Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

Preparative separation and purification of bufadienolides from ChanSu by high-speed counter-current chromatography combined with preparative HPLC

Eight bufadienolides were successfully isolated and purified from ChanSu by high-speed counter-current chromatography (HSCCC) combined with preparative HPLC (prep-HPLC). First, a stepwise elution mode of HSCCC with the solvent system composed of petroleum ether - ethyl acetate - methanol - water (4:6:4:6, 4:6:5:5, v/v) was employed and four bufadienolides, two partially purified fractions were obtained from 200 mg of crude extract. The partially purified fractions III and VI were then further separated by prep-HPLC, respectively, and another four bufadienolides were recovered. Their structures were confirmed by ESI-MS and ¹H-NMR spectra.

Separation and preconcentration of copper in environmental samples on Amberlite XAD-8 resin after complexation with a carbothioamide derivative

A new solid phase extraction (SPE) method has been developed for the selective separation and preconcentration of Cu (II) ions in food and water samples prior to its flame atomic absorption spectrometry determination. The method is based on the adsorption of the Cu(II) - 2-{[4-Amino-3-(4-methylphenyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]acetyl}-N-phenyl hydrazinecarbothioamide complex on Amberlite XAD-8 resin. The metal complex retained on the resin was eluted with 7.5 mL of 2.0 mol L-1 HCl in acetone. The optimum conditions for the SPE of Cu(II) ions were investigated, and the method was subsequently applied to sea water, stream water, rice, tea, and tobacco samples for the determination of Cu(II) levels.

Preparative separation of polyphenols from artichoke by polyamide column chromatography and high-speed counter-current chromatography

An efficient method for the rapid separation and purification of polyphenols from artichoke by polyamide column chromatography in combination with high-speed counter-current chromatography (HSCCC) was successfully built. The crude ethanol extracts from dry artichoke were first pre-separated by polyamide column chromatography and divided in two parts as sample 1 and sample 2. Then, the samples were further separated by HSCCC and yielded 7.8 mg of chlorogenic acid (compound I), 24.5 mg of luteolin-7-O-β-D-rutinoside (compound II), 18.4 mg of luteolin-7-O-β-D-glucoside (compound III), and 33.4 mg of cynarin (compound IV) with purity levels of 92.0%, 98.2%, 98.5%, and 98.0%, respectively, as determined by high-performance liquid chromatography (HPLC) method. The chemical structures of these compounds were identified by electrospray ionization-mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR).

Preparative separation of C19-diterpenoid alkaloids from Aconitum carmichaelii Debx by pH‑zone-refining counter-current chromatography

The technique of pH-zone-refining counter-current chromatography was successfully applied to preparatively separate three C19-diterpenoid alkaloids from the crude extracts of Aconitum carmichaelii for the first time using a two-phase solvent system of petroleum ether-ethyl acetate-methanol-water (5:5:1:9, v/v/v/v). Mesaconitine (I), hypaconitine (II), and deoxyaconitine (III) were obtained from 2.5 g of the crude alkaloids in a one-step separation; the yields were 4.16%, 16.96%, and 5.05%, respectively. The purities of compounds I, II, and III were 93.0%, 95%, and 96%, respectively, as determined by HPLC. The chemical structures of the three compounds were identified by electrospray ionization mass spectrometry (ESI-MS) and NMR.

Separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography

An effective method for the rapid separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was successfully established. In the present study, a two-phase solvent system composed of chloroform-n-butanol-methanol-water (4:1:4:2, v/v/v/v) was used for HSCCC separation. A one-step separation in 4 h from 150 mg of crude extract produced 26.3 mg of trans-resveratrol-3-O-glucoside, 42.0 mg of pieceid-2"-O-gallate, and 17.9 mg of trans-resveratrol with purities of 99.1%, 97.8%, and 99.4%, respectively, as determined by high-performance liquid chromatography (HPLC). The chemical structures of these compounds were identified by nuclear magnetic resonance (NMR) spectroscopy.

DISPOSITIVO PARA EXTRAÇÃO LÍQUIDO-LÍQUIDO EM SISTEMAS DE ANÁLISES EM FLUXO

AbstractA device comprising a lab-made chamber with mechanical stirring and computer-controlled solenoid valves is proposed for the mechanization of liquid-liquid extractions. The performance was demonstrated by the extraction of ethanol from biodiesel as a model of the extraction of analytes from organic immiscible samples to an aqueous medium. The volumes of the sample and extractant were precisely defined by the flow-rates and switching times of the valves, while the mechanic stirring increased interaction between the phases. Stirring was stopped for phase separation, and a precise time-control also allowed a successful phase separation (i.e., the absence of the organic phase in the aqueous extract). In the model system, a linear response between the analytical response and the number of extractions was observed, indicating the potential for analyte preconcentration in the extract. The efficiency and reproducibility of the extractions were demonstrated by recoveries of ethanol spiked to biodiesel samples within 96% and 100% with coefficients of variation lower than 3.0%.

OBTENÇÃO DE COMPÓSITOS HÍBRIDOS BASEADOS EM HIDROGÉIS E CIMENTO PORTLAND

In this study, a novel hybrid composite based on biodegradable hydrogel and Portland cement with promising technological properties was reported. In the first step, a full 23 with central point factorial design was utilized to obtain the enhanced polyacrylamide-carboxymethylcellulose hydrogel compositions. A mathematical model was devised, indicating that the 3 main variables were significant and the AAm and MBAAm variables positively contributed to the mode and showing that the CMC variable had the opposite contribution. In the second step, these compositions were mixed with Portland cement to obtain the hybrid composites. The presence of cement improved the mechanical properties of polymeric matrices, and electronic microscopic micrographics revealed that the hydrogels were well adhered to the cement phase and no phase separation between hydrogel and cement was detected. Finally, using the energy dispersive X-ray technique, the elements Na, Mg, Al, Si, S, K, Ca and Fe were detected in the polymeric matrix, consistent with the hybrid composite formation.

Harmonical oscillator and electro-mechanical analogy: an interdiscinary experiment to high precision mass variation measurements

In general, the traditional Physics courses needs examples of the aplications of the Physics concepts in other areas such as Chemistry and Biology. This lacks tend to demotivate Chemistry and Biology students regarding to deal with Physical concepts developed in classroom. In this work, the analogy among mechanic and electric oscillators is investigated to be applied in Chemistry and Biology areas, showing to be valuable due to its aplication in techniques that aims to measure mass variation with high precision. This measure could be made in a direct or indirect way. These techniques are known as electrogravimetric techniques and they are important in biosensor aplications. Thus, this paper explores the electromechanic analogy in an interdisciplinary way involving areas like Physics, Chemistry and Biology. Based on this analogy, it is proposed an experiment that can be applied in different ways, i.e. by an basic approach or more deeper, depending on the students specific formation, in other words, Physics, Chemistry or Biology.

Mechanical behavior of 'Niagara Rosada' grape berry detachment

The 'Niagara Rosada' grape is the main Brazilian table grape belonging to the Labrusca family. It develops medium, cylindrical and compact bunches with berries presenting a pinkish skin and a foxy flavor that is valued in the Brazilian market. These berries are tender and have a pedicel-berry connection provided by the vascular bundles and surrounding skin. This cultivar is very susceptible to berry drop mainly caused by vibration and senescence. The objective of this study was to evaluate the temporal mechanical behavior of the pedicel-berry detachment, using resistance indexes extracted from traction force-deformation curves. Test results showed two different detachment types. In the first one, which exhibited higher average resistance, a considerable portion of the vascular bundle came out attached to the pedicel and in the second type; the vascular bundle was retained inside the berry. The proposed indexes based on maximum detachment force, force at 0.2; 0.5; 1.0 and 1.2 mm, and maximum force to corresponding deformation ratio did not discriminate the senescence of the berry.

Influence of the sample area in the variability of losses in the mechanical harvesting of soybeans

The mechanical harvesting is an important stage in the production process of soybeans and, in this process; the loss of a significant number of grains is common. Despite the existence of mechanisms to monitor these losses, it is still essential to use sampling methods to quantify them. Assuming that the size of the sample area affects the reliability and variability between samples in quantifying losses, this paper aimed to analyze the variability and feasibility of using different sizes of sample area (1, 2 and 3 m²) in quantifying losses in the mechanical harvesting of soybeans. Were sampled 36 sites and the cutting losses, losses by other mechanisms of the combine and total losses were evaluated, as well as the water content in seeds, straw distribution and crop productivity. Data were subjected to statistical analysis (descriptive statistics and analysis of variance) and Statistical Control Process (SCP). The coefficients of variation were similar for the three frames available. Combine losses showed stable behavior, whereas cutting losses and total losses showed unstable behavior. The frame size did not affect the quantification and variability of losses in the mechanical harvesting of soybeans, thus a frame of 1 m² can be used for determining losses.

Mechanical properties of castor beans subject to different drying temperatures aiming to disrupt the bean coat

In castor oil extraction process, the bean coat is abrasive to the equipment and releases substances that modify the oil color, reducing its quality. A potential solution would be to run the extraction by compressing only the endosperm. Due to lack of information, the objective of this study was to evaluate the influence of forced air drying at 40, 60, 80 and 100 ºC and farmyard drying, in the mechanical properties of the beans, aiming to break the bean coat. Castor beans were subjected to compression tests, in two perpendicular directions, at a strain rate of 0.6 mm.s-1. Average values of force, deformation energy, strain, all at rupture, and stiffness were used to evaluate the effects of dehydration. It was observed that the heat treatments did not alter the mechanical properties of castor beans, the strain and stiffness values discriminate the differences between the directions and had the lowest coefficients of variation. It was concluded that forced air drying, more costly than farmyard drying, does not bring benefits to the decortication. However, regardless the heat treatment used, the mechanical stress lengthwise is the most suitable to promote decortication.

Spatial variability of mechanical resistance to penetration evaluated with mobile unit on haplic vertisol cultivated with mango

Since the advent of mechanized farming and intensive use of agricultural machinery and implements on the properties, the soil began to receive greater load of machinery traffic, which can cause increased soil compaction. The aim of this study was to evaluate the spatial variability of soil mechanical resistance to penetration (RP) in the layers of 0.00-0.10, 0.10-0.20, 0.20-0.30 and 0.30-0.40m, using geostatistics in an area cultivated with mango in Haplic Vertisol of the northeastern semi-arid, with mobile unit equipped with electronic penetrometer. The RP data was collected in 56 points from an area of 3 ha, and random soil samples were collected to determine the soil moisture and texture. For RP data analysis we used descriptive statistics and geostatistics. The soil mechanical resistance to penetration presented increased variability, with adjustment of the spherical and exponential semivariograms in the layers. We found that 42% of the area in the layer of 0.10-0.20m showed RP values above 2.70 MPa. Maximum values of RP were found in the layer of 0.19-0.27m, predominantly in 56% of the area.

Mechanical damage during harvest and loading affect orange postharvest quality

Brazil is the world’s largest orange producer; however, part of this production is lost during postharvest. This loss can be minimized by controlling incidence of physical damage throughout the harvest and loading operations. Impacts can negatively modify quantitative and qualitative fruits aspects. The main goal of this study was to measure the impact magnitude in two types of harvest (manual and detachment) and during all steps from picking into bags until loading for transport to the processing industry and additionally evaluating, in laboratory, the physico-chemical quality of the fruit subjected to various impacts, similar to those found in the field. In order to evaluate the impact magnitude, an instrumented sphere was used (760 mm, Techmark, Inc, USA). The following physico-chemical parameters were evaluated during 6-days of storage: weight loss, soluble solids contents, titratable acidity, ascorbic acid content, pH, firmness and peel color. The greatest impacts were observed during harvest, during the detachment practice, and when loading and unloading from bulk storage, with average acceleration values between 249.5 and 531.52G. The impact incidence in oranges were responsible for reducing the soluble solids, titratable acidity, ascorbic acid and weight by to 5.5%; 8.7%; 4.6% and 0.5%, respectively, compared to the control. Impacts during harvest and the various pre-industry manipulation steps must be controlled as they interfere in postharvest quality and physiology of ‘Valência’ oranges.

Quality of peanut mechanical sowing in function of seeding density and size of the seeds

ABSTRACTPeanut crop (Arachis hypogaeaL.) mechanization has been improved over the years; however there are drawbacks that affect the quality of operations. Thus, this article’s objectives were to evaluate the operational performance of the mechanized sowing of peanut crop according to seeding densities (10, 14, and 18 seeds m-1) and seed sizes (21 and 23 mm). It was observed that the seeds of 23 mm had shorter average number of days to emergence and a higher percentage of emergences, occurring the opposite to the seeding density of 18 seeds m-1. The higher the seeding density, the largest was the plant stand, whereas the 23 mm seed obtained the best results and the same with the seeding density of 14 seeds m-1 that had a higher percentage of normal spacing. The densities of 14 and 18 seeds m-1 reflected in higher yields, being always superior to the 23 mm seeds.