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Phenolic compounds of eight pistachio ( Pistacia vera L.) cultivars and their residual cakes and virgin oils (screw pressing) were studied using high-performance liquid chromatography-diode array detection-electrospray ionization-tandem mass spectrometry. A total of 25 compounds were identified and quantified for pistachio nuts and residual cakes, with the presence of five flavonols, six flavanols, and one gallotannin being reported for the first time. Total phenolics in pistachio nuts showed a concentration from 1359 mg/kg (Kastel) to 4507 mg/kg (Larnaka). Flavanols were the most abundant phenolics, at about 90%, with resulting procyanidin B1 and gallocatechin being the main phenolics, depending upon the cultivar. Other phenolic groups, such as anthocyanins (from 54 to 218 mg/kg), flavonols (from 76 to 130 mg/kg), flavanones (from 12 to 71 mg/kg), and gallotannins (from 4 to 46 mg/kg), were also identified. Residual cakes presented the same phenolic profile but with a concentration almost double because of the concentration effect caused by the oil separation. Virgin pistachio oils showed a very low phenolic content, with eriodyctiol being the only compound identified.

Virgin olive oil (VOO) phenolic compounds have high nutritional and biological properties. The purpose of this research was to study the stability of VOO phenolic compounds during long-term storage (18 months) at different temperatures (5, 15, 25, and 50 °C) and to verify the advantage of storing VOO at a temperature lower than the usual commercial conditions (20-25 °C). Four monovarietal VOOs that differed in their fatty acid profile and content of natural antioxidants were used in this study. The degradation of secoiridoid phenolics during storage displayed pseudo-first-order kinetics and depended on the initial content of phenolics related to olive oil variety. The initial degradation rate was similar at 5 and 15 °C but increased considerably at 25 °C and was even faster at 50 °C. Tyrosol derivatives were more stable than hydroxytyrosol compounds, especially in closed bottles with limited oxygen availability. The increase in the content of simple phenolics, the decrease of their secoiridoid derivatives, or the ratio of simple to secoiridoid phenolics could be used as indices of the oxidative and hydrolytic degradation of VOO phenolics. The shelf life of the studied VOO was considerably extended at reduced storage temperature (15 vs 25 °C). Moreover, storage conditions affected VOO phenolic content and therefore the expiration date of the health claim that olive oil polyphenols contribute to the protection of blood lipids from oxidative stress.

Malaxation of olive paste must be considered to be much more than a simple physical separation, because a complex bioprocess takes place that is very relevant to the quality and composition of the final product. A combined study of the effect of kneading temperature and time on the minor composition of olive paste and its corresponding virgin olive oil, processed in an experimental oil mill (Pieralisi, Fattoria) with a working capacity of 200 kg/h, is reported. A large drop in the oleuropein content in the olive paste with respect to its initial content in the olive fruit (between 92 and 96%) was observed, which suggested its almost total degradation during the crushing operation. The major phenolic compound found in the olive paste during kneading was the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA, always higher than 60% of the total phenols). This greatly decreased during malaxation (from 5505 to 2317 mg/kg, on average). The content of phenolic compounds in virgin olive oil was much more affected by the malaxation temperature than the kneading time. For instance, the 3,4-DHPEA-EDA content increased by 220-630% in the two batches when the temperature was increased from 20 to 40 degrees C. A reduction in the C6 aldehydes was found in virgin olive oil as the malaxation temperature increased, especially in E-2-hexenal (30% reduction). In contrast, C6 aldehydes in the oils from the oil mill plant significantly increased as the malaxation time increased from 30 to 90 min, chiefly E-2-hexenal (about a 70% increase).

Oxidative stability should be one of the most important quality markers of edible oils; nevertheless, it is not recognized as a legal parameter. The results reported in this study highlight the differences in the olive oil oxidation process under Rancimat accelerated conditions with respect to long-term storage at room temperature and clearly show the lack of correlation between shelf life and the Rancimat induction period. A better correlation, although not yet satisfactory, was found when the same oxidation end-point was used in both assays. The parameter K 270, a marker of secondary oxidation products, was the first index to reach the established upper legal limit under Rancimat conditions, whereas at 25 degrees C it was an index of primary oxidation products ( K 232). Furthermore, the ratio of oxidation rate at Rancimat conditions to oxidation rate at 25 degrees C was more than double for secondary oxidation products compared with primary ones. Notable differences were also observed in degradation rates of the different unsaturated fatty acids and in rates of formation of polar oxidation compounds. Moreover, under the Rancimat conditions antioxidants such as o-diphenols and alpha-tocopherol rapidly depleted, and when they had practically disappeared, there was a sharp increase in oxidation indices, such as peroxide value, and in oxidation products. At 25 degrees C, on the other hand, the depletion was much lower.

This study investigated the effect of both the degree of ripening of the olive fruit and irrigation management-rain-fed, two different regulated deficit irrigations (RDI), the method proposed by the Food and Agriculture Organization of the United Nations (known as FAO), and 125 FAO (125% FAO)-on the phenolic and volatile composition of Cornicabra virgin olive oils obtained during two crop seasons. Secoiridoid phenolic derivatives greatly decreased upon increase of both irrigation and ripening, for example, the 3,4-DHPEA-EDA content decreased from 770 to 450 mg/kg through fruit ripening under rain-fed conditions and from 676 to 388 mg/kg from rain-fed conditions to FAO irrigation treatment (at a ripeness index of approximately 4). Moreover, secoiridoid derivatives of hydroxytyrosol decreased more than those of tyrosol. The levels of major volatile components decreased in the course of ripening but were higher in irrigated olive oils: for example, the E-2-hexenal content ranged between 4.2 and 2.6 mg/kg (expressed as 4-methyl-2-pentanol) over fruit maturation under rain-fed conditions and between 8.0 and 3.5 mg/kg under FAO scheduling. It is important to note that where water was applied only from the beginning of August (RDI-2), when oil begins to accumulate in the fruit, the resulting virgin olive oil presented a phenol and volatile profile similar to those of the FAO and 125 FAO methods, but with a considerable reduction in the amount of water supplied to the olive orchard.

The degradation of secoiridoid, tocopherol, and antioxidant activity in extra virgin olive oils (EVOOs) was studied during 8 months of storage in closed bottles in the dark, at 40 and 25 degrees C. Picual, Arbequina, Taggiasca, and Colombaia monovarietal EVOOs possessing quite different fatty acid and antioxidant contents were used. The secoiridoid aglycones, namely, the oleuropein and ligstroside derivatives, and alpha-tocopherol decreased following pseudo-first-order kinetics. In all EVOOs oleuropein derivatives were less stable than the corresponding ligstroside derivatives and alpha-tocopherol. Accordingly, overall antioxidant activity decreased following pseudo-first-order kinetics, with rate constants ranging from 0.85 x 10(-)(3) to 4.1 x 10(-)(3) days(-)(1) at 40 degrees C and from 0.8 x 10(-)(3) to 1.5 x 10(-)(3) days(-)(1) at 25 degrees C. According to both the antioxidant activity and the hydrolysis and oxidation indices established by EU regulation to assess EVOO quality, Colombaia oil was the least stable, followed by Taggiasca, Arbequina, and Picual oils. Despite antioxidant degradation, EVOOs with high antioxidant contents were still "excellent" after 240 days of storage at 40 degrees C. These data led to the conclusion that the beneficial properties of EVOOs due to antioxidant activity can be maintained throughout their commercial lives.

The concentration of hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA) in virgin olive oil decreased rapidly when the oil was repeatedly used for preparing french fries in deep-fat frying operations. At the end of the first frying process (10 min at 180 degrees C), the concentration of the dihydroxyphenol components was reduced to 50-60% of the original value, and after six frying operations only about 10% of the initial components remained. However, tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA) in the oil were much more stable during 12 frying operations. The reduction in their original concentration was much smaller than that for hydroxytyrosol and its derivatives and showed a roughly linear relationship with the number of frying operations. The antioxidant activity of the phenolic extract measured using the DPPH test rapidly diminished during the first six frying processes, from a total antioxidant activity higher than 740 micromol of Trolox/kg down to less than 250 micromol/kg. On the other hand, the concentration of polar compounds, oxidized triacylglycerol monomers (oxTGs), dimeric TGs, and polymerized TGs rapidly increased from the sixth frying operation onward, when the antioxidant activity of the phenolic extract was very low, and as a consequence the oil was much more susceptible to oxidation. The loss of antioxidant activity in the phenolic fraction due to deep-fat frying was confirmed by the storage oil and oil-in-water emulsions containing added extracts from olive oil used for 12 frying operations.

This study presents the phenolic compounds profile of commercial Cornicabra virgin olive oils from five successive crop seasons (1995/1996 to 1999/2000; n = 97), determined by solid phase extraction reversed phase high-performance liquid chromatography (SPE RP-HPLC), and its relationship with oxidative stability, processing conditions, and a preliminary study on variety classification. The median of total phenols content was 38 ppm (as syringic acid), although a wide range was observed, from 11 to 76 ppm. The main phenols found were the dialdehydic form of elenolic acid linked to tyrosol (p-HPEA-EDA; 9 +/- 7 ppm, as median and interquartile range), oleuropein aglycon (8 +/- 6 ppm), and the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA; 5 +/- 8 ppm). In many cases the correlation with oxidative stability was higher when the sum of the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA) and oleuropein aglycon (r (2) = 0.91-0.96) or the sum of these two and hydroxytyrosol (r (2) = 0.90-0.97) was considered than was observed with HPLC total phenols (r (2)= 0.91-0.95) and especially with colorimetric determination of total polyphenols and o-diphenols (r (2) = 0.77-0.95 and 0.78-0.92, respectively). 3,4-DHPEA-EDA, p-HPEA-EDA, the aglycons of oleuropein and ligstroside, and HPLC total phenols content presented highly significant differences (p = 0.001-0.010) with respect to the dual- and triple-phase extraction systems used, whereas colorimetric total polyphenols content did not (p = 0.348) and o-diphenols showed a much lower significant difference (p = 0.031). The five variables that most satisfactorily classified the principal commercial Spanish virgin olive oil varieties were 1-acetoxypinoresinol, 4-(acetoxyethyl)-1,2-dihydroxybenzene (3,4-DHPEA-AC), ligstroside aglycon, p-HPEA-EDA, and RT 43.3 contents.