Quantitation of short-chain glycerol-bound compounds in thermoxidized and used frying oils. A monitoring study during thermoxidation of olive and sunflower oils

Major short-chain glycerol-bound compounds were investigated in olive oil (OO) and conventional sunflower oil (SO) during thermoxidation at 180 degrees C for 5, 10, and 15 h. These compounds included methyl heptanoate (C7:0), methyl octanoate (C8:0), methyl 8-oxo-octanoate (8-oxo-C8:0), methyl 9-oxononanoate (9-oxo-C9:0), dimethyl octanodiate (C8:0 diester), and dimethyl nonanodiate (C9:0 diester), which were analyzed by GC after derivatization of triacylglycerols to fatty acid methyl esters. An acceptable linear correlation (r = 0.967) was found between the total content of these compounds and the total content of polar compounds, suggesting that quantitation of the major short-chain glycerol-bound compounds provides a good indication of the total alteration level of oils heated at frying temperature. Samples with levels of polar compounds around 25% on oil showed total contents within 2-3 mg/g of oil. To determine the content of these compounds in used frying oils, 10 samples from restaurants and fried-food outlets in Spain were analyzed. Results showed total levels between 2.13 and 7.56 mg/g of oil in samples with contents of polar compounds ranging from 18.8 to 55.5% on oil. Samples with levels of polar compounds of approximately 25% showed total contents of the short-chain compounds similar to those found in the thermoxidized oils, that is, within 2-3 mg/g of oil.     

Antioxidant activity of ethanolic extracts from several asparagus cultivars

Three different methods (antiradical activity, inhibition of primary oxidation, and ferric reducing power) have been used to evaluate the antioxidant activity of eight different asparagus cultivars and byproducts: white and green asparagus from Alcalá del Río (Guadalquivir Valley, Seville) and American hybrids, native spears, and their byproducts from Huétor-Tájar (Vega de Granada). The correlation between antioxidant activity and total phenol content was studied. Six standards were also tested to validate the modified methods for antioxidant activity determination. Results obtained for antiradical capacity and reducing power were very similar, and a high correlation with phenols was found (R > or = 0.9 for both tests). Sample origin was an important factor, spears from Huétor-Tájar having higher values (ARC between 7 and 10 and P(R) of 0.25-0.33) than those from Alcalá del Río (ARC 0.6-2 and P(R) of 0.05-0.07). Significant differences were found between spears with the same origin, suggesting that genetics are another factor to take into account. Asparagus inhibits lipid primary oxidation, but no correlation between the inhibition percentage and phenols was observed. Asparagus origin was the only factor that led to significant differences: samples from Huétor-Tájar had higher values (POIC between 18 and 32) than those from Alcalá del Río (POIC of 5-9). Byproducts from the canning industry at Huétor-Tájar were also assayed for antioxidant activity; the results obtained suggested that byproducts could be considered as an excellent source of natural antioxidants.     

Pectins as possible source of the copper involved in the green staining alteration of cv. Gordal table olives

The pectic and pigment compositions and Ca and Cu contents of the alcohol-insoluble solid (AIS) residues were determined in cv. Gordal olives treated with NaOH solution and kept at different constant pH values (3.5-6.5). The same controls were made in table olives presenting green staining alteration. The ratio between the various pectin fractions of the more acid pH experiment samples remained similar in fruits not showing green staining. In altered fruits, the protopectin fraction was lower, and the calcium pectate or EDTA soluble pectins were higher. Regarding the presence of Ca and Cu in the AIS, it was observed that, whereas Ca levels fell at the most acid pH values, those of Cu increased. The concentration of Ca was higher in the AIS of altered olives than in nonaltered ones. The same trend was seen for the zone with or without green staining of an altered fruit. In the case of Cu, the relationship was the opposite: a decrease in the levels of AIS Cu in fruits and zones of fruits with green staining. This result was correlated with the highest concentration of Cu-chlorophyll complexes found in such samples and suggested that pectins might act as a reservoir of Cu involved in the alteration.     

Adsorption of pesticides from water by functionalized organobentonites

Replacement of natural inorganic cations of clay minerals with organic cations has been proposed as a strategy to improve the adsorptive capacity of clay minerals for organic compounds, including pesticides. The organic cations most commonly used for this purpose have been quaternary ammonium ions containing alkyl or aryl chains without specific functional groups. In this work, we evaluated the ability of two bentonites (SWy-2 and SAz-1) exchanged with four natural organic cations containing diverse functional groups (L-carnitine, L-cysteine ethyl ester, L-cystine dimethyl ester, and thiamine) as adsorbents of pesticides varying in their chemical structures (simazine, hexazinone, triadimefon, alachlor, carbaryl, and imazethapyr). For comparison purposes, the adsorptive properties of two "classical" organobentonites, hexadecyltrimethylammonium- and phenyltrimethylammonium-exchanged bentonites, were also determined. Most organobentonites displayed higher affinity for the pesticides than the untreated bentonites, but the improvement in adsorption capacity varied depending on the characteristics of the pesticide and the interlayer organic cation. Triadimefon, carbaryl, and imazethapyr displayed the highest affinity for carnitine (K(f) = 229-2377)-, thiamine (K(f) = 83-354)-, and cystine (K(f) = 96-100)-treated bentonites, respectively, whereas alachlor was adsorbed similarly by all organobentonites. In general, pesticide adsorption-desorption hysteresis was greater for adsorbents with the highest adsorption capacities. The results demonstrate that selective modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve their performance for the removal of specific pesticides from the environment.     

Extending applicability of the oxygen radical absorbance capacity (ORAC-fluorescein) assay

The ORAC-fluorescein (ORAC-FL) method recently validated using automatic liquid handling systems has now been adapted to manual handling and using a conventional fluorescence microplate reader. As calculated for Trolox, the precision of the method was <3.0, expressed as percent coefficient of variation. The accuracy of the method was <2.3, expressed as percent variation of the mean. The detection and quantification limits were those corresponding to 0.5- and 1-microM Trolox standard solutions, respectively. The method has been applied to 10 pure compounds (benzoic and cinnamic acids and aldehydes, flavonoids, and butylated hydroxyanisole), to 30 white, rose, and bottled- and oak-aged red wines, and to 7 commercial dietary antioxidant supplements. All samples exhibited a good linear response with concentration. As seen by other methodologies, the chemical structure of a compound determines its antioxidant activity (ORAC-FL value). Of particular interest were the results with oak-aged red wines from different vintages (1989-2002) that confirm influence of vintage, but not origin of the oak, in the antioxidant activity of wines from the same variety. Dietary antioxidant supplements presented a great variability (170-fold difference) in their antioxidant potency. This work proves applicability of the ORAC-FL assay in evaluating the antioxidant activity of diverse food samples.     

Countercurrent supercritical fluid extraction and fractionation of high-added-value compounds from a hexane extract of olive leaves

Countercurrent supercritical fluid extraction (CC-SFE) at a pilot scale plant was used for fractionation of high-added-value products from a raw extract of olive leaves in hexane. Compounds found in the raw extract were waxes, hydrocarbons, squalene, beta-carotene, triglycerides, alpha-tocopherol, beta-sitosterol, and alcohols. The CC-SFE extraction process was investigated according to a 2(3) full factorial experimental design using the following variables and ranges: extraction pressure, 75-200 bar; extraction temperature, 35-50 degrees C; and ethanol as modifier, 0-10%. Data were analyzed in terms of extraction yield, enrichment, recovery, and selectivity. Higher extraction yields were attained at 200 bar. For most of the compounds analyzed enrichment was attained at the same conditions, that is, 75 bar, 35 degrees C, and 10% ethanol. Hydrocarbons were usually recovered in the separators, whereas waxes and alpha-tocopherol remain in the raffinate. Selectivity data reveal that alpha-tocopherol is the most easily separable compound. The influence of the experimental factors on the recovery of all the compounds was studied by means of regression models. The best fitted model was attained for beta-sitosterol, with R2 = 99.25%.     

In vivo antifungal activity of the essential oil of Bupleurum gibraltarium against Plasmopara halstedii in sunflower

The antifungal activity of the essential oil of the aerial parts of Bupleurum gibraltarium was evaluated against Plasmopara halstedii. Fungus spores were inoculated in sunflower seedlings, previously treated with several essential oil solutions, and the sporulation percentage was measured after an 11-day treatment. The oil at a concentration of 5.0 mL/L clearly inhibited the fungus sporulation. The contact between fungus sporangia and essential oil was minimized, so it seems that the oil pretreatment could activate the defense response of the sunflower seedlings against the pathogen invasion. The main compounds in the oil were sabinene (31.1%), alpha-pinene (15.6%), and 2,3,4-trimethylbenzaldehyde (10.9%), among a total of 65 components identified.     

Aroma extract dilution analysis. Precision and optimal experimental design

The odor thresholds of 12 different compounds have been determined in an AEDA experiment using a panel composed of 8 individuals. Only in one case is the distribution of thresholds among judges significantly different from the log-normal. The cause of that departure from normality seems to be a cross adaptation rather than anosmia. The standard deviations (SD) range from 2(0.7) to 2(4.1), with 2(1.8) as average. If the AEDA is carried out at a dilution rate, R, and dilution R(P) (where P = 0, 1, 2.) is the last one at which a compound was detected by a judge, the flavor dilution (FD) factor that should be provided for that judge is R(P+0.5). In the case where several judges carry out the AEDA, the FD for a given compound should be the geometric mean of the FD provided by all the judges. The SD of the distribution of FDs is related to that of the distribution of odor thresholds, but is strongly influenced by the dilution rate, R, being higher with higher R values. The relationship between both SDs can be used to determine the expected precision (measured as the geometric length of the 95% confidence interval) of the result of an AEDA experiment as a function of the dilution rate, the number of judges, and the SD of the distribution of thresholds. Different simulations have shown that in most cases, a dilution rate of 10 is the best option, and that lower dilution rates are advantageous only if the analyzed solution contains compounds with a very narrow distribution of thresholds.     

Coriander essential oil composition from two genotypes grown in different environmental conditions

The objective was to study the essential oil composition of coriander fruits in plants growing in environments differing in soil conditions and weediness level. Factorial field experiments were conducted in two locations from the Rolling Pampas, Argentina, and two coriander landraces (European and Argentinean) were tested under two levels of nitrogen fertilization and weediness. Data were evaluated with uni- and multivariate techniques. The variation in the oil composition was related to the relative proportion of the constituents and not to the presence/absence of a particular component. Weather conditions in 1997 favored linalool and camphor in both landraces. Location, fertilization, and weediness also affected the chemical profile. The European landrace showed a more stable concentration of the major components than the Argentinean landrace. These results, which show the relationships between some environmental conditions and the essential oil composition, are useful in the development of innovative strategies aimed to improve oil composition and to manage crop pests.     

Tequila authenticity assessment by headspace SPME-HRGC-IRMS analysis of 13C/12C and 18O/16O ratios of ethanol

By use of headspace SPME sampling and a PLOT column, on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and the pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta(13)C(VPDB) and delta(18)O(VSMOW) values of ethanol in authentic (n = 14) and commercial tequila samples (n = 15) as well as a number of other spirits (n = 23). Whereas with delta(13)C(VPDB) values ranging from -12.1 to -13.2 per thousand and from -12.5 to -14.8 per thousand similar variations were found for 100% agave and mixed tequilas, respectively, the delta(18)O(VSMOW) data differed slightly within these categories: ranges from +22.1 to +22.8 per thousand and +20.8 to +21.7 per thousand were determined for both the authentic 100% agave and mixed products, respectively. The data recorded for commercial tequilas were less homogeneous; delta(13)C(VPDB) data from -10.6 to -13.9 per thousand and delta(18)O(VSMOW) values from +15.5 to +22.7 per thousand were determined in tequilas of both categories. Owing to overlapping data, attempts to differentiate between white, rested, and aged tequilas within each of the two categories failed. In addition, discrimination of tequila samples from other spirits by means of delta(13)C(VPDB) and delta(18)O(VSMOW) data of ethanol was restricted to the products originating from C(3) as well as C(4)/CAM raw materials.