Thermo-Responsive and Electroconductive Nano Au-PNiPAAm Hydrogel Nanocomposites: Influence of Synthesis Method and Nanoparticle Shape on Physicochemical Properties

Hydrogel nanocomposites that respond to external stimuli and possess switchable electrical properties are considered as emerging materials with potential uses in electrical, electrochemical, and biological devices. This work reports the synthesis and characterization of thermo-responsive and electroconductive hydrogel nanocomposites based on poly(N-isopropylacrylamide) (PNiPAAm) and gold nanoparticles (nanospheres-AuNPs and nanorods-AuNRs) using two different synthetic techniques. Method I involved gamma-irradiation-induced crosslinking of a polymer matrix (hydrogel), followed by radiolytic in situ formation of gold nanoparticles, while Method II included the chemical synthesis of nanoparticles, followed by radiolytic formation of a polymer matrix around the gold nanoparticles. UV-Vis spectral studies revealed the presence of local surface plasmon resonance (LSPR) bands characteristic of nanoparticles of different shapes, confirming their formation and stability inside the polymer matrix. Morphological, structural, and physicochemical analyses indicated the existence of a stable porous polymer matrix, the formation of nanoparticles with a face-centered cubic structure, increased swelling capacity, and a slightly higher volume phase transition temperature (VPTT) for the hydrogel nanocomposites. Comparative electrochemical impedance spectroscopy (EIS) showed an increase in conductivity for the nano Au-PNiPAAm hydrogel nanocomposites compared to the PNiPAAm hydrogel, with a considerable rise detected above the VPTT. By reverting to room temperature, the conductivity decreased, indicating that the investigated hydrogel nanocomposites exhibited a remarkable reversible "on-off" thermo-switchable mechanism. The highest conductivity was observed for the sample with rod-shaped gold nanoparticles. The research findings, which include optical, structural, morphological, and physicochemical characterization, evaluation of the efficiency of the chosen synthesis methods, and conductivity testing, provide a starting point for future research on the given nanocomposite materials with integrated multifunctionality.