Field-Deployable Determinations of Peroxide Index and Total Phenolic Content in Olive Oil Using a Promising Portable Sensor System.

Useful information about the oxidative stability of a virgin olive oil in terms of oxidation products and antioxidant compounds can be obtained by analyzing the peroxide index (PI) and total phenolic content (TPC), respectively. These quality parameters are usually determined in a chemical laboratory using expensive equipment, toxic solvents, and well-trained personnel. This paper presents a novel portable sensor system for in the field and rapid determination of PI and TPC that is particularly suited in the case of small production environments that cannot afford an internal laboratory for quality control analysis. The system is small, can be powered by both USB ports and batteries, is easy to operate, and integrates a Bluetooth module for wireless data transmission. It estimates the PI and TPC in olive oil from the measurement of the optical attenuation of an emulsion between a reagent and the sample under test. The system has been tested on a set of 12 olive oil samples (eight for calibration and four for validation), and the results have shown how the considered parameters can be estimated with good accuracy. The maximum deviation from the results obtained with the reference analytical techniques is 4.7 meq O2/kg in the case of PI and 45.3 ppm in the case of TPC for the calibration set, while it is 14.8 meq O2/kg in the case of PI and 55 ppm in the case of TPC for the validation set.

Stepwise strategy based on 1H-NMR fingerprinting in combination with chemometrics to determine the content of vegetable oils in olive oil mixtures.

1H NMR fingerprinting of edible oils and a set of multivariate classification and regression models organised in a decision tree is proposed as a stepwise strategy to assure the authenticity and traceability of olive oils and their declared blends with other vegetable oils (VOs). Oils of the 'virgin olive oil' and 'olive oil' categories and their mixtures with the most common VOs, i.e. sunflower, high oleic sunflower, hazelnut, avocado, soybean, corn, refined palm olein and desterolized high oleic sunflower oils, were studied. Partial least squares (PLS) discriminant analysis provided stable and robust binary classification models to identify the olive oil type and the VO in the blend. PLS regression afforded models with excellent precisions and acceptable accuracies to determine the percentage of VO in the mixture. The satisfactory performance of this approach, tested with blind samples, confirm its potential to support regulations and control bodies.

Functional and sensory properties of phenolic compounds from unripe grapes in vegetable food prototypes.

Unripe grapes (UGs) from thinning are an unexploited source of phenols useful as functional ingredient. However, phenols may negative affect sensory quality of food. Chemical and sensory properties of UG phenols in plant-based foods were not investigated before. With this aim, an extract from UGs, obtained by a green extraction technique, was used to fortify three plant-based food models: carbohydrates/acidic pH/sweet - beetroot purée, proteins/neutral pH/sweet - pea purée and starch/neutral pH - potato purée. Functional and sensory properties of phenol-enriched foods varied as a function of their composition and original taste. The amount of UG phenols recovered from potato purée was higher than that recovered from beetroot and pea purée, while the antioxidant activity detected in beetroot purée was higher than that in potato and pea purée. Significant variations of sourness, saltiness, bitterness and astringency were induced by UG phenols added to food models. Beetroot purée resulted more appropriate to counteract the negative sensations induced by UG phenols.

Olive oil mixtures. Part one: Decisional trees or how to verify the olive oil percentage in declared blends.

The commercialization of declared blends of olive oil and seed oil is something long approved by the European Union. There, the olive oil percentage must be at least 50% if the producer aims to advertise its presence on the front label, i.e., somewhere other than in the ingredients list. However, the Regulation did not propose any method to verify such proportion. For this purpose, we recommend the use of decisional trees, being the parameters under study those in which the greatest differences between olive and seed oils are shown: triacylglycerols, acyclic saturated hydrocarbons, free sterols, and tocopherols. In this way, to guarantee the presence of olive oil at 50%: i) palmitodiolein must be above 11-15%; ii) the ß/γ-tocopherol ratio must be below 2.4; iii) the alkane sum C21-C25 should be higher than 3.5-6%; and iv) the total sterol content cannot surpass 2400 mg/kg.

Preliminary Study: Comparison of Antioxidant Activity of Cannabidiol (CBD) and α-Tocopherol Added to Refined Olive and Sunflower Oils.

This study evaluates the antioxidant activity of cannabidiol (CBD), added to model systems of refined olive (ROO) and sunflower (SO) oils, by measuring the peroxide value, oxidative stability index (OSI), electron spin resonance (ESR) forced oxidation, and DPPH• assays. Free acidity, a parameter of hydrolytic rancidity, was also examined. CBD was compared using the same analytical scheme with α-tocopherol. CBD, compared to α-tocopherol, showed a higher scavenging capacity, measured by DPPH• assay, but not better oxidative stability (OSI) of the oily systems considered. In particular, α-tocopherol (0.5%) showed an antioxidant activity only in SO, registered by an increase of more than 30% of the OSI (from 4.15 ± 0.07 to 6.28 ± 0.11 h). By ESR-forced oxidation assay, the concentration of free radicals (µM) in ROO decreased from 83.33 ± 4.56 to 11.23 ± 0.28 and in SO from 19.21 ± 1.39 to 6.90 ± 0.53 by adding 0.5% α-tocopherol. On the contrary, the addition of 0.5% CBD caused a worsening of the oxidative stability of ROO (from 23.58 ± 0.32 to 17.28 ± 0.18 h) and SO (from 4.93 ± 0.04 to 3.98 ± 0.04 h). Furthermore, 0.5% of CBD did not lower dramatically the concentration of free radicals (µM) as for α-tocopherol, which passed from 76.94 ± 9.04 to 72.25 ± 4.13 in ROO and from 17.91 ± 0.95 to 16.84 ± 0.25 in SO.

Influences of Psychological Traits and PROP Taster Status on Familiarity with and Choice of Phenol-Rich Foods and Beverages.

Plant phenolics are powerful antioxidants and free radical scavengers that can contribute to the healthy functional properties of plant-based food and beverages. Thus, dietary behaviours rich in plant-based food and beverages are encouraged. However, it is well-known that the bitter taste and other low-appealing sensory properties that characterize vegetables and some other plant-based foods act as an innate barrier for their acceptance. The aim of this study was to investigate the influence of psychological traits and PROP status (the responsiveness to bitter taste of 6-n- propylthiouracil) on the choice of and familiarity with phenol-rich vegetables and beverages varying in recalled level of bitterness and astringency. Study 1 aimed at assessing the variations of the sensory properties of vegetable and coffee/tea items with two check-all-that-apply (CATA) questionnaires (n = 201 and n = 188 individuals, respectively). Study 2 aimed at investigating how sensitivity to punishment, to reward, and to disgust, food neophobia, private body consciousness, alexithymia, and PROP responsiveness affect choice and familiarity with phenol-rich foods (n = 1200 individuals). A Choice Index was calculated for vegetables (CV) and coffee/tea (CC) as a mean of the choices of the more bitter/astringent option of the pairs and four Familiarity Indices were computed for vegetables (FV) and coffee/tea (FC), higher (+) or lower (-) in bitterness and astringency. Subjects higher in food neophobia, sensitivity to punishment or sensitivity to disgust reported significantly lower choice indices than individuals lower in these traits, meaning that they systematically opted for the least bitter/astringent option within the pairs. Familiarity with vegetables was lower in individuals high in sensitivity to punishment, in food neophobia and in alexithymia, irrespective of their sensory properties. The Familiarity Index with coffee/tea characterized by higher bitterness and astringency was lower in individuals high in food neophobia, sensitivity to disgust, and alexithymia. No significant effect of PROP was found on any indices. The proposed approach based on product grouping according to differences in bitterness and astringency allowed the investigation of the role of individual differences in chemosensory perception and of psychological traits as modulators of phenol-rich foods preference and consumption.

Characterization of virgin olive oils produced with autochthonous Galician varieties.

The interest of Galician oil producers (NW Spain) in recovering the ancient autochthonous olive varieties Brava and Mansa has increased substantially in recent years. Virgin olive oils produced by co-crushing both varieties in two different proportions, reflecting the usual and most common practice adopted in this region, have gradually emerged for the production of virgin olive oils. Herein, the sensory and chemical characteristics of such oils were characterized by quality and genuineness-related parameters. The results of chemical analysis are discussed in terms of their effective contribution to the sensory profile, which suggests useful recommendations for olive oil producers to improve the quality of oils. Antioxidant compounds, together with aromas and coloured pigments were determined, and their contribution in determining the functional value and the sensory properties of oils was investigated. In general, given the high levels of phenolic compounds (ranging between 254 and 375mg/kg oil), tocopherols (about 165mg/kg oil) and carotenoids (10-12mg/kg oil); these are oils with long stability, especially under dark storage conditions, because stability is reinforced with the contribution of chlorophylls (15-22mg/kg oil). A major content of phenolic compounds, as well as a predominance of trans-2-hexen-1-al within odor-active compounds (from 897 to 1645µg/kg oil), responsible for bitter sensory notes. This characterization allows to developing new antioxidant-rich and flavour-rich VOOs, when co-crushing with a higher proportion of Brava olives, satisfying the consumers' demand in having access to more healthy dishes and peculiar sensory attributes.

Rapid direct analysis to discriminate geographic origin of extra virgin olive oils by flash gas chromatography electronic nose and chemometrics.

At present, the geographical origin of extra virgin olive oils can be ensured by documented traceability, although chemical analysis may add information that is useful for possible confirmation. This preliminary study investigated the effectiveness of flash gas chromatography electronic nose and multivariate data analysis to perform rapid screening of commercial extra virgin olive oils characterized by a different geographical origin declared in the label. A comparison with solid phase micro extraction coupled to gas chromatography mass spectrometry was also performed. The new method is suitable to verify the geographic origin of extra virgin olive oils based on principal components analysis and discriminant analysis applied to the volatile profile of the headspace as a fingerprint. The selected variables were suitable in discriminating between "100% Italian" and "non-100% Italian" oils. Partial least squares discriminant analysis also allowed prediction of the degree of membership of unknown samples to the classes examined.

Thermal and chemical evaluation of naturally auto-oxidised virgin olive oils: a correlation study.

BACKGROUND: The nature of the relationship between differential scanning calorimetry thermal properties and the oxidation and hydrolysis compounds formed during a real auto-oxidation process in virgin olive oils has not been evaluated so far, as these samples are difficult to find. In this work, 21 samples of virgin olive oil, stored under ideal conditions since their years of production (production range 1991-2005) to develop the natural auto-oxidation process, were analysed in order to evaluate this relationship. RESULTS: Oils stored the longest time showed the highest hydrolytic degradation while the others exhibited higher contents of oxidised fatty acids and triacylglycerols, instead. Thermal properties of transitions were differently influenced by degradation compounds with the onset of both the cooling and heating profiles particularly influenced by diacylglycerols and oxidised lipids. Chemical data and thermal properties were correlated by using principal component analysis. Twenty-three variables were selected for the analysis with the first component fully segregating samples into two groups according to the year of storage and the level of hydrolysis and/or oxidation, on the basis of selected thermal properties obtained by cooling and heating transitions. CONCLUSIONS: These preliminary findings showed that differential scanning calorimetry could be considered an useful tool to evaluate lipid degradation in virgin olive oils, indicating its value as a support to chemical techniques.

Sweet chestnut (Castanea sativa Mill.) bark extract: cardiovascular activity and myocyte protection against oxidative damage.

This work was aimed at evaluating the cardioprotective effects of Castanea sativa Mill. (CSM) bark extract characterized in its phenolic composition by HPLC-DAD-MS analysis. The study was performed using primary cultures of neonatal rat cardiomyocytes to investigate the antioxidant and cytoprotective effects of CSM bark extract and isolated guinea pig left and right atria, left papillary muscle, and aorta to evaluate its direct effect on cholinergic and adrenergic response. In cultured cardiomyocytes the CSM bark extract reduced intracellular reactive oxygen species formation and improved cell viability following oxidative stress in dose-dependent manner. Moreover, the extract decreased the contraction induced by noradrenaline (1 µ M) in guinea pig aortic strips and induced transient negative chronotropic and positive inotropic effects without involvement of cholinergic or adrenergic receptors in the guinea pig atria. Our results indicate that CSM bark extract exhibits antioxidant activity and might induce cardioprotective effect.

New filtration systems for extra-virgin olive oil: effect on antioxidant compounds, oxidative stability, and physicochemical and sensory properties.

The purpose of this work was to evaluate some new filtration systems in relation to the quality of extra-virgin olive oil (EVOO). Filtration processes were undertaken using a polypropylene filter bag and two different inert gas flows as filter aids (argon and nitrogen). Qualitative and quantitative variations of the glyceride composition, antioxidant and pro-oxidant compounds, and water content were correlated with the oxidative stability to establish the effect on EVOO shelf life. The influence on physicochemical and sensorial properties was also evaluated. After filtration, the oxidative stability was reduced. The behavior of the polyphenols and water content on the filtration process could explain the lowest oxidative stability of filtered EVOO. Moreover, the results of the sensorial analysis confirmed that filtration using inert gases did not decrease the intensity of the main positive sensory attributes. The results could help olive-oil producers to improve EVOO quality and establish optimal storage conditions.

Determination of tocopherols and tocotrienols in vegetable oils by nanoliquid chromatography with ultraviolet-visible detection using a silica monolithic column.

A method for the determination of tocopherols and tocotrienols in vegetable oils by nanoliquid chromatography with UV-vis detection has been developed. The separation of tocopherols was optimized in terms of mobile phase composition on the basis of the best compromise between efficiency, resolution, and analysis time. The optimal conditions were achieved using a C18 silica monolithic column (150 mm x 0.1 mm) with an isocratic elution of acetonitrile/methanol/water (acidified with 0.2% acetic acid) at a flow rate of 0.5 microL min(-1), giving a total analysis time below 18 min. The method has been applied to the quantification of tocopherols and tocotrienols present in several vegetable oils with different botanical origins.

Analytical determination of polyphenols in olive oils.

The increasing popularity of olive oil is mainly attributed to its high content of oleic acid, which may affect the plasma lipid/lipoprotein profiles, and its richness in phenolic compounds, which act as natural antioxidants and may contribute to the prevention of human disease. An overview of analytical methods for the measurement of polyphenols in olive oil is presented. In principle, the analytical procedure for the determination of individual phenolic compounds in virgin olive oil involves three basic steps: extraction from the oil sample, analytical separation, and quantification. A great number of procedures for the isolation of the polar phenolic fraction of virgin olive oil, utilizing two basic extraction techniques, LLE or SPE, have been included. The reviewed techniques are those based on spectrophotometric methods, as well as analytical separation (gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrophoresis (CE)). Many reports in the literature determine the total amount of phenolic compounds in olive oils by spectrophometric analysis and characterize their phenolic patterns by capillary gas chromatography (CGC) and, mainly, by reverse phase high-performance liquid chromatography (RP-HPLC); however, CE has recently been applied to the analysis of phenolic compound of olive oil and has opened up great expectations, especially because of the higher resolution, reduced sample volume, and analysis duration. CE might represent a good compromise between analysis time and satisfactory characterization for some classes of phenolic compounds of virgin olive oils.

Oxidative stability and phenolic content of virgin olive oil: an analytical approach by traditional and high resolution techniques.

The characteristic resistance to oxidation of virgin olive oil is related to its unique fatty acid composition in addition to several minor components that have antioxidant properties. Among the latter, phenols are the most important. Several factors can influence the chemical or enzymatic oxidative processes that extend or shorten the shelf-life of olive oil. Furthermore, the amount of phenolic compounds extracted during production is fundamental for the oxidative and nutritional quality of the oil. In fact, it is well known that different steps used for preparation of virgin olive oil may determine differences in the quantities of phenol. At present, various analytical methods are available to analyze the hydrophilic components, including spectrophotometric assays (traditional) and high resolution chromatographic techniques (HRGC, HPLC, HPCE). In this review we summarize these different methodologies and demonstrate that the amount of phenolic compounds in virgin olive oil as determined by both traditional and high resolution techniques can be influenced by different factors including the olive cultivar and degree of ripeness, as well as by production and extraction technologies.

Fast separation and determination of tyrosol, hydroxytyrosol and other phenolic compounds in extra-virgin olive oil by capillary zone electrophoresis with ultraviolet-diode array detection.

Olive oil is the main source of fat in the Mediterranean diet, and its consumption has been related to a low incidence of coronary heart disease and certain cancers. Recent findings demonstrate that olive oil phenolics are powerful in vitro and in vivo antioxidants and display other biological activities that could partially account for the observed healthful effects of the Mediterranean diet. A detailed method optimization plan was carried out to separate the most popular phenols in olive oil for four separation parameters: buffer concentration, buffer pH, applied voltage and temperature. Consequently, an analytical method capable of separating 21 different phenols and polyphenols by capillary zone electrophoresis was developed; the separation was performed within 10 min, using a 40 cm x 50 microm capillary, with a 45 mM sodium tetraborate buffer (pH 9.60), at 27 kV and 30 degrees C. The optimized method was applied to methanolic extracts of several Italian extra-virgin olive oils obtained by different technologies in order to characterize and to compare their antioxidant profile. Positive correlations of phenolic compounds found by capillary zone electrophoresis (CZE) and two colorimetric indexes (total polyphenols and o-diphenols) were found and discussed.

Fast determination of catechins and xanthines in tea beverages by micellar electrokinetic chromatography.

Antioxidant properties and stimulating effects of green tea are related to its content of cathechins and xanthines; tea quality evaluation is based on organoleptic tests and on the presence of those components. In this work, by a MEKC method, eight cathechins and three xanthines were quantified in some tea-based beverages. The best separation was realized using a phosphate-borate running buffer, with sodium dodecyl sulfate as micellar agent. A 40 cm capillary, a temperature of 29 degrees C, a voltage of 30 kV, and UV detection at 200 nm were used. The method showed a very good sensitivity (limit of detection ranging from 0.0011 to 0.0051 microg/mL) and was applied to real tea samples to characterize their antioxidant content. Statistical studies were performed and showed a satisfactory reliability of the data.