Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

Simultaneous degradation of atrazine and simazine by a binary culture of Stenotrophomonas maltophilia and Arthrobacter sp. in a two‐stage biofilm reactor

BACKGROUND: The impact of mixtures of chloro‐triazinic herbicides, such as atrazine and simazine, on aquatic ecosystems is of environmental concern. To study their biodegradation under various operational conditions, a binary community comprising Stenotrophomonas maltophilia and Arthrobacter sp. attached to the porous support of a packed bed reactor, was evaluated. RESULTS: The genetic analysis of the two atrazine‐degrading strains revealed that genes atzA, atzB, atzC are present in both bacteria, but only S. maltophilia possess atzD. Thus, by cultivating Arthrobacter sp. on these herbicides, cyanuric acid accumulation was observed. When the binary community was cultivated in the biofilm reactor, at all the loading rates probed, both herbicides were entirely removed. However, complete biodegradation of cyanuric acid was not achieved. CONCLUSIONS: Even with a two‐stage reactor, cyanuric acid was only partially removed. This fact could be attributed to the absence, in the second stage, of an easily degradable energy source, required by S. maltophilia for the uptake and cometabolic degradation of the recalcitrant heterocyclic ring. Responding to differences in nutritional conditions prevailing at each reactor stage, local differences in species' predominance were clearly detected by microbiological and molecular biology methods. Copyright © 2010 Society of Chemical Industry     

Progress in the design of zeolite catalysts for biomass conversion into biofuels and bio-based chemicals

This article reviews the recent advances in the development of zeolite catalysts for biomass valorization processes to produce both biofuels and/or bio-based chemicals, which is an emerging and fast expanding field. The work deals with different types of feedstocks, including vegetable oils, lignocellulose and sugars, as well as with a number of relevant intermediates and platform molecules. Transformation of biomass into valuable products is hindered by a number of factors, mainly related to its complex composition, as biomass typically consists of bulky molecules with high oxygen content. Accordingly, biomass processing usually requires the combination of multiple steps and severe conditions, hence concepts like atom efficiency, product selectivity, and catalyst deactivation become of special relevance. A great progress has been achieved in the past years engineering the properties of zeolites for being adapted to the challenges associated to biomass valorization. The possibility of tailoring the main physicochemical properties of zeolites has become now a reality, being the major reason that explains the success achieved by this class of materials in a growing variety of biomass conversion pathways, as those described in this work: catalytic cracking and pyrolysis, hydrotreatments, with special relevance for hydrodeoxygenation processes, as well as in a high number of condensation, isomerization, and dehydration reactions. Thus, the development of hierarchical zeolites, exhibiting enhanced accessibility, and the possibility of introducing and combining in a controlled way different types of active sites (Brønsted and Lewis acid centers, basic sites, and metal phases) are the main basis of the excellent performance of zeolites in numerous biomass conversion routes.     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Electrochemical behavior of multifunctional graphene–polyimide nanocomposite film in two different electrolyte solutions

The effect of solvent on specific capacitance, bulk resistance, and charge/discharge capacity of graphene/polyimide composite films is studied by electrochemical methods. Composite films are synthesized by in situ condensation polymerization of poly (amic acid) in the presence of 50 wt % partly exfoliated graphene sheets followed by thermal curing at 250°C. Raman spectrum of the exfoliated graphene sheets show an increase in the ratio of I_D to I_G peak intensities from 0.167 to 0.222, suggesting increased defects in graphene basal planes. Electrochemical measurements carried out by using 0.4M potassium hexafluorophosphate (KPF₆) dissolved in propylene carbonate and N‐methylpyrrolidone at 25°C show that the composite system exhibits both pseudocapacitance and supercapacitance behaviors, with an average capacitance of 40 and 36.5 F g^?1, respectively. Bulk resistance of the composite obtained by using KPF₆–propylene carbonate electrolyte solution is 300% lower than that obtained in KPF₆–N‐methylpyrrolidone solution, with a fairly stable specific capacity of 85 μAhr g^?1, with 80% retention observed after 30 charge–discharge cycles. Fourier transform infrared spectroscopy measurements show shifts in the cyclic imide carbonyl peak from 1778 to 1774 cm^?1, which suggests that some form of interaction exists between the graphene and polyimide. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42673.     

Elastic Properties and Microcracking Behavior of Particulate Titanium Diboride–Silicon Carbide Composites

The spontaneous microcracking of particulate TiB₂–SiC composites is studied as a function of TiB₂ volume fraction. The degree of microcracking was examined by measuring elastic properties from room temperature to 1300°C. The results showed that only one composition contains microcracks. All other compositions did not microcrack regardless of TiB₂ volume fraction. This was attributed to the difference in the sintering aids. In particular, the Al₂O₃ sintering aid needed in these compositions had reacted with SiO₂ to form an amorphous grain boundary phase that allowed residual stresses to relax by viscous flow at moderate to high temperatures. The existence of this amorphous grain boundary phase was directly observed by transmission electron microscopy.     

Synthesis of Nickel Phosphide Nanorods as Catalyst for the Hydrotreating of Methyl Oleate

Arrays of nickel phosphide nanorods were successfully synthesized by nanocasting using mesostructured silica SBA-15 as a hard template (HT-Ni₂P). After temperature-programmed reduction of the phosphate precursor infiltrated within the pore walls of SBA-15, the unsupported material was obtained by removing the silica matrix with diluted HF. The pore channel of the SBA-15 template stabilizes the Ni₂P particles, preventing sintering after the high reduction temperature and shaping their elongated morphology. Moreover, HT-Ni₂P catalyst shows an improvement in the textural properties with a significantly higher surface area than the reference sample synthesized in the absence of template. X-ray diffraction revealed that the only crystalline phase present in this material was Ni₂P. On the other hand, transmission electron microscopy shows that the catalyst is mainly constituted by agglomerates of nanorods. Through EDX microanalysis the efficient removal of silicon was confirmed. Under hydrotreating conditions, nanorods of Ni₂P show a fourfold enhancement in the conversion of methyl oleate with respect to conventional Ni₂P synthesized in absence of hard template. Nevertheless, when these data are normalized to surface area, the specific activity of HT-Ni₂P nanorods is significantly lower than that of the conventionally prepared sample. Differences in selectivity were also observed as Ni₂P nanorods favored the decarboxylation reaction leading to a higher yield of n-heptadecane.     

A DNA Methyltransferase Modulator Inspired by Peyssonenyne Natural Product Structures

A novel epigenetic modulator that displays a DNMT1 inhibition and DNMT3A activation profile was characterized (compound 8 ). This compound is a derivative of palmitic acid that incorporates the putative reactive functional group (diynone) of the peyssonenyne natural products. Other analogues containing the diynone or an acetoxyenediyne did not show the same biological profile. In U937 human leukemia cells, diynone 8 induced cell differentiation and apoptosis, which correlated with the expression of Fas protein. Very surprisingly, diynone 8 was toxic to normal human fibroblasts (BJ) and mouse embryo fibroblasts (MEF), but not to immortalized human fibroblasts (BJEL); this unique effect was not observed with the classical DNMT inhibitor 5‐azacytidine. Therefore, compound 8 interferes in a very specific manner with signaling pathways, the activities of which differ between normal and immortalized cell types. This toxicity is reminiscent of the effects of Dnmt1 ablation on mouse fibroblasts. In fact, some of the genes deregulated by the loss of Dnmt1 are similarly deregulated by 8 , but not by the DNMT inhibitor SGI‐1027.