Thermoresponsive Nanogels of Modified Poly((di(ethylene glycol) methyl ether methacrylate)-co-(2-aminoethyl...

A series of copolymers of di(ethylene glycol) methyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) (P(D-co-A)) with variable ratios of comonomers were synthesized using atom transfer radical polymerization. Then, the amino groups of obtained copolymers were modified to clickable azide or prop-2-yn-1-yl carbamate groups. A thermoresponsive copolymers were obtained with the value of cloud point temperature (T_CP) dependent on the type and number of functional groups in the copolymer and on the concentration of solutions. For P(D-co-A) copolymers, the T_CP increased with increasing content of 2-aminoethyl methacrylate comonomer. The presence of azide and prop-2-yn-1-yl carbamate groups caused the changes of T_CP of modified copolymers. All studied copolymers in dilute aqueous solutions aggregated above T_CP to nanoparticles with sizes dependent on the solution concentration, heating procedures, and types and numbers of functional groups present in a copolymer chain. The presence of hydrophilic elements in the chain and the increase in the copolymer concentration led to the enlargement of the particle sizes. Aggregates were crosslinked using click reaction between an azide and prop-2-yn-1-yl carbamate groups that led to stable thermoresponsive nanogels. A systematic study of the behavior of copolymers allowed the determination of the chains useful for possible application in drug delivery.