Importance of pH in Synthesis of pH-Responsive Cationic Nano- and Microgels

While cationic microgels are potentially useful for the transfection or transformation of cells, their synthesis has certain drawbacks regarding size, polydispersity, yield, and incorporation of the cationic comonomers. In this work, a range of poly(N-isopropylacrylamide) (PNIPAM) microgels with different amounts of the primary amine N-(3-aminopropyl)methacrylamide hydrochloride (APMH) as the cationic comonomer were synthesized. Moreover, the pH-value during reaction was varied for the synthesis of microgels with 10 mol% APMH-feed. The microgels were analyzed by means of their size, thermoresponsive swelling behavior, synthesis yield, polydispersity and APMH-incorporation. The copolymerization of APMH leads to a strong decrease in size and yield of the microgels, while less than one third of the nominal APMH monomer feed is incorporated into the microgels. With an increase of the reaction pH up to 9.5, the negative effects of APMH copolymerization were significantly reduced. Above this pH, synthesis was not feasible due to aggregation. The results show that the reaction pH has a strong influence on the synthesis of pH-responsive cationic microgels and therefore it can be used to tailor the microgel properties.