Highly efficient catalytic pyrolysis of polyethylene waste to derive fuel products by novel polyoxometalate/kaolin composites.

We report here alumina-substituted Keggin tungstoborate/kaolin clay composite materials (KAB/kaolin) as polyethylene cracking catalysts. KAB/kaolin composites with varying concentrations of KAB (10-50 wt.%) were synthesized by the wet impregnation method and successfully characterized by Fourier-transform infrared spectroscopy, powder X-ray diffraction, thermo-gravimetric analysis and scanning electron microscopy with energy dispersive X-ray spectroscopy analytical techniques. Use of KAB loaded kaolin composites as the catalyst for low-density polyethylene (LDPE) cracking exhibited a higher percentage of polymer conversion (99%), producing 84 wt.% of fuel oil and negligible amount (˂ 1 wt.%) of solid residue while thermal cracking produced ~22 wt.% residue. Furthermore, gas chromatography-mass spectrometry analysis of oil obtained by non-catalytic cracking exhibited a high selectivity to high molecular weight hydrocarbons (C13-C23) compared to the catalytic cracking where 70 mol.% of gasoline range hydrocarbons (C5-C12) were produced. We propose that higher cracking ability of our prepared catalysts might ensue from both Brønsted and Lewis acid sites (from KAB and kaolin respectively), which enhanced the yield of liquid fuel products and reduced the cracking temperature of LDPE. These findings suggest that the prepared composites were cost-effective and excellent cracking catalysts that could be recommended for highly efficient conversion of waste plastic materials to petrochemicals at an industrial scale.

An Overview on Recent Progress in Electrochemical Biosensors for Antimicrobial Drug Residues in Animal-Derived Food.

Anti-microbial drugs are widely employed for the treatment and cure of diseases in animals, promotion of animal growth, and feed efficiency. However, the scientific literature has indicated the possible presence of antimicrobial drug residues in animal-derived food, making it one of the key public concerns for food safety. Therefore, it is highly desirable to design fast and accurate methodologies to monitor antimicrobial drug residues in animal-derived food. Legislation is in place in many countries to ensure antimicrobial drug residue quantities are less than the maximum residue limits (MRL) defined on the basis of food safety. In this context, the recent years have witnessed a special interest in the field of electrochemical biosensors for food safety, based on their unique analytical features. This review article is focused on the recent progress in the domain of electrochemical biosensors to monitor antimicrobial drug residues in animal-derived food.

Electron transfer to covalently immobilized Keggin polyoxotungstates on gold.

Spontaneously adsorbed monolayers have been formed on gold electrodes using a Keggin polyoxotungstate with covalently attached alkanethiol linkers of two different lengths. Films of both polyoxotungstates show two well-defined reduction processes associated with the polyoxotungstate centers where the ionic liquid, [BMIM][BF4], acts as supporting electrolyte. The surface coverages are both less than that expected for a close-packed monolayer. For the short and long linkers, the voltammetric response can be described in terms of the Butler-Volmer response involving a surface confined species using standard heterogeneous electron transfer rate constants of 170 and 140 s(-1) for the first reduction and 150 and 100 s(-1) for the second reduction processes, respectively. The rate of electron transfer to a solution phase redox probe, ferrocyanide, is significantly more sensitive to the length of the linker than the rate of electron transfer to the tungstate centers. This behavior probably arises due to potential-induced changes in the film structure.

Organic-Inorganic Hybrid Films of the Sulfate Dawson Polyoxometalate, [S2W18O62]4-, and Polypyrrole for Iodate Electrocatalysis.

The Dawson-type sulfate polyoxometalate (POM) [S2W18O62]4- has successfully been entrapped in polypyrrole (PPy) films on glassy carbon electrode (GCE) surfaces through pyrrole electropolymerization. Films of varying POM loadings (i.e., thickness) were grown by chronocoulometry. Film-coated electrodes were then characterized using voltammetry, revealing POM surface coverages ranging from 1.9 to 11.7 × 10-9 mol·cm-2, and were stable over 100 redox cycles. Typical film morphology and composition were revealed to be porous using atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, and the effects of this porosity on POM redox activity were probed using AC impedance. The hybrid organic-inorganic films exhibited a good electrocatalytic response toward the reduction of iodate with a sensitivity of 0.769 µA·cm-2·µM-1.

Development of Iron Sequester Antioxidant Quercetin@ZnO Nanoparticles with Photoprotective Effects on UVA-Irradiated HaCaT Cells.

BACKGROUND: Solar ultraviolet radiation A (UVA, 320-400 nm) is a significant risk factor leading to various human skin conditions such as premature aging or photoaging. This condition is enhanced by UVA-mediated iron release from cellular iron proteins affecting huge populations across the globe. PURPOSE: Quercetin-loaded zinc oxide nanoparticles (quercetin@ZnO NPs) were prepared to examine its cellular iron sequestration ability to prevent the production of reactive oxygen species (ROS) and inflammatory responses in HaCaT cells. METHODS: Quercetin@ZnO NPs were synthesized through a homogenous precipitation method, and the functional groups were characterized by Fourier transform infrared (FTIR) spectroscopy, whereas scanning electron microscopy (SEM) described the morphologies of NPs. MTT and qRT-PCR assays were used to examine cell viability and the expression levels of various inflammatory cytokines. The cyclic voltammetry (CV) was employed to evaluate the redox potential of quercetin-Fe3+/quercetin-Fe2+ complexes. RESULTS: The material characterization results supported the loading of quercetin molecules on ZnO NPs. The CV and redox potential assays gave Fe-binding capability of quercetin at 0.15 mM and 0.3 mM of Fe(NO3)3. Cytotoxicity assays using quercetin@ZnO NPs with human HaCaT cells showed no cytotoxic effects and help regain cell viability loss following UVA (150 kJ/m2). CONCLUSION: Quercetin@ZnO NPs showed that efficient quercetin release action is UV-controlled, and the released quercetin molecules have excellent antioxidant, anti-inflammatory, and iron sequestration potential. Quercetin@ZnO NPs have superior biocompatibility to provide UVA protection and medication at once for antiphotoaging therapeutics.

Investigations into the electrochemical, surface, and electrocatalytic properties of the surface-immobilized polyoxometalate, TBA3K[SiW10O36(PhPO)2].

Surface anchoring of an organic functionalized POM, TBA3K[SiW10O36(PhPO)2] was carried out by two methods, the layer-by-layer (LBL) assembly technique by employing a pentaerythritol-based ruthenium(II) metallodendrimer as a cationic moiety and also by entrapping the POM in a conducting polypyrrole film. The redox behavior of the constructed films was studied by using cyclic voltammetry and electrochemical impedance spectroscopy. The surface morphologies of the constructed multilayers were examined by scanning electron microscopy and atomic force microscopy. X-ray photoelectron spectroscopy was conducted to confirm the elements present within the fabricated films. The multilayer assembly was also investigated for its catalytic efficiency towards the reduction of nitrite.

Surface immobilization of a tetra-ruthenium substituted polyoxometalate water oxidation catalyst through the employment of conducting polypyrrole and the layer-by-layer (LBL) technique.

A tetra Ru-substituted polyoxometalate Na10[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] (Ru4POM) has been successfully immobilised onto glassy carbon electrodes and indium tin oxide (ITO) coated glass slides through the employment of a conducting polypyrrole matrix and the layer-by-layer (LBL) technique. The resulting Ru4POM doped polypyrrole films showed stable redox behavior associated with the Ru centres within the Ru4POM, whereas, the POM's tungsten-oxo redox centres were not accessible. The films showed pH dependent redox behavior within the pH range 2-5 whilst exhibiting excellent stability towards redox cycling. The layer-by-layer assembly was constructed onto poly(diallyldimethylammonium chloride) (PDDA) modified carbon electrodes by alternate depositions of Ru4POM and a Ru(II) metallodendrimer. The resulting Ru4POM assemblies showed stable redox behavior for the redox processes associated with Ru4POM in the pH range 2-5. The charge transfer resistance of the LBL films was calculated through AC-Impedance. Surface characterization of both the polymer and LBL Ru4POM films was carried out using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Initial investigations into the ability of the Ru4POM LBL films to electrocatalytically oxidise water at pH 7 have also been conducted.