Preparation and properties of cryogel based on poly(hydroxypropyl methacrylate)

A novel supermacroporous poly(hydroxypropyl methacrylate) (p(HPMA)) cryogel was synthesized by cryogelation method at -16 °C. In this synthesis process, HPMA was used as a monomer, and N,N'-methylenebisacrylamide (MBAAm) was used as cross-linker; the reaction was carried out in the presence of redox initiator pair N,N,N',N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS). The effect of monomer concentration, cross-linker content, cooling rate, and dioxane co-solvent were determined with respect to the pore structure, mechanical behavior, swelling degree, and porosity of cryogel. The ESEM images indicate that the pore wall structure of cryogels was rough; moreover, small holes were present in the pore walls of cryogels. The result of compression test indicates that cryogels can be compressed by at least 80% without any breakdown. The result of swelling kinetics indicates that cryogels attain swelling equilibrium in 10 s. Furthermore, p(HPMA)-Cu²⁺ cryogel was prepared by loading Cu²⁺ ions on functionalized poly(hydroxypropyl methacrylate)-iminodiacetic acid (p(HPMA)-IDA) cryogel. We investigated the adsorption of bovine serum albumin (BSA) on cryogels. The results indicate that compared to Freundlich isotherm, Langmuir isotherm could more suitably describe the adsorption process of BSA on cryogels. Meanwhile, the adsorption capacity of p(HPMA)-Cu²⁺ cryogel was significantly greater than that of p(HPMA) cryogel. The maximum adsorption capacity of BSA on p(HPMA)-Cu²⁺ cryogel, which was treated with 1 M Cu²⁺ ions, was as high as 196.87 mg/g cryogel (equivalent to 20.48 mg/mL cryogel) at 25 °C and pH = 7.8; therefore, the maximum adsorption capacity of BSA on p(HPMA)-Cu²⁺ cryogel was 4.35 times higher than that of p(HPMA) cryogel. Thus, the adsorption capacity of cryogels was strongly influenced by Cu²⁺ concentration, moreover, temperature changes clearly affected the adsorption capacity of p(HPMA)-Cu²⁺cryogel. The adsorption capacity at 25 °C was twice as that at 15 °C. By calculating Gibbs free energy change (∆G) of adsorption, we found that the adsorption process was spontaneous; moreover, adsorption process occurred better at higher temperature.