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The contamination of water bodies by synthetic organic compounds coupled with climate change and the growing demand for water supply calls for new approaches to water management and treatment. To tackle the decontamination issue, the activation of peroxymonosulfate (PMS) using copper magnetic ferrite (CuMF) nanoparticles prepared under distinct synthesis conditions was assessed to oxidize imidacloprid (IMD) insecticide. After optimization of some operational variables, such as CuMF load (62.5-250 mg L-1), PMS concentration (250-1000 µM), and solution pH (3-10), IMD was completely oxidized in 2 h without interferences from leached metal ions. Such performance was also achieved when using tap water but was inhibited by a simulated municipal wastewater due to scavenging effects promoted by inorganic and organic species. Although there was evidence of the presence of sulfate radicals and singlet oxygen oxidizing species, only four intermediate compounds were detected by liquid chromatography coupled to mass spectrometry analysis, mainly due to hydroxyl addition reactions. Concerning the changes in surface properties of CuMF after use, no morphological or structural changes were observed except a small increase in the charge transfer resistance. Based on the changes of terminal surface groups, PMS activation occurred on Fe sites.

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Nanometric cobalt magnetic ferrite (CoFe2O4) synthesized by distinct methods was used for in situ chemical activation of peroxymonosulfate (PMS) under neutral conditions to oxidize imidacloprid (IMD) insecticide. The effect of CoFe2O4 load (0.125-1.0 g L-1) and PMS concentration (250-1000 µM) was investigated as well as the influence of phosphate buffer and Co(II) ions. PMS activation by Co(II) ions, including those leached from CoFe2O4 (>50 µg L-1), exhibited a strong influence on IMD oxidation and, apparently, without substantial contributions from the solid phase. Within the prepared solid materials (i.e., using sol-gel and co-precipitation methods), high oxidation rates (ca. 0.5 min-1) of IMD were attained in ultrapure water. Phosphate buffer had no significant influence on the IMD oxidation rate and level, however, its use and solution pH have shown to be important parameters, since higher PMS consumption was observed in the presence of buffered solutions at pH 7. IMD byproducts resulting from hydroxylation reactions and rupture of the imidazolidine ring were detected by mass spectrometry. At optimum conditions (0.125 g L-1 of CoFe2O4 and 500 µM of PMS), the CoFe2O4 nanoparticles exhibited an increase in the charge transfer resistance and an enhancement in the surface hydroxylation after PMS activation, which led to radical (HO● and SO4●-) and nonradical (1O2) species. The latter specie led to high levels of IMD oxidation, even in a complex water matrix, such as simulated municipal wastewater at the expense of one-order decrease in the IMD oxidation rate.

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BACKGROUND: Accumulated evidence demonstrates cisplatin, a recommended chemotherapy, modulating pro-survival autophagic response that contributes to treatment failure in lung cancer patients. However, distinct mechanisms involved in cisplatin-induced autophagy in human lung cancer cells are still unclear. RESULTS: Herein, role of autophagy in cisplatin resistance was indicated by a decreased cell viability and increased apoptosis in lung cancer H460 cells pre-incubated with wortmannin, an autophagy inhibitor, prior to treatment with 50 µM cisplatin for 24 h. The elevated level of hydroxyl radicals detected via flow-cytometry corresponded to autophagic response, as evidenced by the formation of autophagosomes and autolysosomes in cisplatin-treated cells. Interestingly, apoptosis resistance, autophagosome formation, and the alteration of the autophagic markers, LC3-II/LC3-I and p62, as well as autophagy-regulating proteins Atg7 and Atg3, induced by cisplatin was abrogated by pretreatment of H460 cells with deferoxamine, a specific hydroxyl radical scavenger. The modulations in autophagic response were also indicated in the cells treated with hydroxyl radicals generated via Fenton reaction, and likewise inhibited by pretreatment with deferoxamine. CONCLUSIONS: In summary, the possible role of hydroxyl radicals as a key mediator in the autophagic response to cisplatin treatment, which was firstly revealed in this study would benefit for the further development of novel therapies for lung cancer.

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BACKGROUND: Accumulated evidence demonstrates cisplatin, a recommended chemotherapy, modulating pro-survival autophagic response that contributes to treatment failure in lung cancer patients. However, distinct mechanisms involved in cisplatin-induced autophagy in human lung cancer cells are still unclear. RESULTS: Herein, role of autophagy in cisplatin resistance was indicated by a decreased cell viability and increased apoptosis in lung cancer H460 cells pre-incubated with wortmannin, an autophagy inhibitor, prior to treatment with 50 µM cisplatin for 24 h. The elevated level of hydroxyl radicals detected via flow-cytometry corresponded to autophagic response, as evidenced by the formation of autophagosomes and autolysosomes in cisplatin-treated cells. Interestingly, apoptosis resistance, autophagosome formation, and the alteration of the autophagic markers, LC3-II/LC3-I and p62, as well as autophagy-regulating proteins Atg7 and Atg3, induced by cisplatin was abrogated by pretreatment of H460 cells with deferoxamine, a specific hydroxyl radical scavenger. The modulations in autophagic response were also indicated in the cells treated with hydroxyl radicals generated via Fenton reaction, and likewise inhibited by pretreatment with deferoxamine. CONCLUSIONS: In summary, the possible role of hydroxyl radicals as a key mediator in the autophagic response to cisplatin treatment, which was firstly revealed in this study would benefit for the further development of novel therapies for lung cancer.

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The carbamazepine (CBZ) abatement is herein evaluated using catalytic ozonation at different NiO concentrations as catalyst: 100, 300, and 500 mg L-1, revealing its total destruction after 5 min of reaction either by conventional or catalytic ozonation. The NiO incorporation in the reactor does not increase the destruction rate, but the catalyst presence enhances the partial mineralization of the contaminant by conversion into oxalic and formic acids and the removal of total organic carbon (TOC) associated with the formation of oxidant species such as hydroxyl radical. Evidence for this behavior is the accumulation rate of the above acids which rise proportionally to the NiO concentration. The highest NiO concentration (500 mg L-1) reached a maximum TOC removal of 79.2%, which exceeds by 50% the outcome of the conventional treatment. The accumulation-decomposition profiles of oxalic and formic acids suggest the occurrence of simultaneous reaction mechanisms (hydroxyl radicals and complex formations) on the catalyst during CBZ ozonation. According to XPS analysis, the presence of nitrogen species in the NiO-ozonated was attributable to byproducts of CBZ decomposition. The toxicity bioassay based on Lactuca sativa seeds demonstrate that ozonated samples attained similar plant germination than the reference substance (water) after 120 min of treatment. This result is comparable with or without the catalyst presence, indicating the formation of non-toxic accumulated byproducts at the end of the ozonation reaction.

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The rate coefficient for the reaction CH3 OH+OH was determined by means of a relative method in a simulation chamber under quasi-real atmospheric conditions (294 K, 1 atm of air) and variable humidity or water concentration. Under these conditions, a quadratic dependence of the rate coefficient for the reaction CH3 OH+OH on the water concentration was found. Thus the catalytic effect of water is not only important at low temperatures, but also at room temperature. The detailed mechanism responsible of the reaction acceleration is still unknown. However, this dependence should be included in the atmospheric global models since it is expected to be important in humid regions as in the tropics. Additionally, it could explain several differences regarding the global and local atmospheric concentration of methanol in tropical areas, for which many speculations about the sinks and sources of methanol have been reported.

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Hospitals consume a large volume of water to carry out their activities and, hence, generate a large volume of effluent that is commonly discharged into the local sewage system without any treatment. Among the various sectors of healthcare facilities, the laundry is responsible for the majority of water consumption and generates a highly complex effluent. Although several advanced oxidation processes (AOPs) are currently under investigation on the degradation of a variety of contaminants, few of them are based on real wastewater samples. In this paper, the UV/H2O2 AOP was evaluated on the treatment of a hospital laundry wastewater, after the application of a physicochemical pretreatment composed of coagulation-flocculation and anthracite filtration. For the UV/H2O2 process, a photoreactor equipped with a low-pressure UV-C lamp was used and the effects of initial pH and [H2O2]/chemical oxygen demand (COD) ratio on COD removal were investigated through a randomized factorial block design that considered the batches of effluent as blocks. The results indicated that the initial pH had no significant effect on the COD removal, and the process was favored by the increase in [H2O2]/COD ratio. Color and turbidity were satisfactorily reduced after the application of the physicochemical pretreatment, and COD was completely removed by the UV/H2O2 process under suitable conditions. The results of this study show that the UV/H2O2 AOP is a promising candidate for hospital laundry wastewater treatment and should be explored to enable wastewater reuse in the washing process.

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The main objective of this study was to investigate the optimum conditions for the Fenton-like process on phenol degradation, using Mn(2+) as a supporting catalyst in the Fenton reaction. The effect of the independent factors [H2O2], [Fe(2+)], [Mn(2+)] and t (reaction time) was evaluated on the efficiency of phenol degradation at two pHs (3 and 5). The experimental arrangement adopted was the Box-Behnken delineation, with the phenol concentration after the treatments suggested as response variable. At less acidic pH (5), regardless of [Mn(2+)], it was observed that the conventional Fenton process was the most efficient alternative, considering the optimum condition: 2.65 mmol L(-1) for [H2O2], 0.36 mmol L(-1) for [Fe(2+)], and 90 min for t. It was observed that the addition of Mn(2+) helped the phenol degradation at more acidic pH (3), obtaining the optimum condition: 6.17 mmol L(-1) for [H2O2], 0.36 mmol L(-1) for [Fe(2+)], 1.09 mmol L(-1) for [Mn(2+)], and 90 min for t.

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The Cr(VI) reducing capability of growing cells of the environmental A. tubingensis Ed8 strain is remarkably efficient compared to reference strains A. niger FGSC322 and A. tubingensis NRRL593. Extracellular glucose oxidase (GOX) activity levels were clearly higher in colonies developed in solid medium and in concentrated extracts of the spent medium of liquid cultures of the Ed8 strain in comparison with the reference strains. In addition, concentrated extracts of the spent medium of A. tubingensis Ed8, but not those of the reference strains, exhibited the ability to reduce Cr(VI). In line with this observation, it was found that A. niger purified GOX is capable of mediating the conversion of Cr(VI) to Cr(III) in a reaction dependent on the presence of glucose that is stimulated by organic acids. Furthermore, it was found that a decrease in Cr(VI) may occur in the absence of the GOX enzyme, as long as the reaction products gluconolactone and hydrogen peroxide are present; this conversion of Cr(VI) is stimulated by organic acids in a reaction that generates hydroxyl radicals, which may involve the formation of an intermediate peroxichromate(V) complex. These findings indicated that fungal glucose oxidase acts an indirect chromate reductase through the formation of Cr(VI) reducing molecules, which interact cooperatively with other fungal metabolites in the biotransformation of Cr(VI).

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Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals (OH) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by OH radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation.

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Identification of metabolic targets of environmental stress factors is critical to improve the stress tolerance of plants. Studying the biochemical and physiological responses of plants with different capacities to deal with stress is a valid approach to reach this objective. Lotus corniculatus (lotus) and Trifolium pratense (clover) are legumes with contrasting summer stress tolerances. In stress conditions, which are defined as drought, heat or a combination of both, we found that differential biochemical responses of leaves explain these behaviours. Lotus and clover showed differences in water loss control, proline accumulation and antioxidant enzymatic capacity. Drought and/or heat stress induced a large accumulation of proline in the tolerant species (lotus), whereas heat stress did not cause proline accumulation in the sensitive species (clover). In lotus, Mn-SOD and Fe-SOD were induced by drought, but in clover, the SOD-isoform profile was not affected by stress. Moreover, lotus has more SOD-isoforms and a higher total SOD activity than clover. The functionality and electrophoretic profile of photosystem II (PSII) proteins under stress also exhibited differences between the two species. In lotus, PSII activity was drastically affected by combined stress and, interestingly, was correlated with D2 protein degradation. Possible implications of this event as an adaption mechanism in tolerant species are discussed. We conclude that the stress-tolerant capability of lotus is related to its ability to respond to oxidative damage and adaption of the photosynthetic machinery. This reveals that these two aspects should be included in the evaluation of the tolerance of species to stress conditions.

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Al extracto acuoso de la corteza de Rhizophora mangle L se le ha demostrado un amplio espectro de usos medicinales: en el tratamiento de la mastitis bovina, la curación de heridas,las infecciones uterinas y las úlceras gastroduodenales; debido a sus propiedades antiséptica, cicatrizante, antiinflamatoria y antioxidante. Sin embargo, no se han completado los estudios de la actividad antioxidante a todos los niveles de complejidad para dilucidar los mecanismos de acción involucrados en este efecto farmacológico. Objetivo: determinar si el extracto acuoso de R. mangle y su fracción polifenólica protegen a las principales biomoléculas del daño oxidativo. La evaluación de la actividad antioxidante del extracto de R mangle y su fracción polifenólica sobre las principales biomoléculas se determinó mediante ensayo de daño oxidativo a la albúmina de suero bovino expuesta a los radicales hidroxilo generados en el sistema Fenton y ensayo de degradación oxidativa del ADN inducido por el sistema bleomicina-Fe3+.El extracto de R. mangle y su fracción polifenólica, a la máxima concentración ensayada, disminuyeron la oxidación de los grupos sulfidrilos en 87,3 y 89,1 por ciento; e inhibieron la degradación del ADN en 98,4 y 91,9 por ciento, respectivamente. El análisis de regresión mostró que ambos efectos fueron dependientes de la concentración de taninos en el extracto y su fracción. La comparación de las líneas de regresión reveló que el extracto y su fracción resultaron igualmente eficaces en proteger a la albúmina de suero bovino de la oxidación por los radicales hidroxilos, sin embargo, el extracto fue más eficaz en proteger al ADN de la degradación oxidativa que su fracción. El extracto acuoso de R. mangle mostró un efecto protector a las principales biomoléculas del daño oxidativo, evidenciado por la inhibición de la pérdida de grupos sulfidrilos en la albúmina de suero bovino y la disminución de la degradación del ADN...

The aqueous extract from Rhizophora mangle (L) bark has demonstrated a broad spectrum of medicinal uses; for example, in treating bovine mastitis, wound healing, uterine infections and gastroduodenal ulcers, due to its antiseptic, healing, anti-inflammatory and antioxidant properties. However, the antioxidant activity in its whole complexity has not been fully studied in order to elucidate the mechanisms of action involved in this pharmacological effect. Objective: to determine if R. mangle bark aqueous extract and its polyphenolic fraction protect the main biomolecules from oxidative damage. The antioxidant activity of R. mangle extract and its polyphenolic fraction on the main biomolecules was determined by the following methods: oxidative damage trial on bovine serum albumin exposed to hydroxyl radicals generated in the Fenton system and the bleomycin-Fe3+ system-induced DNA oxidative degradation trial. Results: the R. mangle bark extract and its polyphenolic fraction, at the highest tested concentration, reduced the sulfhydryl group oxidation by 87,3 percent and 89,1 percent and they also inhibited the DNA degradation by 98.4 percent and 91.9 percent respectively. The regression analysis demonstrated that both effects depended on tannin concentration in the extract and its fraction. The comparison of regression lines revealed that the extract and its fraction were equally effective in protecting bovine serum albumin from oxidation by hydroxyl radicals; however, the extract was more effective when protecting DNA from oxidative degradation than its fraction. The R mangle aqueous extract showed a protective effect on the main biomolecules from the oxidative damage, evidenced by inhibiting loss of sulfhydryl group in bovine serum albumin and decreasing the DNA degradation. At the same time, it was shown that polyphenolic compounds present in the extract were the main responsible for the antioxidant effects observed in this study

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