Compressive elasticity of epoxy functionalized Chitosan-based semi-IPN cryobeads of N-alkyl methacrylate esters: Validity of the Hertzian model with experiments

Abstract

In situ forming poly(dimethylaminoethyl methacrylate-co-glycidylmethacrylate)/Chitosan, P(DMAEMA-co-GMA)/Chitosan, (PDG/CS) cryobeads based on "dropwise freezing into cryogenic liquid method" combined with "blending with polymer method" are promising for applications due to their pH-responsiveness and stability under physiological conditions. Based on classical contact mechanics, Hertzian elasticity of semi-interpenetrated network (semi-IPN) cryobeads was analyzed to examine whether there is a direct correlation between elastic properties of single particle and its macroscopic behavior. A one-step procedure has been proposed to design chitosan-interpenetrated cryobeads with a cationic nature via combination of structural properties as well as functionality of chitosan containing primary and secondary hydroxyl and amino groups. The study is focused on characterization of network formation kinetics in different shapes and how different production variables affect the elasticity/swelling performance of cross-linked system. The elastic properties of semi-IPN cryobeads were improved by both adding chitosan to copolymer PDG structure and lowering the gelation temperature to cryogelation conditions. The results obtained highlighted the importance of composition to modulate elasticity, the influence of preparation temperature and shape of cryobeads on their elasticity. Findings regarding the topography-dependent local elastic properties of chitosan-incorporated semi-IPN gels offer possibilities for modulating the behavior of chitosan-based soft materials.