Optimization of chromatographic conditions and comparison of extraction efficiencies of four different methods for determination and quantification of pesticide content in bovine milk by UFLC-MS/MS

This paper describes the optimization of a multiresidue chromatographic analysis for the identification and quantification of 20 pesticides in bovine milk, including three carbamates, a carbamate oxime, six organophosphates, two strobilurins, a pyrethroid, an oxazolidinedione, an aryloxyphenoxypropionate acid/ester, a neonicotinoid, a dicarboximide, and three triazoles. The influences of different chromatographic columns and gradients were evaluated. Furthermore, four different extraction methods were evaluated; each utilized both different solvents, including ethyl acetate, methanol, and acetonitrile, and different workup steps. The best results were obtained by a modified QuEChERS method that lacked a workup step, and that included freezing the sample for 2 hours at -20 ºC. The results were satisfactory, yielding coefficients of variation of less than 20%, with the exception of the 50 µg L-1 sample of famoxadone, and recoveries between 70 and 120%, with the exception of acephate and bifenthrin; however, both analytes exhibited coefficients of variation of less than 20%.

INFLUÊNCIA DO CONTEÚDO DE XILANAS NA BRANQUEABILIDADE, PROPRIEDADES HIGROSCÓPICAS, FISICO-MECÂNICAS E ÓPTICA DE POLPAS BRANQUEADAS DE EUCALIPTO

Bleached eucalypt kraft pulps are widely used in print and writing (P&W) and tissue paper manufacture. Among the quality requirements of pulp for these papers, xylan content has been controversial. The objective of this study was to evaluate the influence of xylan content on bleachability, hygroscopic, physic-mechanical and optical properties of the pulp. In this study industrial unbleached eucalyptus kraft pulp (15.6% xylans) treated with different NaOH loads to change its xylan content was used. Subsequently, pulps were bleached by the ODHT(EP)D sequence to achieve 90% ISO of brightness, then refined and submitted to hygroscopic, physicomechanical and optical tests. NaOH treatments decreased the xylan content to 14.5-5.9% using NaOH loads of 10-70 g L-1. Pulp bleachability was not significantly affected by xylan content decrease. The decrease in xylan content negatively affected the water retention value and Klemm capillarity of the pulp, while water absorption capacity was positively affected. Tensile and tear index were negatively influenced by the reduction in xylan content, whereas bulk and light scattering coefficient increased.

VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

Extraction and spectrophotometric determination of Hg2+ as complex anion HgI3-

A method has been developed for the extraction and spectrophotometric determination of Hg2+ in a concentration range of 0.2-1.0 mg L-1; following the Lambert-Beer's law using high molecular weight quaternary ammonium salts dissolved in chloroform. The metal complex anion was determined in the extract in the region UV (260 nm).

Determination of herbicides residues in soil by small scale extraction

Herbicides such as trifluralin, simazine, atrazine, metribuzin and metolachlor are used in Brazilian agriculture. The efficiency of a small scale method for determination of these herbicides and two degradation products (deisopropylatrazine and deethylatrazine) in soil samples was evaluated. The compounds were extracted from soil samples (5 g) with 20 ml of ethyl acetate in a mechanical shaker for 50 min. Following the extraction, the supernatant was dried through anhydrous sodium sulphate, concentrated and analysed by high resolution gas chromatography (HRGC) with thermionic specific detection (TSD). Mean recoveries obtained from soil samples fortified at three different levels ranged from 81 to 115% with relative standard deviation (RSD) values varying from 1.2 to 12.7%. The method detection limits ranged from 0.01 to 0.06 mg kg-1. The methodology was applied using soil samples from farms located near the town of Araraquara, in the State of São Paulo, Brazil.

Synthesis, characterization and thermal behaviour on solid pyruvates of light trivalent lanthanides

Solid State Ln-L compounds, where Ln stands for light trivalent lanthanides (La - Gd) and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, thermal behaviour and thermal decomposition of the isolated compounds.

Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Flavonoid extraction from Alpinia zerumbet (Pers.) Burtt et Smith leaves using different techniques and solvents

The current study aims to verify the best method for a rapid and efficient extraction of flavonoids from Alpinia zerumbet. Dried leaves were extracted using distillated water and ethanol 70% by extraction methods of shaking maceration, ultrasonic, microwave and stirring. By the application of TLC and reversed-phase HPLC techniques the rutin and kaempferol-3-O-glucuronide were detected. Ethanol 70% was more efficient for flavonoids extraction than water. No significant yielding variation was verified for ultrasonic, microwave and stirring methods using ethanol 70% (11 to 14%). The relative concentration of rutin and kaempferol-3-O-glucuronide, respectively, was higher by ultrasonic (1.5 and 5.62 mg g-1 dried leaves, respectively) and by microwave (1.0 and 6.64 mg g-1 dried leaves) methods using ethanol. Rapid and simplified extraction proceeding optimize phytochemical work and acquisition of secondary metabolites.

Flavonoids extraction from Alpinia zerumbet (Pers.) Burtt et Smith leaves using different procedures

The current study aims to verify the best method for a rapid and efficient extraction of flavonoids from Alpinia zerumbet. Dried leaves were extracted using distillated water and ethanol 70% by extraction methods of shaking maceration, ultrasonic, microwave and stirring. By the application of TLC and reversed-phase HPLC techniques the rutin and kaempferol-3-O-glucuronide were detected. Ethanol 70% was more efficient for flavonoids extraction than water. No significant yielding variation was verified for ultrasonic, microwave and stirring methods using ethanol 70% (11 to 14%). Relative concentration of rutin and kaempferol-3-O-glucuronide, respectively, was higher by ultrasonic (1.5 and 5.62 mg g-1 dried leaves) and by microwave (1.0 and 6.64 mg g-1 dried leaves) methods using 70% ethanol. Rapid and simplified extraction proceeding optimize phytochemical work and acquisition of secondary metabolites.

Optimization of NMP extraction in 1, 3-butadiene production line

N-methylpyrrolidone is a powerful solvent for variety of chemical processes due to its vast chemical properties. It has been used in manufacturing processes of polymers, detergents, pharmaceuticals rubber and many more chemical substances. However, it creates large amount of residue in some of these processes which has to be dealt with. Many well known methods such as BASF in rubber producing units have tried to regenerate the solvent at the end of each run, however, there is still discarding of large amount of residue containing NMP, which over time, could cause environmental concerns. In this study, we have tried to optimize regeneration of the NMP extraction from butadiene production. It is shown that at higher temperatures NMP is separated from the residue with close to 90% efficiency, and the solvent residue proved to be the most effective with a 6: 1 ratio.

Influence of substrates, light, filter paper and pH on the sporulation of Cercospora sojina

Fungi require special substrates for their isolation, vegetative growth and sporulation. In experiments conducted in the laboratory, the influence of substrates, light, filter paper and pH on the sporulation of Cercospora sojina conidia, the causal agent of soybean frogeye leaf spot, was assessed. The media potato sucrose agar, V-8 agar, tomato extract agar, soybean leaf extract agar, soybean seed extract agar, soybean meal agar, soybean flour agar and wheat flour agar were tested, added on the surface, with and without filter paper and under two light regimes, with 12 h light at 25°± 2°C and in the dark. A triple factorial 8x2x2 (substrates x light/dark x with/without filter paper) design with four replicates was used. V-8 agar medium was employed and the pH was adjusted with HCl 0.1N or NaOH 0.1N before autoclaving to the values: 3, 4, 5, 6, 7 and 8, and the pH of V-8 agar medium is 6.7. The evaluation was done on the seventh day of incubation. Data underwent regression analysis. Sporulation was maximized on the agar media V-8, seed extract, oat flour, tomato extract, and potato sucrose in the presence of filter paper and 12h light. On V-8 medium, maximal sporulation was obtained with pH 6.7.

Effects of different light levels on the initial growth and photosynthesis of Croton urucurana Baill. in southeastern Brazil

Four levels of shading (full sunlight (0%), 30, 50, 70% of solar radiation interception on growth, chlorophyll concentration and photosynthetic rate were studied in Croton urucurana Baill., a pioneer plant species. This species seedlings are of potential interest for reforestation projects and recovery of degraded areas. The seedlings were grown in pots containing soil and sand (2:1) and later transferred to plastic bags of 3 dm³ and submitted to different levels of shading (30, 50, 70%) of solar radiation and full sunlight, as control. The experimental design was completely randomized with five replicates and each experimental unit was composed of five plants. The results suggest that plants submitted to 70% shading showed higher dry weight accumulation in leaf and root, and higher plant height and leaf area. However, the seedlings root system showed higher dry biomass under full sunlight. It was observed a tendency to increase chlorophyll concentration and to decrease photosynthetic rate with the increase of the shading level.

Effect of light intensity and growth substratum on plant development and production of secondary metabolites in Cordia curassavica (Jacq.) Roem. & Schult

Cordia curassavica (Jacq.) Roem. & Schult. (Boraginaceae), also referred to as Cordia verbenacea DC, has been traditionally used for medicinal purposes. This study was driven to verify the behavior of the species in similar conditions to its natural environment, such as high light intensity and sandbank soil, and in conditions of low light intensity and fertilized substratum (dystroferric red nitosoil plus earthworm humus). The growth of the plant, the income of leaf crude extracts and, in the alcoholic extract, the number of substances found in thin layer cromatography and the toxicity of the substratum was observed. The results indicated that the growth of the root biomass, stem and leaves in discharge or lower light intensity was similar, but smaller in sandbank soil than in fertilized soil. The relative income of extracts in ether of petroleum and alcohol was larger in high light intensity and fertilized substratum. The light intensity and the substratum type didn't affect the number of substances detected in the alcoholic extract or the toxicity of this extract. Stains corresponding to the rosmarinic acid were only evidenced in some samples of the alcoholic extract, not allowing the verification of the effect of the treatments about its production.

Initial growth of Bauhinia variegata trees under different colored shade nets and light conditions

Bauhinia variegata and B. variegata var. candida, commonly known as orchid trees, are small sized trees widely used for urban forestry and landscaping. Adult plants grow under full sun; in Brazil, however, seedlings are generally cultivated in commercial nurseries under natural half-shading. The objective of this study was to evaluate the influence of different colored shade nets and light conditions on the initial growth of B. variegata and B. variegata var. candida. The influence of six light conditions (red net with 50% shading; blue net with 50% shading; black net with 70% shading; black net with 50% shading; black net with 30% shading; and full sun) on the initial growth of B. variegata and B. variegata var. candida were evaluated along 160 days, and growth relationships were calculated. Seedlings showed more efficiency on the use of photoassimilated compounds when grown under full sun. Such condition is the most appropriate for seedling production of B. variegata and B. variegata var. candida, contradicting what has been performed in practice.

Evaluation of protein extraction methods to obtain protein concentrate from cassava leaf

The cassava leaf, waste generated in the harvest of the roots, is characterized by high content of protein, vitamins and minerals; however, its use is limited due to the high fiber content and antinutritional substances, which can be removed by obtaining protein concentrates. In this context, the objective of this study was to evaluate protein extraction processes, aiming the use of cassava leaves (Manihot esculenta Crantz) as an alternative protein. Four methods were tested: 1) Coagulation of Proteins by Lowering the Temperature, 2) Extraction by Isoelectric Precipitation, 3) Solubilization of Proteins and 4) Fermentation of Filter Leaf Juice. To obtain the concentrates, the use of fresh or dried leaves and extraction in one or two steps were also evaluated. The solubilization of proteins (method 3) showed a higher extraction yield; however, with concentrate of low quality. The fermentation of the juice (method 4) produced concentrates with higher quality and lower costs and the isoelectric precipitation (method 2) promoted the obtention of concentrates in less time, both with good prospects for use. The use of two extraction steps was not advantageous to the process and there was no difference between the use of fresh or dried leaf, and the use of fresh leaves is presented as a good option for the simplicity of the method.