Analysis of Ag-DP25/PET plasmonic nano-composites as a visible-light photocatalyst for wastewater treatment: Experimental/theoretical studies, and the DFT-MB degradation mechanism.

The development of polymeric-composites Agx%DP25-PET (x = 0,1,2,3) may significantly boost the potential application of Agx%DP25 (x = 0,1,2,3) photocatalytic powders. Producing large-scale nano-composites with hybrid-surfaces, that are also flexible materials and easy to employ in a variety of environments. A set of photocatalytic nan-composites embedded with the polymeric binder poly (acrylonitrile-co-butadiene)-dicarboxy terminated (C7H9N) were performed and evaluated for wastewater treatment applications. The results reveal that the flexible polymeric composites (Agx%DP25-PET, x = 0,1,2,3) have photocatalytic activity in aqua media to degrade methylene blue (MB) under visible-light. The addition of C7H9N to immobilize photocatalytic powders on the PET surface reduces photo-generated electron-hole recombination. The materials were characterized by HR-TEM, SEM/EDX, XRD, FT-IR, UV-Vis DRS and PL. The Agx%DP25-PET (x = 0,1,2,3) photocatalytic reactions exhibited productive discoloration/degradation rates, in both aerobic (AE) and anaerobic (AN) environments. The superior photodegradation of Ag2%DP25-PET was attributed to a combination of two effects: LSPR (localized surface plasmon resonance) and Ag-TiO2/environment affinities. The findings of molecular dynamics (MD) simulation and Fukui Function (FF) based on density functional theory (DFT) provide significant insight into the photocatalytic requirements for MB discoloration/degradation. The experimental/theoretical analysis aimed to offer an in-depth understanding of medium/surface interactions on decorated TiO2 materials, as well as how these interactions affect overall degradation behavior.

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts.

Recently, interest in converting bio-derived fatty acid methyl esters (FAMEs) into added-value products has significantly increased. The selectivity of ketonization reaction in the conversion of the FAMEs has significantly hampered the efficiency of this process. Herein, this work reports the preparation of catalysts with different levels of oxygen vacancies while the crystal phase remained unchanged. The catalyst with the highest level of oxygen vacancy exhibited the maximum selectivity. The density functional theory (DFT) simulation showed an increase in interatomic distances leading to the formation of frustrated Lewis pairs (FLPs) upon the creation of oxygen vacancies. The surface measurements, type and density of acid sites of the catalysts, showed that the Lewis acid sites enhanced the selectivity for ketone production; while Bronsted acid sites increased the formation of by-products. Moreover, the ketone formation rate was directly proportional to acid density. The findings of this research provide a different approach for catalyst design, based on defects engineering and their effect on the surface activity, which could be used for enhancing the catalytic performance of novel metal oxides.

Thyroid hormone modulation of VIP's induced salivary secretion in the submaxillary glands of rats.

The effect of changes in thyroid function upon vasoactive intestinal peptide (VIP) induced secretion of saliva were studied in male Wistar rats. Hyperthyroidism was induced by the sc administration every 12 h of 10 micrograms/100 g bw of I-triiodothyronine; hypothyroidism was induced by surgical thyroidectomy 2 weeks before the experiments. Preganglionar parasympathetic denervation was induced by sectioning the chorda tympani on the left side. The dose-response curves to increasing doses of VIP showed in the hypothyroid animals increased salivary secretion, while in the hyperthyroid ones the dose-response to the drug was reduced. This effect was seen on both sides, the denervated and the control ones. In the denervated glands there was a marked hypersensitivity to the administration of VIP producing greater responses with the same doses, in the 3 groups of animals. The negative modulation by thyroid hormones of the salivary response to VIP administration is compared with the positive modulation they induce in the salivary response to beta-adrenergic and cholinergic drugs.

Inhibitory action of dipyrone on rat thyroid peroxidase and lactoperoxidase activities.

Previous studies have shown that phenylbutazone, another pyrazolone, inhibits thyroid peroxidase activity and interferes with iodide organification. We have developed "in vitro" studies with rat particulated peroxidase and lactoperoxidase (LPO) to study the effects of dipyrone upon thyroid peroxidase and to determine the type of inhibition. The 3-monoiodothyrosine (MIT) and 3,5-diiodothyrosine (DIT) synthesis was markedly affected by 6 X 10(-4) M dipyrone with inhibitions of 59% and 30% respectively. No difference was observed with lower concentrations. Inhibition of peroxidase activity (Triiodide assay) was found when crude rat peroxidase preparations and LPO were incubated with dipyrone in concentrations ranging from 10(-3) M to 10(-8) M, with a Ki of 2.5 X 10(-5) M and 4 X 10(-5) M respectively. Guaiacol peroxidation was scarcely affected by the action of the drug; 10(-3) M produced inhibition of 50%. Line weaver-Burk: plots were used to investigate the inhibition of LPO activity by dipyrone. The inhibition by the drug was competitive with the iodide. We may conclude that dipyrone and other drugs of the pyrazolone group act upon peroxidase activity "in vitro", by an inhibition of competitive type and in presence of iodide.

Inhibitory action of dipyrone on rat thyroid peroxidase and lactoperoxidase activities.

Previous studies have shown that phenylbutazone, another pyrazolone, inhibits thyroid peroxidase activity and interferes with iodide organification. We have developed [quot ]in vitro[quot ] studies with rat particulated peroxidase and lactoperoxidase (LPO) to study the effects of dipyrone upon thyroid peroxidase and to determine the type of inhibition. The 3-monoiodothyrosine (MIT) and 3,5-diiodothyrosine (DIT) synthesis was markedly affected by 6 X 10(-4) M dipyrone with inhibitions of 59

and 30

respectively. No difference was observed with lower concentrations. Inhibition of peroxidase activity (Triiodide assay) was found when crude rat peroxidase preparations and LPO were incubated with dipyrone in concentrations ranging from 10(-3) M to 10(-8) M, with a Ki of 2.5 X 10(-5) M and 4 X 10(-5) M respectively. Guaiacol peroxidation was scarcely affected by the action of the drug; 10(-3) M produced inhibition of 50

. Line weaver-Burk: plots were used to investigate the inhibition of LPO activity by dipyrone. The inhibition by the drug was competitive with the iodide. We may conclude that dipyrone and other drugs of the pyrazolone group act upon peroxidase activity [quot ]in vitro[quot ], by an inhibition of competitive type and in presence of iodide.