Characterization of antioxidant olive oil biophenols by spectroscopic methods

BACKGROUND: Olive oil contains numerous phenolic components with well‐recognized health‐beneficial activity. The major phenolic compounds present in olives and virgin olive oil—hydroxytyrosol, oleuropein and the oleuropein aglycones 3,4‐DHPEA‐EA and 3,4‐DHPEA‐EDA—as well as some of their metabolites were studied in the present work, regarding their main structural preferences. Vibrational spectroscopy (Raman) coupled to theoretical methods were used, aiming at fully characterizing the systems and therefore enabling their quick and reliable identification in food samples. RESULTS: The Raman data, assisted by the theoretical simulations, allowed us to obtain the main geometrical and spectroscopic features of the olive oil constituents under study, which determine their known antioxidant and chemoprotective properties. In fact, it was verified that the spectra comprise distinctive bands for each compound, allowing their ready detection and differentiation. CONCLUSION: This is the first reported study on the structural behaviour of olive oil phenolic compounds, and it established Raman spectroscopy as a rapid, non‐destructive and reliable analytical technique for identifying these bioactive components in dietary extracts. It can surpass other analytical methods currently used, once it allows the concomitant identification of several olive oil components in a particular sample. Copyright © 2010 Society of Chemical Industry     

Characterisation of phenolic extracts from olive pulp and olive pomace by electrospray mass spectrometry

Methanol extracts of olive pomace (two‐phase olive oil extraction) and olive pulp were analysed by reverse phase HPLC and the eluted fractions were characterised by electrospray ionisation mass spectrometry. This technique allowed the identification of some common phenolic compounds, namely, verbascoside, rutin, caffeoyl‐quinic acid, luteolin‐4‐glucoside and 11‐methyl‐oleoside. Hydroxytyrosol‐1′‐β‐glucoside, luteolin‐7‐rutinoside and oleoside were also detected. Moreover, this technique enabled the identification, for the first time in Olea europaea tissues, of two oleoside derivatives, 6′‐β‐glucopyranosyl‐oleoside and 6′‐β‐rhamnopyranosyl‐oleoside, and of 10‐hydroxy‐oleuropein. Also, an oleuropein glucoside that had previously been identified in olive leaves was now detected in olive fruit, both in olive pulp and olive pomace. With the exception of oleoside and oleuropein, the majority of phenolic compounds were found to occur in equivalent amounts in olive pulp and olive pomace. Oleoside was the main phenolic compound in olive pulp (31.6 mg g^?1) but was reduced to 3.6 mg g^?1 in olive pomace, and oleuropein (2.7 mg g^?1 in the pulp) almost disappeared (<0.1 mg g^?1 in the pomace). Both these phenolic compounds were degraded during the olive oil extraction process. Copyright © 2004 Society of Chemical Industry     

Antioxidant activity of virgin olive oil phenolic compounds in a micellar system†

The antioxidant activity of two virgin olive oils, obtained from the same olive (Olea europaea sativa) batch but processed with different hammer crushing conditions, was evaluated by measuring their protective action towards linoleic acid peroxidation in a micellar system. The antioxidant efficiency (AE) of the oil phenolic fraction was higher when the olives were processed with a higher hammer crusher rotation rate. HPLC analysis demonstrated that one of the main derivatives of oleuropein, indicated as 3,4-DHPEA-EDA (the dialdehydic form of elenolic acid linked with 3,4-dihydroxyphenylethanol), is present only in the oil with higher AE. 3,4-DHPEA-EDA showed the greatest antioxidant ability among virgin olive oil phenols. Its greater efficiency in the micellar system in comparison with 3,4-dihydroxyphenylethanol (3,4-DHPEA) is related to its greater lipophilicity. It is suggested that the behaviour in the water–micellar environment is representative of that in a real system such as tomato-based sauce with added virgin olive oil. © 1999 Society of Chemical Industry     

BITTER TASTE AND PHENOLIC COMPOUNDS IN EXTRA VIRGIN OLIVE OIL: AN EMPIRICAL RELATIONSHIP

Bitter taste of extra virgin olive oil is known to be affected by the phenolic composition. However, contribution of each individual phenol to this sensory note has not been clearly defined. The aims of this study were to verify whether there was a relationship between bitter sensation and phenolic compound concentration, to determine which compounds were involved in bitter taste and to evaluate quantitatively this correlation. Results confirmed that a positive correlation did exist between total phenolic amount and bitter intensity. Data processing showed that this correlation was significantly dependent upon a relationship between oleuropein aglycon (3,4‐DHPEA‐EA) and bitter intensity. An empirical exponential model was set up and validated.     

Production of hydrogen peroxide is responsible for the induction of apoptosis by hydroxytyrosol on HL60 cells

Hydroxytyrosol [3,4‐dihydroxyphenylethanol (3,4‐DHPEA)], a phenolic compound found exclusively in olive oil, exerts growth‐suppressive and pro‐apoptotic effects on different cancer cells. Although some molecular mechanisms involved in the pro‐apoptotic activity of 3,4‐DHPEA have been proposed, the initial stress signals responsible of this phenomenon are not known. Our aim was to assess the involvement of reactive oxygen species as mediators of apoptosis induced by 3,4‐DHPEA on HL60 cells. Apoptosis was determined by analyzing the nuclear fragmentation by both fluorescence microscopy and flow cytometry. The externalization of phosphatidylserine was evidenced using an Annexin V‐FITC kit. The concentration of H₂O₂ in the culture medium was measured by the ferrous ion oxidation‐xylenol orange method. The pro‐apoptotic effect of 3,4‐DHPEA (100 μM) was prevented by N‐acetyl‐cysteine, ascorbate, and α‐tocopherol. Catalase suppressed the 3,4‐DHPEA‐induced apoptosis, while the Fe(II)‐chelating reagent o‐phenantroline showed no effect, suggesting the involvement of H₂O₂ but not of OH^?. Indeed, 3,4‐DHPEA caused accumulation of H₂O₂ in the culture medium. Tyrosol (p‐hydroxyphenylethanol) and caffeic acid, compounds structurally similar to 3,4‐DHPEA but not able to generate H₂O₂, did not induce an appreciable apoptotic effect. This is the first study demonstrating that apoptosis induction by 3,4‐DHPEA is mediated by the extracellular production of H₂O₂.     

Olive byproducts and their bioactive compounds as a valuable source for food packaging applications

Among the most important agro-industrial activities in the Mediterranean basin, olive oil production has a high impact on the economy of many Mediterranean countries. However, olive oil extraction generates huge quantities of byproducts, including leaves, pomace residues, stones and wastewater, which have severe environmental impacts mainly because of their phytotoxicity and great organic content. Olive oil byproducts are regarded as inexpensive and abundant raw materials rich in bioactive compounds with high and varied health-related activities. Several phenolic compounds and terpenoids were recovered from olive byproducts using different conventional and advanced extraction methods due to their potential to be used in food, packaging, pharmaceutical, and cosmetic industries. Recently, the use of olive byproducts and their functional compounds to enhance the functional properties of packaging systems was investigated as a sustainable strategy for food preservation, fostering the sustainability of the olive-oil chain, and promoting circular economy. In this framework, the main goals of this review are to summarize the main bioactive compounds in olive byproducts, to review the main advancements in their extraction, purification, and characterization, and finally to discuss their applications in food packaging systems as well as safety-related aspects.     

Functional compounds from olive pomace to obtain high‐added value foods – a review

Olive pomace, the solid by‐product from virgin olive oil extraction, constitutes a remarkable source of functional compounds and has been exploited by several authors to formulate high value‐added foods and, consequently, to foster the sustainability of the olive‐oil chain. In this framework, the aim of the present review was to summarize the results on the application of functional compounds from olive pomace in food products. Phenolic‐rich extracts from olive pomace were added to vegetable oils, fish burgers, fermented milk, and in the edible coating of fruit, to take advantage of their antioxidant and antimicrobial effects. Olive pomace was also used directly in the formulation of pasta and baked goods, by exploiting polyunsaturated fatty acids, phenolic compounds, and dietary fiber to obtain high value‐added healthy foods and / or to extend their shelf‐life. With the same scope, olive pomace was also added to animal feeds, providing healthy, improved animal products. Different authors used olive pomace to produce biodegradable materials and / or active packaging able to increase the content of bioactive compounds and the oxidative stability of foods. Overall, the results highlighted, in most cases, the effectiveness of the addition of olive pomace‐derived functional compounds in improving nutritional value, quality, and / or the shelf‐life of foods. However, the direct addition of olive pomace was found to be more challenging, especially due to alterations in the sensory and textural features of food. © 2020 Society of Chemical Industry     

Contribution of olive seed to the phenolic profile and related quality parameters of virgin olive oil

BACKGROUND: Conflicting results have been reported about the effect of fruit de‐stoning on the virgin olive oil (VOO) phenolic profile. The aim of the present study was to determine whether olive seed plays any role in the synthesis of this oil phenolic fraction. RESULTS: Increases of around 25% of total phenolic compounds were observed in oils obtained from de‐stoned olive fruits in three main Spanish cultivars. To investigate the involvement of olive seed in determining the phenolic profile of VOO, whole intact olive fruits were added with up to 400% olive stones. Excellent regression coefficients were found in general for the decrease of total phenolic compounds and, particularly, of o‐diphenolics in the resulting oils. On the other hand, it was found that olive seed contains a high level of peroxidase (POX) activity (72.4 U g^?1 FW), accounting for more than 98% of total POX activity in the whole fruit. This activity is able to modify VOO phenolics in vitro, similar to the effect of adding stones during VOO extraction. CONCLUSION: Olive seed plays an important role in determining VOO phenolic profile during the process to obtain an oil that seems to be associated with a high level of POX activity. Copyright © 2007 Society of Chemical Industry     

Addition of enzymes complex during olive oil extraction improves oil recovery and bioactivity of Western Australian Frantoio olive oil

Olive oil consumption has increased as many studies revealed the health benefits of regular consumption of olive oil. There is a need to find effective oil extraction techniques capable of increasing oil recovery without compromising its quality. This study investigated the impact of adding enzymes complex Viscozymes during olive oil extraction on oil recovery, total phenolic compounds, antiradical activity and the standard quality parameters. It was found that at a concentration of 0.30 g mL^?1, Viscozymes could significantly improve the oil recovery from 49 to 69% (P < 0.001) when compared to the Control sample. The concentration of total phenolic compounds was also significantly improved from 110 to 266 mg kg^?1 oil (P < 0.01) and the antiradical activity increased from 31 to 48% inhibition of 2,2‐diphenyl‐1‐picrylhydrazil radical (P < 0.001). Addition of Viscozymes therefore represents an effective extraction technique that increases oil recovery without compromising the concentration of total phenolic compounds and antiradical activity.     

Influence of ethanol/water ratio in ultrasound and high‐pressure/high‐temperature phenolic compound extraction from agri‐food waste

The valorisation and management of agri‐food waste are currently hot investigation topics which probe the recovery of valuable compounds, such as polyphenols. In this study, high‐pressure/high‐temperature extraction (HPTE) and ultrasound‐assisted extraction (UAE) have been used to study the recovery of phenolic compounds from grape marc and olive pomace in hydroalcoholic solutions. The main phenolic compounds in both extracts were identified by HPLC‐DAD. Besides extraction yield (total polyphenol and flavonoid content) and the antiradical power, polyphenol degradation under HPTE and UAE has also been studied. HPTE with ethanol 75% gave higher phenolic extraction yields: 73.8 ± 1.4 mg of gallic acid equivalents per gram of dried matter and 60.0 mg of caffeic acid equivalents per gram of dried matter for grape marc and olive pomace, respectively. In this study, the efficient combination of ethanol/water mixture with HPTE or UAE has been used to enhance the recovery of phenolic compounds from grape marc and olive pomace. HPLC‐DAD showed that UAE prevents phenolic species degradation damage because of its milder operative conditions.     

Two by-products of the olive oil extraction industry as oleic acid supplement source for Iberian pigs: effect on the meat's chemical composition and induced lipoperoxidation

BACKGROUND: The objective of the present study was to evaluate the effect of two by‐products of the olive oil extraction industry—olive soapstocks and olive‐pomace oil—as added fat sources into feed concentrates, in two different rearing systems (free‐range complemented with concentrates and intensive rearing with concentrates) on the chemical composition and oxidative stability of Iberian pig meat. RESULTS: No differences in the chemical composition, colour and fatty acid composition of gluteobiceps m. were found due to added fat source. However, the feeding system had a significant effect on protein (P < 0.05), γ‐tocopherol (P < 0.05), colour (P < 0.01) and fatty acid composition of gluteobiceps m. Neither added fat source nor the feeding system had an effect on the malondialdehyde content. CONCLUSION: The addition of olive soapstock or olive‐pomace oil as fat sources into concentrates did not influence meat composition or fatty acid profile. However, there are differences in the fatty acid composition of meat from Iberian pigs as a result of the production system used. Copyright © 2012 Society of Chemical Industry     

Microwave heating of different commercial categories of olive oil: Part I. Effect on chemical oxidative stability indices and phenolic compounds

The effect of microwave heating of extra virgin olive oil (EVOo), olive oil (Oo) and pomace olive oil (Po) in domestic appliances, was investigated in terms of chemical oxidative indices (peroxide, p-anisidine and Totox values), free acidity, water content, total phenol content and different classes of phenolic compounds.     

Saturated hydrocarbon content in olive fruits and crude olive pomace oils

Olive fruits contain an n-alkane series of saturated hydrocarbons mainly in the pulp. Lower amounts of a complex mixture of paraffins, unresolved by gas chromatography (UCM – unresolved complex mixture), have been found in cuticle, stone (woody shell and seed), olive leaves, and talc used as an aid to olive oil extraction. The amounts of both kinds of hydrocarbons are related to the olive cultivar and are transferred to oils in a proportion depending on the oil-obtaining process (centrifugation or solvent extraction). In olive oil obtained by centrifugation, only n-alkanes were detected. However, in olive oil extracted by second centrifugation, small amounts of UCM paraffins were detected together with the n-alkanes. Olive pomace oils showed a very variable content of both types of hydrocarbons according to the different obtaining process, such as double centrifugation, solvent extraction or centrifugation followed by solvent extraction. ‘White mineral oil’ used in oil extraction machinery is the source of the high concentrations of UCM paraffins found in some olive and olive pomace oils. In the case of second centrifugation olive oil, a maximum limit of 50 mg kg^?1 of UCM is suggested, whereas in the case of crude olive pomace oil, it amounts to 250 mg kg^?1 plus an additional minimum of 1.0 for the n-alkanes/UCM ratio.     

Effect of growing location,malaxation duration and citric acid treatment on the quality of olive oil

BACKGROUND: The total phenolic compounds of olive oil exert antiradical activity at cellular level and can prevent cardiovascular disease, metabolic syndrome and cancer. Increased awareness of its health benefits has increased the consumption of olive oil around the world. An alternative processing technique effective in increasing the amount of oil extracted while maintaining the oil quality is needed to meet the rising global demand for olive oil. RESULTS: Addition of 0.3 g mL^?1 citric acid at 1:1000 (v/w) to olive paste followed by a 30 min malaxation period significantly increased the oil recovery, concentration of total phenolic compounds and antiradical activity by 46.23, 120.27 and 31.48% respectively. While there was no significant effect on the acidity, the peroxide value was significantly reduced by 63.85%. The organoleptic characteristics of the olive oil extracted with citric acid were also comparable to those of the control. CONCLUSION: Addition of 0.3 g mL^?1 citric acid (i.e. 30% w/v) at 1:1000 (v/w) to olive paste followed by a 30 min malaxation period in a Blixer^® 4.0 blender is the most promising extraction technique to improve the oil recovery, concentration of total phenolic compounds and antiradical activity of the extracted olive oil without compromising other quality parameters. © 2012 Society of Chemical Industry     

Antitumor Perspectives of Oleuropein and Its Metabolite Hydroxytyrosol: Recent Updates

Olive fruit is a significant and promising source of potential bioactive compounds such as oleuropein and hydroxytyrosol. Oleuropein is the ester of elenolic acid and 3,4‐dihydroxyphenyl ethanol (HT). It is the main glycoside in olives, the degradation of which results in the formation of hydroxytyrosol in olive oil. Both plays a significant role in the reduction of coronary heart diseases and a certain type of cancers. Both olive oil phenols have an effective role counter to cell proliferation, cell growth, migration, invasion, and angiogenesis. They down regulate the expression of BCL‐2 and COX‐2 proteins, and reduced DNA damage. Hydroxytyrosol and oleuropein inhibited the multiple stages in colon carcinogenesis; initiation, promotion, and metastasis. They also provide protection against various human cancers including colorectal, skin, breast, thyroid, digestive, lung, brain, blood, and cervical. This review article discusses the anticancer perspectives and mechanisms of oleuropein and hydroxytyrosol in cell cultures and animal and human studies.     

Influence of O2 on the quality of virgin olive oil during malaxation

The aim of this work was to investigate the effect of malaxation operating conditions on virgin olive oil quality. Legal, sensory and nutritional parameters of olive oil were evaluated by identifying the role played by enzymes. A comparison was made between oil obtained from a traditional malaxation plant and oil obtained from malaxation equipment (LOM) able to work at low oxygen level and temperature. Research results showed that, during malaxation, oxygen had an effect on both phenolic compounds and fatty acids, mainly favouring enzyme phenomena. Malaxation at a low oxygen level was found to be selective for the formation of both phenolic and C₆ compounds. Oil obtained from malaxation LOM equipment was shown to be richer in both aldehydes such as trans‐2‐hexenal and phenolic compounds than oil obtained from traditional processing. Copyright © 2006 Society of Chemical Industry     

Effect of olive ripeness on chemical properties and phenolic composition of chétoui virgin olive oil

BACKGROUND: The aim of the present work was to investigate the influence of fruit ripening on oil quality in an attempt to establish an optimum harvesting time for Chétoui olives, the second main olive variety cultivated in Tunisia. RESULTS: Our results showed that many analytical parameters, i.e., peroxide value, UV absorbance at 232 and 270 nm, chlorophyll pigments, carotenoids and oleic acid contents decreased during ripening, whilst oil content and linolenic acid increased. Free acidity remained practically stable with a very slight rise at the highest maturity index. The trend of oxidative stability, total phenols and o‐diphenols, showed an increase at the early stages followed by a reduction at more advanced stages of maturity. The major phenolic compounds, such as hydroxytyrosol, ligstroside aglycon, elenolic acid, acetoxy‐pinoresinol and oleuropein aglycon, seemed to have the same behaviour. In the case of tyrosol, a strong decrease was observed directly related with the ripening progress. CONLUSION: On the basis of the evolution of the analytical parameters studied, the best stage of Chétoui olive fruits for oil processing seems to be at ripeness index higher than 2.0 and lower than 3.0. Copyright © 2009 Society of Chemical Industry     

Possibility of improving the quality characteristics of olive‐pomace oil and enhancing its differentiation from refined olive‐pomace oil

An investigation was carried out to evaluate the oxidative and hydrolytic degradation of 37 olive‐pomace oils marketed in southern Italy and to compare the results with those obtained from 10 deodorised olive‐pomace oils representative of large stocks of oil obtained after the final step of refining. One aim of the research was to ascertain the quality characteristics of commercial olive‐pomace oils; another was to verify whether the legally prescribed addition of virgin olive oil to refined pomace oil, so that the final product may be classified commercially as olive‐pomace oil, was actually sufficient to justify upgrading. The analytical methods used were silica gel column chromatography and high‐performance size exclusion chromatography. The data obtained showed that the final retail olive‐pomace oils had a lower degree of oxidative degradation than the refined oils, as indicated by the lower values obtained when summing the proportions of triglyceride oligopolymers and oxidised triglycerides. Conversely, hydrolytic degradation, which was evaluated by determining diglycerides, proved to be the same in the two categories of oil. The proportions of virgin olive oil added are small, as indicated by the statistically indistinguishable values of triglyceride oligopolymers and free fatty acids obtained. The possibility of setting a limit to the amount of triglyceride oligopolymers present in the commercial category of olive‐pomace oil has been considered. This limit would ensure standardisation of the level of oxidation and, consequently, of the quality of marketed oils and would enhance differentiation between olive‐pomace oil and refined olive‐pomace oil. © 2000 Society of Chemical Industry     

Prediction of Polyphenol Fraction in Virgin Olive Oil Using Mid-Infrared Attenuated Total Reflectance Attenuated Total Reflectance Accessory–Mid-Infrared Coupled With Partial Least Squares Regression

This study focuses on the quantification of virgin olive oil phenolic compound while using mid-infrared spectroscopy with chemometrics. For that, 100 samples of virgin olive oils in phenolic compounds which varied between 1.04 and 10.33 g/L were picked up in Morocco’s regions and subjected to infrared analysis. The aim was to develop a calibration model for the prediction of phenolic compounds in olive oil by using Fourier transform-infrared spectroscopy. The spectral transmissions of all samples were obtained in the spectral range of 600–4000 cm^–1. The values obtained for correlation coefficient and root mean square errors of prediction were 0.99 and 0.11, respectively. These results showed the capability of the Fourier transform-infrared spectroscopy and the chemometric in developing accurate models to predict the phenolic compounds in virgin olive oil.