Hydrogel nanocomposites containing silver nanoparticles of size 15–21 nm were prepared by diffusion and in-situ chemical reduction in chemically crosslinked polymers based on N-acryloyl-N′-ethyl piperazine (AcrNEP) and N-isopropylacrylamide (NIPAM). The polymer chains of the hydrogel network offered control and stabilization of silver nanoparticles without the need for additional stabilizers. The presence of silver nanoparticles and their size was quantified by UV-Vis absorption spectroscopy and scanning electron microscopy. The nanocomposite hydrogels were responsive to pH and temperature changes of the external environment. The equilibrium weight swelling ratio of the hydrogel nanocomposite was lower in comparison with the precursor hydrogel. Silver nanoparticles present in the nanocomposite offered additional physical crosslinking which influenced media diffusion and penetration velocity. The release of silver nanoparticles from the hydrogel matrix in response to external pH changes was studied. The rate of release of silver nanoparticles was higher in a solution of pH 2.5 due to maximum swelling caused by ionization of the gel network. No significant release of nanoparticles was observed in a solution of pH 7.
Poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels were prepared by thermal free‐radical copolymerization of N‐acryloyl‐N′‐ethyl piperazine (AcrNEP) and N‐isopropylacrylamide (NIPAM) in solution using N, N′‐methylene bisacrylamide as the crosslinking agent. The gels were responsive to changes in external stimuli such as pH and temperature. The pH and temperature responsive character of the gels was greatly dependent on the monomer content, namely AcrNEP and NIPAM, respectively. The gels swelled in acidic (pH 2) and de‐swelled in basic (pH 10) solutions with a response time of 60 min. With increase in temperature from 23 to 80 °C the swelling of the gels decreased continuously and this effect was different in acidic and basic solutions. The temperature dependence of equilibrium water content of the gels was evaluated by the Gibbs–Helmholtz equation. Detailed analysis of the swelling properties of these new gels in relation to molecular heterogeneity in acidic (pH 2) and basic (pH 10) solutions were performed. Water transport property of the gels was studied gravimetrically. In acidic solution, the diffusion process was non‐Fickian (anomalous) while in basic solution, the diffusion was quasi‐Fickian. The effect was more evident in solution of pH 2 than in pH 10. Various structural parameters of the gels such as number‐average molar mass between crosslink (Mc), the crosslink density (ρc), and the mesh size (ξ) were evaluated. The mesh sizes of the hydrogels were between 64 and 783 Å in the swollen state in acidic solution and 20 and 195 Å in the collapsed state in basic solution. The mesh size increased between three to four times during the pH‐dependent swelling process. The amount of unbound water (free water) and bound water of the gels was also evaluated using differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
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