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Since the discovery of tocopherols a century ago, α-tocopherol has been distinguished for its unique biological functions. In this study, we aim to elucidate the unique characteristics of α-tocopherol from a chemical perspective. Utilizing density functional theory (DFT) calculations, we evaluated the thermodynamic and kinetic properties of tocopherols, tocotrienols and their oxidation products. Our findings highlight the superior thermodynamic and kinetic properties of α-tocopherol. Although tocopherol substrates generally exhibit similar reactivities, α-tocopherol is distinguished by a larger gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in intermediates, indicating a potential for greater energy release and favoring reaction progression. Moreover, α-tocopherol shows enhanced efficiency in quenching radical intermediates, especially when combined with vitamin C. All these dates provide valuable support for the naming of vitamin E., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The effect of the antioxidant activity of α-tocopherol incorporated into different carriers on the oxidative stability of oil in water emulsion was investigated. The antioxidant activity of free and encapsulated α-tocopherol was measured in a 2,2-diphenyl-1-picrylhydrazyl reaction. Apart from α-tocopherol micelles, the samples showed similar antioxidant activity. The number of primary oxidation products in the emulsion with tocopherol liposomes and niosomes was lower than in the emulsion with micelles. During storage, the lipid peroxides gradually increased, whereas in emulsion with no α-tocopherol carriers added they remained constant. The content of the conjugated dienes first increased, and after 14 days at the end of testing time it remained stable in both types of emulsions. Our results might suggest that α-tocopherol when encapsulated into carriers exhibits lower antioxidant activity. The results obtained could be due to the better solubility of α-tocopherol in lipid droplets and thus the lower availability for the interfacial region, which is thought to be the place of the most pronounced lipid oxidation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

This study aimed to investigate the effect of dietary hazelnut skin (HNS), a by-product of confectionery industry, on the oxidative stability of lamb meat. Twenty-two finishing lambs were randomly assigned to 2 groups and fed ad libitum for 56 days on different concentrate-based diets: one control and one experimental, in which 150 g/kg of corn was replaced by HNS. After slaughter, the fat-soluble vitamins content and hydrophilic antioxidant capacity were assessed in fresh meat, as well as color, lipid and protein stability over 7 days of shelf-life trial. Dietary HNS increased (P < 0.001) the tocopherols content of meat and reduced (P < 0.001) lipid oxidation during 7 days of refrigerated storage. Meat from lambs fed HNS showed different (P < 0.05) instrumental color parameters. No diet effect (P > 0.05) was observed on the development of metmyoglobin, hydroperoxides, thiol groups, and carbonyl groups. Feeding HNS to lambs improves the oxidative stability of raw meat by delaying lipid oxidation thanks to the antioxidant molecules (tocopherols and phenolic compounds) contained in this by-product., Competing Interests: Declaration of Competing Interest None., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Garambullo (Myrtillocactus geometrizans) is endemic in México, and although popularly consumed locally, its nutritional characteristics and value have not been studied in details. The objective of this work was to investigate the bioactive compounds and antioxidant activity in garambullo fruit from different sites at three ripening stages. Fruit from the three ripening stages (red, purple, and dark purple) were investigated for their physicochemical characteristics, hydrophilic (phenolic compounds, betalains, and ascorbic acid), and lipophilic (carotenoids, tocopherols, and fatty acids) bioactive compounds, using spectrophotometry, gas chromatography (GC-FID), and high-pressure liquid chromatography coupled to mass spectrometry (HPLC/DAD-ESI-MS). The antioxidant capacity was measured with the 2,2'-diphenyl-1-picrylhydrazyl and the ferric-ion-reducing antioxidant power assays. The color components of the fruit, chroma and a* values increased, whereas lightness (L*) and b* significantly decreased during ripening. Five betacyanins and four betaxanthins were tentatively identified with HPLC/DAD-ESI-MS, and betacyanins were more abundant than betaxanthins. Betalains content and antioxidant capacity of hydrophilic extracts significantly increased during ripening. Ten phenolic compounds were identified, with ferulic acid being the most abundant. Tocopherols were low (0.023-0.033 mg/100 g fw). Five fatty acids were abundant, and linoleic acid was the most important. Phenolic compounds, ascorbic acid, total carotenoids, and fatty acids decreased during fruit ripening. Garambullo fruit is rich in phytochemical compounds of importance for human nutrition and health. PRACTICAL APPLICATION: The physicochemical and bioactive compounds characterization in garambullo fruit is important to establish maturation and harvesting indices, postharvest strategies to preserve fruit quality and prolong postharvest life, promote the consumption and utilization of the fruit, and the designing of proper functional foods. In addition, the knowledge on the bioactive components might be useful to include this fruit in personalized nutritional approaches for patients with risks of certain chronic diseases. The methodology used in this study could be useful for the study of other fruits, especially those from the Cactaceae family., (© 2023 Institute of Food Technologists.)

Among the eight forms of vitamin E, only tocopherols are essential compounds that are distributed throughout the entire plant kingdom, with α-tocopherol being the most predominant form in photosynthetic tissues. At the cellular level, α-tocopherol is of special relevance inside the chloroplast, where it eliminates singlet oxygen and modulates lipid peroxidation. This is of utmost relevance since tocopherols are the only antioxidants that counteract lipid peroxidation. Moreover, at the whole-plant level, α-tocopherol appears to modulate several physiological processes from germination to senescence. The antioxidant role of α-tocopherol at the cellular level can have profound effects at the whole-plant level, including the modulation of physiological processes that are apparently not related to redox processes and could be considered non-antioxidant functions. Here, we discuss whether non-antioxidant functions of α-tocopherol at the whole-plant level are mediated by its antioxidant role in chloroplasts and the regulation of redox processes at the cellular level., Competing Interests: Declaration of competing interest All the authors declare that they have no conflict of interest., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This article presents an optimized ultrasound-assisted ethanolic extraction (UAEE) and characterization of selected high-value components from Gemlik olive fruit (GOF) harvested from Potohar region of Pakistan. Response surface methodology (RSM), involving central composite design (CCD), was applied to optimize the extraction variables i. e., temperature (25-65 °C), extraction time (15-45 min) and aqueous ethanol concentration (60-90 %) for optimal recovery of bioactives extract, total phenolic contents (TPC) and DPPH free radical scavengers. Under the optimized set of conditions such as 43 °C temperature, 32 min extraction time and 80 % aqueous ethanol, the best extract yield (218.82 mg/g), TPC (19.87 mg GAE/g) and DPPH scavenging activity (63.04 %) were recorded. A quadratic polynomial model was found to be reasonably fitted to the observed results for extract yield (p<0.0001 and R 2 =0.9941), TPC (p<0.0001 and R 2 =0.9891), and DPPH radical scavenging activity (p<0.0001 and R 2 =0.9692). Potent phenolic compounds were identified by GC/MS in GOF extract and considerable amount of essential fatty acids were also detected. The current findings support the use of UAEE as an effective green route for optimized recovery of high-value components from GOF and hence its applications can be extended to functional food and nutra-pharmaceutical developments., (© 2023 The Authors. Chemistry & Biodiversity published by Wiley-VHCA AG, Zurich, Switzerland.)

Wheat roll enhanced by buckwheat hull was used as a model for determining the retention of bioactive compounds during technological steps. The research included analysis of the formation of Maillard reaction products (MRPs) and retention of bioactive compounds such as tocopherols, glutathione, or antioxidant capacity. About a 30% decrease in the content of available lysine in the roll was observed compared to the value obtained for fermented dough. Free FIC, FAST index, and browning index were highest for the final products. The increase of analyzed tocopherols (α-, β-,γ-, and δ-T) was noticed during the technological steps, with the highest values found for the roll with 3% of buckwheat hull. A significant reduction in GSH and GSSG content occurred during the baking process. The observed increase in the value of the antioxidant capacity after the baking process may be the result of the formation of new antioxidant compounds., Competing Interests: The authors declare no conflicts of interest.

The use of efficient solar ovens can be a way for progressing ecofriendly technologies in the field of food preparation. In most performing direct solar ovens, the sun rays reach the foods directly, therefore, it becomes essential to check whether, in these conditions, foods can retain theirnutraceutical properties (antioxidants, vitamins and carotenoids). In the present research work, to investigate this issue, several foods (vegetables, meats, and a fish sample) were analyzed before and after cooking (traditional oven, solar oven, and solar oven with a UV filter). The content of lipophilic vitamins and carotenoids (analyzed via HPLC-MS) and the variation of total phenolic content (TPC), and antioxidant capacity (via Folin-Ciocalteu and DPPH assays) have evidenced that cooking with the direct solar oven allows to preserve some nutrients (i.e., tocopherols) and, sometimes, to enhance nutraceutical properties of vegetables (for example, solar oven-cooked eggplants showed 38% higher TPC compared to electric oven cooked sample) and meats. The specific isomerization of all-trans-β-carotene to 9-cis was also detected. The use of a UV filter is advisable to avoid UV drawbacks (for instance, a significant carotenoid degradation) without losing the beneficial effects of the other radiations.

Extended, chemically detailed kinetic models at the molecular basis are constructed to identify the reactions involved in the reversal of the antioxidant action of α-, β-, γ- and δ-tocopherols during methyl linoleate oxidation. The reaction mechanisms were numerically simulated and subjected to analysis to quantify the significance of individual chemical steps by the value-based method. Results of the obtained kinetic models agreed well with the experimental data. The significant individual reactions contributing to the observed antioxidant and pro-oxidant behavior of the different tocopherols were identified. It is revealed that the reverse order of antioxidant potency and a complex nonlinear dependency of the antioxidant potency of tocopherols with the increase in their concentration are due to the increasing contribution of pro-oxidant relative to the antioxidant reactions. Once the approach presented here can be applied to more complex systems, engineered optimization of antioxidant protection strategies may be reached., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Macauba is a palm tree native to Brazil, which fruits are rich in oil. Macauba pulp oil has high contents of oleic acid, carotenoids, and tocopherol, but its effect on health is unknown. We hypothesized that macauba pulp oil would prevent adipogenesis and inflammation in mice. Thus, the purpose of this study was to evaluate the effects of macauba pulp oil on the metabolic changes in C57Bl/6 mice fed a high-fat diet. Three experimental groups were used ( n = 10): control diet (CD), high-fat diet (HFD), and high-fat diet with macauba pulp oil (HFM). The HFM reduced malondialdehyde and increased SOD activity and antioxidant capacity (TAC), showing high positive correlations between total tocopherol, oleic acid, and carotenoid intakes and SOD activity (r = 0.9642, r = 0.8770, and r = 0.8585, respectively). The animals fed the HFM had lower levels of PPAR-γ and NF-κB, which were negatively correlated with oleic acid intake (r = -0.7809 and r = -0.7831, respectively). Moreover, the consumption of macauba pulp oil reduced inflammatory infiltrate, adipocyte number and length, (mRNA) TNF-α , and (mRNA) SREBP-1c in the adipose tissue, and it increased (mRNA) Adiponectin . Therefore, macauba pulp oil prevents oxidative stress, inflammation, and adipogenesis and increases antioxidant capacity; these results highlight its potential against metabolic changes induced by an HFD.

Gamma irradiation has been applied as an efficient and inexpensive method for the sterilization of nuts for years. However, along with the benefits of such treatment, negative effects are possible because of the formation of reactive oxygen species with a toxic effect on important biologically active substances. Because of the scarce and contradictory information in the literature about gamma-irradiated almonds, the aim of our work was the examination of the lipid changes, antioxidant activity, and oxidative stability of almonds treated by 10 and 25 kGy gamma rays, as well as changes in intensity of the EPR spectra as an indicator for the stability of radiation-induced free radicals. The results revealed no significant differences in the EPR spectra of almonds treated at 10 and 25 kGy doses, neither in their intensity nor in kinetic behaviour. The EPR signals decayed exponentially over 250 days, with a decreasing of central line by 90%, with satellite lines by about 73%. No significant changes in the fat content, fatty acids composition, and acid value of irradiated almonds were observed. However, the amount of (alpha)tocopherols decreased from 292 to 175 mg/kg, whereas the conjugated dienes and trienes increased, K 232 from 1.3 to 3 and K 268 from 0.04 to 0.15, respectively, with the increasing of irradiation dose. The same was observed for total polyphenols in defatted almonds (1374 to 1520 mg/100 g), where in vitro antioxidant activity determined by ORAC and HORAC methods increased from 100 to 156 µmol TE/g and from 61 to 86 µmol GAE/g, respectively. The oxidative stability of oil decreased from 6 to 4 h at 120 °C and from 24.6 to 18.6 h at 100 °C (measured by Rancimat equipment). The kinetic parameters characterizing the oxidative stability of oil from 10 kGy irradiated almonds were studied before and after addition of different concentrations of ascorbyl palmitate as a synergist of tocopherols. Its effectiveness was concentration-dependent, and 0.75 mM ensured the same induction period as that of non-irradiated nut oil. Further enrichment with alpha-tocopherol in equimolar ratio with palmitate did not improve the oil stability. In conclusion, gamma irradiation is an appropriate method for the treatment of almonds without significant changes in fat content and fatty acids composition. The decreasing of oxidative stability after higher irradiation could be prevented by the addition of ascorbyl palmitate.

Tocopherols are natural bioactive compounds with several health benefits. This study evaluated the effect of different ratios of α- and δ- tocopherol homologs to protect sunflower oil (SO) and olive pomace oil (OPO) against oxidation. A synergistic effect was recorded when the two tocopherols were combined at a ratio of 7:1 (α-T/δ-T). The oil samples were exposed to accelerated oxidation conditions using a Rancimat (90 °C and airflow of 15 L/h for 24 h) and protection from tocopherols was compared with that from butylated hydroxytoluene (BHT). Assessment of oil stability was examined using well-known parameters such as peroxide value (PV), thiobarbituric acid reactive substances (TBARS), p-anisidine value (p-AV), conjugated dienes (CD) and trienes (CT), and total oxidation (Totox) value, which were all significantly reduced when tocopherols were added at a ratio of 7:1 α-T/δ-T. Primary oxidative compounds measured according to PV were only reduced in SO samples (6.11%). Off-flavor compounds measured via TBARS assay in SO samples were reduced by above 20%, while p-AV was also reduced. CDvalue was correlated with PV in SO samples, while the 7:1 mixture was more effective than BHT for CTvalue. Total oxidation values in SO samples and OPO samples were reduced by 6.02% and 12.62%, respectively. These values in SO samples also provided a remarkable correlation (R2 > 0.95) with incubation time. Moreover, the synergistic effect was not only effective in reducing the oxidation values of oil samples, but also in lowering the degradation rate of tocopherols. Protective effects from tocopherols were mainly observed in SO samples, as OPO samples were more resistant to oxidation processes. This effect was even observed in fatty acid analysis, where the 7:1 mixture provided better results than BHT-spiked samples. Thus, it is suggested that tocopherol mixtures might be used as a natural preservative in the food industry to restrain lipid oxidation processes.

Tomato is a widely distributed, cultivated, and commercialized vegetable crop. It contains antioxidant constituents including lycopene, tocopherols, vitamin C, γ -aminobutyric acid, phenols, and flavonoids. This study determined the contents of the antioxidant components and activities of the pulp with skin of ten regular, six medium-sized, and two small cherry tomato cultivars at red ripe (BR + 10) stage cultivated in Korea. The relationships among the Hunter color coordinates, the content of each component, and antioxidant activities were measured by Pearson's correlation coefficients. As the a* value increased, the carotenoid and vitamin C contents increased, while the L * value, hue angle and tocopherol content decreased. As the b* value increased, the lycopene and total carotenoid contents decreased, and the flavonoid content in the hydrophilic extracts increased. The contents of vitamin C and total carotenoids including lycopene showed high positive correlations with the DPPH radical scavenging activities of both the lipophilic and hydrophilic extracts. Tocopherols and total phenolics in the hydrophilic and lipophilic extracts were not major positive contributors to the antioxidant activity. These findings suggest the quality standards for consumer requirements and inputs for on-going research for the development of better breeds.

This study aimed to evaluate the effects of peanut varieties cultivated in Morocco ( Virginia and Valencia ) and extraction methods (cold press, CP; Soxhlet, Sox and maceration, and Mac) on the fatty acid profile, phytosterol, and tocopherol contents, quality characteristics, and antioxidant potential of peanut seed oil. The DPPH method was used to determine the antioxidant activity of the oils. The results revealed that fatty acid content was slightly affected by the extraction technique. However, the CP method was shown to be an excellent approach for extracting oil with desirable quality features compared to the Sox and Mac methods. Furthermore, the peanut oil extracted via CP carried a higher amount of bioactive compounds and exhibited remarkable antioxidant activities. The findings also revealed higher oleic acid levels from the Virginia oil, ranging from 56.46% to 56.99%. Besides, a higher total phytosterol and tocopherol content and DPPH scavenging capacity were obtained from the Valencia oil. Analyzing the study, it can be inferred that extraction method and variety both affect the composition of the peanut oil's bioactive compounds and antioxidant activity. This information is relevant for extracting peanut oil with a greater level of compounds of industrial interest.

The function of vitamin E in biomembranes remains a prominent topic of discussion. As its limitations as an antioxidant persist and novel functions are discovered, our understanding of the role of vitamin E becomes increasingly enigmatic. As a group of lipophilic molecules (tocopherols and tocotrienols), vitamin E has been shown to influence the properties of its host membrane, and a wealth of research has connected vitamin E to polyunsaturated fatty acid (PUFA) lipids. Here, we use contrast-matched small-angle neutron scattering and differential scanning calorimetry to integrate these fields by examining the influence of vitamin E on lipid domain stability in PUFA-based lipid mixtures. The influence of α-tocopherol, γ-tocopherol, and α-tocopherylquinone on the lateral organization of a 1:1 lipid mixture of saturated distearoylphosphatidylcholine (DSPC) and polyunsaturated palmitoyl-linoleoylphosphatidylcholine (PLiPC) with cholesterol provides a complement to our growing understanding of the influence of tocopherol on lipid phases. Characterization of domain melting suggests a slight depression in the transition temperature and a decrease in transition cooperativity. Tocopherol concentrations that are an order of magnitude higher than anticipated physiological concentrations (2 mol percent) do not significantly perturb lipid domains; however, addition of 10 mol percent is able to destabilize domains and promote lipid mixing. In contrast to this behavior, increasing concentrations of the oxidized product of α-tocopherol (α-tocopherylquinone) induces a proportional increase in domain stabilization. We speculate how the contrasting effect of the oxidized product may supplement the antioxidant response of vitamin E.

Linusorbs (LOs, cyclolinopeptides) are a class of naturally occurring cyclic hydrophobic peptides found in flaxseed oil, whose oxidation states indicate the oxidative stability and bitterness of flaxseed oil. Subjected to 63 °C accelerated oxidation, most Met-containing LOs in cold-pressed flaxseed oil entirely depleted by the 6th day except CLP, and MetO 2 -containing LOs became the dominant ones. However, no MetO 2 form of Trp-containing LOs, such as CLD, CLF and CLG, were detected. Given their oxidative kinetics, methionine sulfoxide (MetO) residue in some LOs was less sensitive toward oxidation in the presence of Trp (Tryptophan) group, and the oxidative stability of Met-containing LOs was CLP < CLB < CLL ≈ CLM < CLO, as compared to MetO-containing LOs: CLD < CLE < CLC < CLF ≈ CLG. When antioxidant was added into cold-pressed flaxseed oil to assess the additives' antioxidant effect, no significant difference was observed on oil oxidative indices in early stage except α-tocopherol, where they vary dramatically in suppressing Met oxidation of LOs: L-AP (L-ascorbyl palmitate) > TBHQ (tert-butyl hydroquinone) > γ-tocopherol > carnosic acid > α-tocopherol. Besides its ability to suppress oxidation of Trp-containing LOs, L-AP also exhibits superior antioxidant effect on non-Trp-containing LOs due to its amphiphilic property. Due to the prooxidative effects of both α- and γ-tocopherol on LOs that contain Trp, it has been suggested that tocopherols may repair Trp residue on LOs, leading to increased tendency of MetO residues to oxidize. The findings of this research are critical for elucidating the antioxidative mechanism of LOs, which can further lead to the establishment of strategies in suppressing bitter after taste to produce high-quality flaxseed oil., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The aim of this work was to study the effects of microwaves (MW) and hot air (HA) treatments on enzyme activities and quality parameters in wheat germ (WG). Both MW and HA were effective at inactivating lipases. MW treatment inactivated lipases more at lower temperatures (60 and 70 °C) than HA (150-200 °C). Peroxide values, acidity, and fatty acid profiles of WG oil remained unaltered after HA and MW treatments. Loss of α-tocopherol contents was observed following HA treatment, but total tocopherol content remained above 77% baselines values in all treated samples. The main antioxidant mechanism of WG extracts was associated with inactivation of radicals, rather than reducing capacity. MW treatment at 60 and 70 °C enhanced radical scavenging activity, while total polyphenol contents and reducing capacities were negatively affected. Therefore, MW treatment is a promising technology to stabilise WG, retaining quality and antioxidant activity., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Several studies suggested the association of COVID-19 with systemic oxidative stress, in particular with lipid peroxidation and vascular stress. Therefore, this study aimed to evaluate the antioxidant signaling in the plasma of eighty-eight patients upon admission to the Clinical Hospital Dubrava in Zagreb, of which twenty-two died within a week, while the other recovered. The differences between the deceased and the survivors were found, especially in the reduction of superoxide dismutases (SOD-1 and SOD-2) activity, which was accompanied by the alteration in glutathione-dependent system and the intensification of the thioredoxin-dependent system. Reduced levels of non-enzymatic antioxidants, especially tocopherol, were also observed, which correlated with enhanced lipid peroxidation (determined by 4-hydroxynonenal (4-HNE) and neuroprostane levels) and oxidative modifications of proteins assessed as 4-HNE-protein adducts and carbonyl groups. These findings confirm the onset of systemic oxidative stress in patients with severe SARS-CoV-2, especially those who died from COVID-19, as manifested by strongly reduced tocopherol level and SOD activity associated with lipid peroxidation. Therefore, we propose that preventive and/or supplementary use of antioxidants, especially of lipophilic nature, could be beneficial for the treatment of COVID-19 patients.

The impact of malting on antioxidant, nutritional, and antinutritional features of two industrial hemp cultivars was investigated. The seeds were steeped (5 h; RT), germinated (3-days; 24 °C), and kilned at different temperatures (6 h; 50 °C or 70 °C). The following determinations were performed on malted and unmalted samples: total phenolic content, polyphenol profile, total antioxidant capacity, tocopherol composition, proximate analysis, fatty acids profile, trypsin inhibitors and phytate content. The results showed that malting increased the protein content up to 9%, without affecting the fat amount, and the fatty acids profile. Total phenolic content, tocopherol profile and total antioxidant capacity were also improved. 70 °C kilning temperature resulted effective to reduce the trypsin inhibitors (up to -27%), increase the reducing power and the level of N-trans-caffeoyltyramine and cannabisin A. Based on this, malting using 3 germination days and 70 °C as kilning temperature could be considered suitable transformation process for improving hempseeds quality., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Natural substances have traditionally been used in skin care for centuries. There is now an ongoing search for new natural bioactives that not only promote skin health but also protect the skin against various harmful factors, including ultraviolet radiation and free radicals. Free radicals, by disrupting defence and restoration mechanisms, significantly contribute to skin damage and accelerate ageing. Natural compounds present in plants exhibit antioxidant properties and the ability to scavenge free radicals. The increased interest in plant chemistry is linked to the growing interest in plant materials as natural antioxidants. This review focuses on aromatic and medicinal plants as a source of antioxidant substances, such as polyphenols, tocopherols, carotenoids, ascorbic acid, and macromolecules (including polysaccharides and peptides) as well as components of essential oils, and their role in skin health and the ageing process.

Lipid oxidation is a major concern in the food, cosmetic, and pharmaceutical sectors. The degradation of unsaturated lipids affects the nutritional, physicochemical, and organoleptic properties of products and can lead to off-flavors and to the formation of potentially harmful oxidation compounds. To prevent or slow down lipid oxidation, different antioxidant additives are used alone or in combination to achieve the best possible efficiency with the minimum possible quantities. In manufactured products, that is, heterogeneous systems containing lipids as emulsions or bulk phase, the efficiency of an antioxidant is determined not only by its chemical reactivity, but also by its physical properties and its interaction with other compounds present in the products. The antioxidants most widely used on the industrial scale are probably tocopherols, either as natural extracts or pure synthetic molecules. Considerable research has been conducted on their antioxidant activity, but results regarding their efficiency are contradictory. Here, we review the known mechanisms behind the antioxidant activity of tocopherols and discuss the chemical and physical features that determine their efficacy. We first describe their chemical reactivity linked with the main factors that modulate it between efficient antioxidant capacity and potential prooxidant effects. We then describe their chemical interactions with other molecules (phenolic compounds, metals, vitamin C, carotenes, proteins, and phospholipids) that have potential additive, synergistic, or antagonist effects. Finally, we discuss other physical parameters that influence their activity in complex systems including their specific interactions with surfactants in emulsions and their behavior in the presence of association colloids in bulk oils., (© 2021 Institute of Food Technologists®.)

The demand for natural products isolated from microalgae has increased over the last decade and has drawn the attention from the food, cosmetic and nutraceutical industries. Among these natural products, the demand for natural antioxidants as an alternative to synthetic antioxidants has increased. In addition, microalgae combine several advantages for the development of biotechnological applications: high biodiversity, photosynthetic yield, growth, productivity and a metabolic plasticity that can be orientated using culture conditions. Regarding the wide diversity of antioxidant compounds and mode of action combined with the diversity of reactive oxygen species (ROS), this review covers a brief presentation of antioxidant molecules with their role and mode of action, to summarize and evaluate common and recent assays used to assess antioxidant activity of microalgae. The aim is to improve our ability to choose the right assay to assess microalgae antioxidant activity regarding the antioxidant molecules studied.

Tocopherols and tocotrienols are natural compounds of plant origin, available in the nature. They are supplied in various amounts in a diet, mainly from vegetable oils, some oilseeds, and nuts. The main forms in the diet are α- and γ-tocopherol, due to the highest content in food products. Nevertheless, α-tocopherol is the main form of vitamin E with the highest tissue concentration. The α- forms of both tocopherols and tocotrienols are considered as the most metabolically active. Currently, research results indicate also a greater antioxidant potential of tocotrienols than tocopherols. Moreover, the biological role of vitamin E metabolites have received increasing interest. The aim of this review is to update the knowledge of tocopherol and tocotrienol bioactivity, with a particular focus on their bioavailability, distribution, and metabolism determinants in humans. Almost one hundred years after the start of research on α-tocopherol, its biological properties are still under investigation. For several decades, researchers' interest in the biological importance of other forms of vitamin E has also been growing. Some of the functions, for instance the antioxidant functions of α- and γ-tocopherols, have been confirmed in humans, while others, such as the relationship with metabolic disorders, are still under investigation. Some studies, which analyzed the biological role and mechanisms of tocopherols and tocotrienols over the past few years described new and even unexpected cellular and molecular properties that will be the subject of future research.

Plant prenyllipids, especially isoprenoid chromanols and quinols, are very efficient low-molecular-weight lipophilic antioxidants, protecting membranes and storage lipids from reactive oxygen species (ROS). ROS are byproducts of aerobic metabolism that can damage cell components, they are also known to play a role in signaling. Plants are particularly prone to oxidative damage because oxygenic photosynthesis results in O 2 formation in their green tissues. In addition, the photosynthetic electron transfer chain is an important source of ROS. Therefore, chloroplasts are the main site of ROS generation in plant cells during the light reactions of photosynthesis, and plastidic antioxidants are crucial to prevent oxidative stress, which occurs when plants are exposed to various types of stress factors, both biotic and abiotic. The increase in antioxidant content during stress acclimation is a common phenomenon. In the present review, we describe the mechanisms of ROS (singlet oxygen, superoxide, hydrogen peroxide and hydroxyl radical) production in chloroplasts in general and during exposure to abiotic stress factors, such as high light, low temperature, drought and salinity. We highlight the dual role of their presence: negative (i.e., lipid peroxidation, pigment and protein oxidation) and positive (i.e., contribution in redox-based physiological processes). Then we provide a summary of current knowledge concerning plastidic prenyllipid antioxidants belonging to isoprenoid chromanols and quinols, as well as their structure, occurrence, biosynthesis and function both in ROS detoxification and signaling.

Singlet oxygen ( 1 O 2 ) is the major reactive oxygen species ROS causing photooxidative stress in plants which is formed predominantly in the reaction center of photosystem II during photosynthesis. To avoid deleterious effects of 1 O 2 oxygen on photosynthetic membrane components, plant synthesize a variety of 1 O 2 quenchers of lipophilic character, such as carotenoids or phenolic prenyllipids (tocopherols, plastochromanol-8, plastoquinol). In the process of chemical quenching of 1 O 2 by the antioxidants, both short-lived products, such as oxidized carotenoids, or relative long-lived compounds, such as oxidized phenolic prenyllipids are formed. The other target of 1 O 2 are unsaturated fatty acids of membrane lipids that undergo peroxidation as a result of the reaction. Some of the 1 O 2 oxidation products, like β-cyclocitral can be components of 1 O 2 -signallingsignaling pathway leading to acclimatory responses of plants, while some others further fulfill antioxidant functions, like hydroxy-plastochromanol or hydroxy-plastoquinol. As most of the 1 O 2 oxidation products are specific compounds formed only as a results of 1 O 2 action, they can be very useful, specific molecular markers of 1 O 2 -dependent oxidative stress in vivo., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Kainth fruit, as traditional medicine, has been used in the Himalayan region for its health-promoting properties. However, the phytochemicals and lipidomes of Kainth Seed Oil (KSO) are still scarce. Here, we investigated the physicochemical characterization of KSO and its nutraceuticals, antioxidant potentials. Kainth seeds contain 19-20% oil rich in polyunsaturated fatty acids (PUFA, 82.22%), particularly linoleic acid (C18:2). Lipidome analysis of KSO using high-resolution mass spectrometry showed that trilinoleate (C54:6) was the dominant triacylglycerol (TAG) species. Further, the characteristics of PUFA-rich oil were validated by Fourier transforms infrared spectroscopy (FTIR) and Differential Scanning calorimetry (DSC). The nutraceuticals profiling of KSO depicted the presence of tocopherols (86.72 mg) and phytosterols (32.25 mg) in 100 g oil with significant antioxidant activity. The oil cake contained 19.09% protein and minerals and can be a source for dietary protein. Collectively these results suggest that KSO will be a suitable source for PUFA and nutraceuticals potential., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Vitamin E, essential for human health, is widely used worldwide for therapeutic or dietary reasons. The differences in the metabolism and excretion of the multiple vitamin E forms are presented in this review. The important steps that influence the kinetics of each form and the distribution and processing of vitamin E forms by the liver are considered. The antioxidant as well as non-antioxidant properties of vitamin E forms are discussed. Finally, synthetic tocopherol and trolox derivatives, based on the design of multitarget directed compounds, are reviewed. It is demonstrated that selected derivatization of vitamin E or trolox structures can produce improved antioxidants, agents against cancer, cardiovascular and neurodegenerative disorders., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Background: Oxidative stress and inflammation are some of the proposed mechanisms involved in the pathogenesis of atopic dermatitis (AD). Current pharmacotherapeutic approaches are effective yet they are not without adverse effects. Vitamin E has great potential as an adjunctive treatment for AD owing to its antioxidant and anti-inflammatory bioactivities., Summary: This review article summarizes the current available evidence from cellular, animal and clinical studies on the relationship between vitamin E and AD. The future prospects of vitamin E are also discussed. Vitamin E in practice does not show any toxicity to humans within a range of reasonable dosage. Albeit rarely, vitamin E as a contact allergen should be considered. Collectively, this review envisaged vitamin E as an adjunctive treatment for AD patients. Future research on the distinct effects of different vitamin E isoforms as well as their delivery system in skin disorders is needed., (© 2020 S. Karger AG, Basel.)

In this study, bioactive lipid components such as fatty acid composition, tocopherol and total phenolics content and antioxidant activity of few wild plant seed extracts were determined. The oil contents of seed samples changed between 3.75 g/100 g (Onobrychis viciifolia Scop) and 17.94 g/100 g (Pimpinella saxifrage L.). While oleic acid contents of seed oils change between 10.4% (Trifolium repens) and 29.5% (Onobrychis viciifolia Scop), linoleic acid contents of oil samples varied from 16.3% (Onobrychis viciifolia Scop) and 64.2% (Trifolium repens) (p < 0.05). While α-tocopherol contents of oil samples change between 2.112 (Pimpinella saxifrage L.) and 228.279 mg/100 g (Trifolium pratense), ɣ-tocopherol contents ranged from 0.466 (Phleum pratense) to 67.128 mg/100 g (Onobrychis viciifolia Scop). Also, α-tocotrienol contents of Onobrychis viciifolia Scop and Phleum pratense were 30.815 and 23.787 mg/100 g, respectively. Results showed some differences in total phenol contents and antioxidant activity values of extracts depending on plant species. The present study indicates that this seed oils are rich in fatty acid and tocopherol.

Microalgae, including cyanobacteria, represent a valuable source of natural compounds that have remarkable bioactive properties. Each microalga species produces a mixture of antioxidants with different amounts of each compound. Three aspects are important in the production of bioactive compounds: the microalga species, the medium composition including light supplied and the photobioreactor design, and operation characteristics. In this study, the antioxidant content and productivity performance of four microalgae were assessed in batch and continuous cultures. Biomass productivity by the four microalgae was substantially enhanced under continuous cultivation by 5.9 to 6.3 times in comparison with batch cultures. The energetic yield, under the experimental conditions studied, ranged from 0.03 to 0.041 g biomass kJ -1 . Phenols, terpenoids, and alkaloids were produced by Spirulina platensis , Isochrysis , whereas tocopherols and carotenoids were produced by the four microalgae, except for phycocyanin and allophycocyanin, which were only produced by galbana , and Tetraselmis . The findings demonstrate that the continuous cultivation of microalgae in photobioreactors is a convenient method of efficiently producing antioxidants.suecica , whereas tocopherols and carotenoids were produced by the four microalgae, except for phycocyanin and allophycocyanin, which were only produced by S. platensis and Porphyridium cruentum . The findings demonstrate that the continuous cultivation of microalgae in photobioreactors is a convenient method of efficiently producing antioxidants.

We studied changes in gas exchange, photochemical activity and the antioxidant system in cucumber leaves locally infected with Pseudomonas syringae pv lachrymans and in uninfected systemic ones. Infection-induced declined net photosynthesis rate and the related changes in transpiration rate, the intracellular CO 2 concentration, and prolonged reduction in maximal PSII quantum yield (Fv/Fm), accompanied by an increase in non-photochemical quenching (NPQ), were observed only in the infected leaves, along with full disease symptom development. Infection severely affected the ROS/redox homeostasis at the cellular level and in chloroplasts. Superoxide dismutase, ascorbate, and tocopherol were preferentially induced at the early stage of pathogenesis, whereas catalase, glutathione, and the ascorbate-glutathione cycle enzymes were activated later. Systemic leaves retained their net photosynthesis rate and the changes in the antioxidant system were partly like those in the infected leaves, although they occurred later and were less intense. Re-balancing of ascorbate and glutathione in systemic leaves generated a specific redox signature in chloroplasts. We suggest that it could be a regulatory element playing a role in integrating photosynthesis and redox regulation of stress, aimed at increasing the defense capacity and maintaining the growth of the infected plant.

Walnut ( Juglans regia L.) septum represents an interesting bioactive compound source by-product. In our study, a rich phenolic walnut septum extract, previously selected, was further examined. The tocopherol content determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) revealed higher amounts of α-tocopherol compared to γ- and δ-tocopherols. Moreover, several biological activities were investigated. The in vitro inhibiting assessment against acetylcholinesterase, α-glucosidase, or lipase attested a real management potential in diabetes or obesity. The extract demonstrated very strong antimicrobial potential against Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella enteritidis . It also revealed moderate (36.08%) and strong (43.27%) antimutagenic inhibitory effects against TA 98 and TA 100 strains. The cytotoxicity of the extract was assessed on cancerous (A549, T47D-KBluc, MCF-7) and normal (human gingival fibroblasts (HGF)) cell lines. Flow cytometry measurements confirmed the cytotoxicity of the extract in the cancerous cell lines. Additionally, the extract demonstrated antioxidant activity on all four cell types, as well as anti-inflammatory activity by lowering the inflammatory cytokines (interleukin-6 (IL-6), interleukin-8 (IL-8), interleukin-1 β (IL-1β)) evaluated in HGF cells. To the best of our knowledge, most of the cellular model analyses were performed for the first time in this matrix. The results prove that walnut septum may be a potential phytochemical source for pharmaceutical and food industry.

Human milk fat is specially tailored to supply the developing infant with adequate and balanced nutrients. The present study aimed to quantify the composition of fatty acids, tocopherols and carotenoids in human milk, with special emphasis on the lactational changes. Colostrum, transitional and mature milk samples were collected longitudinally from the same forty-two healthy, well-nourished Chinese mothers. Fatty acids were quantified by GC with carotenoids (carotenes and xanthophylls) and tocopherols (α-, γ-tocopherol) determined by HPLC. Total fatty acid (TFA) content increased from 15·09 g/l in colostrum to 32·57 g/l in mature milk with the percentages of DHA and arachidonic acid (ARA) decreased. The ratio of n-6:n-3 PUFA and ARA:DHA remained constant during lactation at about 11:1 and 1·3:1, respectively. Both α-tocopherol and γ-tocopherol decreased over lactation with the ratio of α-:γ-tocopherol declined significantly from 7·21:1 to 4·21:1 (P < 0·001). Carotenoids all dropped from colostrum to mature milk as the less polar carotenes dropped by 88·67 %, while xanthophylls only dropped by 35·92 %. Lutein was predominated in both transitional and mature milk carotenoids (51·64-52·49 %), while colostrum carotenoids were mainly composed of lycopene (32·83 %) and β-carotene (30·78 %). The concentrations of tocopherols and xanthophylls but not carotenes were positively associated with TFA content in milk. These results suggested that colostrum and mature milk contained divergent lipid profiles and selective transfer mechanisms related to polarity might be involved. The present outcomes provide new insights for future breast-feeding studies, which also add in scientific evidences for the design of both initial and follow-on infant formulas.

α-Tocopherol (α-T) is the major form of vitamin E (VE) in animals and has the highest activity in carrying out the essential antioxidant functions of VE. Because of the involvement of oxidative stress in carcinogenesis, the cancer prevention activity of α-T has been studied extensively. Lower VE intake or nutritional status has been shown to be associated with increased cancer risk, and supplementation of α-T to populations with VE insufficiency has shown beneficial effects in lowering the cancer risk in some intervention studies. However, several large intervention studies with α-T conducted in North America have not demonstrated a cancer prevention effect. More recent studies have centered on the γ- and δ-forms of tocopherols and tocotrienols (T3). In comparison with α-T, these forms have much lower systemic bioavailability but have shown stronger cancer-preventive activities in many studies in animal models and cell lines. γ-T3 and δ-T3 generally have even higher activities than γ-T and δ-T. In this article, we review recent results from human and laboratory studies on the cancer-preventive activities of different forms of tocopherols and tocotrienols, at nutritional and pharmacological levels. We aim to elucidate the possible mechanisms of the preventive actions and discuss the possible application of the available information for human cancer prevention by different VE forms., (© 2020 Wiley Periodicals, Inc.)

The interest in antioxidant compound breeding in maize ( Zea mays L.), a major food crop, has increased in recent years. However, breeding of antioxidant compounds in maize can be hampered, given the complex genetic nature of these compounds. In this work, we followed a genome-wide association approach, using a unique germplasm collection (containing Portuguese germplasm), to study the genetic basis of several antioxidants in maize. Sixty-seven genomic regions associated with seven antioxidant compounds and two color-related traits were identified. Several significant associations were located within or near genes involved in the carotenoid (Zm00001d036345) and tocopherol biosynthetic pathways (Zm00001d017746). Some indications of a negative selection against α-tocopherol levels were detected in the Portuguese maize germplasm. The strongest single nucleotide polymorphism (SNP)-trait associations and the SNP alleles with larger effect sizes were pinpointed and set as priority for future validation studies; these associations detected now constitute a benchmark for developing molecular selection tools for antioxidant compound selection in maize.

Although the biosynthesis and function of tocochromanols in leaves and seeds have been extensively studied, their occurrence and function in underground tissues, such as roots and nodules, is very poorly understood. Here, we performed a comparative study of the presence of tocochromanols in different plant organs (leaves, roots and nodules) of three legumes (soybean, alfalfa and pea plants). Additionally, we measured variations in tocochromanols as a function of the severity of water stress and evaluated their relationship with the extent of membrane lipid peroxidation and nodule performance (as indicated by thiobarbituric acid-reactive substances assay and 15 N isotope labeling, respectively). Results showed the presence of endogenous tocopherols, mainly α-tocopherol, in the three studied organs of the three legumes. Nodules showed higher concentrations of α-tocopherol than roots, but lower than leaves. α-Tocopherol content increased under water shortage in nodules, roots and leaves of soybean as well as in roots of alfalfa, but not in the other plant systems. A strong negative correlation between α-tocopherol and thiobarbituric acid-reactive substances contents was found for roots and especially for nodules. Furthermore, nodule α-tocopherol content positively correlated with nodule N 2 fixation (estimated by 15 N isotope labeling). We conclude that α-tocopherol is a major antioxidant found in legume nodules., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Phyllanthus phillyreifolius (Euphorbiaceae), poorly studied plant species, was fractionated using conventional and high pressure extraction techniques such as supercritical fluid and pressurized liquid extractions. Lipophilic substances were extracted with n-hexane and supercritical CO 2 with or without co-solvent ethanol, meanwhile higher polarity fractions were recovered with acetone and 70% ethanol. Antioxidant potential was assessed by various chemical assays, which revealed that 70% ethanol was the most effective solvent for recovery of antioxidants. UPLC-MS phytochemical analysis of hydrophilic extracts confirmed geraniin as the main constituent of P. phillyreifolius . Other quantitatively important compounds were phyllanthusiin D and elaeocarpusin. Three isomers of tocopherol (α, β and γ) were quantified by HPLC in lipofhilic extracts. Generally, the results from this study revealed high antioxidant potential of P. phillyreifolius ; consequently the plant may be considered as a promising source of antioxidants for functional foods, nutraceuticals and pharmaceutical formulations.

Background: Vitamin E is comprised of α, β, γ and δ-tocopherols (Ts) and α, β, γ and δ- tocotrienols (T3s). Vitamin E has neuroprotective antioxidant, anti-cancer, and cholesterol-lowering effects. Intracellular trafficking of these isomers remains largely unknown, except for αT which is selectively transported by αT transfer protein (αTTP)., Objective: This study aimed to determine the binding of vitamin E isomers on transport proteins using in silico docking., Methods: Transport proteins were selected using AmiGo Gene Ontology tool based on the same molecular function annotation as αTTP. Protein structures were obtained from the Protein Data Bank. Ligands structures were obtained from ZINC database. In silico docking was performed using SwissDock., Results and Discussion: A total of 6 transport proteins were found: SEC14-like protein 2, glycolipid transfer protein (GLTP), pleckstrin homology domain-containing family A member 8, collagen type IV alpha-3-binding protein, ceramide-1-phosphate transfer protein and afamin. Compared with other transport proteins, αTTP had the highest affinities for all isomers except βT3. Binding order of vitamin E isomers toward αTTP was γT > βT > αT > δT > αT3 > γT3 > δT3 > βT3. GLTP had a higher affinity for tocotrienols than tocopherols. βT3 bound stronger to GLTP than αTTP., Conclusion: αTTP remained as the most preferred transport protein for most of the isomers. The binding affinity of αT toward αTTP was not the highest than other isomers suggested that other intracellular trafficking mechanisms of these isomers may exist. GLTP may mediate the intracellular transport of tocotrienols, especially βT3. Improving the bioavailability of these isomers may enhance their beneficial effects to human., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Emulsion fat products due to the presence of the aqueous phase are more prone to oxidative damage than pure oils and fats, which requires the use of antioxidants. Based on a social request for the use of natural antioxidants in the food industry, tocopherols, their mixtures, as well as ascorbic acid are widespread. However, most natural antioxidants (vitamins, plant extracts) have lower antioxidant activity in fats than synthetic ones and require more incorporation into the product, which can negatively affect its organoleptic properties and the cost of the finished emulsion fat product. One way to solve this problem is to use new micellized forms of antioxidants. The micellization of various types of waterand fat-soluble antioxidants can increase their specific activity, which is apparently associated with an increase in the relative interaction surface in the product. The development of emulsion fat products using new technological forms of natural antioxidants in order to increase their shelf life is relevant and practically significant for the food industry. The aim of the study was a comparative assessment of the effectiveness of natural antioxidants in native and micellized forms in the margarine formulation. Material and methods . Antioxidants (tocopherols, rosemary extract and ascorbic acid) in the native and micellized forms were selected as objects of the study for their introduction into margarine with a mass fraction of fat of 82%. Peroxide Value and p-anizidin Value were determined in dynamics during storage of margarine in its fatty phase. Results . Experimental data have been obtained on the action of the studied antioxidants in various technological forms on the formation of primary and secondary oxidation products in margarine during storage at the temperature 23±3 °С. It was determined that the introduction of micellized forms of various antioxidants into margarine at a concentration of 0.015-0.03% most effectively slows down the formation of oxidation products compared to using their native forms in an amount equivalent to the active substances. Conclusion . It has been experimentally established that the use of micellized forms of tocopherols, ascorbic acid and rosemary extract allows more efficient creation of emulsion fat products with an extended shelf life., Competing Interests: The authors declare no overt and potential conflict of interest related to the publication of this article., (Copyright© GEOTAR-Media Publishing Group.)

Tree nuts and peanuts are healthy foods with a proven track record of helping to reduce the incidence of chronic diseases, most notably cardiovascular disease. At the point of consumption, all nuts contain low moisture and ≥ 50% lipid contents, but this is where similarities end. The levels of key nutrients and bioactives including vitamin C, vitamin E, L-arginine, minerals (such as selenium and zinc), and phenolics can differ markedly. Distinctions in the types and quantities of phenolic constituents for tree nut species, as well as the impact of digestion, will affect the nuts' antioxidant potential in vivo. This work provides some insight into the different types of phenolics found in tree nuts and peanuts, the antioxidant potential of their phenolic extracts using in vitro chemical assays, the effect of thermal processing on the stability of the nuts' endogenous phenolics, and the impact on biomarkers of human health arising from randomized clinical trials. Key biomarkers include measures in the reduction of LDL oxidation as well as increases in the levels of vitamin E and selected phenolic compounds in blood plasma postprandially from those of baseline., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Objective: Tocotrienols (T3s) have been hypothesized to have greater antioxidant capacity than tocopherols (Ts) due to differences in biokinetics that affect their absorption and function. The present trial compares the antioxidant effectiveness following postprandial challenge of two different doses of α-T or palm T3-rich fraction (TRF) treatments and evaluates their dose-response effects on antioxidant status., Methods: Ten healthy volunteers were given four different doses of vitamin E formulations (268 mg α-T, 537 mg α-T, 263 mg TRF or 526 mg TRF) in a cross-over postprandial trial. Blood was sampled at 0, 2, 4, 5, 6 and 8 hours after meal consumption and plasma antioxidant status including total glutathione, superoxide dismutase, malondialdehyde (MDA), ferric reducing antioxidant potential and trolox-equivalent antioxidant capacity, was analyzed., Results: Supplementation with the different doses of either α-T or TRF did not significantly improve overall antioxidant status. There was no significant difference in overall antioxidant status among treatments at the different doses compared. However, a significant dose-response effect was observed for plasma MDA throughout the 8-hour postprandial period. MDA was significantly lower after the 537 mg α-T treatment, compared to the 268 mg α-T treatment; it was also lower after the 526 mg TRF treatment compared to the 263 mg TRF treatment (P < 0.05)., Conclusion: T3 and α-T demonstrated similar antioxidant capacity, despite markedly lower levels of T3 in blood and lipoproteins, compared to α-T., (Copyright © 2019 Shanghai Changhai Hospital. Published by Elsevier B.V. All rights reserved.)

In the present study, the effect of biostimulants application on the nutritional quality and bioactive properties of spinach cultivated in protected environment under water stress conditions was evaluated. For this purpose, four commercially available biostimulant products (Megafol (MEG), Aminovert (AM), Veramin Ca (V), Twin Antistress (TA), and two spinach genotypes (Fuji F1 and Viroflay) were tested under two irrigation regimes (normal irrigation (W+), and water-holding (W-). Fat and carbohydrates content was favored by water stress when Megafol (MEGW+) and Veramin (VW+) were applied on Fuji plants, while calorific value was also increased by MEGW+ treatment. In contrast, protein and ash content increased when AMW- and TAW+ were applied on Viroflay plants. Raffinose and glucose were the most abundant sugars, followed by sucrose and fructose, with the highest contents recorded for Fuji plants when AMW+ (fructose, glucose and total carbohydrates), CW- (sucrose), and TAW- (raffinose) treatments were applied. Regarding organic acids, oxalic and malic acid which had the highest contents for the TAW- (Viroflay plants) and AMW- (Fuji plants) treatments, respectively. α- and γ -tocopherol were the only isoforms detected with MEGW- and VW- inducing the biosynthesis of α -tocopherol, while AMW+ increased γ -tocopherol content in Fuji plants. The main fatty acids were α -linolenic and linoleic acids which were detected in the highest amounts in AMW-, AMW+, and TAW+ the former and in AMW-, VW-, and CW+ the latter. Regarding phenolic compounds content, peak 12 (5,3',4'-Trihydroxy-3-methoxy-6:7-methylenedioxyflavone-4'-glucuronide) was the most abundant compound, especially in Viroflay plants under normal irrigation and no biostimulants added (CW-). The antioxidant and cytotoxic activity of the tested samples did not show promising results when compared with the positive controls, while a variable antibacterial activity was recorded depending on the tested biostimulant, irrigation regime and genotype. In conclusion, a variable effect of the tested biostimulants and irrigation regimes was observed on bioactive properties and chemical composition of both spinach genotypes which highlights the need for further research in order to make profound conclusions regarding the positive effects of biostimulants under water stress conditions.

Main Conclusion: Seasonal accumulation of hormonal and photoprotective isoprenoids, particularly α-tocopherol, carotenoids and abscisic acid, indicate their important role in protecting Cistus albidus plants from environmental stress during a Mediterranean winter. The high diurnal amounts of α-tocopherol and xanthophylls 3 h before maximum light intensity suggest a photoprotective response against the prevailing diurnal changes. The timing to modulate acclimatory/defense responses under changing environmental conditions is one of the most critical points for plant fitness and stress tolerance. Here, we report seasonal and diurnal changes in the contents of isoprenoids originated from the methylerythritol phosphate pathway, including chlorophylls, carotenoids, tocochromanols, and phytohormones (abscisic acid, cytokinins, and gibberellins) in C. albidus during a Mediterranean winter. Plants were subjected not only to typically low winter temperatures but also to drought, as shown by a mean plant water status of 54% during the experimental period. The maximum PSII efficiency, however, remained consistently high (F v /F m  > 0.8), proving that C. albidus had efficient mechanisms to tolerate combined stress conditions during winter. While seasonal α-tocopherol contents remained high (200-300 µg/g DW) during the experimental period, carotenoid contents increased during winter attaining maximum levels in February (minimum air temperature ≤ 5 °C for 13 days). Following the initial transient increases of bioactive trans-zeatin (about fivefold) during winter, the increased abscisic acid contents proved its important role during abiotic stress tolerance. Diurnal amounts of α-tocopherol and xanthophylls, particularly lutein, zeaxanthin and neoxanthin including the de-epoxidation state, reached maximum levels as early as 2 h after dawn, when solar intensity was 68% lower than the maximum solar radiation at noon. It is concluded that (1) given their proven antioxidant properties, both α-tocopherol and carotenoids seem to play a crucial role protecting the photosynthetic apparatus under severe stress conditions; (2) high seasonal amounts of abscisic acid indicate its important role in abiotic stress tolerance within plant hormones, although under specific environmental conditions, accumulation of bioactive cytokinins appears to be involved to enhance stress tolerance; (3) the concerted diurnal adjustment of α-tocopherol and xanthophylls as early as 3 h before maximum light intensity suggests that plants anticipated the predictable diurnal changes in the environment to protect the photosynthetic apparatus.

The ultimate health benefits of peanuts and tree nuts partially depend on the effective gastrointestinal delivery of their phytochemicals. The chemical composition and in vitro bioaccessibility of tocopherols, tocotrienols and phenolic compounds from peanuts and seven tree nuts were evaluated by analytical and chemometric methods. Total fat and dietary fiber (g 100 g -1 ) ranged from 34.2 (Emory oak acorn) to 72.5 (pink pine nut; PPN) and from 1.2 (PPN) to 22.5 (pistachio). Samples were rich in oleic and linoleic acids (56-87 g 100 g -1 oil). Tocopherols and tocotrienols (mg·kg -1 ) ranged from 48.1 (peanut) to 156.3 (almond) and 0 (almond, pecan) to 22.1 (PPN) and hydrophilic phenolics from 533 (PPN) to 12,896 (Emory oak acorn); flavonoids and condensed tannins (mg CE.100 g -1 ) ranged from 142 (white pine nut) to 1833 (Emory oak acorn) and 14 (PPN) to 460 (Emory oak acorn). Three principal components explained 90% of the variance associated with the diversity of antioxidant phytochemicals in samples. In vitro bioaccessibility of tocopherols, tocotrienols, hydrophilic phenolics, flavonoids, and condensed tannins ranged from 11-51%, 16-79%, 25-55%, 0-100%, and 0-94%, respectively. Multiple regression analyses revealed a potential influence of dietary fiber, fats and/or unsaturated fatty acids on phytochemical bioaccessibility, in a structure-specific manner.

The aim of the study was to characterize the antioxidant properties; establish the profile of polyphenolic compounds and evaluate the content of tocopherols in walnuts of three varieties (Leopold; Apollo; Resovia) differing in the degree of maturity (harvest date). The profile of polyphenolic compounds was established by UPLC-PDA-ESI-MS. The content of tocopherols was determined by HPLC-FLD. It was found that the content of dry matter and fat increased and the antioxidant properties decreased with the maturation of nuts. Walnuts of the Leopold cultivar harvested in July exhibited the highest content of total polyphenol (2149.08 mg/100 g dry mass). In their polyphenolic profile; 26 compounds were identified; mainly belonging to the class of ellagitannins. The polyphenolic content decreased with the maturation of nuts. The total content of tocopherols in the tested nuts increased with ripening and ranged from 1.76 mg/100g (Apollo VII) to 18.30 mg/100g (Resovia IX)., Competing Interests: “The authors have declared no conflict of interests”.

Monguba fruit has a seed with a chestnut-like flavor that can be consumed boiled, fried, and roasted. These nutritious seeds also have been used in popular medicine to treat several diseases. Nevertheless, the nutritional and functional potential of monguba seed is still underexploited. In this sense, we investigated the nutritional and functional components of monguba seeds. These seeds showed high total content of sugars, mainly sucrose, whereas the content of the raffinose family oligosaccharides was low. The mineral assay showed high amount of minerals, namely potassium, calcium, magnesium and zinc, which indicate that monguba seeds can be a new source of these minerals. UHPLC-ESI-MS/MS analysis showed caffeic, ferulic and 4-hydroxybenzoic acids as the main phenolic compounds, mainly in the esterified form, in these seeds. Monguba seed showed high lipid content, in which the main compounds were palmitic acid and γ-tocopherol. The soluble and insoluble phenolic fractions from monguba seeds showed high antioxidant activity measured by the oxygen radical absorption capacity (ORAC) and the trolox equivalent antioxidant capacity (TEAC) assays. Therefore, the monguba seeds have great potential to be explored by food, pharmaceutical and cosmetic industries due to their chemical composition., (Copyright © 2019. Published by Elsevier Ltd.)

Of the antioxidant vitamin E isoforms, α-tocopherol (αT) and γ-tocopherol (γT) are the most abundant in the human diet, and αT is consumed from both natural and synthetic sources. αT and γT may differentially impact inflammation and influence cardiovascular outcomes, in part by modulating gene expression. The goal of this study was to compare the effects of natural αT, synthetic αT, and γT on gene expression in two human cell lines. Human aortic smooth muscle cells (HASMC) and endothelial cells (HAEC) were either: (1) treated with 25 μM tocopherols alone, or (2) pretreated with tocopherols prior to a pro-inflammatory cytokine (tumor necrosis factor-alpha, TNF-α) stimulation. The expression of atherosclerosis-related genes was measured using RT 2 Profiler PCR arrays. Tocopherol treatments alone did not significantly modulate the expression of genes in unstimulated HASMC or HAEC. TNF-α stimulation significantly upregulated genes involved with apoptosis and stress response in both cell lines. Pretreating cells with tocopherols did not normalize the gene expression changes induced by TNF-α. However, αT pretreatments, but not γT pretreatments, attenuated TNF expression in both HASMC and HAEC. These findings suggest that under stimulated conditions, αT modestly modulates the expression of selective genes and that αT may be more anti-inflammatory than γT., (© 2019 AOCS.)

The aim of the present research was to study the effects of olive leaf addition (0 and 3%) on the major antioxidants and the antioxidant activity of Neb Jmel and Oueslati olive oils. Olives and leaves of the two Tunisian varieties were harvested during the 2016/2017 crop season. Both leaves and oils were characterised for their concentrations in phenolics, tocopherols and antioxidant power. Other parameters such as free acidity, peroxide value, chlorophyll and carotenoid concentrations were also taken into consideration. Compared to Oueslati, the Neb Jmel oil showed a lower free acidity (50%) and peroxide value (5.6-fold), and higher chlorophyll (1.6-fold), total phenolics (1.3-fold), flavonoid (3-fold) and oleuropein derivative (1.5-fold) concentrations, in addition to an increased antioxidant activity (1.6-fold). Leaf addition promoted a significant increment in total chlorophyll, α-tocopherol and phenolics in both varieties, above all in Oueslati oil, due to a higher abundance of bioactive constituents in the corresponding leaves. In particular, chlorophyll and carotenoid concentrations reached values twice higher than in Neb Jmel leaves, and flavonoids and oleouperin derivatives were three-fold higher. This prevented the oxidation and the formation of peroxides, reducing the peroxide value of the fortified oil to the half. The results provide evidence on the performance of the Tunisian Neb Jmel and Oueslati varieties, showing that their oils present a chemical profile corresponding to the extra virgin olive oil category and that, after leaf addition, their nutritional value was improved.

In this study, physico-chemical properties, fatty acid composition, and tocopherol contents of several walnut kernel oils obtained through cold-press and Soxhlet extractions were investigated. The acidity, peroxide, and unsaponifiable matter of oil samples extracted in the Soxhlet system were found higher. Total phenol contents of the oils obtained in cold press and Soxhlet extraction systems were 121.9 mg GAE/100g (Kaman-2) and 154.6 mg GAE/ 100g (Büyükoba), and between 135.9 mg GAE/100g (Kaman-2) and 163.8 mg GAE/100g (Büyükoba), respectively (p < 0.05). In addition, antioxidant activity valuesof walnut oils obtained in cold press and Soxhlet extractions varied between 17.3% (Kaman-2) and 19.7% (Kaman-5), and between 18.4% (Kaman-2) and 23.8% (Büyükoba), respectively (p < 0.05). Linoleic acid contents of the oil samples extracted in cold-press varied between 55.19% (Kaman-5) and 56.71% (Kaman-2), while that extracted from Soxhlet extraction system varied between 54.47% (Kaman-2) and 55.93% (Büyükoba). ɣ-Tocopherol contents of walnut oils extracted in cold press and Soxhlet extraction ranged between 9.41 mg/100g (Büyükoba) and 10.83 mg/100g (Kaman-2), and 8.76 mg/100g (Kaman-5) and 9.33 mg/100g (Kaman-2), respectively, and were statistically significant (p < 0.05).

In this study, the effect of refining process on the content of phytochemicals, antioxidant capacity and oxidative stability of hazelnut oil was investigated. The oil samples were taken at the consecutive steps of hazelnut refining process and analyzed for some compositional properties along with the antioxidant capacity and oxidative stability. The results have shown that, carotenoid content of the hazelnut oil was decreased during the refining process. The main carotenoids of hazelnut oil were found to be lutein and zeaxanthin and these compounds were lost completely during bleaching step of the refining. On the other hand, phenolic compounds and tocopherols were also partly removed from hazelnut oil to a degree. Loses in antioxidant compounds caused a clear decrease in antioxidant capacity measured in either the oils or polar extract of oils. Oxidative stability of the oil samples was measured by Rancimat method and it was found that neutralization caused an increase in oxidative stability compared to the crude oil. However, deodorization step caused a slight decrease in oxidative stability probably as a result of partial removal of tocopherols at this stage., (Copyright © 2018 Elsevier Ltd. All rights reserved.)