Mechanism of deactivation of triplet-excited riboflavin by ascorbate, carotenoids, and tocopherols in homogeneous and heterogeneous aqueous food model systems

Tocopherols (alpha, beta, gamma, and delta) and Trolox were found to deactivate triplet-excited riboflavin in homogeneous aqueous solution (7:3 v/v tert-butanol/water) with second-order reaction rates close to diffusion control [k2 between 4.8 x 10(8) (delta-tocopherol) and 6.2 x 10(8) L mol(-1) s(-1) (Trolox) at 24.0 +/- 0.2 degrees C] as determined by laser flash photolysis transient absorption spectroscopy. In aqueous buffer (pH 6.4) the rate constant for Trolox was 2.6 x 10(9) L mol(-1) s1 and comparable to the rate constant found for ascorbate (2.0 x 10(9) L mol(-1) s(-1)). The deactivation rate constant was found to be inferior in heterogeneous systems as shown for alpha-tocopherol and Trolox in aqueous Tween-20 emulsion (approximately by a factor of 4 compared to 7:3 v/v tert-butanol/water). Neither beta-carotene (7:3 v/v tert-butanol/water and Tween-20 emulsion), lycopene (7:3 v/v tert-butanol/water), nor crocin (aqueous buffer at pH 6.4, 7:3 v/v tert-butanol/water, and Tween-20 emulsion) showed any quenching on the triplet excited state of riboflavin. Therefore, all carotenoids seem to reduce the formation of triplet-excited riboflavin through an inner-filter effect. Activation parameters were based on the temperature dependence of the triplet-excited deactivation between 15 and 35 degrees C, and the isokinetic behavior, which was found to include purine derivatives previously studied, confirms a common deactivation mechanism with a bimolecular diffusion-controlled encounter with electron (or hydrogen atom) transfer as rate-determining step. DeltaH for deactivation by ascorbic acid, Trolox, and homologue tocopherols (ranging from 18 kJ mol(-1) for Trolox in Tween-20 emulsion to 184 kJ mol(-1) for ascorbic acid in aqueous buffer at pH 6.4) showed a linear dependence on DeltaS (ranging from -19 J mol(-1) K(-1) for Trolox in aqueous buffer at pH 6.4 to +550 J mol(-1) K(-1) for ascorbic acid in aqueous buffer pH 6.4). Among photooxidation products from the chemical quenching, lumicrome, alpha-tocopherol quinones and epoxyquinones, and alpha-tocopherol dimers were identified by ESI-QqTOF-MS.     

Structural ripening-related changes of the arabinan-rich pectic polysaccharides from olive pulp cell walls

In this study, the structural features and ripening-related changes that occur in the arabinan-rich pectic polysaccharides highly enmeshed in the cellulosic matrix of the olive pulp fruit were evaluated. These pectic polysaccharides, obtained from two consecutive harvests at green, cherry, and black ripening stages, account for 11-19% of the total pectic polysaccharides found in the olive pulp cell walls and were previously shown to occur as calcium chelating dimers. On the basis of the 13C NMR, (1H, 13C) gHSQC, 2D COSYPR, and (1H,13C) gHMBC carbon and proton resonances of the variously linked arabinosyl residues, we propose a tentative structure. This structure is particularly characterized by T-beta-Araf (1-->5)-linked to (1-->3,5)-Araf residues and by the occurrence of branched and linear blocks in the arabinan backbone. Methylation analysis showed that these pectic polysaccharides of black olives have more arabinan side chains, which were shorter (less (1-->5)-Araf), highly branched (more (1-->3,5)-Araf), and with shorter side chains (fewer (1-->3)-Araf) than those of green and cherry olives. Quantitative 13C NMR data indicated that these modifications involved the disappearance of the characteristic terminally linked beta-Araf residue of the arabinans. This odd feature can be used as a diagnostic tool in the evaluation of the stage of ripening of this fruit, as well as a marker for the presence of olive pulp in matrices containing pectic polysaccharides samples.     

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.     

Volumetric properties of sunflower methyl ester oil at high pressure

Biodiesel is an alternative to diesel oil (DO), because it is a fuel obtained from renewable resources that has lower emissions than DO. Biomass production should promote agricultural activity to obtain fuels for the transport sector. The study of the behavior of biodiesel at varying pressure and temperature is very interesting because diesel engines are mechanical systems that work with fuels submitted to high pressure. The specific volume, isothermal compressibility, and cubic expansion coefficients of refined sunflower methyl ester oil (SMEO) and unrefined sunflower methyl ester oil (URSMEO) were obtained and compared with those of DO from 0.1 to 350 MPa and 288.15 to 328.15 K. This work shows that oil refinement did not significantly modify any of the properties studied of the final biodiesel. Compared with DO, both SMEOs were about 6% denser, whereas isothermal compressibility and cubic expansion coefficients were bigger or smaller for DO depending on pressure and temperature.     

Multivariate analysis for the evaluation of fiber, sugars, and organic acids in commercial presentations of table olives

Table olives constitute an important part of the Mediterranean diet and the diet of many non-olive-producing countries. The aim of this work was to determine the fiber, sugar, and organic acid contents in Spanish commercial presentations of table olives and characterize them by means of a multivariate analysis. The selection of variables was carried out on the basis of a canonical analysis and their classification, according to processing styles and cultivars, through a linear discriminant analysis. Values of dietary fiber in table olives ranged from 2 to 5 g/100 g edible portion (e.p.). Some stuffing materials (almond, hot red pepper, and hazelnut) or the addition of capers produced a significant increase in the total dietary fiber in green olives. Glucose, fructose, and mannitol were usually found in the ranges of 0-55, 0-70, and 0-107 mg/100 g e.p., respectively. Succinic acid was detected only in green and directly brined olives (0-40 mg/100 g e.p.), while lactic and acetic acids were used within the ranges of 0-681 and 5-492.8 mg/100 g e.p., respectively. A multivariate analysis showed that fiber, mannitol, and succinic, lactic, and acetic acids can be used to discriminate between processing styles (95.5% correct assignations) and cultivars (61.20%). Current data can also be used in the evaluation of the dietary value of table olives.     

Beta-carotene isomer composition of sub- and supercritical carbon dioxide extracts. Antioxidant activity measurement

In the present work sub- and supercritical extraction conditions using carbon dioxide were studied in order to obtain extracts with different compositions from the green microalgae Dunaliella salina. Different compositions of beta-carotene isomers were identified in the extracts by using HPLC-DAD. Also, antioxidant activity of the extracts was measured using a TEAC assay. An experimental design was applied considering two factors, extraction pressure and temperature, in a wide range of values, trying to maximize the extraction yield. Higher yields were obtained at high pressures and low temperatures, that is, at higher CO2 densities. Attempts were made to correlate the antioxidant activity of the extracts with their chemical composition by means of principal component analysis. A certain relationship was found between their antioxidant activity and the isomeric composition of beta-carotenes. As a result, an original equation is proposed to predict the antioxidant activity of extracts from D. salina in terms of the ratio 9-cis-beta-carotene/all-trans-beta-carotene, the concentration of alpha-carotene, and, especially, the concentration of 9-cis-beta-carotene.     

Less is more: Little seed processing required for direct seeding in seasonal tropics

Seed processing and dormancy break treatments are recommended for rendering seeds restoration-ready. Conversely, fruit structures and seed coats may protect seeds from environmental harm in the field. We evaluated the effects of seed processing (by either keeping fruit structures or extracting seeds) and/or scarification (of physically dormant seeds) on the seedling emergence and establishment of 10 legume tree species from tropical forests and savannas of Central Brazil. We sowed seeds in a greenhouse for reference and in a field experiment conducted in tilled ready-to-seed sites. We monitored seedling emergence and survival for a year. We calculated the costs of harvesting, processing, and pretreating seeds, and considered the final cost of a 1-year-old seedling. Seed extraction resulted in lower emergence for most species in the greenhouse and in the field. It also accelerated emergence of three and four species in the greenhouse and the field, respectively. Scarification resulted in lower seedling emergence in the field for half of the species, while it increased emergence of three species in the greenhouse. Most species presented accelerated emergence both in the greenhouse and the field. The seedling cost was 1.6 to 74.6 times higher when seeds were processed, and 1.3 to 6.0 times when seeds were scarified, except for one species. Keeping fruit structures and seed coats reduced the costs of seeds and increased the success of direct seeding.

     

Essential oils-based repellents for the management of Myzus persicae and Macrosiphum euphorbiae

Journal of Pest Science - Aphids are one of the major agricultural pests in the world. Their pest management in pepper greenhouses is based on integrated control with release of natural enemies and...     

Changes in soil carbon and nitrogen stocks after conversion of subtropical natural forest to loblolly pine plantations

Pinus plantations have increased in Brazil, and native forest areas have been converted for timber production. The clearing and the long-term loblolly pine (Pinus taeda L.) land-use effects on soil carbon and nitrogen stocks were evaluated in a natural broadleaved forest and in loblolly pine sites cultivated for 29, 35, 38 and 49 years, as well the soil contribution as ecosystem carbon pool. According to the exponential-decay model fitted to changes in carbon stock, the initial soil carbon stock of 200 Mg ha^?1 to a depth of 100 cm in the natural forest decreased by 36% over 49 years of pine cultivation (around 72.4 Mg ha^?1 of C). Around two-thirds of this decrease occurred in the top 30 cm of the soil and intensively in the first 12 years of cultivation, but slowly faded as carbon stock tended to reach a new steady state after approximately 49 years of cultivation. The soil nitrogen stock in the natural forest was 14.2 Mg ha^?1 to a depth of 100 cm and decreased by 36% over the 49 years. This decrease was linear according to the fitted model, especially in the top 30 cm where nitrogen decline was 83% and was proportionally more intense than the carbon decline. Despite the soil carbon decrease, soil remained the largest carbon reservoir in the ecosystem for the growing rotation time of loblolly pine in this region.

     

Yield map generation of perennial crops for fresh consumption

Yield mapping technologies can help to increase the quantity and quality of agricultural production. Current systems only focus on the quantification of the harvest, but the quality has equal or greater importance in some perennial crops and impacts directly on the financial profitability. Therefore, a system was developed to quantify and relate the quality obtained in the classification line with the plants of the orchard and for decision-making. The system is comprised of hardware, which obtains the location of the harvester bag during harvesting and unloading at the unloading site, and software that processes the collected data. The cloud of real-time data contributed from the different collectors (bins) allows the construction of yield maps, considering the multi-stage harvesting system. Further, the system enables the creation of a detailed map of the plants and fruits harvested. As the harvest focuses on quality, it takes place in stages, depending on the ripening of the fruits. In addition to the yield maps, the system allows identification of the efficiency of each worker undertaking the harvest by the number of performed discharges and by the time spent. The system was developed in partnership with the Federal Technological University of Paraná and Embrapa Uva & Vinho and was tested in apple orchards in southern Brazil. Although the system was evaluated with only data from apple cultivation, monitoring the quality and quantifying other orchard fruits can positively impact the fruit sector.