β-Cyclodextrin-Functionalized MGO-g-GMA Copolymer for the Adsorptive Removal of Anticancer Drugs from Aqueous Solutions
摘要
A novel adsorptive removal system (ARS) based on a graft copolymer was developed for the efficient elimination of anticancer drugs from aqueous solutions. The copolymer (MGO-g-GMA) was synthesized via free-radical polymerization of glycidyl methacrylate (GMA) onto magnetic graphene oxide (MGO) using 3-(trimethoxysilyl)-1-propanethiol as a chain-transfer agent and 2,2′-azobisisobutyronitrile as the initiator. To enhance the adsorption performance, β-cyclodextrin was covalently immobilized through an epoxy ring-opening reaction, forming a host–guest functional architecture. Gemcitabine was selected as the model drug, and the adsorption process was optimized using response surface methodology based on a Box–Behnken design. Under optimal conditions (adsorbent dosage: 0.0197 g, pH 6.57, temperature: 25.40 °C, contact time: 7.22 min), a maximum adsorption capacity of 844.51 mg g⁻¹ was achieved at an initial concentration of 1000 mg L− 1. Thermodynamic and isotherm analyses revealed a spontaneous, exothermic, and predominantly monolayer adsorption process governed by physical interactions, whereas mass transfer analysis identified intraparticle diffusion as the main rate-limiting step. The ARS exhibited excellent reusability, retaining approximately 90% and 75% of its initial efficiency after six and ten cycles, respectively. The application of the adsorbent to real hospital wastewater resulted in 94.2% gemcitabine removal and an 87% reduction in total dissolved solids, confirming its effectiveness in complex matrixes. Cytotoxicity assays on L-929 fibroblast cells demonstrated negligible toxicity and high biocompatibility of ARS. Overall, the developed ARS is a highly efficient, magnetically separable, reusable, and biocompatible adsorbent with a strong potential for the removal of anticancer drugs from aqueous solutions.