Redox- and Enzyme-Responsive Macrospheres Gatekept by Polysaccharides for Controlled Release of Agrochemicals.

Stimuli-responsive materials afford researchers an opportunity to synthesize controlled-release carriers with various potential applications, especially for reducing the abuse of chemical reagents in farmland soil. To enhance the efficiency of agrochemical utilization, redox- and enzyme-responsive macrospheres were prepared by self-assembling β-cyclodextrin-modified zeolite and ferrocenecarboxylic acid (FcA)-grafted carboxymethyl cellulose (CMC). Scanning electron microscopy and Brunauer-Emmett-Teller analysis revealed that pores of zeolite were sealed by the surface coupling of FcA-modified CMC via the formation of an inclusion complex. Salicylic acid (SA) was loaded as a model agrochemical. The release of SA from macrospheres could be triggered in the presence of hydrogen peroxide (oxidant) and cellulase (enzyme); and the corresponding release percentages, 85.2 and 80.4%, were much higher than those of the control sample without responsive groups in water (12.6%) after 12 h. A release kinetic study showed that cellulase could promote carrier dissolution more effectively than the oxidant. The results demonstrate that the dual-responsive macrospheres are promising as a smart and effective carrier for the controlled release of agrochemicals.