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 ß-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.

Controlled Release of Agrochemicals Using pH and Redox Dual-Responsive Cellulose Nanogels.

A novel pH and redox dual-responsive cellulose-based nanogel was prepared for the controlled release of agrochemicals. To synthesize the responsive nanogel, palmitoyl chloride and glyoxal were modified on carboxymethyl cellulose sequentially and 3,3'-dithiobis(propionohydrazide) was used as a cross-linker to assemble the nanogel. The morphology, structure, and physical properties of nanogels were characterized with transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), particle size analysis, and zeta-potential measurement. Facing pH and redox stimulation, the nanogel showed reversible sol-gel transitions, indicating good pH- and redox-responsiveness. The nanogel loaded with agrochemicals exhibited high loading capacity and various release behaviors. In addition, the experiment of nanogel on heavy metal ions complexation displayed the potential of improving soil condition while delivering agrochemicals.

Controlled release of agrochemicals and heavy metal ion capture dual-functional redox-responsive hydrogel for soil remediation.

Novel redox-responsive hydrogels were prepared based on disulfide-crosslinked carboxymethyl cellulose for the controlled-release of agrochemicals. After release, the reduced hydrogels could capture heavy metal ions in soil via strong complexation between the ions and thiol groups generated by disconnected disulfide bonds, thus benefiting plant growth and soil remediation synchronously.

Study on cellulose microfilaments based composite spheres: Microwave-assisted synthesis, characterization, and application in pollutant removal.

A novel study of synthesizing the temperature-responsive polymer grafted cellulose filaments/Poly (N-isopropylacrylamide) (NIPAM) spheres (P-MCCBs) was carried out for the removal of dyes and heavy metal ions. The novelty of the presented work consists of the application of the nano-sized pore-forming agent (Calcium Carbonate) and the introduction of a temperature-responsive monomer (NIPAM) while preparing the adsorbents. In addition, the spherical adsorbents were synthesized through an in-situ free radical polymerization using a microwave-assisted heating approach. The morphology, chemical structure, pH, and thermal sensitivity of P-MCCBs were characterized properly. The adsorption and desorption behaviors of dyes and heavy metal ions on P-MCCBs were also investigated. The results showed that P-MCCBs exhibited a fast adsorption rate, the adsorption equilibrium reached within 80 min and 40 min for MB and Pb2+, respectively (25 °C). Moreover, around 5-8% and 20% of adsorbed MB and Pb2+ were released at the temperature above 45 °C. The adsorption kinetics followed pseudo-second-order model, and the desorption process was fit well using Higuchi and Korsmeyer-Peppas models. These results indicated that P-MCCBs could be served as a novel material for controllable adsorption and desorption processes of various contaminants.

Preparation of Novel Nano-Sized Hydrogel Microcapsules via Layer-By-Layer Assembly as Delivery Vehicles for Drugs onto Hygiene Paper.

Hydrogel microcapsules are improved transplantation delivery vehicles for pharmaceuticals by effectively segregating the active ingredients from the surroundings and delivering them to a certain target site. Layer-by-layer (LbL) assembly is an attractive process to fabricate the nano-sized hydrogel microcapsules. In this study, nano-sized hydrogel microcapsules were prepared through LbL assembly using calcium carbonate nanoparticles (CaCO3 NPs) as the sacrificial inorganic template, sodium alginate (SA) and polyethyleneimine (PEI) as the shell materials. Ciprofloxacin was used to study the encapsulation and release properties of the hydrogel microcapsules. The hydrogel microcapsules were further adsorbed onto the paper to render antimicrobial properties. The results showed that the mean size of the CaCO3 template was reduced after dispersing into sodium n-dodecyl sulfate (SDS) solution under sonication. Transmission electron microscope (TEM) and atomic force microscope (AFM) revealed that some hydrogel microcapsules had a diameter under 200 nm, typical creases and collapses were found on the surface. The nano-sized PEI/SA hydrogel microcapsules showed high loading capacity of ciprofloxacin and a sustained release. PEI/SA hydrogel microcapsules rendered good antimicrobial properties onto the paper by the adsorption of hydrogel microcapsules, however, the mechanical properties of the hygiene paper were decreased.

Immobilizing Laccase on Modified Cellulose/CF Beads to Degrade Chlorinated Biphenyl in Wastewater.

Novel modified cellulose/cellulose fibril (CF) beads (MCCBs) loaded with laccase were prepared to degrade polychlorinated biphenyls (PCBs) in wastewater. The proper porous structure in MCCBs was achieved by introducing nano CaCO3 (as a pore forming agent) in cellulose/CF (CCBs) beads during the preparation process. Cellulose/CF composite beads were modified by maleic anhydride to introduce carboxyl groups. Laccase was immobilized on the MCCBs through electrostatic adsorption and covalent bonding. The effects of pH, laccase concentration and contact time on immobilization yields and recovered activity were investigated. The best conditions were pH 4, concentration 16 g/L and contact time 3 h. The immobilized laccase under these conditions showed a good performance in thermal and operational stability. The laccase immobilized on MCCB beads can remove 85% of 20 mg/L 4-hydroxy-3,5-dichlorobiphenyl (HO-DiCB) in wastewater. The results demonstrated that MCCBs, as a new type of green-based support, are very promising in material immobilizing laccase. This technology may be of potential advantage for the removal of polychlorinated biphenyls in wastewater from an environmental point of view.