Avaliação de NO2 na atmosfera de ambientes externos e internos na cidade de Araraquara, São Paulo

The seasonal behavior of NO2 concentration shows a maximum occurring during sugarcane crop and this suggests that the biomass burning is significant source of emission at this time of the year. Along the day, the variation of the NO2 showed a decrease during the increased sunlight and an increase thereafter, caused by occurrence of photochemical reactions. Measurements of NO2 were done inside of residential and industrial kitchens and also inside of a parking garage located in the underground of a supermarket building. The indoor concentrations of NO2 were significantly higher than the concentrations of the external atmosphere and it shows the importance of the sources of internal emissions.

Evaluación de la toxicidad de cobre en suelos a través de biomarcadores de estrés oxidativo en eisenia foetida

Copper toxicity in soil was evaluated using biomarkers of oxidative stress (catalase enzyme activity, superoxide dismutase and lipid peroxidation) in the earthworm Eisenia foetida. Agricultural topsoils from mining areas of the Aconcagua river basin were collected. Total copper concentrations were in the range of 94-959 mg kg-1, while the exchangeable copper concentrations were in the range of 46-2225 µg kg-1. Earthworms exposed to soil with exchangeable copper concentrations above 32 µg kg-1 showed an increase in catalase activity. Parameters of antioxidant activity were more sensitive than the weight change and thus can be used as appropriate biomarkers in Eisenia foetida.

Degradação de corantes reativos por processo foto-fenton envolvendo o uso de peneira molecular 4A modificada com Fe3+

In this work the preparation and characterization of a supported catalyst intended for degradation of reactive dyes by Fenton-like processes is described. The photocatalyst was prepared by immobilization of Fe3+ into the molecular sieve (4A type) surface and characterized by x-ray diffractometry and infrared, Mössbauer and EPR spectroscopy. The solid containing 0.94% (w/w) of ferric ions was used in degradation studies of aqueous reactive-dyes samples with really promissory results. Generally, Vis-assisted photochemical processes leads to almost total decolorization of all tested dyes at reaction times lower than 30 min. It was also observed that the iron-molecular sieve matrix can be reused.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Estudo da decomposição fotoquímica por exposição à luz UV de fotorresinas positivas

Positive photoresists are widely used in lithographic process in microelectronics and in optics for the fabrication of relief components. With the aim of identifying molecular modifications among positive photoresists unexposed and previously exposed to ultraviolet light the electron stimulated ion desorption technique coupled to time-of-flight mass spectrometry was employed in the study of the AZ-1518 photoresist. Mass spectra were obtained as a function of the electron beam energy, showing specific changes related to the photochemical decomposition of the photoresist. This reinforces the applicability of the technique to investigate and characterize structural changes in photosensitive materials.

Antioxidant activities of isolated compounds from stems of Mimosa invisa Mart. ex Colla

This work describes the phytochemical study of stems of Mimosa invisa (Mimosaceae) and the evaluation of the antioxidant potential of isolated compounds. Cromatografic techniques were employed to isolate salicifoliol, pinoresinol, quercetin, quercetin-3-O-rhamnopyranosyl, quercetin-3-O-arabinofuranosyl lupeol, β-amyrin, sitosterol, p-hydroxy coumaric acid, 4-hydroxy-3-methoxy benzaldehyde (vanillin), 4-hydroxy-3,5-dimethoxy benzaldehyde, 4-hydroxy-3-methoxy benzoic acid and 4',6,7- trimethoxy flavonol. The latter had been previously described but the spectrometric data shown indicated the structure required review. The antioxidant activity of the compounds was evaluated by the DPPH test and capability of NBT reduction by superoxide radicals. Quercetin glycosides showed lower antioxidant potential than quercetin and, salicifoliol was found to be more active than pinoresinol.

Processo UV/H2O2 como pós-tratamento para remoção de cor e polimento final em efluentes têxteis

Several problems are involved the treatment plants of textile effluents, mainly the low efficiency of color removal. This paper presents an alternative of post-treatment by UV/H2O2 process, for color removal in biologically treated textile effluents. The tests were performed in a photochemical reactor and samples were taken at different times to perform analyses. Using 250 mgH2O2.L-1, 96% removal of color was verified, indicating the dyes degradation. A reduction of 84% of aromatics compounds, 90% of TSS removal, and a further reduction of the organic fraction were observed, demonstrating that the process is effective as a post-treatment of effluents from textile industries.

Degradação de poluentes emergentes por processos Fenton e foto-Fenton

A continuous photochemical treatment system was developed for aiming the treatment of aqueous solutions containing relevant micro-pollutants (microcystin-LR, sulfamethoxazole and 17-b estradiol). The continuous photo-Fenton process provided high degradation efficiency. However, contact time between samples and the irradiated region is short relative to total treatment time, indicating that observed changes are predominantly due to the Fenton process. Higher degradation efficiency was observed in systems operated using two treatment cycles, the first involving a batch Fenton process and the second a continuous photo-Fenton treatment.

Um reator fotoquímico barato e eficiente para experimentos de química

In this work, we present an efficient and inexpensive device for undergraduate chemistry classes aimed at teaching and learning the photolytic synthesis concepts. A photochemical reactor was tested for the synthesis of the organometallic compound enneacarbonyldiiron from iron pentacarbonyl in acetic acid, and its formation evidenced by FTIR analysis. Although similar devices have been described in other studies, none of these offered the simplicity, low cost, class-compatible reaction times and good yields afforded by the procedure reported herein.

Aplicação da radiação ultravioleta como forma de contribuição para a química verde e construção de um reator fotoquímico alternativo e de baixo custo, para pré-tratamento de amostras

Ultraviolet radiation corresponds to a fraction of electromagnetic radiation, covering wavelengths between 1 and 400 nm. Methods based on UV irradiation have become popular because it is possible to treat samples simply by applying energy, avoiding procedures that require the use of toxic substances, thus contributing to the development of Green Chemistry. This study aimed to assess the main applications of UV radiation reported in the literature and thoroughly described the construction of an alternative and low-cost photochemical reactor to be used for the pretreatment of samples in the laboratory. The use of this new photochemical reactor in the clean-up of milk samples for spectrofluorimetric measurements was also reported.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Antioxidant and cytotoxic studies for kaempferol, quercetin and isoquercitrin

The aim of the present study was to investigate a cytotoxic oxidative cell stress related and the antioxidant profile of kaempferol, quercetin, and isoquercitrin. The flavonol compounds were able to act as scavengers of superoxide anion (but not hydrogen peroxide), hypochlorous acid, chloramine and nitric oxide. Although flavonoids are widely described as antioxidants and this activity is generally related to beneficial effects on human health, here we show important cytotoxic actions of three well known flavonoids. They were able to promote hemolysis which one was exacerbated on the presence of hypochlorous acid but not by AAPH radical. Therefore, despite they expected scavenger action over free radicals an oxidants, these compounds could be very lesive to living organisms by acting over erythrocytes and maybe other cellular types.

Chlorophyll fluorescence of tropical tree species in a semi-deciduous forest gap

The characterization of different ecological groups in a forest formation/succession is unclear. To better define the different successional classes, we have to consider ecophysiological aspects, such as the capacity to use or dissipate the light energy available. The main objective of this work was to assess the chlorophyll fluorescence emission of tropical tree species growing in a gap of a semi-deciduous forest. Three species of different ecological groups were selected: Croton floribundus Spreng. (pioneer, P), Astronium graveolens Jacq. (early secondary, Si), and Esenbeckia febrifuga A. Juss. (late secondary, St). The potential (Fv/Fm) and effective (deltaF/Fm') quantum efficiency of photosystem II, apparent electron transport rate (ETR), non-photochemical (qN) and photochemical (qP) quenching of fluorescence were evaluated, using a modulated fluorometer, between 7:30 and 11:00 h. Values of Fv/Fm remained constant in St, decreasing in P and Si after 9:30 h, indicating the occurrence of photoinhibition. Concerning the measurements taken under light conditions (deltaF/Fm', ETR, qP and qN), P and Si showed better photochemical performance, i.e., values of deltaF/Fm', ETR and qP were higher than St when light intensity was increased. Values of qN indicated that P and Si had an increasing tendency of dissipating the excess of energy absorbed by the leaf, whereas the opposite was found for St. The principal component analysis (PCA), considering all evaluated parameters, showed a clear distinction between St, P and Si, with P and Si being closer. The PCA results suggest that chlorophyll fluorescence may be a potential tool to differentiate tree species from distinct successional groups.

NADPH-Dependent Thioredoxin System In Regulation of Chloroplast Functions

Photosynthesis, the process in which carbon dioxide is converted into sugars using the energy of sunlight, is vital for heterotrophic life on Earth. In plants, photosynthesis takes place in specific organelles called chloroplasts. During chloroplast biogenesis, light is a prerequisite for the development of functional photosynthetic structures. In addition to photosynthesis, a number of other metabolic processes such as nitrogen assimilation, the biosynthesis of fatty acids, amino acids, vitamins, and hormones are localized to plant chloroplasts. The biosynthetic pathways in chloroplasts are tightly regulated, and especially the reduction/oxidation (redox) signals play important roles in controlling many developmental and metabolic processes in chloroplasts. Thioredoxins are universal regulatory proteins that mediate redox signals in chloroplasts. They are able to modify the structure and function of their target proteins by reduction of disulfide bonds. Oxidized thioredoxins are restored via the action of thioredoxin reductases. Two thioredoxin reductase systems exist in plant chloroplasts, the NADPHdependent thioredoxin reductase C (NTRC) and ferredoxin-thioredoxin reductase (FTR). The ferredoxin-thioredoxin system that is linked to photosynthetic light reactions is involved in light-activation of chloroplast proteins. NADPH can be produced via both the photosynthetic electron transfer reactions in light, and in darkness via the pentose phosphate pathway. These different pathways of NADPH production enable the regulation of diverse metabolic pathways in chloroplasts by the NADPH-dependent thioredoxin system. In this thesis, the role of NADPH-dependent thioredoxin system in the redox-control of chloroplast development and metabolism was studied by characterization of Arabidopsis thaliana T-DNA insertion lines of NTRC gene (ntrc) and by identification of chloroplast proteins regulated by NTRC. The ntrc plants showed the strongest visible phenotypes when grown under short 8-h photoperiod. This indicates that i) chloroplast NADPH-dependent thioredoxin system is non-redundant to ferredoxinthioredoxin system and that ii) NTRC particularly controls the chloroplast processes that are easily imbalanced in daily light/dark rhythms with short day and long night. I identified four processes and the redox-regulated proteins therein that are potentially regulated by NTRC; i) chloroplast development, ii) starch biosynthesis, iii) aromatic amino acid biosynthesis and iv) detoxification of H₂O₂. Such regulation can be achieved directly by modulating the redox state of intramolecular or intermolecular disulfide bridges of enzymes, or by protecting enzymes from oxidation in conjunction with 2-cysteine peroxiredoxins. This thesis work also demonstrated that the enzymatic antioxidant systems in chloroplasts, ascorbate peroxidases, superoxide dismutase and NTRC-dependent 2-cysteine peroxiredoxins are tightly linked up to prevent the detrimental accumulation of reactive oxygen species in plants.

Photosynthetic performance of mangroves Rhizophora mangle and Laguncularia racemosa under field conditions

In mature mangrove plants Rhizophora mangle L. and Laguncularia racemosa Gaerth. growing under field conditions, photosystem 2 (PS2) photochemical efficiency, determined by the ratio of variable to maximum fluorescence (Fν/Fm), increased during the day in response to salinity in the rainy seasons. During the dry season, fluorescence values (Fo) were higher than those observed in rainy season. In addition, Fo decreased during the day in both season and species, except for R. mangle during the dry season. A positive correlation among Fν/Fm and salinity values was obtained for R. mangle and L. Racemosa during the dry and rainy seasons, showing that photosynthetic performance is maintained in both species under high salinities. Carotenoid content was higher in L. Racemosa in both seasons, which represents an additional mechanism against damage to the photosynthetic machinery. The chlorophyll content was not affected by salinity in either species.