Nanoparticulate Double-Heterojunction Photocatalysts Comprising TiO2(Anatase)/WO3/TiO2(Rutile) with Enhanced Photocatalytic Activity toward the Degradation of Methyl Orange under Near-Ultraviolet and Visible Light.

Nanoparticulate double-heterojunction photocatalysts comprising TiO2(Anatase)/WO3/TiO2(Rutile) were produced by a sol-gel method. The resulting photocatalysts exhibit clear synergistic effects when tested toward the degradation of methyl orange under both UV and visible light. Kinetic studies indicate that the degradation rate on the best double-heterojunction photocatalyst (10 wt % WO3-TiO2) depends mainly on the amount of dye concentration, contrary to pure oxides in which the degradation rate is limited by diffusion-controlled processes. The synergistic effects were confirmed through systematic and careful studies including holes and OH radical formation, X-ray diffraction, electron microscopy, elemental analysis, UV-vis diffuse reflectance spectroscopy, and surface area analysis. Our results indicate that the successful formation of a double heterojunction in the TiO2(Anatase)/WO3/TiO2(Rutile) system leads to enhanced photoactivity when compared to individual oxides and commercial TiO2 P25.

Green and facile sol-gel synthesis of the mesoporous SiO2-TiO2 catalyst by four different activation modes.

The most environmentally friendly protocol for obtaining mesoporous SiO2-TiO2 catalysts has been sought. Water has been employed as a green solvent, the energy input has been minimized, and three further principles (1, 3, and 12) of Green Chemistry have been considered. Four different modes for promoting the reaction have been comparatively evaluated, namely near-infrared and microwave electromagnetic irradiations, ultrasound, and traditional mantle heating. Brunauer-Emmett-Teller (BET) analyses of the catalysts produced revealed that the non-conventional activation modes afforded both large surface areas (335-441 m2 g-1) and smaller crystal sizes (7.2-15.3 nm) than the mantle heating process. These modes also generated the catalysts in shorter reaction times than traditional mantle heating, 10-30 min versus 3 h, with anatase as the sole crystalline phase. The photocatalytic degradation of 4-chlorophenol has been carried out to assess the catalytic efficiencies of the hybrid materials. The catalyst synthesized with microwave assistance showed the best mineralization activity (97%), followed by those prepared with ultrasound, near-infrared, and mantle heating. The materials have been extensively characterized by FTIR, XRD, DRS-UV/Vis, SEM, 29Si MAS NMR, and BET analyses. To the best of our knowledge, this is the first such comparative assessment of green energetic alternatives in developing a sol-gel process.

Oregano (Lippia graveolens) essential oil added within pectin edible coatings prevents fungal decay and increases the antioxidant capacity of treated tomatoes.

BACKGROUND: Tomato is a fruit widely consumed due to its flavor and nutritional value; however, it is susceptible to fungi contamination. Oregano essential oil (OEO) is a fungicide whose constituents are volatile; therefore, their incorporation within edible coatings can protect them and maintain their efficacy. In this context, this study evaluated the effect of OEO applied within pectin coatings on the inhibition of Alternaria alternata growth, antioxidant content and sensorial acceptability of tomatoes. RESULTS: The major volatile compounds of OEO were carvacrol (47.41%), p-cymene (26.44%) and thymol (3.02%). All the applied OEO concentrations (15.7, 25.9 and 36.1 g L(-1) ) inhibited the in vitro growth of A. alternata, whereas the in vivo effective concentrations were 25.9 and 36.1 g L(-1) . Additionally, there was an increment of total phenols and antioxidant activity in coated tomatoes compared to controls. Aroma acceptability of tomatoes was not affected by the pectin-OEO coating; additionally, the pectin, pectin-OEO 15.7 g L(-1) treatments and control tomatoes showed higher flavor acceptability than those coated with pectin-OEO 25.9 and 36.1 g L(-1) . CONCLUSION: Pectin-OEO coatings showed antifungal effect and increased the antioxidant activity without negative effects on the sensorial acceptability of tomatoes. © 2015 Society of Chemical Industry.

Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds.

Photodegradation of indigo carmine and methylene blue dyes in aqueous solution by SiC-TiO2 catalysts prepared by sol-gel.

Indigo carmine and methylene blue dyes in aqueous solution were photodegraded using SiC-TiO(2) catalysts prepared by sol-gel method. After thermal treatment at 450°C, SiC-TiO(2) catalysts prepared in this work showed the presence of SiC and TiO(2) anatase phase. Those compounds showed specific surface area values around 22-25 m(2)g(-1), and energy band gap values close to 3.05 eV. In comparison with TiO(2) (P25), SiC-TiO(2) catalysts showed the highest activity for indigo carmine and methylene blue degradation, but this activity cannot be attributed to the properties above mentioned. Therefore, photocatalytic performance is due to the synergy effect between SiC and TiO(2) particles caused by the sol-gel method used to prepare the SiC-TiO(2) catalysts. TiO(2) nanoparticles are well dispersed onto SiC surface allowing the transfer of electronic charges between SiC and TiO(2) semiconductors, which avoid the fast recombination of the electron-hole pair during the photocatalytic process.

Polar fractionation affects the antioxidant properties of methanolic extracts from species of genus Phellinus quel. (higher Basidiomycetes).

The main objective of this study was to evaluate the antioxidant capacity of methanolic extracts from species of genus Phellinus: Ph. fastuosus, Ph. grenadensis, Ph. Merrillii, and Ph. Badius, in their respective polar fractions (aqueous) and nonpolar extracts (ethyl acetate), through tests of free-radical inactivation and hemolysis inhibition. The fungus species that gave the extract with the highest phenol content, total flavonoids, and antioxidant capacity [DPPH·, Trolox equivalents antioxidant capacity (TEAC), and hemolysis inhibition] was Ph. Merrillii, followed by Ph. fastuosus, Ph. Grenadensis, and Ph. Badius. The antioxidant capacities of the extracts, in descending order, were as follows: Ph. Merrillii (nonpolar), Ph. Fastuosus (nonpolar), Ph. Grenadensis (nonpolar), Ph. Fastuosus (polar), Ph. Merrillii (polar), Ph. Grenadensis (polar), Ph. Badius (nonpolar), and Ph. Badius (polar). Antioxidant capacity in the above Phellinus fungi species had EC50 values for DPPH inhibition of 0.45, 0.88, 1.31, 1.89, 2.14, 2.22, 3.42, and 6.00 mg/mL, respectively; TEAC values of 10400.29, 7635.53, 4855.05, 4415.39, 4041.68, 2989.2, 1937.7, and 842.42 µmol TE/g, respectively; and hemolysis inhibition values of 72.83, 66.95, 50.87, 50.28, 48.5, 42.82, 42.37, and 37.91%, respectively. In general, the fungus extract with the highest antioxidant capacity was the nonpolar fraction of Ph. Merrillii. The Phellinus species studied represent potential natural sources of bioactive compounds with antioxidant activity.

Antisense suppression of a beta-galactosidase gene (TB G6) in tomato increases fruit cracking.

Antisense suppression of a tomato beta-galactosidase gene (TBG6) was used to study its role in fruit development, cell wall-modification, and fruit firmness. TBG6 mRNA is highly abundant during the early stages of fruit development, but the levels decline sharply after the breaker stage with the start of the respiratory climacteric and a concomitant increase in ethylene production. Two antisense lines were obtained with significantly reduced levels of TBG6 mRNA at all stages of fruit development. At 30 d after pollination (dap), TBG6 mRNA levels were reduced by up to 98% and 88% in lines 6-2 and 6-10, respectively. Morphological phenotypes observed in the antisense lines included increased fruit cracking, reduced locular space, and a doubling in the thickness of the fruit cuticle. Two biochemical changes in antisense lines, compared with wild-type lines, were a reduction of exo-galactanase activity at the breaker +3 d stage and a reduction in the cell wall galactosyl content at the 20 dap stage. In addition, transgenic lines exhibited a 35-39% reduction in fruit firmness at the 20 dap stage, but their texture was equivalent to the wild type at 30 dap and beyond. Although the exact function of the TBG6 product is still unknown, these results implicate an important role for this enzyme in early fruit growth and development in tomato.

Indole acetic acid distribution coincides with vascular differentiation pattern during Arabidopsis leaf ontogeny.

We used an anti-indole acetic acid (IAA or auxin) monoclonal antibody-based immunocytochemical procedure to monitor IAA level in Arabidopsis tissues. Using immunocytochemistry and the IAA-driven beta-glucuronidase (GUS) activity of Aux/IAA promoter::GUS constructs to detect IAA distribution, we investigated the role of polar auxin transport in vascular differentiation during leaf development in Arabidopsis. We found that shoot apical cells contain high levels of IAA and that IAA decreases as leaf primordia expand. However, seedlings grown in the presence of IAA transport inhibitors showed very low IAA signal in the shoot apical meristem (SAM) and the youngest pair of leaf primordia. Older leaf primordia accumulate IAA in the leaf tip in the presence or absence of IAA transport inhibition. We propose that the IAA in the SAM and the youngest pair of leaf primordia is transported from outside sources, perhaps the cotyledons, which accumulate more IAA in the presence than in the absence of transport inhibition. The temporal and spatial pattern of IAA localization in the shoot apex indicates a change in IAA source during leaf ontogeny that would influence flow direction and, consequently, the direction of vascular differentiation. The IAA production and transport pattern suggested by our results could explain the venation pattern, and the vascular hypertrophy caused by IAA transport inhibition. An outside IAA source for the SAM supports the notion that IAA transport and procambium differentiation dictate phyllotaxy and organogenesis.