The photocatalytic Fenton process, which produces a strong oxidant in the form of hydroxyl radicals, is a useful method to degrade organic contaminants in water. The Fenton reaction uses hydrogen peroxide and Fe2+ ions under relatively acidic conditions (typically pH 2–3) to maintain solubility of the iron catalyst but is troublesome due to the large volumes of decontaminated yet highly acidic water generated. Starch-stabilized iron (Fe2+/Fe3+) oxide nanoparticles were synthesized to serve as a colloidal catalyst system as the hydrophilic starch effectively prevents precipitation of the nanoparticles under conditions closer to neutrality. To evaluate the usefulness of this catalyst system for the photo-Fenton degradation of methylene blue as a model dye, the preparation protocol used and the iron loading in the starch were varied. The photocatalytic Fenton reaction was investigated at pH values up to 4. Not only were the starch-stabilized catalysts able to decolorize the dye but also to mineralize it in part, that is, to degrade it to carbon dioxide and water. The catalysts could be reused in several degradation cycles. This demonstrates that starch is an efficient stabilizer for iron oxide nanoparticles in aqueous media, enabling their use as environmentally friendly and cost-effective photo-Fenton catalysts. These starch-stabilized iron nanoparticles may also be useful to degrade other dyes and pollutants in water, such as pesticides.

Chitosan is a polysaccharide extracted from animal sources such as crab and shrimp shells. In this work, chitosan films were modified by grafting them with a thermoresponsive polymer, poly(di(ethylene glycol) methyl ether methacrylate) (PMEO2MA). The films were modified to introduce functional groups useful as reversible addition–fragmentation chain transfer (RAFT) agents. PMEO2MA chains were then grown from the films via RAFT polymerization, making the chitosan films thermoresponsive. The degree of substitution of the chitosan-based RAFT agent and the amount of monomer added in the grafting reaction were varied to control the length of the grafted PMEO2MA chain segments. The chains were cleaved from the film substrates for characterization using 1H NMR and a gel permeation chromatography analysis. Temperature-dependent contact angle measurements were used to demonstrate that the hydrophilic–hydrophobic nature of the film surface varied with temperature. Due to the enhanced hydrophobic character of PMEO2MA above its lower critical solution temperature (LCST), the ability of PMEO2MA-grafted chitosan films to serve as a substrate for cell growth at 37 °C (incubation temperature) was tested. Interactions with cells (fibroblasts, macrophages, and corneal epithelial cells) were assessed. The modified chitosan films supported cell viability and proliferation. As the temperature is lowered to 4 °C (refrigeration temperature, below the LCST), the grafted chitosan films become less hydrophobic, and cell adhesion should decrease, facilitating their removal from the surface. Our results indicated that the cells were detached from the films following a short incubation period at 4 °C, were viable, and retained their ability to proliferate.

Starch nanoparticles (SNPs) useful for the extraction of bitumen from oil sands were obtained by modification with thermoresponsive poly(di(ethylene glycol) methyl ether methacrylate) (PMEO2MA) segments through RAFT (Reversible Addition–Fragmentation chain Transfer) grafting. Since PMEO2MA exhibits a Lower Critical Aggregation Temperature (LCAT), the polymer-grafted SNPs are amphiphilic above the LCAT of the thermoresponsive polymer and can interact efficiently with bitumen in the oil sands, facilitating its extraction. The PMEO2MA-grafted SNPs form micellar aggregates that remain dispersed in water but can shuttle the bitumen component out of the sand and silt mixture in the extraction process above the LCAT. Upon cooling, the hydrophobic PMEO2MA domains become hydrophilic again and the grafted SNPs remain in the water phase, while the extracted oil floats on the aqueous phase and can be skimmed off. The aqueous polymer solution may be reused in other extraction cycles. Extraction by tumbling of the oil-water-SNP mixtures in vials at 45 °C reached over 80% efficiency. The synthetic methods used provide easy control over the characteristics of the grafted SNPs (number and length of grafted PMEO2MA segments), and therefore over their hydrophilic-lipophilic balance (HLB). The SNP-g-PMEO2MA samples were characterized by 1H NMR, UV-visible spectroscopy and dynamic light scattering analysis, and the grafted PMEO2MA chains were cleaved from the starch substrates for analysis by gel permeation chromatography.