Polyelectrolyte Complex Hydrogels from Controlled Kneading and Annealing-Induced Tightly Wound and Highly Entangled Natural Polysaccharides.

Hydrogels usually are fabricated by using monomers or preexisting polymers in precursor solutions. Here, a polyelectrolyte complex biohydrogel (Bio-PEC hydrogel) made from a precursor dough, by kneading, annealing, and crosslinking the dough of two oppositely charged polysaccharides, cationic chitosan quaternary ammonium salt (HACC) and anionic sodium hyaluronate (HA), photoinitiator (α-ketoglutaric acid), crosslinker glycidyl methacrylate (GMA), and water of very small quantity is reported. Controlled kneading and annealing homogenized the dough with respect to transforming randomly distributed, individual polymer chains into tightly wound double-stranded structures, which, upon UV irradiation, covalently sparsely crosslinked into a highly entangled network and subsequently, upon fully swollen in water, results in Bio-PEC hydrogel, HACC/HA, exhibiting near-perfect elasticity, high tensile strength, and high swelling resistance. Via the same kneading and annealing, tetracarboxyphenylporphyrin iron (Fe-TCPP) metal nanoclusters are incorporated into HACC/HA to obtain photocatalytic, antibacterial, and biocompatible Bio-PEC hydrogel composite, Fe-TCPP@HACC/HA. Using SD rat models, the efficacy of Fe-TCPP@HACC/HA in inhibiting Escherichia coli (E. coli) growth in vitro and the ability to promote wound healing and scar-free skin regeneration in vivo, or its high potential as a wound dressing material for biomedical applications are demonstrated.

Engineering Antioxidative Cascade Metal-Phenolic Nanozymes for Alleviating Oxidative Stress during Extracorporeal Blood Purification.

Oxidative stress is a compelling risk factor in chronic kidney diseases and is further aggravated for individuals during extracorporeal blood purification, ultimately leading to multiple complications. Herein, antioxidative cascade metal-phenolic nanozymes (metal-tannic acid nanozymes, M-TA NMs) are synthesized via metal ions-mediated oxidative coupling of polyphenols; then M-TA NMs engineered hemoperfusion microspheres (Cu-TAn@PMS) are constructed for alleviating oxidative stress. M-TA NMs show adjustable broad-spectrum antioxidative activities toward multiple reactive nitrogen and oxygen species (RNOS) due to the adjustable catalytic active centers. Importantly, M-TA NMs could mimic the cascade processes of superoxide dismutase and catalase to maintain intracellular redox balance. Detailed structural and spectral analyses reveal that the existence of a transition metal could decrease the electronic energy band gaps of M-TA NMs to offer better electron transfers for RNOS scavenging. Notably, dynamic blood experiments demonstrate that Cu-TAn@PMS could serve as an antioxidant defense system for blood in hemoperfusion to scavenge intracellular reactive oxygen species (ROS) effectively even in the complex blood environment and further protect endogenous antioxidative enzymes and molecules. In general, this work developed antioxidative cascade nanozymes engineered microspheres with excellent therapeutic efficacy for the treatment of oxidative stress-related diseases, which exhibited potential for clinical blood purification and extended the biomedical applications of nanozymes.

Performance of Pd/Sn catalysts supported by chelating resin prestoring reductant for nitrate reduction in actual water.

Catalytic hydrogen reduction has appeared as a promising strategy for chemical denitrification with advantages of high activity and simple operation. However, the risk and low utilization of H2 is the disadvantage of catalytic hydrogen reduction. In recent years, catalytic reduction reactions in the presence of sodium borohydride (NaBH4) have been extensively studied. NaBH4 can be used as an electron source to generate electrons on the surface of the catalyst and can catalyze the reduction of pollutants. But it makes commercialization costly and causes significant environmental pollution if widely use NaBH4. In this study, we prepared supported Pd/Sn bimetallic nanoparticles which could adsorb NaBH4 during the preparation of the Pd/Sn bimetallic catalyst as the prestoring reductant. No additional reducing agent is required during nitrate reduction process. The performance and mechanism for nitrate reduction by using Pd/Sn bimetallic nanoparticles were discussed. Moreover, the catalyst D-Pd1/Sn1 reached a complete nitrate removal in the municipal wastewater treatment plant effluent water within 3 h. The results provide a prospect for denitrification in biological wastewater treatment plants.

A new supported Cu/Pd bimetallic nanoparticles composites prestoring reductant for nitrate removal: high reactivity and N2 selectivity.

Catalytic hydrogen reduction appears to be a promising strategy for nitrate removal. However, the danger and low utilization of H2 are the disadvantages of catalytic hydrogen reduction. Sodium borohydride (NaBH4), considered a potential candidate for hydrogen storage, has been investigated as an electron source for the catalytic reduction of contaminants. However, extensive use of NaBH4 makes commercialization costly and causes environmental pollution. In this study, we prepared supported Cu/Pd bimetallic nanoparticles that could prestore hydrogen. No additional reducing agent was required during the nitrate reduction process. The performance and mechanism of Cu/Pd bimetallic nanoparticles for nitrate reduction are discussed. Good performance was obtained with high reactivity (99.04% nitrate removal efficiency) and high selectivity for N2 (94.71%). The Cu/Pd bimetallic catalyst could be recovered by NaBH4 for 5 cycles. Moreover, a 97.49% nitrate removal efficiency was obtained for actual wastewater, indicating good prospects for nitrate reduction applications.

Pretreatment by NaOH swelling and then HCl regeneration to enhance the acid hydrolysis of cellulose to glucose.

A simple pretreatment method, NaOH swelling at a low temperature and then HCl regeneration, was developed for depolymerization of cellulose to glucose. Cellulose was transformed into amorphous hydrogel during the treatment; and due to the easy diffusion of H(+) and Cl(-) ions into the cellulose hydrogel network as well as the strong ability of Cl(-) to disrupt the massive hydrogen bond, the hydrolysis rate was greatly enhanced. The method is effective for α-cellulose, microcrystalline cellulose, filter paper, ramie fiber and absorbent cotton. Even at a high α-cellulose concentration of 50g/L, 29.1% yield of glucose was still obtained within 10min at 160°C under microwave irradiation, where up to 16.2g/L of glucose solution was given. The influence of NaOH concentration, HCl concentration, hydrolysis temperature and time on the hydrolysis rate was investigated. The structure of cellulose hydrogel was also studied to confirm the reaction mechanism.

Efficient production of glucose by microwave-assisted acid hydrolysis of cellulose hydrogel.

To improve the production of glucose from cellulose, a simple and effective route was developed. This process uses a combination of a step of cellulose dissolution in aqueous NaOH/urea solution and then regeneration with water, followed by an acid hydrolysis step under microwave irradiation. The method is effective to obtain glucose from α-cellulose, microcrystalline cellulose, filter paper, ramie fiber and absorbent cotton. Increased with the acid concentration the glucose yield from hydrogel hydrolysis increased from 0.42% to 44.6% at 160 °C for 10 min. Moreover, the ozone treatment of cellulose in NaOH/urea solution before regeneration significantly enhanced the hydrolysis efficiency with a glucose yield of 59.1%. It is believed that the chains in cellulose hydrogel are relatively free approached, making that the acids easily access the ß-glycosidic bonds.