Major dietary lipids in nutrition and health.

In this chapter, an overview of the major lipids in the diet with emphasis in nutritional aspects is provided. Triacylglycerols, i.e., glycerol esterified with three fatty acids, are the predominant constituents in dietary lipids. Therefore, this chapter focuses on the nature and nutritional significance of the main fatty acids in the diet and their possible modifications during food processing and commercialization. The main fatty acids in dietary lipids are grouped into saturated, monounsaturated and polyunsaturated fatty acids. Nutritional implications, the latest intervention trials and health recommendations will be discussed. A brief description of the major sources of lipids in the diet is included, oils and fats standing out. Other food sources shortly commented are milk and dairy products, meat, poultry and eggs, fish, and structured lipids designed to improve functional and nutritional properties. Modifications of fatty acids as a result of processing and commercialization are discussed because of their great relevance for their health implications, especially oxidation compounds and trans fatty acids.

A chemometric study on the identification of 5-methylfurfural and 2-acetylfuran as particular volatile compounds of oxidized fish oil based on SHS-GC-IMS.

Fish oil develops particular off-odors, mainly fishy odor, from the oxidation of its characteristic fatty acids, docosahexaenoic (DHA) and eicosapentaenoic (EPA). Anchovy oil (AO) was taken as representative of fish oils. This was compared to three vegetable oils with different fatty acid compositions, i.e. camellia, sunflower and linseed oil, and differential volatile compounds were identified by static-headspace gas-chromatography ion-mobility-spectrometry (SHS-GC-IMS) and orthogonal partial-least-squares discriminant analysis (OPLS-DA) during oxidation at 60 °C. Three groups of differential volatile compounds detected at higher concentrations in the AO were screened out and two compounds, identified as 5-methylfurfural and 2-acetylfuran, were characteristic to the AO and not found in the vegetable oils. They were formed from both EPA and DHA, only present in the AO, and their formation mechanisms were proposed. The contents of 5-methylfurfural and 2-acetylfuran increased linearly with the oxidation time and consequently they could be used as oxidative markers of fish oils.

Characterization of press and solvent extraction oils from new sunflower seeds with modified phytosterol compositions.

BACKGROUND: Phytosterols are plant components with health benefits. Oleaginous seed hybridization can be relevant to increase phytosterols in diet through enriched oils. Sunflower oils obtained by press (PO) and subsequent solvent extraction (SO) from three types of phytosterol-enriched seeds were characterized. One presented a phytosterol composition of common sunflower seeds, whereas the other two were rich in campesterol and Δ7-stigmasterol, respectively. Seeds from two different harvests, 2015 and 2017, were studied. RESULTS: The type of extraction did not have a significant influence on the fatty acid composition. However, considerable differences were found between harvests. The oleic-to-linoleic ratio decreased from 0.71 in 2015 to 0.47 in 2017. The phytosterol compositions of the PO were similar to their SO homologues and no substantial differences were found between harvests. However, the SO presented higher total contents of phytosterols (4849-9249 mg kg-1 ) than the PO (2839-5284 mg kg-1 ) and the oils of 2017 showed higher levels (4476-9249 mg kg-1 ) compared to 2015 (2839-5754 mg kg-1 ). Unlike phytosterols, no significant differences were found in the tocopherol contents between the PO and SO or between harvests. The PO met Codex specifications for edible oils, except for trace metals, with concentrations close or above the limits for Cu, Fe, Pb and As. CONCLUSIONS: Differences in environmental and/or cultivation conditions between harvests may result in substantial differences in the fatty acid composition and phytosterol content in oils from the new sunflower seeds. Rigorous measures and controls to avoid trace metal contamination are required so that the PO can be considered as edible virgin oils. © 2020 Society of Chemical Industry.

ESR spin trapping for in situ detection of radicals involved in the early stages of lipid oxidation of dried microencapsulated oils.

Different studies have shown that detection of free radicals by ESR spin trapping provides useful information on the susceptibility to oxidation of bulk oils and accordingly on the oxidative stability of different samples for comparative purposes. With the same goal, ESR spin trapping was evaluated in this work for in situ detection of radicals in dried microencapsulated oils (DMOs). By testing different oils, encapsulation matrices and oxidation conditions, results showed that ESR spin trapping can be useful to evaluate the oxidative susceptibility of DMOs, but ESR data should be interpreted cautiously, as the great complexity of the reactions involved may lead to data misinterpretations. Conditions for oxygen availability can have important impacts on the rates of both spin trapping and spin-adduct quenching affecting the levels of radicals observed. The kinetics of oxidation, spin trapping and spin-adduct decay should be known first in bulk oils for correct data interpretation in DMOs.

Concentrates of triterpenic acids obtained from crude olive pomace oils: characterization and evaluation of their potential antioxidant activity.

BACKGROUND: Pentacyclic triterpenic acids (TA) are phytochemicals of increasing nutritional interest owing to their bioactive properties, such as anti-inflammatory, antitumoral, antihyperglycemic and hepatoprotective. Crude olive pomace oils constitute a non-exploited significant source of these compounds. In the present study, concentrates of TA were extracted and characterized from crude olive pomace oils that were obtained by centrifugation and subsequent solvent extraction, respectively. Specifically, the concentrates were obtained from the byproduct generated in the filtration of the oils. The solids were subjected to Soxhlet extractions with hexane to remove the residual oil and then with ethanol for the TA extraction. RESULTS: Concentrates containing 850-980 g kg-1 TA were isolated from the oils obtained by centrifugation, whereas those isolated from oils obtained by hexane extraction presented levels of TA that ranged from 510 to 900 g kg-1 . Oleanolic (OA) and maslinic (MA) acids were the TA found in the concentrates. The relative contents of OA and MA were, respectively, 30:70 (w/w) and 77:23 (w/w). All concentrates also presented phenolic compounds at levels of g kg-1 and displayed slight antioxidant properties. CONCLUSION: Concentrates of TA, containing MA and OA, can be readily obtained from a byproduct generated by filtration of crude olive pomace oils. Concentrates isolated from oils obtained by centrifugation were rich in MA, whereas those from oils extracted with hexane were rich in OA. The concentrates showed slight antioxidant properties that can be mainly attributed to the presence of phenolic compounds and not to TA. © 2018 Society of Chemical Industry.

Quantitative determination of major oxidation products in edible oils by direct NP-HPLC-DAD analysis.

The objective of the present study was to explore the possibilities of the direct analysis of vegetable oils by normal-phase HPLC-DAD to evaluate the amounts of the main oxidation products of triacylglycerols containing linoleate, i.e. hydroperoxy-, keto- and hydroxy-dienes. A follow-up of oxidation at 40 °C of trilinolein, used as a simplified model lipid system, high-linoleic sunflower oil and high-oleic sunflower oil was performed to evaluate samples with different fatty acid compositions and different oxidation levels. The results showed that the HPLC-DAD method proposed allows for determining the concentrations of mono-hydroperoxydienes in edible oils without applying any isolation or derivatization step. The method was found to be direct, sensitive (LOQ 0.06 mmol/kg oil), precise (CV ≤ 5%) and also accurate, with 99% of analyte recovery. It also enabled the estimation of the minor amounts of ketodienes, but not those of hydroxydienes, which presented wide chromatographic bands and coeluted with a number of different minor oxidation compounds.

Microencapsulation of H. pluvialis oleoresins with different fatty acid composition: Kinetic stability of astaxanthin and alpha-tocopherol.

Haematococcus pluvialis is a natural source of astaxanthin (AX). However, AX loses its natural protection when extracted from this microalga. In this study, a supercritical fluid extract (SFE) of H. pluvialis was obtained and added to oils with different fatty acid compositions (sunflower oil (SO) or high oleic sunflower oil (HOSO)). The oleoresins of H. pluvialis ((SO+SFE) and (HOSO+SFE)) were encapsulated with Capsul by spray drying. The stability of the oleoresins and powders were studied at 40, 50 and 70° C. AX and alpha-tocopherol (AT) degradation followed a zero-order and first-order kinetic model, respectively, for all systems. The encapsulation of oleoresins improved the stability of AX and AT to a greater extent in oleoresins with a monounsaturated fatty acid profile, as shown by the significantly lowest degradation rate constants and longest half-lives. Therefore, the encapsulation of H. pluvialis oleoresins is an alternative to developing a functional ingredient for healthy food design.

Effectiveness of α-, γ- and δ-Tocopherol in a CLA-Rich Oil.

Conjugated linoleic acid (CLA) is a mixture of positional and geometric isomers of octadecadienoic acid with conjugated double bounds. Positive health properties have been attributed to some isomers, such as anticarcinogenic activity, antiartherosclerotic effects and reduction of body fat gain. Hence, oils rich in CLA such as Tonalin(®) oil (TO), normally obtained through alkaline isomerization of safflower oil (SO), an oil rich in linoleic acid (LA), are currently used in functional foods. However, special care must be taken to protect them from oxidation to ensure the quality of the supplemented foods. The objective of this work was to evaluate the oxidation and effectiveness of different tocopherol homologues (α-, γ- and δ-), alone or in combination with synergists (ascorbyl palmitate and lecithin), in TO compared to SO at different conditions, ambient temperature (25 °C) and accelerated conditions in Rancimat (100 °C). The oils, the oils devoid of their antioxidants and the latter containing the antioxidants added were assayed. Results showed great differences between SO and TO in terms of formation of hydroperoxides and polymers and also in the effectiveness of tocopherols to delay oxidation. TO showed higher levels of polymerization and, in general, the effectiveness of tocopherol homologues, alone or in combination with synergists, was also lower in the TO.

Influence of fatty acid composition on chemical changes in blends of sunflower oils during thermoxidation and frying.

The influence of fatty acid composition on formation of new compounds at frying temperatures has been studied in seven samples of sunflower oils widely differing in their fatty acid composition. Thermal oxidation assays as well as frying experiments were carried out and samples were evaluated by measuring the new compounds formed, i.e. polymers, polar compounds and their distribution by molecular weight, and polar fatty acids and their distribution by molecular weight. The levels of all the new compounds analysed strongly depended on the degree of oil unsaturation; the two least unsaturated oils with low content of linoleic acid and high content of palmitic acid behaved exceptionally well. When considering polar compounds or polar fatty acids, the polymers/oxidised monomers ratio increased significantly as the level of degradation increased. The new compounds formed are practically identical when analysed in the used frying oils or in the lipids extracted from the counterpart fried potatoes, independently of the level of degradation.

Evaporative light scattering detector in normal-phase high-performance liquid chromatography determination of FAME oxidation products.

The use of an ELS detector in NP-HPLC for quantitative analysis of oxidation products in FAME obtained from oils is evaluated in this study. The results obtained have shown that the ELS detector enables the quantitative determination of the hydroperoxides of oleic and linoleic acid methyl esters as a whole, and connected in series with a UV detector makes it possible to determine both groups of compounds by difference, providing useful complementary information. The limits of detection (LOD) and quantification (LOQ) found for hydroperoxides were respectively 2.5 and 5.7 µg mL⁻¹ and precision of quantitation expressed as coefficient of variation was lower than 10%. Due to a low sensitivity the ELS detector shows limitations to determine the low contents of secondary oxidation products in the direct analysis of FAME oxidized at low or moderate temperature. Analysis of FAME samples obtained either from high linoleic sunflower oil (HLSO) or high oleic sunflower oil (HOSO) and oxidized at 80 °C showed that only ketodienes formed from methyl linoleate can be determined in samples with relatively high oxidation, being the LOD and LOQ 0.2 and 0.4 mg/g FAME, respectively, at the analytical conditions applied. The ELS detector also enabled the determination of methyl cis-9,10-epoxystearate and methyl trans-9,10-epoxystearate, which were resolved at the chromatographic conditions applied. Results showed that these compounds, which are formed from methyl oleate, were not detected in the high-linoleic sample, but occurred at non-negligible levels in the oxidized FAME obtained from HOSO.

Quantitative analysis of hydroperoxy-, keto- and hydroxy-dienes in refined vegetable oils.

Quantitative analysis of the main oxidation products of linoleic acid - hydroperoxy-, keto- and hydroxy-dienes - in refined oils is proposed in this study. The analytical approach consists of derivatization of TAGs into FAMEs and direct analysis by HPLC-UV. Two transmethylation methods run at room temperature were evaluated. The reactants were KOH in methanol in method 1 and sodium methoxide (NaOMe) in method 2. Method 1 was ruled out because resulted in losses of hydroperoxydienes as high as 90 wt%. Transmethylation with NaOMe resulted to be appropriate as derivatization procedure, although inevitably also gives rise to losses of hydroperoxydienes, which were lower than 10 wt%, and formation of keto- and hydroxy-dienes as a result. An amount of 0.6-2.1 wt% of hydroperoxydienes was transformed into keto- and hydroxy-dienes, being the formation of the former as much as three times higher. The method showed satisfactory sensitivity (quantification limits of 0.3 µg/mL for hydroperoxy- and keto-dienes and 0.6 µg/mL for hydroxydienes), precision (coefficients of variation ≤ 6% for hydroperoxydienes and ≤ 15% for keto- and hydroxy-dienes) and accuracy (recovery values of 85(± 4), 99(± 2) and 97.0(± 0.6) % for hydroperoxy-, keto- and hydroxy-dienes, respectively). The method was applied to samples of high-linoleic (HLSO), high-oleic (HOSO) and high-stearic high-oleic (HSHOSO) sunflower oils oxidized at 40 °C. Results showed that the higher the linoleic-to-oleic ratio, the higher were the levels of hydroperoxy-, keto- and hydroxy-dienes when tocopherols were completely depleted, i.e. at the end of the induction period (IP). Levels of 23.7, 2.7 and 1.1 mg/g oil were found for hydroperoxy-, keto- and hydroxy-dienes, respectively, in the HLSO when tocopherol was practically exhausted. It was estimated that hydroperoxydienes constituted approximately 100, 95 and 60% of total hydroperoxides in the HLSO, HOSO and HSHOSO, respectively, along the IP.

Heterogeneous aspects of lipid oxidation in dried microencapsulated oils.

This work was aimed at studying lipid oxidation in dried microencapsulated oils (DMOs) during long-term storage. Samples were prepared by freeze-drying of emulsions containing sodium caseinate and lactose as encapsulating components. Evaluation of lipid oxidation was approached by quantitative analysis of nonvolatile lipid oxidation products and tocopherol. Lipid oxidation products were analyzed by separation of polar compounds by adsorption chromatography followed by HPSEC with refraction index detection for quantitation of oxidized triglyceride monomers, dimers, and oligomers. The analytical method applied enabled the detection of different oxidative patterns between the free and encapsulated oil fractions. The free oil fraction of DMOs showed a typical oxidative pattern for oils in continuous phase, which consisted of a clear induction period, in which hydroperoxides (oxidized triglyceride monomers) accumulated, before oxidation accelerated. The end of the induction period was marked by the total loss of tocopherol and the initiation of polymerization. On the contrary, the encapsulated oil showed a pattern characteristic of a mixture of oils with different oxidation status. Thus, high contents of advanced oxidation compounds (polymerization compounds) were detected when the antioxidant (tocopherol) was still present in high amounts. It is concluded that the encapsulated oil was comprised of oil globules with very different oxidation status. The results obtained in this study gave evidence of heterogeneous aspects of lipid oxidation in a dispersed-lipid food system.

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.

Electron spin resonance spin trapping for analysis of lipid oxidation in oils: inhibiting effect of the spin trap alpha-phenyl-N-tert-butylnitrone on lipid oxidation.

The electron spin resonance (ESR) spin trapping technique was investigated as an analytical approach to follow lipid oxidation of rapeseed oil, sunflower oil, and fish oil during storage at 40 degrees C. Unlike previous investigations, alpha-phenyl-N-tert-butylnitrone (PBN), used as spin trap, was added to the fresh oils and formation of radicals was monitored during storage. Results were compared with the development in peroxide value (PV) and the thiobarbituric acid index (TBA). Increasing radical development was detected during the initial stages of oxidation, during which no significant changes in PV and TBA were observed. Evidence of spin adduct depletion was found during prolonged storage, suggesting that although spin trapping of radicals may be used to follow early events in lipid oxidation, it is not a suitable parameter for long periods of time. Addition of the spin trap after sequential samplings is recommended for getting an insight of oxidative changes during storage. Further, the influence of the spin trap (PBN) on lipid oxidation was studied in detail by application of PV and TBA and by following the depletion of naturally occurring tocopherol. PBN was found to possess a profound inhibiting effect on lipid oxidation. Such an effect was found to be dependent on the nature of the oil, and it was observed that the lower the oxidative stability, the larger the effect of PBN on lipid oxidation. This effect was interpreted in terms of the capability of PBN to react with peroxyl radicals, which in turn depends on the initial tocopherol content of the oils.

Formation and evolution of monoepoxy fatty acids in thermoxidized olive and sunflower oils and quantitation in used frying oils from restaurants and fried-food outlets.

The formation and evolution of monoepoxy fatty acids, arising from oleic and linoleic acids, were investigated in olive oil and conventional sunflower oil, representatives of monounsaturated and polyunsaturated oils, respectively, during thermoxidation at 180 degrees C for 5, 10, and 15 h. Six monoepoxy fatty acids, cis-9,10- and trans-9,10-epoxystearate, arising from oleic acid, and cis-9,10-, trans-9,10-, cis-12,13-, and trans-12,13-epoxyoleate, arising from linoleic acid, were analyzed by gas chromatography after oil derivatization to fatty acid methyl esters. Considerable amounts, ranging from 4.29 to 14.24 mg/g of oil in olive oil and from 5.10 to 9.44 mg/g of oil in sunflower oil, were found after the heating periods assayed. Results showed that the monoepoxides quantitated constituted a major group among the oxidized fatty acid monomers formed at high temperature. For similar levels of degradation, higher contents of the monoepoxides were found in olive oil than in sunflower oil. Ten used frying oils from restaurants and fried-food outlets in Spain were analyzed to determine the contents of the monoepoxides in real frying oil samples. Levels ranged from 3.37 to 14.42 mg/g of oil. Results show that, for similar degradation levels, the monoepoxides were more abundant in the monounsaturated oils than in the polyunsaturated oils.

Influence of thermal treatments simulating cooking processes on the polyphenol content in virgin olive oil.

Virgin olive oils were subjected to simulated common domestic processing, including frying, microwave heating, and boiling with water in a pressure cooker. The impact of these processes on polyphenol content and physicochemical characteristics of oils was assessed. Thermal oxidation of oils at 180 degrees C caused a significant decrease in hydroxytyrosol- and tyrosol-like substances. In contrast, oils heated for 25 h still retained a high proportion of the lignans 1-acetoxypinoresinol and pinoresinol. Thermal oxidation also resulted in a rapid degradation of alpha-tocopherol and the glyceridic fraction of oils. Microwave heating of oils for 10 min caused only minor losses in polyphenols, and the oil degradation was lower than that in thermoxidation assays. Again, lignans were the least affected polyphenols and did not change during microwave heating. Boiling a mixture of virgin olive oil and water in a pressure cooker for 30 min provoked the hydrolysis of the secoiridoid aglycons and the diffusion of the free phenolics hydroxytyrosol and tyrosol from the oil to the water phase. Losses of polyphenols were detected only at pH lower than 6. Moreover, alpha-tocopherol and the glyceridic fraction of oils were not modified during this process. It is worth noting that all the heating methods assayed resulted in more severe polyphenols losses and oil degradation for Arbequina than for Picual oil, which could be related to the lower content in polyunsaturated fatty acids of the latter olive cultivar. These findings may be relevant to the choice of cooking method and olive oil cultivar to increase the intake of olive polyphenols.