Kinetic model for the antiradical activity of the isolated p-catechol group in flavanone type structures using the free stable radical 2,2-diphenyl-1-picrylhydrazyl as the antiradical probe

The time evolution of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH*) concentration in four solvents (methanol, ethanol, propanol, and acetonitrile) during its reduction by three flavanones containing an isolated p-catechol group (taxifolin, eriodyctiol, and fustin) as well as the time evolution of the mass spectra of the reaction mixture has been determined by spectrophotometry and liquid mass spectrometry, respectively. In alcoholic solvents the reduction curves consisted of an initial short but fast kinetics step followed by a longer slow kinetics step; in contrast, in acetonitrile the reduction curves completely lacked the slow kinetics step. From the results, a kinetic model for the reaction of reduction of the DPPH* by the isolated p-catechol group in flavanone type structures is proposed. According to this model, the p-catechol group rapidly transfers two hydrogen atoms to DPPH*, through a fast rate constant k1, yielding the corresponding o-quinone. Then, the intermediate o-quinone forms an adduct with the alcoholic solvent, through a slow rate constant k2, and regenerates the p-catechol group. The regenerated p-catechol group reduces additional DPPH* through a fast rate constant k3, yielding the corresponding o-quinone, which can form a new adduct with the solvent to regenerate the p-catechol group, and so on. From the kinetics model, two explicit kinetics equations have been derived that fit very well the experimental data points acquired from all assayed compounds in all of the experiments carried out, thus allowing an accurate determination of the corresponding rate and stoichiometric constants.     

Occurrence of naturally acetylated lignin units

This work examines the occurrence of native acetylated lignin in a large set of vascular plants, including both angiosperms and gymnosperms, by a modification of the so-called Derivatization Followed by Reductive Cleavage (DFRC) method. Acetylated lignin units were found in the milled wood lignins of all angiosperms selected for this study, including mono- and eudicotyledons, but were absent in the gymnosperms analyzed. In some plants (e.g., abaca, sisal, kenaf, or hornbeam), lignin acetylation occurred at a very high extent, exceeding 45% of the uncondensed (alkyl-aryl ether linked) syringyl lignin units. Acetylation was observed exclusively at the gamma-carbon of the lignin side chain and predominantly on syringyl units, although a predominance of acetylated guaiacyl over syringyl units was observed in some plants. In all cases, acetylation appears to occur at the monomer stage, and sinapyl and coniferyl acetates seem to behave as real lignin monomers participating in lignification.     

Determination of the crop coefficient for grafted ‘Tahiti’ lime trees and soil evaporation coefficient of Rhodic Kandiudalf clay soil in Sao Paulo,Brazil

The expansion of permanent trickle irrigation systems in Sao Paulo (Brazil) citrus has changed the focus of irrigation scheduling from determining irrigation timing to quantifying irrigation amounts. The water requirements of citrus orchards are difficult to estimate, since they are influenced by heterogeneous factors such as age, planting density and irrigation system. In this study, we estimated the water requirements of young ‘Tahiti’ lime orchards, considering the independent contributions from soil evaporation and crop transpiration by splitting the crop coefficient (Kc = ETc/ETo) into two separate coefficients; Ke, a soil evaporation coefficient and Kcb, a crop transpiration coefficient. Hence, the water requirement in young ‘Tahiti’ lime (ET_y) is ET_y = (Ke + Kcb) · ETo, where ETo is the reference crop evapotranspiration. Mature tree water requirement (ET_m) is ET_m = Kcb · ETo, assuming no soil water evaporation. Two lysimeters were used; one was 1.6 m in diameter and 0.7 m deep, and the other was 2.7 m in diameter and 0.8-m deep. The first one was used to calculate evaporation and the second one was used for transpiration. ETo was estimated by the Penman–Monteith method (FAO-56). The measurements were conducted during a period between August 2002 and April 2005 in Piracicaba, Sao Paulo state, Brazil. The lysimeters were installed at the center of a 1.0-ha plot planted with ‘Tahiti’ lime trees grafted on ‘Swingle’ citrumelo rootstock. The trees were 1-year old at planting, spaced 7 × 4 m, and were irrigated by a drip irrigation system. During the study period, Kc varied between 0.6 and 1.22, and Kcb varied between 0.4 and 1.0. The results suggested that for young lime trees, the volume of water per tree calculated by Ke + Kcb is about 80% higher than the volume calculated using Kc. For mature trees, the volume of water per tree calculated using just Kcb can be 10% less than using Kc. The independent influence of soil evaporation and transpiration is important to better understand the water consumption of young lime trees during growth compared to mature lime trees.     

Changes in the volatile composition of a semihard ewe milk cheese induced by high-pressure treatment of 300 MPa

The effect of high-pressure (HP) treatment (300 MPa, 10 min) on the volatile profile of semihard ewe milk cheeses was investigated. The HP treatment was applied at two different stages of ripening (1 and 15 days; 3P1 and 3P15) and microbiota, proteolysis indexes (soluble nitrogen and total free amino acid content), and volatile compounds were assayed at 15, 60, 90, and 150 days of ripening. The intensity of odor and aroma of cheeses was also assayed. 3P1 cheeses presented the highest content of free amino acids and were characterized by the lowest amounts of aldehydes, ketones, short-chain free fatty acids, and terpenes and higher levels of ethanol and ethyl esters. 3P15 cheeses were characterized by the highest content of short-chain free fatty acids and pyruvaldehyde and the lowest abundance of secondary alcohols and were more similar to control cheeses than those HP-treated on the first day. Intensities of odor and aroma were not significantly influenced by the HP treatment. However, the panellists found some differences in 3P1 as compared with control and 3P15 cheeses in what they perceived as lower odor and aroma quality.     

Method of determination of nitrosamines in sausages by CO2 supercritical fluid extraction (SFE) and micellar electrokinetic chromatography (MEKC)

In this paper, the use of supercritical fluid extraction (SFE) and micellar electrokinetic capillary chromatography (MEKC) is proposed for the complete analysis of volatile nitrosamines in sausages. The extraction fluid used was CO2 and variables such as density, temperature of thimbles, extraction time, modifier, fluid flow, and kind of traps were investigated. Several experiments were carried out to obtain the most favorable conditions for analysis of volatile nitrosamines in sausages. The recoveries ranged from 21 to 82% for the five nitrosamines studied. The optimal condition of extraction was 0.2 g of sample fortified with 10 mg/kg, using dynamic extraction during 20 min and with adsorbent Florisil in the trap. The solvent selected for the elution of the analytes was methanol.     

Quantitative structure-antifungal activity relationships of some benzohydrazides against Botrytis cinerea

Fourteen benzohydrazides have been synthesized and evaluated for their in vitro antifungal activity against the phytopathogenic fungus Botrytis cinerea. The best antifungal activity was observed for the N',N'-dibenzylbenzohydrazides 3b-d and for the N-aminoisoindoline-derived benzohydrazide 5. A quantitative structure-activity relationship (QSAR) study has been developed using a topological substructural molecular design (TOPS-MODE) approach to interpret the antifungal activity of these synthetic compounds. The model described 98.3% of the experimental variance, with a standard deviation of 4.02. The influence of an ortho substituent on the conformation of the benzohydrazides was investigated by X-ray crystallography and supported by QSAR study. Several aspects of the structure-activity relationships are discussed in terms of the contribution of different bonds to the antifungal activity, thereby making the relationships between structure and biological activity more transparent.     

Effects of agricultural practices on color, carotenoids composition, and minerals contents of sweet peppers, cv. Almuden

Consumers demand organic products because they believe they are more flavorful and respectful to the environment and human health. The effects of conventional, integrated, and organic farming, grown in a controlled greenhouse, on color, minerals, and carotenoids of sweet pepper fruits ( Capsicum annuum), cv. Almuden, were studied. Experimental results proved that organic farming provided peppers with the highest (a) intensities of red and yellow colors, (b) contents of minerals, and (c) total carotenoids. Integrated fruits presented intermediate values of the quality parameters under study, and conventional fruits were those with the lowest values of minerals, carotenoids, and color intensity. As an example, the concentrations of total carotenoids were 3231, 2493, and 1829 mg kg (-1) for organic, integrated, and conventional sweet peppers, respectively. Finally, organic red peppers could be considered as those having the highest antioxidant activity of all studied peppers (agricultural farming and development stage).     

Testing MACRO (version 5.1) for pesticide leaching in a Dutch clay soil

Testing of pesticide leaching models against comprehensive field-scale measurements is necessary to increase confidence in their predictive ability when used as regulatory tools. Version 5.1 of the MACRO model was tested against measurements of water flow and the behaviour of bromide, bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide] and imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] in a cracked clay soil. In keeping with EU (FOCUS) procedures, the model was first calibrated against the measured moisture profiles and bromide concentrations in soil and in drain water. Uncalibrated pesticide simulations based on laboratory measurements of sorption and degradation were then compared with field data on the leaching of bentazone and imidacloprid. Calibrated parameter values indicated that a high degree of physical non-equilibrium (i.e. strong macropore flow) was necessary to describe solute transport in this soil. Comparison of measured and simulated bentazone concentration profiles revealed that the bulk of the bentazone movement in this soil was underestimated by MACRO. Nevertheless, the model simulated the dynamics of the bentazone breakthrough in drain water rather well and, in particular, accurately simulated the timing and the concentration level of the early bentazone breakthrough in drain water. The imidacloprid concentration profiles and its persistence in soil were simulated well. Moreover, the timing of the early imidacloprid breakthrough in the drain water was simulated well, although the simulated concentrations were about 2-3 times larger than measured. Deep groundwater concentrations for all substances were underestimated by MACRO, although it simulated concentrations in the shallow groundwater reasonably well. It is concluded that, in the context of ecotoxicological risk assessments for surface water, MACRO can give reasonably good simulations of pesticide concentrations in water draining from cracking clay soils, but that prior calibration against hydrologic and tracer data is desirable to reduce uncertainty and improve accuracy.     

Permeability profile estimation of flavonoids and other phenolic compounds by biopartitioning micellar capillary chromatography

This paper points out the usefulness of biopartitioning micellar chromatography (BMC) using capillary columns as a high-throughput primary screening tool providing key information about the oral absorption, skin permeability, and brain-blood distribution coefficients of 15 polyphenols (6 flavones, 2 flavonols, a flavanone, 2 flavan-3-ols, 3 phenolic acids, and a phloroglucinol) in a simple and economical way. For the compounds studied, except vicenin-2, rutin, chlorogenic acid, p-hydroxycinnamic acid, and 4-hydroxybenzoic acid, maximal oral absorption (>90%) can be expected, if there are not solubility problems or metabolic processes. On the other hand, the most retained compounds in BMC, that is, 5-hydroxyflavone, flavone, and flavanone, show the highest brain-blood distribution coefficients and skin permeability coefficients.     

Dietary fiber intake in two European diets with high (copenhagen, Denmark) and low (Murcia, Spain) colorectal cancer incidence

Contradictory results have been reported in studies associating dietary fiber (DF) intake and the incidence of colorectal cancer. Most studies focused mainly on the amount of total DF, but DF is a heterogeneous complex and its components are generally ignored. The aim of this work was to compare the amount and composition of DF intake in Murcia (Spain) and Copenhagen (Denmark). Total dietary fiber intake was a 31% higher in Murcia than in Copenhagen, the ratio of insoluble DF/soluble DF being similar in the two diets. DF in Murcia contains major amounts of nonstarch polysaccharides and polyphenolic compounds, mainly derived from the high consumption of fruits and vegetables (6.7 servings). Resistant starch intake was of the same order in the two regions while resistant protein intake was higher in Murcia. The quantitative and qualitative differences in DF intake may contribute to understand the differences in colorectal cancer incidence in Mediterranean and Scandinavian areas.