Bioactive cinchona alkaloids from Remijia peruviana

Three known Cinchona alkaloids of the quinine type, quinine (1), cupreine (2), cinchonine (3), and the possible artifact cinchonine-HCl (3-HCl), along with two new ones, acetylcupreine (4) and N-ethylquinine (5), have been isolated from the bark of Remijia peruviana (Rubiaceae). Their stereochemical structures were established by high resolution NMR spectroscopy. Alkaloids 2-4 had antifeedant effects on Leptinotarsa decemlineata with varying potencies. Compound 4 was cytotoxic to both insect Sf9 and mammalian CHO cells after 48 h of incubation, while 3-HCl had stronger and selective cytotoxicity to Sf9. Quinine 1 had a moderate to low effect on Trypanosoma cruzi. Tumoral cells were also affected by these alkaloids, with 4 and 3-HCl being the most cytotoxic to all the cell lines tested. Overall, the 8R, 9S configurations, as in 3 and 3-HCl, as well as the C-6'acetylated alkaloid 4, with an 8S, 9R configuration, showed stronger biological effects.     

Multiresidue analysis of pesticides in soil by gas chromatography with nitrogen-phosphorus detection and gas chromatography mass spectrometry

A rapid multiresidue method for the simultaneous determination of 25 fungicides and insecticides in soil was developed. Soil samples are extracted by sonication with a water-acetonitrile mixture, and the pesticides are partitioned into dichloromethane. Final determination was made by gas chromatography (GC) with nitrogen-phosphorus detection (NPD). Confirmation analysis of pesticides was carried out by GC-MS in the selected ion monitoring (SIM) mode. The identification of compounds was based on retention time and on comparison of the primary and secondary ions. The average recovery by the GC-NPD method obtained for these compounds varied from 68.5% to 112.1% with a relative standard deviation between 1.8% and 6.2%. The GC-NPD method presents good linearity over the range assayed 50-2000 microg/L, and the detection limit for the pesticides studied varied from 0.1 to 10.4 microg/kg. The proposed method was used to determine pesticide levels in soil samples from experimental greenhouse pepper cultivation.     

Improved method to obtain pure alpha-galactosides from lupin seeds

Improvement of a previously described method of purification of alpha-galactosides, members of the raffinose family of oligosaccharides (RFOs), has been developed for lupins. The considerable amount of sucrose present in the RFO preparations obtained by the previous method has been removed by modifying the purification stage on diatomaceous earth and charcoal. The present method allows for the preparation of high-purity RFOs containing approximately 99.4% of RFOs in the form of a white fine powder, which provides new perspectives for the production of pure alpha-galactoside preparations for their use as prebiotics in functional foods.     

A comparative study of the precipitation acidity in two cities in Cantabria (Spain) with different degrees of industrialization

A study was carried out on the pH values obtained from bulk (wet and dry) precipitation samples collected simultaneously in two cities in Cantabria (Spain), Santander and Torrelavega over a period of a year. It was observed that the annual weighted average values for the pH of precipitation, 4.42 and 4.21, respectively, differ significantly although the difference is less than that existing between their pollution levels. The difference is greater when total annual H⁺ depositions are compared. The study also demonstrated the strong influence of long-range transport effect on acidity and to a lesser degree the effect of mid-range transport.     

Direct and combined methods for the determination of chromium, copper, and nickel in honey by electrothermal atomic absorption spectroscopy

In the present work, direct methods for the determination of chromium, copper, and nickel in honey by electrothermal atomic absorption spectroscopy were developed using experimental design as an optimization tool. Once the optimum conditions for the individual methods were established, a direct method for the combined determination of the three elements was optimized using the response surface tool. Palladium was used as chemical modifier in all cases. Honey was diluted in water, hydrogen peroxide, and nitric acid. Triton X-100 was added to minimize the matrix effect and the viscosity of the sample. The RSD (better than 10%) and the analytical recovery (98-103%) were acceptable for all of the developed methods. Calibration graphs were used in the four methods to determine the concentration of the analytes in the sample. The detection limits of the combined method (0.21, 0.35, and 0.37 microg L(-)(1) for Cr, Cu, and Ni, respectively) were similar to those obtained for the individual methods (LOD = 0.17, 0.21, 0.33 microg L(-)(1) for Cr, Cu, and Ni, respectively). The direct-combined proposed method has been applied to the determination of chromium, copper, and nickel content in representative honey samples from Galicia (northwestern Spain). The concentrations found in the analyzed samples were in the range of (5.75 +/- 0.64)-(26.4 +/- 0.38) ng g(-)(1) of Cr, (79 +/- 7.8)-(2049 +/- 80) ng g(-)(1) of Cu, and (12.6 +/- 1.36)-(172 +/- 6.88) ng g(-)(1) of Ni.     

Effect of germination on the carbohydrate composition of the dietary fiber of peas (Pisum sativum L.)

The effect of different conditions of pea germination on dietary fiber (DF) composition was studied. Insoluble dietary fiber (IDF) and soluble dietary fiber (SDF) were subjected to acid hydrolysis, and the resultant neutral sugars, uronic acids, and Klason lignin were quantified. Germinated peas exhibited significantly higher contents of total dietary fiber (TDF) than the raw sample, due to the increases of both DF fractions. Under darkness conditions, germination exhibited the highest contents of IDF and SDF. Decreasing IDF/SDF ratios showed that the carbohydrate changes did not take place to the same extent during germination, the SDF fraction being the most affected. The detailed chemical composition of fiber fractions reveals increases of cellulose in the IDF of germinated samples, whereas SDF exhibits a decrease of pectic polysaccharides and also increases of polysaccharides rich in glucose and mannose. The DF results were corroborated by a comparative examination of the cell wall carbohydrate composition.     

Effect of cooking temperatures on chemical changes in species of organic arsenic in seafood

The concentrations of arsenobetaine (AB), tetramethylarsonium ion (TMA(+)), and trimethylarsine oxide (TMAO) were determined in samples of sole, dory, hake, and sardine, raw and after being subjected to cooking processes--baking, frying, and grilling--at various temperatures. In all cases, the temperature attained inside the product during the cooking process was measured. The arsenic species extracted from the samples with methanol/water were separated by means of a column switching technique between a PRP-X100 column and a PRP-X200 column. AB was detected by hydride generation atomic absorption spectrometry, whereas TMA(+) and TMAO were detected by hydride generation atomic fluorescence spectrometry. The results obtained showed that, in all of the types of seafood studied, TMA(+) appeared after cooking, possibly because heating facilitates decarboxylation of AB to TMA(+).     

Remediation of As-Contaminated Soils in the Guadiamar River Basin (SW, Spain)

In 1998, the pond containing the ore wastes from a pyrite mine in Aznalcóllar (SW, Spain) broke open, spilling some 36×10⁵ m³ of acidic waters and 9?×?10⁵ m³ of tailings containing high concentrations of As and heavy metals. The affected area was around 55 km² of predominantly agricultural soils. After the clean-up of the tailings, many remediation actions were undertaken and the use of blocking agents to immobilize the As was one of the most extended measure. The first experiment performed was to determine the most important soil components in As adsorption under acidic conditions. A second experiment was conducted to neutralize the acidity caused by the solution coming from the tailings undergoing oxidation; an adequate liming material (sugar-refinery scum) was selected and the application rates were established. After the remediation measures, the zone was monitored for three years. A detailed study in four experimental plots located in the most polluted sector was carried out to test the influence of iron oxides in the As immobilization. The use of red soils of the area (rich in free-iron oxides Fe_d) was established as an appropriate material in the remediation of the area.     

Browning evaluation of ready-to-eat apples as affected by modified atmosphere packaging

The color and polyphenol oxidase (PPO) activity of fresh-cut Golden delicious apples were evaluated throughout cold storage under modified atmospheres. The shelf life of cut apples was extended to several weeks, especially when an initial atmosphere of 90.5% N(2) + 7% CO(2) + 2.5% O(2) and plastic pouches of 30 cm(3)/cm(2) x bar x 24 h were used. Under these conditions, a maximum 62% PPO activity depletion was observed. In all cases, the faster the initial PPO activity decays, the less the color changes. A fractional conversion first-order model was proposed for predicting color changes in minimally processed apples. Browning was better described through lightness (L) (k(L) = 0.017 - 0.07 day(-1)) and color difference (Delta E*) values (k(Delta E) = 0.015 - 0.073 day(-1)), which fitted the model with enough accuracy.     

Improvement of table grapes quality and safety by the combination of modified atmosphere packaging (MAP) and eugenol, menthol, or thymol

Table grape is a nonclimacteric fruit that shows a rapid loss of quality during storage and is very susceptible to colonization by fungi, especially Botrytis cinerea, which is considered the most important disease of this commodity. To solve this problem, synthetic fungicides have been used, although legal restrictions and consumer's concern demand the search of other safe means. In the present paper, and as an alternative of synthetic fungicides, an active packaging to improve MAP effectiveness on preserving table grape (cv. Crimson Seedless) quality and safety was developed by the addition of 0.5 mL of eugenol, thymol, or menthol inside the packages. Packages were stored at 1 degree C for 35 days. The final gas composition inside the packages was 1.4-2.0 and 10.0-14.5 kPa of CO(2) and O(2), respectively, with no significant slight differences among treatments. Results showed that the addition of eugenol, thymol, or menthol improved the beneficial effect of MAP in terms of delaying weight loss and color changes, retarding degrees Brix/acidity ratio evolution, and maintaining of firmness. Thereafter, these treatments showed additional benefit in terms of delayed rates of rachis deterioration and berry decay. Finally, the total viable counts for both mesophilic aerobics and especially yeast and molds were significantly reduced in the grapes packaged with the natural antimicrobial compounds. All of the above effects led to maintenance of table grape quality and safety for longer storage periods (3 additional weeks as compared to controls under MAP only).