Cyclic Swelling as a Phenomenon Inherent to Biodegradable Polyesters

The aim of this study is to evaluate and describe the phenomenon and mechanism of the spontaneous cyclic swelling and deswelling of linear and branched aliphatic polyesters in the aqueous medium. The fluctuation of gel volume in one or several cycles as an inherent property of biodegradable and bioerodible materials has not yet been described. We have observed the process at linear and branched polyesters of aliphatic α‐hydroxy acids. The period of duration of cycles was in order of hours to days, as influenced by the size of the bodies ranging from 25 to 1000 mg, the temperature in the range of 7°C-42°C, ionic strength, and pH value. The results demonstrated that swelling is accompanied by hydrolysis of ester bonds with the development of small water‐soluble osmotically active molecules. After reaching a higher degree of swelling, the obstruction effect of the gel decreases and the diffusion of soluble degradation products from the body to the environment prevails. A decrease in osmotic pressure inside the body and a decrease in the hydrophilic character of the gel matrix result in deswelling by a collapse of the structure, probably due to hydrophobic interactions of nonpolar polyester chains.