Unveiling the self-assembly behavior of copolymers of AAc and DMAPMA in situ to form smart hydrogels displaying nanogels-within-macrogel hierarchical morphology

Stimulus responsive hydrogels are being considered as one of the most crucial biomaterials of current generation. A new technique has been established for developing hydrogels based on Acrylic acid (AAc) and N-[3-(Dimethylamino)propyl]-methacrylamide (DMAPMA), and relevant mechanism has been delineated. Aqueous redox copolymerization of different molar ratios of AAc and DMAPMA at 41 ± 1 °C, leading to the formation of interlocked nanogels of ∼300 nm diameter, which acted as the building blocks of a series of superabsorbent hydrogels having robust, honey-comb type three-dimensional architecture. Monomer composition, monomer feed ratio and water content in feed has been found to be important factors in the development of the stable poly(AAc-co-DMAPMA) hydrogel membranes (PADMAs) without any active crosslinking agent. At the cues of pH change from 7.0 to 3.5, pulsatile swelling–deswelling behavior varied, ranging from ∼5900% to ∼60% (mass) respectively, underlining smart hydrogel characteristics needed for specific biomedical applications. Elastic modulus of the gels, equilibrated at pH 7.0, is recorded to be >15 kPa under uniaxial compression. Underlying mechanism of the formation of such robust three-dimensional structures in poly(AAc-co-DMAPMA) hydrogel membranes, and the origin of hierarchical ‘nano-to-macro’ scale morphological features has been proposed.