Removal of Persistent Sulfamethoxazole and Carbamazepine from Water by Horseradish Peroxidase Encapsulated into Poly(Vinyl Chloride) Electrospun Fibers.

Enzymatic conversion of pharmaceutically active ingredients (API), using immobilized enzymes should be considered as a promising industrial tool due to improved reusability and stability of the biocatalysts at harsh process conditions. Therefore, in this study horseradish peroxidase was immobilized into sodium alginate capsules and then trapped into poly(vinyl chloride) electrospun fibers to provide additional enzyme stabilization and protection against the negative effect of harsh process conditions. Due to encapsulation immobilization, 100% of immobilization yield was achieved leading to loading of 25 µg of enzyme in 1 mg of the support. Immobilized in such a way, enzyme showed over 80% activity retention. Further, only slight changes in kinetic parameters of free (Km = 1.54 mM) and immobilized horseradish peroxidase (Km = 1.83 mM) were noticed, indicating retention of high catalytic properties and high substrate affinity by encapsulated biocatalyst. Encapsulated horseradish peroxidase was tested in biodegradation of two frequently occurring in wastewater API, sulfamethoxazole (antibiotic) and carbamazepine (anticonvulsant). Over 80% of both pharmaceutics was removed by immobilized enzyme after 24 h of the process from the solution at a concentration of 1 mg/L, under optimal conditions, which were found to be pH 7, temperature 25 °C and 2 mM of H2O2. However, even from 10 mg/L solutions, it was possible to remove over 40% of both pharmaceuticals. Finally, the reusability and storage stability study of immobilized horseradish peroxidase showed retention of over 60% of initial activity after 20 days of storage at 4 °C and after 10 repeated catalytic cycles, indicating great practical application potential. By contrast, the free enzyme showed less than 20% of its initial activity after 20 days of storage and exhibited no recycling potential.

Treatment of model solutions and wastewater containing selected hazardous metal ions using a chitin/lignin hybrid material as an effective sorbent.

A chitin/lignin material with defined physicochemical and morphological properties was used as an effective adsorbent of environmentally toxic metals from model systems. Particularly significant is its use in the neutralization of real industrial wastes. The ions Ni2+, Cu2+, Zn2+ and Pb2+ were adsorbed on the functional sorbent, confirming the high sorption capacity of the newly obtained product, primarily due to the presence on its surface of numerous active functional groups from the component biopolymers. The kinetics of the process of ion adsorption from model solution were investigated, and the experimental data were found to fit significantly better to a type 1 pseudo-second-order kinetic model, as confirmed by the high correlation coefficient of 0.999 for adsorption of both nickel(II) copper(II) zinc(II) and lead(II) ions. The experimental data obtained on the basis of adsorption isotherms corresponded to the Langmuir model. The sorption capacity of the chitin/lignin material was measured at 70.41 mg(Ni2+)/g, 75.70 mg(Cu2+)/g, 82.41 mg(Zn2+)/g and 91.74 mg(Pb2+)/g. Analysis of thermodynamic parameters confirmed the endothermic nature of the process. It was also shown that nitric acid is a very effective desorbing (regenerating) agent, enabling the chitin/lignin material to be reused as an effective sorbent of metal ions. The sorption abilities of the chitin/lignin system with respect to particular metal ions can be ordered in the sequence Ni2+

More than just a beer - Brewers' spent grain, spent hops, and spent yeast as potential functional fillers for polymer composites.

Beer is among the most popular beverages in the world, with the production distributed uniformly between the biggest continents, so the utilization of brewing by-products is essential on a global scale. Among their potential recipients, the plastics industry offers extensive range of potential products. Herein, the presented study investigated the application of currently underutilized solid brewing by-products (brewers' spent grain, spent hops, spent yeast) as fillers for highly-filled poly(ε-caprolactone)-based composites, providing the first direct connection between spent hops or spent yeast and the polymer composites. Comprehensive by-product characterization revealed differences in chemical composition. The elemental C:O ratio, protein content, and Trolox equivalent antioxidant capacity varied from 1.40 to 1.89, 12.9 to 32.4 wt%, and 2.41 to 10.24 mg/g, respectively, which was mirrored in the composites' structure and performance. Morphological analysis pointed to the composition-driven hydrophilicity gap limiting interfacial adhesion for high shares of brewers' spent grain and spent hops, due to high hydrophilicity induced by carbohydrate content. Phytochemicals and other components of applied by-products stimulated composites' oxidative resistance, shifting oxidation onset temperature from 261 °C for matrix over 360 °C for high spent yeast shares. Simultaneously, spent yeast also provided compatibilizing effects for poly(ε-caprolactone)-based composites, reducing complex viscosity compared to other fillers and indicating its highest affinity to poly(ε-caprolactone)due to the lowest hydrophilicity gap. The presented results indicate that the proper selection of brewing by-products and adjustment of their shares creates an exciting possibility of engineering composites' structure and performance, which can be transferred to other polymers differing with hydrophilicity.

Management of ground tire rubber waste by incorporation into polyurethane-based composite foams.

Rapid economic growth implicated the developing multiple industry sectors, including the automotive branch, increasing waste generation since recycling and utilization methods have not been established simultaneously. A very severe threat is the generation of enormous amounts of post-consumer tires considered burdensome waste, e.g., due to the substantial emissions of volatile organic compounds (VOCs). Therefore, it is essential to develop novel, environmentally friendly methods for their utilization, which would hinder their environmental impacts. One of the most promising approaches is shredding, resulting in the generation of ground tire rubber (GTR), which can be introduced into polymeric materials as filler. The presented work is related to the thermomechanical treatment of GTR in a twin-screw extruder with zinc borate, whose incorporation is aimed to enhance shear forces within the extruder barrel. Modified GTR was introduced into flexible polyurethane (PU) foams, and the impact of modification parameters on the cellular structure, static and dynamic mechanical performance, thermal stability, as well as thermal insulation, and acoustic properties was investigated. Emissions of VOCs from applied fillers and prepared composites were monitored and evaluated. Depending on the treatment parameters, beneficial changes in foams' cellular structure were noted, which enhanced their thermal insulation performance, mechanical strength, and thermal stability. It was proven that the proposed method of GTR thermomechanical treatment assisted by zinc borate particles might benefit the performance of flexible PU foamed composites and hinder VOC emissions, which could broaden the application range of GTR and provide novel ways for its efficient utilization.

Naturally prefabricated 3D chitinous skeletal scaffold of marine demosponge origin, biomineralized ex vivo as a functional biomaterial.

Solutions developed by nature for structural and functional optimization of three-dimensional (3D) skeletal structures provide unique windows not only into the evolutionary pathways of organisms, but also into bioinspired materials science and biomimetics. Great examples are naturally formed 3D chitinous scaffolds of marine sponge remain a focus of modern biomedicine and tissue engineering. Due to its properties like renewability, bioactivity, and biodegradability such constructs became very interesting players as components of organic-inorganic biocomposites. Herein, we developed chitin-based biocomposites by biomimetic ex vivo deposition of calcium carbonate particles using hemolymph from the cultivated mollusk Cornu aspersum and chitinous matrix from the marine demosponge Aplysina fistularis. The biological potential of the developed biofunctionalized scaffolds for bone tissue engineering was evaluated by investigating the spreading and viability of a human fetal osteoblast cell line has been determined for the first time. Performed analyses like dynamic mechanical analysis and atomic force microscopy shown that biofunctionalized scaffold possess about 4 times higher mechanical resistance. Moreover, several topographical changes have been observed, as e.g., surface roughness (Rq) increased from 31.75 ± 2.7 nm to 120.7 ± 0.3 nm. The results are indicating its potential for use in the modification of cell delivery systems in future biomedical applications.