Avaliação da fotodegradação de poliolefinas através de exposição natural e artificial

Samples of polypropylene (PP) and low-density polyethylene (LDPE) were submitted to ultraviolet radiation, in the natural environment and also in the laboratory. Chemical modifications were quantified by the carbonyl index (CI), mechanical properties and melt flow index. The degradation in the laboratory was comparatively faster than in the environment for both types of polymers. The accelerating factor was determined for the various properties investigated. This parameter, however, showed a large variation with the degradation criteria and the type of polymer. The existence of a "universal accelerating factor", therefore, was not observed in the current study.

Digestão de óleo lubrificante encapsulado em forno de microondas com radiação focalizada por adição de amostra ao reagente pré-aquecido

The applicability of the recently proposed procedure based on gradual sample addition to microwave-assisted pre-heated concentrated acid is limited by the sample viscosity. In this work, lubricating oil samples with high viscosity were encapsulated and manually added to the microwave-assisted pre-heated concentrated digestion mixture. The procedure was applied for determination of Al, Ca, Cr, Cu, Fe, Mg, Ni, P, Pb, Si, Sn, Sr, V, W, and Zn in lubricating oil by inductively coupled plasma optical emission spectrometry (ICP OES). Determined and certified values for Ca, Mg, P, and Zn in lubricating oil were in agreement at a 95% confidence level.

De Svante Arrhenius ao peagâmetro digital: 100 anos de medida de acidez

This work describes the establishment of the concept of pH and the evolution of its measurement. The origin of the pH definition can be found in the development of the chemistry of aqueous solutions during the XIXth century. The electrolytic dissociation theory by Svante Arrhenius played a central role. After the proposal of the pH scale by Sörensen, many years were necessary for the acceptance of this new parameter among chemists in general. Its importance was first recognized in biochemistry and related areas. Twenty years after, its importance had been recognized in many industrial and laboratorial practices. The previous methods were based on colorimetric and electrometric methods, but both suffered from many problems. Acceptance of pH in Chemistry was only possible after the development of experimental trustable measurements. The invention of the pH meter was the primordial step.

Aplicação de radiação UV artificial e solar no tratamento fotocatalítico de efluentes de curtume

Tannery effluents are very dangerous for the environment since they contain large amounts of dangerous and biorecalcitrant contaminants (organic matter and Cr(VI)). This paper reports the efficiency of heterogeneous photocatalysis, based on the application of solar and artificial radiation, furnished by UV lamps, using TiO2 fixed on a flat plate, in the treatment of synthetic effluents. The results of COD and Cr(VI) demonstrate that the use of solar radiation is the most efficient way to perform the photocatalytic treatment of these effluents since a minimum removal of 62 and 61% was observed for Cr(VI) and organic matter, respectively.

Determinação voltamétrica de metais em águas e fluidos biológicos empregando mineralização de amostras com radiação ultravioleta

This work describes the optimization of pretreatment steps for the destruction of organic matter in samples of waters and biological fluids, by using an UV irradiation system with a high power UV radiation source (400 W). The efficiency of the system constructed for the photo-decomposition of samples of model waters, natural waters and biological fluids was investigated by performing recovery experiments of the metallic species Zn(II), Cd(II), Pb(II), Cu(II), Al(III) and Fe(III). The use of UV irradiation allowed the liberation of metals bound to the organic matrix and the determination of the total content of elements in the samples.

Quantificação simultânea de indicadores biológicos de exposição a solventes orgânicos por cromatografia líquida de alta eficiência

Biological monitoring is very important to guarantee health to workers. This method was developed for simultaneous determination of xylene, toluene, styrene and ethylbenzene metabolites. It involves only dilution and centrifugation of urine samples and improved chromatographic conditions. Analyses show recovery > 95%; r² > 0.99; intermediate precision CV% < 6% and % bias < ±10. Exposed subjects presented at least three metabolites in urine. The method proved to be feasible, reliable and important in biological monitoring, especially in exposure to organic solvent mixtures.

Determinação simultânea de creatinina e indicadores biológicos de exposição ao tolueno, estireno e xilenos em urina por cromatografia líquida de alta eficiência

A simple liquid chromatographic method for the simultaneous determination of creatinine, hippuric acid, mandelic acid, phenylglyoxylic acid and o, m and p-methylhippuric acids was developed and validated. Sample preparation was only dilution with water (1:10), followed by centrifugation. Analysis was performed in a reversed phase column (Lichrospher RP 8ec), 250 x 4.0 mm, with isocratic elution with phosphate buffer pH 2.3 and acetonitrile (90:10, v/v). The method presents adequate linearity, precision and accuracy and allows the simultaneous determination of the biomarkers of exposure to toluene, xylene and styrene together with creatinine, reducing cost and laboratory time.

Extracción y medida de peroxidasa en pulpa de arazá (Eugenia stipitata MC Vaugh)

A technique for both extraction and activity measurement of peroxidase extracted from arazá (Eugenia stipitata Mc Vaugh) is described. Peroxidase from arazá pulp fruit was extracted using a combination of protein precipitation with acetone and extraction with 50 mM sodium buffer phosphate (pH 6.0). Optimum activity using guaiacol as H-donor was obtained at pH from 5.0 to 6.5, temperature from 60 to 75 °C, H2O2 between 10 to 15 mM and guaiacol from 80 to 160 mM. Thermal inactivation showed a first-order inactivation kinetic. Reactivation was observed when extracts were heated at 80 °C and afterwards incubated at 25 °C.

Dosimetria esporular: Bacillus subtilis TKJ6312 como biossensor de radiação solar biologicamente ativa

Since 2000, spore dosimetry and spectral photometry have been performed in parallel at the Southern Space Observatory, São Martinho da Serra (Southern Brazil). A comparative study involving data from Punta Arenas - Chile (53.2º S), São Martinho da Serra (29.5º S), Padang - Indonesia (0.9ºS), Brussels - Belgium (50.9º N) and Kiyotake - Japan (31.9º N) from 2000 to 2006 is presented. The Spore Inactivation Doses presented the higher values in summer (973 ± 73 for Punta Arenas and 4,369 ± 202 for São Martinho da Serra, as well 1,402 ± 170 and 3,400 ± 1,674 for Brussels and Kiyotake, respectively). The simplicity, robustness and high resistance of bacterial spores makes the biosensor an potential biological tool for UV-B monitoring.

Exposição humana a substâncias químicas potencialmente tóxicas na dieta e os riscos para saúde

Humans are exposed to a variety of chemicals from the consumption of food, including undesirable compounds such as pesticides and mycotoxins. Chemical human risk assessment is a process intended to estimate the risk to a given population from the exposure to a chemical (or to a chemical group having the same mechanism of action). The process consists of four steps, namely hazard identification, hazard characterization, exposure assessment and risk characterization. Chemical dietary risk assessment is an essential procedure to establish safe food standards. In this review the tools and data sources currently used in the risk assessment process will be discussed.

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.

Síntese e hidrólise de azalactonas de Erlenmeyer-Plöchl mediadas por radiação micro-ondas em aparelhos doméstico e dedicado: experimentos de química orgânica para a graduação

This work describes a green chemistry experiment for the synthesis of Erlenmeyer-Plöchl azalactones mediated by microwave irradiation, employing both dedicated and domestic equipment. Hippuric acid was reacted with equimolar amounts of benzaldehyde, p-chloro-benzaldehyde or p-N,N-dimethyl-benzaldehyde in acetic anhydride as the solvent. Acid hydrolysis of obtained 4-benzylidene-2-phenyloxazol-5(4H)-one under microwave and convectional heating afforded Z-α-(benzoylamino)cinnamic acid at a 51-61.5% yield. The UV-Vis molecular spectra of 4-benzylidene-2-phenyloxazol-5(4H)-one and 4-(4'-N,N-dimethylbenzylidene)-2-phenyloxazol-5(4H)-one were obtained in ethanol, CH2Cl2 and DMSO and bathochromic shift was observed for the latter azalactone.

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.

ADAPTAÇÃO DA METODOLOGIA DE ANÁLISE DE METEMOGLOBINA COMO BIOMARCADOR DE EFEITO DA EXPOSIÇÃO AO AGROTÓXICO DIFLUBENZURON

This work aimed to adapt the analysis of methemoglobin recommended by Evelyn - Malloy (visible spectrophotometry), in order to facilitate its application in the field, or to analysis in clinical laboratory, of existing sites of diflubenzuron application. The parameters changed included: centrifuge rotation speed; time between the collection of biological sample and analysis, and storage temperature of the samples; and the volume of reagents. The comparison of the rotation speed (rpm) of the reference methodology with the rpm of a "clinical centrifuge" did not reveal a statistically significant difference in the levels of methemoglobin. The time between the collection of biological sample and analysis was extended for a period of up to 48 hours for both conservation by refrigeration and ambient temperature, producing no statistically significant difference when compared to the standard duration of 2 hours. Regarding the reagents, the reference methodology already uses the volume necessary to ensure complete reaction, whereas a wider range from the recommended volume to a 5-fold reduction in comparison to the reference methodology could be used. It was concluded that the proposed changes to the methodology for adapting the analysis are applicable to studies of field / workplace exposure and ensure the reliability of results. The adapted methodology was inter-laboratory validated and the parameters changed can be selected according to the requirements of the laboratory at which the methemoglobin is to be measured.

Relações entre intensidade da doença, refletância da radiação solar e rendimento de grãos no patossistema ferrugem da folha de trigo Embrapa 16

Em experimentos com o cultivar de trigo Embrapa 16 conduzidos em Passo Fundo e Não-Me-Toque nas safras de 1999 e 2000 houve uma relação inversa entre a incidência foliar da ferrugem da folha do trigo, a severidade, o número de pústulas por centímetro quadrado e a área abaixo da curva de progresso da doença com o rendimento de grãos, e uma relação direta entre a refletância da radiação solar, na faixa de 810 nm, com o rendimento de grãos. A refletância da radiação solar na faixa permitiu estimar o rendimento de grãos do trigo, a severidade da doença e o número de pústulas cm-2. As equações da função de dano com maior R² obtidas pela análise de regressão permitem o cálculo do limiar de dano econômico (LDE) em diferentes estádios fenológicos da cultura. O LDE pode servir de critério indicador do momento para o controle da ferrugem da folha do trigo. Os danos causados pela doença atingiram um máximo de 43%, com uma média de 40 %.