Conversion of Plastic Waste into Supports for Nanostructured Heterogeneous Catalysts: Application in Environmental Remediation

Plastics are ubiquitous in our society and are used in many industries, such as packaging, electronics, the automotive industry, and medical and health sectors, and plastic waste is among the types of waste of higher environmental concern. The increase in the amount of plastic waste produced daily has increased environmental problems, such as pollution by micro-plastics, contamination of the food chain, biodiversity degradation and economic losses. The selective and efficient conversion of plastic waste for applications in environmental remediation, such as by obtaining composites, is a strategy of the scientific community for the recovery of plastic waste. The development of polymeric supports for efficient, sustainable, and low-cost heterogeneous catalysts for the treatment of organic/inorganic contaminants is highly desirable yet still a great challenge; this will be the main focus of this work. Common commercial polymers, like polystyrene, polypropylene, polyethylene therephthalate, polyethylene and polyvinyl chloride, are addressed herein, as are their main physicochemical properties, such as molecular mass, degree of crystallinity and others. Additionally, we discuss the environmental and health risks of plastic debris and the main recycling technologies as well as their issues and environmental impact. The use of nanomaterials raises concerns about toxicity and reinforces the need to apply supports; this means that the recycling of plastics in this way may tackle two issues. Finally, we dissert about the advances in turning plastic waste into support for nanocatalysts for environmental remediation, mainly metal and metal oxide nanoparticles.

Expanding the Biocatalytic Scope of Enzyme-Loaded Polymeric Hydrogels

In recent years, polymeric hydrogels have appeared promising matrices for enzyme immobilization to design, signify and expand bio-catalysis engineering. Therefore, the development and deployment of polymeric supports in the form of hydrogels and other robust geometries are continuously growing to green the twenty-first-century bio-catalysis. Furthermore, adequately fabricated polymeric hydrogel materials offer numerous advantages that shield pristine enzymes from denaturation under harsh reaction environments. For instance, cross-linking modulation of hydrogels, distinct rheological behavior, tunable surface entities along with elasticity and mesh size, larger surface-volume area, and hydrogels’ mechanical cushioning attributes are of supreme interest makes them the ideal candidate for enzyme immobilization. Furthermore, suitable coordination of polymeric hydrogels with requisite enzyme fraction enables pronounced loading, elevated biocatalytic activity, and exceptional stability. Additionally, the unique catalytic harmony of enzyme-loaded polymeric hydrogels offers numerous applications, such as hydrogels as immobilization matrix, bio-catalysis, sensing, detection and monitoring, tissue engineering, wound healing, and drug delivery applications. In this review, we spotlight the applied perspective of enzyme-loaded polymeric hydrogels with recent and relevant examples. The work also signifies the combined use of multienzyme systems and the future directions that should be attempted in this field.

Pd Nanoparticles-Loaded Vinyl Polymer Gels: Preparation, Structure and Catalysis

Four vinyl polymer gels (VPGs) were synthesized by free radical polymerization of divinylbenzene, ethane-1,2-diyl dimethacrylate, and copolymerization of divinylbenzene with styrene, and ethane-1,2-diyl dimethacrylate with methyl methacrylate, as supports for palladium nanoparticles. VPGs obtained from divinylbenzene and from divinylbenzene with styrene had spherical shapes while those obtained from ethane-1,2-diyl dimethacrylate and from ethane-1,2-diyl dimethacrylate with methyl methacrylate did not have any specific shapes. Pd(OAc)2 was impregnated onto VPGs and reduced to form Pd0 nanoparticles within VPGs. The structures of Pd0-loaded VPGs were analyzed by XRD, TEM, and nitrogen gas adsorption. Pd0-loaded VPGs had nanocrystals of Pd0 within and on the surface of the polymeric supports. Pd0/VPGs efficiently catalyzed the oxidation/disproportionation of benzyl alcohol into benzaldehyde/toluene, where activity and selectivity between benzaldehyde and toluene varied, depending on the structure of VPG and the weight percentage loading of Pd0. The catalysts were stable and Pd leaching to liquid phase did not occur. The catalysts were separated and reused for five times without any significant decrease in the catalytic activity.

POLYMERIC SUPPORTS FOR ENZYMES IMMOBILIZATION IN SYNTHESIS OF BIOLOGICALLY ACTIVE COMPOUNDS

The report presents the synthesis of biocatalysts based on horseradish peroxidase immobilized on commercially available polymeric supports: hyper cross-linked polystyrene MN-100 and Sepabeads EC-HA. The immobilization was carried out by covalent crosslinking of the enzyme with the support using glutaraldehyde. The optimal amount of glutaraldehyde for covalent binding of HRP was found to be 0.2 g/l. The peroxidase/MN-100 and peroxidase/Sepabeads EC-HA biocatalysts presented in the work showed good activity in the oxidation of 2-methylnaphthol to 2 methyl-1,4-naphthohydroquinone (vitamin K4). The biocatalyst based on MN-100 showed higher activity compared to the biocatalyst based on Sepabeads EC-HA, which is likely due to the different surface structure of the original polymer supports. The samples retained their activity in ten consecutive reuses. The high reusability of peroxidase/MN-100 and peroxidase/Sepabeads EC-HA is explained by the high sorption ability of commercial polymer supports MN-100 and Sepabeads EC-HA and the formation of strong covalent bonds between the enzyme and the support. The optimal conditions for the oxidation of 2-methylnaphthol to 2-methyl-1,4-naphthohydroquinone using synthesized biocatalytic systems were also selected. The temperature of 40 °C and pH 7.2 were found to be optimal for the oxidation of the proposed substrate. The presented results will undoubtedly make a positive contribution to the development of the chemical and pharmaceutical industry.