Application of low-pressure gas chromatography-ion-trap mass spectrometry to the analysis of the essential oil of Turnera diffusa (Ward.) Urb.

Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 mum) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved. (C) 2003 Elsevier B.V. All rights reserved.

Determination of cocaine in samples of hair using the chromatographic column, ISRP-C-18

A method has been developed for the determination of the cocaine levels in samples of hair, using a chromatographic column internal surface reverse phase (ISRP)-C-18, for direct injection of the extracts of hair, without purification or derivation of the sample. The method allows monitoring an individual stopped for using or making cocaine. This method allowed the determination of levels of cocaine concentration in 75% of the analyzed samples of chemical dependents' hair, with cocaine detected at levels of 0.37-16.85 mug g(-1). In the other analyzed samples (25%), the drug was not detected, because the corresponding individuals told us that they consumed cocaine infrequently and in small amounts. The detection

Determination of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography with electrochemical detection

A new methodology was developed for analysis of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography (HPLC) coupled to electrochemical detection. The electrochemical oxidation of 5-hydroxymetkylfurfural, 2-furfuraldehyde, butyraldehyde, acetone and methyl ethyl ketone derivatized with 2,4-dinitrophenylhydrazine (DNPH) at glassy carbon electrode present a well defined wave at +0.94 V; +0.99 V; +1.29 V; +1.15 V and +1.18 V, respectively which are the basis for its determination on electrochemical defector. The carbonyl compounds derivatized were separated by a reverse-phase column under isocratic conditions with a mobile phase containing a binary mixture of methanol /LiClO4(aq) at a concentration of 1.0 x 10(-3) mol L-1 (80:20 v/v) and a flow-rate of 1.1 mL min(-1). The optimum potential for the electrochemical detection of aldehydes-DNPH and ketones-DNPH was +1.0 V vs. Ag/AgCl. The analytical curve of aldehydes-DNPH and ketones-DNPH presented linearity over the range 5.0 to 400.0 ng mL(-1), with detection limits of 1.7 to 2.0 ng mL(-1) and quantification limits from 5.0 to 6.2 ng mL(-1), using injection volume of 20 mu L. The proposed methodology was simple, low time-consuming (15 min/analysis) and presented analytical recovery higher than 95%.

Environmental Behaviour of Metolachlor and Diuron in a Tropical Soil in the Central Region of Brazil

The environmental behaviour of metolachlor and diuron was studied in the Central-western region of Brazil, by means of a field study where six experimental plots were installed. The soil was classified as a Latosol, and the soil horizons were characterized. Sorption of metolachlor and diuron was evaluated in laboratory batch experiments. Metolachlor and diuron were applied to the experimental plots on uncultivated soil in October 2003. From this date to March 2004, the following processes were studied: leaching, runoff and dissipation in top soil. K (oc) of metolachlor varied from 179 to 264 mL g(-1) in the soil horizons. K (oc) of diuron in the Ap horizon was 917 mL g(-1), decreasing significantly in the deeper horizons. Field dissipation half-lives of metolachlor and diuron were 18 and 15 days, respectively. In percolated water, metolachlor was detected in concentrations ranging from 0.02 to 2.84 mu g L-1. In runoff water and sediment, metolachlor was detected in decreasing concentrations throughout the period of study. Losses of 0.02% and 0.54% of the applied amount by leaching and runoff, respectively, were observed confirming the high mobility of this herbicide in the environment. In percolated water, diuron was detected with low frequency but in relatively high concentrations (up to 6.29 mu g L-1). In runoff water and soil, diuron was detected in decreasing concentrations until 70 days after application, totalizing 13.9% during the whole sampling period. These results show the importance of practices to reduce runoff avoiding surface water contamination by these pesticides, particularly diuron.

Influence of sugar cane vinasse on the sorption and degradation of herbicides in soil under controlled conditions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Bacterial leaching of uranium ore from Figueira-PR, Brazil, at laboratory and pilot scale

A bacterial leaching program was carried out in order to evaluate the potential of applying this process to leach uranium from the ore of Figueira-PR, Brazil. The experiments were carried out in shake flasks, column percolation (laboratory and semipilot scale) and in heap leaching. In shake flasks and in column percolation experiments at laboratory scale, bacterial activity on the ore was confirmed: approximately 60% of uranium was leached, against around 30% in sterilized controls. Column percolation experiments at semipilot scale and heap leaching (850 tons of ore) showed uranium extractions of approximately 50%. In both experiments, a complementary sulfuric acid attack, after the bacterial leaching phase, was necessary to reach this level of uranium extraction.

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of γ-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7:3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the in vitro fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, γ-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil. © Springer-Verlag 1996.

Determination of the geometrical diarylpropenamine isomers in feces by high-performance liquid chromatography

Diarylpropenamine derivatives are a class of compounds which have been evaluated as potential drug candidates. Here a specific and reproducible HPLC method for the determination of cis- and trans-isomers of the unsubstituted derivative, 3-(4'-bromo-[1,1'-biphenyl]-4-yl)-3-(4-X-phenyl-N,N-dimethyl-2-propen-1-amine (I, where X=H) in feces is described. The analyte I and internal standard, nitro derivative (II, where X=NO2), were isolated from the basified biological matrix using a liquid-liquid extraction with ethyl acetate followed by a solid-phase procedure performed on a silica cartridge. The organic phase was evaporated to dryness, the residue was reconstituted in mobile phase and injected into the HPLC system. The analytes were eluted with ethyl acetate-hexane-triethylamine (59:40:1) in HPLC column (silica) and detected by UV spectrophotometry at 272 nm. Linearity, precision and accuracy data for feces standards after extraction were acceptable. The method has been applied to analyses of feces samples from rats dosed with I, in which it could be anticipated that fecal excretion is quantitatively the major route for I elimination. Copyright (C) 1999 Elsevier Science B.V.

Determination of flutamide in tablets by high-performance liquid chromatography

Flutamide is a potent antiandrogen used for the treatment of prostatic cancer. A simple, sensitive and accurate high-performance liquid Chromatographic (HPLC) method is presented for quantitative determination of flutamide in tablets, using a reversed-phase technique and UV detection at 240 nm. The isocratic elution was used to quantify the analyte. The samples were chromatographed on Luna-C18 column and the mobile phase was 0.05 M phosphate buffer pH 4.0 - acetonitrile (50:50, v/v). The method was linear between 2.9 - 11.6 mg L -1. Over the tested concentration range the intra-day relative standard deviation for replicate analysis in tablets ranged from 0.44 to 0.78%. It was also found that the excipients in the commercial tablets did not interfere with the method.

Potassium leaching from millet straw as affected by rainfall and potassium rates

Pearl millet (Penisetum glaucum) is an interesting species to be used as cover crop in tropical areas, showing a high ability in potassium uptake. Potassium (K) is not linked to organic compounds in the plant, and can easily be released from decaying straw becoming available for subsequent crops. This experiment evaluated K leaching from millet straw grown under potassium rates (0, 100, 200, and 300 mg dm-3), and submitted to five levels of simulated rain (5, 10, 20, 40, and 80 mm). Plants were grown in soil filled pots in a greenhouse. On the 50th day after emergence, the plants were desiccated with glyphosate. Artificial rain was applied over the straw. Potassium deficiency speeds up millet dehydration after herbicide application and increases lightly rain water retention in the straw. The amount of K leached right after plant desiccation is correlated with the residue nutrient content and can be as high as 64 kg ha-1 considering a mulch of 8 t ha -1. Although well-nourished millet plants release considerable amounts of K with the first rains, a large percentage of the nutrient is still retained in the straw. Copyright © Taylor & Francis, Inc.

Antibiótico antifungico produzido por um estreptomiceto da região de Araraquara

With the significant increase in the incidence of invasive fungal infections during the last decade, mainly in patients with cancer, AIDS and other hospitalized patients who stay for long periods in intensive care units, there is an urgent need to screen for new antifungal agents possessing some advantages over known ones. This article reports a search in the field for a microorganism producing antibacterial and antifungal substances. Strains from soil samples collected in the region of Araraquara, Brazil, were isolated and analyzed for their antimicrobial potential against standard microorganisms (fungi Candida albicans and Aspergillus oryzae and bacteria Staphylococcus aureus and Escherichia coli). Out of the 64 strains isolated, 34 produced detectable antimicrobial activity. The streptomycete strain Ar4014 was chosen for further study, owing to its good antimicrobial activity against Candida albicans. Two of the fermentation media tested, 608-K and 602-B, were found to be best for the production and extraction of the antibiotic from Ar4014. After chromatographic separation of the crude extract on a silica column, the active fractions obtained showed UV-VIS absorption peaks characteristic of normal pentaenic antibiotics. The antibiotic was provisionally designated Ara 4014-75.

Influence of organic and mineral soil fertilization on essential oil of Spilanthes oleracea cv. Jambuarana

In the present study, the composition of essential oil of leaves and inflorescences of jambu (Spilanthes oleracea. Jambuarana), under organic manuring and mineral fertilization, was stuhed. Jambu plants show important chemical properties and their production has been addressed for the extraction of the essential oils for cosmetics industries, due to their pharmacolopcal properties. The experimental area of treatments contained urea as mineral fertilizer (120 g m2), applied twice and organic fertilizer (8 kg m2), applied at the planting. Jambu leaves and flowers were harvested twice: the first at 90 days after seedling transplantation and at the opening of the flower buds. Branches were cut at 7 cm from the soil, thus new branches can bud for the accomplishment of the second crop which happened 40 days after the re-budhng. The essential oil was analyzed by gas chromatography coupled with mass-spectrometry. According to our results the most representative compounds were trans-caryophyllene, germacrene-D, 1-dodecene, spathulenol and spilanthol (a compound presenting anesthetic properties) occurring in inflorescences. Fertilization procedure does not affect the content and the quality of the essential oil in Jambu plants. © 2012 Academic Journals Inc.

Phosphorus and potassium budget in the soil-plant system in crop rotations under no-till

Soil management and crop rotations can affect P and K budget in soil, decreasing losses, and increasing fertilizer use efficiency. The P and K budget in the soil-plant system at depths up to 60. cm was studied for different soil managements and crop rotations under no-till for three years in Botucatu, São Paulo, Brazil. The investigated crop rotations were: triticale (X Triticosecale) and sunflower (Helianthus annuus) cropped in autumn-winter; pearl millet (Pennisetum glaucum), forage sorghum (Sorghum bicolor), and Sunn hemp (Crotalaria juncea) were grown in the spring, as well as an additional treatment with chiseling followed by a fallow period; and soybean (Glycini max, L., Merril) was cropped in the summer. Each year triticale and sunflower were grown in plots and pearl millet, forage sorghum, Sunn hemp and of chisel/fallow in sub-plots. The triticale/millet rotation led to the largest decrease in available P within the 0-0.60. m layer of the soil profile and the largest K increase within the 0-0.05. m layer. Potassium mobility in the soil profile and the increases in the available K content in the 0.40-0.60. m layer were independent of the management system. Crop rotations with or without chiseling are not effective in preventing soil P losses. There is considerable K leaching below 0.60. m, but chiseling and the use of high K accumulating plants as triticale results in lower K losses. © 2012 Elsevier B.V.

Mineralização de nitrogênio de solos e de resíduo orgânico em laboratório e em campo

Pós-graduação em Agronomia (Ciência do Solo) - FCAV

Continuous vs. segmented second-dimension system gradients for comprehensive two-dimensional liquid chromatography of sugarcane (Saccharum spp.)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)