pH-Responsive Cellulose/Silk/Fe3O4 Hydrogel Microbeads Designed for Biomedical Applications.

In this study, cellulose/Fe3O4 hydrogel microbeads were prepared through the sol-gel transition of a solvent-in-oil emulsion using various cellulose-dissolving solvents and soybean oil without surfactants. Particularly, 40% tetrabutylammonium hydroxide (TBAH) and 40% tetrabutylphosphonium hydroxide (TBPH) dissolved cellulose at room temperature and effectively dispersed Fe3O4, forming cellulose/Fe3O4 microbeads with an average diameter of ~15 µm. Additionally, these solvents co-dissolved cellulose and silk, allowing for the manufacture of cellulose/silk/Fe3O4 hydrogel microbeads with altered surface characteristics. Owing to the negatively charged surface characteristics, the adsorption capacity of the cellulose/silk/Fe3O4 microbeads for the cationic dye crystal violet was >10 times higher than that of the cellulose/Fe3O4 microbeads. When prepared with TBAH, the initial adsorption rate of bovine serum albumin (BSA) on the cellulose/silk/Fe3O4 microbeads was 18.1 times higher than that on the cellulose/Fe3O4 microbeads. When preparing TBPH, the equilibrium adsorption capacity of the cellulose/silk/Fe3O4 microbeads for BSA (1.6 g/g) was 8.5 times higher than that of the cellulose/Fe3O4 microbeads. The pH-dependent BSA release from the cellulose/silk/Fe3O4 microbeads prepared with TBPH revealed 6.1-fold slower initial desorption rates and 5.2-fold lower desorption amounts at pH 2.2 than those at pH 7.4. Cytotoxicity tests on the cellulose and cellulose/silk composites regenerated with TBAH and TBPH yielded nontoxic results. Therefore, cellulose/silk/Fe3O4 microbeads are considered suitable pH-responsive supports for orally administered protein pharmaceuticals.

Development of Blended Biopolymer-Based Photocatalytic Hydrogel Beads for Adsorption and Photodegradation of Dyes.

Blended biopolymer-based photocatalytic hydrogel beads were synthesized by dissolving the biopolymers in 1-ethyl-3-methylimidazolium acetate ([Emim][Ac]), adding TiO2, and reconstituting the beads with ethanol. The incorporation of modifying biopolymer significantly enhanced the adsorption capacity of the cellulose/TiO2 beads. Cellulose/carrageenan/TiO2 beads exhibited a 7.0-fold increase in adsorption capacity for methylene blue (MB). In contrast, cellulose/chitosan/TiO2 beads showed a 4.8-fold increase in adsorption capacity for methyl orange (MO) compared with cellulose/TiO2 beads. In addition, cellulose/TiO2 microbeads were prepared through the sol-gel transition of the [Emim][Ac]-in-oil emulsion to enhance photodegradation activity. These microbeads displayed a 4.6-fold higher adsorption capacity and 2.8-fold higher photodegradation activity for MB than the millimeter-sized beads. Furthermore, they exhibited superior dye removal efficiencies for various dyes such as Congo red, MO, MB, crystal violet, and rhodamine B, surpassing the performance of larger beads. To expand the industrial applicability of the microbeads, biopolymer/TiO2 magnetic microbeads were developed by incorporating Fe2O3. These magnetic microbeads outperformed millimeter-sized beads regarding the efficiency and time required for MB removal from aqueous solutions. Furthermore, the physicochemical properties of magnetic microbeads can be easily controlled by adjusting the type of biopolymer modifier, the TiO2 and magnetic particle content, and the ratio of each component based on the target molecule. Therefore, biopolymer-based photocatalytic magnetic microbeads have great potential not only in environmental fields but also in biomedical fields.