Fabrication, Structure and Functional Characterizations of pH-Responsive Hydrogels Derived from Phytoglycogen.

The pH-responsive hydrogels were obtained through successive carboxymethylation and phosphorylase elongatation of phytoglycogen and their structure and functional characterizations were investigated. Phytoglycogen (PG) was first carboxymethylated to obtain carboxymethyl phytoglycogen (CM-PG) with degree of substitution (DS) at 0.15, 0.25, 0.30, and 0.40, respectively. Iodine staining and X-ray diffraction analysis suggested that the linear glucan chains were successfully phosphorylase-elongated from the non-reducing ends at the CM-PG surface and assembled into the double helical segments, leading to formation of the hydrogel. The DS of CM-PG significantly influenced elongation of glucan chains. Specifically, fewer glucan chains were elongated for CM-PG with higher DS and the final glucan chains were shorter, resulting in lower gelation rate of chain-elongated CM-PG and lower firmness of the corresponding hydrogels. Scanning electron microscope observed that the hydrogels exhibited a porous and interconnected morphology. The swelling ratio and volume of hydrogels was low at pH 3-5 and then became larger at pH 6-8 due to electrostatic repulsion resulting from deprotonated carboxymethyl groups. Particularly, the hydrogel prepared from chain-elongated CM-PG (DS = 0.25) showed the highest sensitivity to pH. These results suggested that phosphorylase-treated CM-PG formed the pH-responsive hydrogel and that the elongation degree and the properties of hydrogels depended on the carboxymethylation degree. Thus, it was inferred that these hydrogels was a potential carrier system of bioactive substances for their targeted releasing in small intestine.