Experimento didático sobre cromatografia gasosa: uma abordagem analítica e ambiental

This paper describes an experiment to teach the principles of gas chromatography exploring the boiling points and polarities to explain the elution order of a series of alcohols, benzene and n-propanone, as well as to teach the response factor concept and the internal standard addition method. Retention times and response factors are used for qualitative identification and quantitative analysis of a hypothetical contamination source in a simulated water sample. The internal standard n-propanol is further used for quantification of benzene and n-butanol in the water sample. This experiment has been taught in the instrumental analysis course offered to chemistry and oceanography students.

A convenient method for lecithin purification from fresh eggs

The increasing demand for fatty acid-free lecithin required modifications in existing purification methods. In this technical note we describe a purification procedure with the following steps: a) homogenization and extraction of yolks obtained from fresh eggs with acetone, b) solubilization with ethanol and solvent elimination and c) repeated solubilization/precipitation with petroleum ether/acetone. This crude extract was chromatographed on neutral alumina, which was exhaustively washed with chloroform before elution with chloroform:methanol, allowing the sequential separation of fatty acids and lecithin. Chromatographic behavior and mass spectra of the product are presented. This fast procedure yields fatty acid-free lecithin at a competitive cost.

Fracionamento dos carboidratos pelas equações do Cornell Net Carbohydrate and Protein System de três cultivares de girassol na presença ou não de irrigação

Objetivou-se quantificar as frações de carboidratos pelas equações do Cornell Net Carbohydrate and Protein System (CNCPS) de três cultivares de girassol (Helianthus annuus L.) cultivados na presença ou não de irrigação. A utilização de uma preparação fibrosa, denominada parede celular (PC), nas equações da CNCPS, em substituição à fibra em detergente neutro (FDN) não promoveu diferenças nas frações de carboidratos B1 e C, mas influenciou as frações A e B2. Como os valores da fração B1, obtidos pelo modelo CNCPS foram menores que os teores de amido e pectina determinados em laboratório, supõe-se que a pectina e outros oligossacarídeos da parede celular, solubilizados pela solução de detergente neutro (fibra solúvel), nunca fizeram parte da fração B1, e sim da fração A. Apesar de os carboidratos da fibra solúvel apresentarem elevadas taxas de degradação, não parece adequada a caracterização da fibra solúvel na fração A. Parece mais adequado que a fibra solúvel (que inclui a pectina) seja alocada a uma fração exclusivamente sua, que pode ser a fração B2, e que seja criada uma nova fração, a B3, para os carboidratos digeríveis da parede celular. Assim, a fração B1 seria composta apenas de amido. A equação da fração C, que estima os carboidratos indigeríveis da parede celular, pode ser simplificada, relacionando a fração indigerível ao teor de lignina na matéria seca, e não à FDN isenta de cinzas e proteína, como atualmente utilizado. Esta proposta tem implicações práticas, uma vez que a fração indigerível da parede celular tem sido expressa em relação à FDN, e não na MS, com base no fato de que os efeitos inibitórios da lignina ocorrem sobre os componentes fibrosos da parede celular vegetal, e não sobre o conteúdo celular.

O papel das selenoproteínas no câncer

Evidências têm demonstrado que distúrbios do metabolismo são comuns em células tumorais, levando ao aumento do estresse oxidativo. A elevação na produção de espécies reativas de oxigênio (EROs) associada à baixa atividade antioxidante tem sido relacionada a vários tipos de câncer. O selênio, micronutriente antioxidante, pode funcionar como um agente antimutagênico, prevenindo transformações malignas de células normais. Realizou-se um levantamento bibliográfico no período 2000 a 2009 mediante consulta à base de dados PubMed (National Library of Medicine´s Medline Biomedical Literature, USA), selecionando-se 39 artigos que avaliaram a relação entre câncer, estresse oxidativo e suplementação com selênio. O efeito protetor desse mineral é especialmente associado à sua presença na glutationa peroxidase e na tioredoxina redutase, enzimas protetoras do DNA e outros componentes celulares contra o dano oxidativo causado pelas EROs. Vários estudos têm demonstrado a expressão reduzida destas enzimas em diversos tipos de câncer, principalmente quando associados a uma baixa ingestão de selênio, que pode acentuar os danos causados. A suplementação de selênio parece ocasionar redução do risco de alguns tipos de câncer diminuindo o estresse oxidativo e o dano ao DNA. No entanto, mais estudos são necessários para esclarecer as doses de selênio adequadas para cada situação (sexo, localização geográfica e tipo de câncer)

Alkaloids from Stems of Esenbeckia leiocarpa Engl. (Rutaceae) as Potential Treatment for Alzheimer Disease

Esenbeckia leiocarpa Engl. (Rutaceae), popularly known as guaranta, goiabeira, is a native tree from Brazil. Bioactivity-guided fractionation of the ethanol stems extract afforded the isolation of six alkaloids: leiokinine A, leptomerine, kokusaginine, skimmianine, maculine and flindersiamine. All isolated compounds were tested for acetyl cholinesterase inhibition, in vitro and displayed anticholinesterasic activity. The alkaloid leptomerine showed the highest activity (IC(50) = 2.5 mu M), similar to that of the reference compound galanthamine (IC(50) = 1.7 mu M). The results showed for the first time the presence of alkaloids leptomerine and skimmianine in E. leiocarpa (Engl.) with potent anticholinesterasic activity.

Antileishmanial Activity of the Hydroalcoholic Extract of Miconia langsdorffii, Isolated Compounds, and Semi-Synthetic Derivatives

The in vitro activity of the crude hydroalcoholic extract of the aerial parts of Miconia langsdorffii Cogn. was evaluated against the promastigote forms of L. amazonensis, the causative agent of cutaneous leishmaniasis in humans. The bioassay-guided fractionation of this extract led to identification of the triterpenes ursolic acid and oleanolic acid as the major compounds in the fraction that displayed the highest activity. Several ursolic acid semi-synthetic derivatives were prepared, to find out whether more active compounds could be obtained. Among these ursolic acid-derived substances, the C-28 methyl ester derivative exhibited the best antileishmanial activity.

Cytogenetic Instability in Childhood Acute Lymphoblastic Leukemia Survivors

Contemporary anticancer therapies have largely improved the outcome for children with cancer, especially for Acute Lymphoblastic Leukemia (ALL). Actually, between 78% and 85% of patients achieve complete remission and are alive after 5 years of therapy completion. However, as cure rates increase, new concerns about the late effects of genotoxic treatment emerge, being the risk of developing secondary neoplasias, the most serious life-threatening rising problem. In the present paper, we describe and review the cytogenetic findings in peripheral lymphocytes from ALL survivors, and discuss aspects associated to the occurrence of increased chromosome rearrangements in this growing cohort.

A Lagrangian Identification of the Main Sources of Moisture Affecting Northeastern Brazil during Its Pre-Rainy and Rainy Seasons

This work examines the sources of moisture affecting the semi-arid Brazilian Northeast (NEB) during its pre-rainy and rainy season (JFMAM) through a Lagrangian diagnosis method. The FLEXPART model identifies the humidity contributions to the moisture budget over a region through the continuous computation of changes in the specific humidity along back or forward trajectories up to 10 days period. The numerical experiments were done for the period that spans between 2000 and 2004 and results were aggregated on a monthly basis. Results show that besides a minor local recycling component, the vast majority of moisture reaching NEB area is originated in the south Atlantic basin and that the nearby wet Amazon basin bears almost no impact. Moreover, although the maximum precipitation in the ""Poligono das Secas'' region (PS) occurs in March and the maximum precipitation associated with air parcels emanating from the South Atlantic towards PS is observed along January to March, the highest moisture contribution from this oceanic region occurs slightly later (April). A dynamical analysis suggests that the maximum precipitation observed in the PS sector does not coincide with the maximum moisture supply probably due to the combined effect of the Walker and Hadley cells in inhibiting the rising motions over the region in the months following April.

Rotation curve bifurcations as indicators of close recent galaxy encounters

Context. Rotation curves of interacting galaxies often show that velocities are either rising or falling in the direction of the companion galaxy. Aims. We seek to reproduce and analyse these features in the rotation curves of simulated equal-mass galaxies suffering a one-to-one encounter as possible indicators of close encounters. Methods. Using simulations of major mergers in 3D, we study the time evolution of these asymmetries in a pair of galaxies during the first passage. Results. Our main results are: (a) the rotation curve asymmetries appear right at pericentre of the first passage, (b) the significant disturbed rotation velocities occur within a small time interval, of similar to 0.5 Gyr h(-1), and, therefore, the presence of bifurcation in the velocity curve could be used as an indicator of the pericentre occurrence. These results are in qualitative agreement with previous findings for minor mergers and flybys.

Development and validation of a fast RP-HPLC method to determine the analogue of the thyroid hormone, 3,5,3 '-triiodothyroacetic acid (TRIAC), in polymeric nanoparticles

The objective of this work was to develop and validate a rapid Reversed-Phase High-Performance Liquid Chromatography method for the quantification of 3,5,3 '-triiodothyroacetic acid (TRIAC) in nanoparticles delivery system prepared in different polymeric matrices. Special attention was given to developing a reliable reproductive technique for the pretreatment of the samples. Chromatographic runs were performed on an Agilent 1200 Series HPLC with a RP Phenomenex (R) Gemini C18 (150 x 4, 6 mm i.d., 5 mu m) column using acetonitrile and triethylamine buffer 0.1% (TEA) (40 : 60 v/v) as a mobile phase in an isocratic elution, pH 5.6 at a flow rate of 1 ml min(-1). TRIAC was detected at a wavelength of 220 nm. The injection volume was 20 mu l and the column temperature was maintained at 35 degrees C. The validation characteristics included accuracy, precision, specificity, linearity, recovery, and robustness. The standard curve was found to have a linear relationship (r(2) - 0.9996) over the analytical range of 5-100 mu g ml(-1) . The detection and quantitation limits were 1.3 and 3.8 mu g ml(-1), respectively. The recovery and loaded TRIAC in colloidal system delivery was nearly 100% and 98%, respectively. The method was successfully applied in polycaprolactone, polyhydroxybutyrate, and polymethylmethacrylate nanoparticles.

Distribution and behavior of manganese in the Alto do Paranapanema Basin

This paper reports manganese (Mn) fractionation in samples collected from the water column and sediments in an environmental protection area in the Alto do Paranapanema Basin (Sao Paulo State, Brazil). The three locations studied showed equivalent Mn levels, with moderate seasonal differences (p < 0.05). The sediment samples contained five Mn species (p < 0.05): iron and manganese (hydr)oxides > Mn bound to carbonates approximate to exchangeable Mn approximate to Mn bound to silicates > Mn bound to organic matter (p < 0.05). The water samples contained three species (p < 0.05): particulate Mn > labile Mn approximate to non-labile Mn. The data suggest that Mn has a natural origin (Enrichment Factor EF < 2; Geoaccumulation Index I(geo) < 0) and moderate environmental risk (Risk Assessment Code RAC similar to 30%). At the same time, under certain conditions some manganese species could be present in a state of equilibrium between the water column and sediment. These results could provide a basis for Mn management in the Alto do Paranapanema Basin.

Dissolved carbon in an urban area of a river in the Brazilian Amazon

The main objective of this study was to evaluate dissolved organic and inorganic carbon dynamics along upstream and downstream reaches of the Acre River draining the city of Rio Branco, in the state of Acre, Brazil. Dissolved organic carbon (DOC) concentrations in the Acre River were significantly higher during the wet season, ranging from 385 +/- A 160 to 430 +/- A 131 mu M among the stations, with no difference in upstream and downstream concentrations. Dissolved inorganic carbon (DIC) showed an inverse pattern, with higher concentrations in the dry season, ranging from 816 +/- A 215 to 998 +/- A 754 mu M among the stations, as well as no difference in upstream and downstream DIC concentrations. Bicarbonate was the dominant DIC fraction and was mainly observed during the dry season. Due to lower pH values during the wet season, CO(2) partial pressure (pCO(2)) in the Acre River was higher in the wet season, with values ranging from 4,567 +/- A 1,813 to 4,893 +/- A 837 ppm among the stations. Our results indicate that, although the Acre River drains a large city with significant sewage disposal into the river, seasonal hydrological processes are the main driver of dissolved carbon dynamics, even in the downstream study reach directly influenced by urbanization.

ACCUMULATION AND TRANSLOCATION OF SILICON IN RICE AND BEAN PLANTS USING THE 30SI STABLE ISOTOPE

The 30Si silicon isotope stable was used for assessing the accumulation and translocation of Si in rice and bean plants grown in labeled nutritive solution. The isotopic silicon composition in plant materials was determined by mass spectrometry (IRMS) using the method based on SiF4 formation. Considering the total-Si added into nutritive solutions, the quantity absorbed by plants was near to 51% for rice and 15% for bean plants. The accumulated amounts of Si per plant were about 150g in rice and 8.6g in bean. Approximately 70% of the total-Si accumulated was found in leaves. At presented experimental conditions, the results confirmed that once Si is accumulated in the old parts of rice and bean plant tissues it is not redistributed to new parts, even when Si is not supplied to plants from nutritive solution.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

Isotopic determination of silicon by mass spectrometry in plants and soils labeled with Si-30

A method for isotopic determination of silicon by mass spectrometry in plants and soils labeled with Si-30 is reported. The development of this method is for use with studies involving the physiological process of absorption, transport, and redistribution of Si in the soil-plant system by use of the stable isotope Si-30 as a tracer. The procedure leads to SiF4 formation, and the isotopic determination of Si was based on the measurements of the (SiF3+)-Si-28, (SiF3+)-Si-29, and (SiF3+)-Si-30 signals. Relative standard deviation of Si-30 abundance measurements (n = 6) were lower than 0.1%, and the detection limit was 0.5 mg Si (dry mass).