide) blocks were synthesized and tested as agents to remove environmental pollutants from an aqueous solution. The percent of pollutant removed and equilibrium inclusion constants were calculated for the polymers. These values were compared to previously known removal agents for their effectiveness.ResultsTriblock copolymer samples removed over 70% of the polycyclic aromatic hydrocarbon (PAH) phenanthrene from an aqueous solution, with selectivity for the adsorption of phenanthrene over other PAHs tested. The inclusion constant was 7.4 × 105 M−1 and adsorption capacity was 5.8 × 10−7 mol phenanthrene/g polymer. Rose Bengal was used to further probe the nature of interactions between the copolymers and a small molecule guest. Solid samples of the block-poly(l-lactide)–block-poly(ε-caprolactone)–block-poly(l-lactide) (PLLA–PCL–PLLA) systems were found to rapidly remove over 90% of Rose Bengal from aqueous solution, resulting in a complete disappearance of the characteristic pink color. Solutions of the copolymers in dichloromethane also removed Rose Bengal from water with a similar level of efficiency. Large inclusion constant values were obtained, ranging from 1.0 × 105 to 7.9 × 105 M−1, and the average adsorption capacity value of 6.2 × 10−7 mol/g polymer was determined. Aged polymer samples exhibited different adsorption characteristics and mechanistic theories for the removal of Rose Bengal were determined.ConclusionThe triblock copolymer consisting of l-lactide and ε-caprolactone was effective in removing various organic pollutants in aqueous environments. It is a biorenewable material which leads to minimal waste production during its lifecycle. These polymers were in general more effective in removing organic pollutants than commercially available pollution removal systems.