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SCOPE: The antioxidant plastochromanol-8 (PC-8) is a tocochromanol which differs from γ-tocotrienol in having an unsaturated side chain of eight instead of three isoprene units. The recent isolation of PC-8 from flaxseed oil indicates the additional presence of lower shares of two previously unknown homologues, plastochromanol-7 (PC-7) and plastochromanol-9 (PC-9), which feature seven and nine isoprenoid units respectively on the γ-chromanol backbone. Here, a fast LC-Orbitrap-HRMS method is applied for the determination of PC-7 and PC-9 in seven plant oils and a plant extract. METHODS AND RESULTS: The presence of PC-7, PC-8, and PC-9 is confirmed in all eight investigated samples by LC-Orbitrap-HRMS analysis after saponification. PC-8 amounts of ≈315-350 mg kg-1 in two flaxseed oils, ≈75 mg kg-1 in rapeseed oil, ≈38 mg kg-1 in camelina oil, ≈80-120 mg kg-1 in two mustard oils, ≈90 mg kg-1 in candle nut oil, and ≈900 mg kg-1 dry weight in Cecropia leaves are determined by quantification. Semi-quantification of PC-7 and PC-9 indicated the presence of ≈0.1-1% of PC-7 and PC-9 in varied relative ratios. CONCLUSION: The novel plastochromanol homologues are of particular interest to researchers with focus on vitamin E and other tocochromanols because of their unexplored bioactivity.

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The naturally occurring antioxidant plastochromanol-8 (PC-8) is a member of the tocochromanol (vitamin E) family which features eight unsaturated isoprene units in the side chain compared to three in the case of γ-tocotrienol. Due to the lack of a commercially available PC-8 standard, we developed a route to gain relevant amounts of highly pure PC-8. Specifically, ∼320 g flaxseed oil was saponified and the bulky PC-8 was enriched by gel permeation chromatography. It followed countercurrent chromatography using the solvent system n-hexane/benzotrifluoride/acetonitrile (20:7:13, v/v/v). The final purification was achieved by centrifugal partition chromatography using the novel solvent system hexamethyldisiloxane/acetonitrile (1:1, v/v). This step provided ∼26 mg PC-8 (>99.5 %, according to HPLC, GC and NMR analysis). Two further, hitherto unknown minor tocochromanols (<1 % of PC-8) were detected and could be identified to be plastochromanol-7 (PC-7) and plastochromanol-9 (PC-9), i.e. tocochromanols with seven and nine unsaturated isoprene units, respectively, in the side chain.

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Singlet oxygen (1O2) 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 1O2 oxygen on photosynthetic membrane components, plant synthesize a variety of 1O2 quenchers of lipophilic character, such as carotenoids or phenolic prenyllipids (tocopherols, plastochromanol-8, plastoquinol). In the process of chemical quenching of 1O2 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 1O2 are unsaturated fatty acids of membrane lipids that undergo peroxidation as a result of the reaction. Some of the 1O2 oxidation products, like ß-cyclocitral can be components of 1O2-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 1O2 oxidation products are specific compounds formed only as a results of 1O2 action, they can be very useful, specific molecular markers of 1O2-dependent oxidative stress in vivo.

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Tocochromanols are a group of lipid-soluble antioxidants that include tocopherols, tocotrienols and plastochromanol-8. Here, we examined a putative differential accumulation of tocochromanols in photosynthetic and non-photosynthetic tissues (including leaves and whole fruits) of strawberry (Fragaria x ananassa cv. Albion) plants and evaluated their endogenous variations in response to a reiterated water deficit during a vegetative (non-productive) and a fruiting (productive) period. In addition, we evaluated the concentration of tocochromanols in achenes (true fruits) and flesh of strawberries (whole fruits) at the white and full-red stages both under optimal and stress conditions. Results showed that leaves mainly accumulated α-tocopherol, with plastochromanol-8 and γ-tocopherol being present at low amounts. In contrast, whole fruits did not accumulate plastochromanol-8, γ-tocopherol being the major tocochromanol in the achenes (true fruit) and α-tocopherol in the flesh. While α-tocopherol content in leaves increased up to seven-fold after 12 weeks of stress during the fruiting period, it kept unaltered during the vegetative period. Neither plastochromanol-8 nor γ-tocopherol contents increased in leaves of stressed plants. During the fruiting period, γ-tocopherol content increased in whole fruits of stressed plants (most of it being accumulated in the achenes). Among the compounds examined, the flesh of strawberries accumulated α-tocopherol only, both at the white and full-red stages. It is concluded that (i) α-tocopherol is the major tocochromanol in leaves, while γ-tocopherol is the major tocochromanol in achenes (ii) reiterated water deficit promotes the accumulation of α-tocopherol in leaves and γ-tocopherol in fruits, (iii) α-tocopherol not only accumulates in photosynthetic tissues (leaves and whole fruits at green stages), but also in non-photosynthetic tissues (flesh of whole fruits at the white and full-red stages), and (iv) achenes (true fruits) of strawberry plants are an extraordinary rich source of tocopherols.

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(1) Background: Tocochromanols are a group of fat-soluble compounds including vitamin E (tocopherols and tocotrienols) and plastochromanol-8, and just one avocado can contain up to 20% of the required vitamin E daily intake. (2) Methods: HPLC and LC-MS/MS analyses were performed in avocados of various varieties and origin for the identification and quantification of tocopherols, tocotrienols and plastochromanol-8. After selection of the variety with the highest vitamin E content, we evaluated to what extent short- (4 h) and long-term (10 d) cold storage influences the accumulation of tocochromanols. (3) Results: Analyses revealed that "Bacon" avocados (Persea americana Mill. cv. Bacon) were the richest in vitamin E compared to other avocado varieties (including the highly commercialized Hass variety), and they not only accumulated tocopherols (with 110 µg of a-tocopherol per g dry matter), but also tocotrienols (mostly in the form of g-tocotrienol, with 3 µg per g dry matter) and plastochromanol-8 (4.5 µg per g dry matter). While short-term cold shock did not negatively influence a-tocopherol contents, it increased those of g-tocopherol, g-tocotrienol, and plastochromanol-8 and decreased those of d-tocotrienol. Furthermore, storage of Bacon avocados for 10d led to a 20% decrease in the contents of a-tocopherol, whereas the contents of other tocopherols, tocotrienols and plastochromanol-8 were not affected. (4) Conclusions: It is concluded that Bacon avocados (i) are very rich in a-tocopherol, (ii) not only contain tocopherols, but also tocotrienols and plastochromanol-8, and (iii) their nutritional vitamin E value is negatively influenced by long-term cold storage.

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Rapeseed oil is the second most abundant produced edible oil in the world with low erucic acid and low glucosinolate. Thus, the quality of rapeseed oil had attracted global attention. Cold-pressed rapeseed oil appeared to be a preferred choice than refined oil as no solvent and less processing involved in the cold-pressing. The methods of cold-pressing and microwave pre-treatment on the extraction yield and bioactive compounds of rapeseed oil have been reviewed in this paper. Cold-pressed rapeseed oil offers health benefits due to its preserved fatty acid profile and bioactive compounds. High phenolic compounds, tocopherols, phytosterols, and carotenoids contents in the cold-pressed rapeseed oil offer health benefits like regulating blood lipid profile, insulin sensitivity, and glycemic control, as well as offer antioxidant and cytotoxic activity. Besides using as edible oil, cold-pressed rapeseed oil find applications in animal feed, chemical, and fuel.

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Vitamin E is a family of related compounds with different vitamin E activities and antioxidant properties that includes tocopherols, tocotrienols and plastochromanol-8. Plant oils could serve as an industrial source not only of tocopherols, but also tocotrienols and plastochromanol-8, which exhibit much stronger antioxidant activities than tocopherols. The aim of this study was a quantitative and qualitative analysis of vitamin E in certain plant oils. We demonstrated the presence of vitamin E derivatives in all the plant oils tested. The highest tocopherol contents were in pomegranate, wheat germ and raspberry seed oils. In general, γ-tocopherol was the predominant tocopherol homologue. Tocotrienols were also identified in most of the oils, but their content was much lower. The highest concentration of tocotrienols was in coriander seed oil. Plastochromanol-8 was present in most of the oils, but wheat germ oil was the richest source.

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BACKGROUND: The aim of the study was to determine the effect of genotype × environment interaction on the levels of α-, ß-, γ- and δ-tocopherol (α-T, ß-T, γ-T and δ-T, respectively) and plastochromanol-8 (PC-8) in seeds of 17 doubled haploids (DHs) obtained from the F1 hybrid derived from crossing black (DH H2 -26) × yellow (DH Z-114) seeds of winter oilseed rape. RESULTS: The content of tocopherols in the tested DH lines ranged from 415.6 to 540.1 mg kg-1 seeds, while PC-8 content ranged from 56.3 to 89.0 mg kg-1 seeds. The α-T/γ-T ratio reached a level of 0.78-1.29. Studies have shown that heritability for α-T, ß-T, γ-T, total-T and PC-8 is mainly due to genotypic variation. For the δ-T homologue the level was dependent on environmental effect. CONCLUSION: The obtained DH lines population of oilseed rape is characterized by high heritability coefficients for α-T, ß-T, γ-T, total-T and PC-8 levels, which indicates a greater influence of genotype than the environment on the content of these compounds. Among all studied doubled haploids, seven DHs were selected which were characterized by stable contents of α-T, ß-T, γ-T, δ-T and total-T with the simultaneous stable content of PC-8. © 2017 Society of Chemical Industry.

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Vitamin E inhibits the propagation of lipid peroxidation and helps protecting photosystem II from photoinhibition, but little is known about its possible role in plant response to Pi availability. Here, we aimed at examining the effect of vitamin E deficiency in Arabidopsis thaliana vte mutants on phytohormone contents and the expression of transcription factors in plants exposed to contrasting Pi availability. Plants were subjected to two doses of Pi, either unprimed (controls) or previously exposed to low Pi (primed). In the wild type, α-tocopherol contents increased significantly in response to repeated periods of low Pi, which was paralleled by increased growth, indicative of a priming effect. This growth-stimulating effect was, however, abolished in vte mutants. Hormonal profiling revealed significant effects of Pi availability, priming and genotype on the contents of jasmonates and salicylates; remarkably, vte mutants showed enhanced accumulation of both hormones under low Pi. Furthermore, expression profiling of 1,880 transcription factors by qRT-PCR revealed a pronounced effect of priming on the transcript levels of 45 transcription factors mainly associated with growth and stress in wild-type plants in response to low Pi availability; while distinct differences in the transcriptional response were detected in vte mutants. We conclude that α-tocopherol plays a major role in the response of plants to Pi availability not only by protecting plants from photo-oxidative stress, but also by exerting a control over growth- and defense-related transcriptional reprogramming and hormonal modulation.

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Plastochromanol-8 (PC-8) belongs to the group of tocochromanols, and together with tocopherols and carotenoids, might help protect photosystem II from photoinhibition during environmental stresses. Here, we aimed to unravel the time course evolution of PC-8 together with that of vitamin E compounds, in maize (Zea mays L.) plants exposed to reiterated drought. Measurements were performed in plants grown in a greenhouse subjected to two consecutive cycles of drought-recovery. PC-8 contents, which accounted for more than 25% of tocochromanols in maize leaves, increased progressively in response to reiterated drought stress. PC-8 contents paralleled with those of vitamin E, particularly α-tocopherol. Profiling of the stress-related phytohormones (ABA, jasmonic acid and salicylic acid) was consistent with a role of ABA in the regulation of PC-8 and vitamin E biosynthesis during drought stress. Results also suggest that PC-8 may help tocopherols prevent damage to the photosynthetic apparatus. A better knowledge of the ABA-dependent regulation of PC-8 may help us manipulate the contents of this important antioxidant in crops.

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Vitamin E is one of the 13 vitamins that are essential to animals that do not produce them. To date, six natural organic compounds belonging to the chemical family of tocochromanols-four tocopherols and two tocotrienols-have been demonstrated as exhibiting vitamin E activity in animals. Edible plant-derived products, notably seed oils, are the main sources of vitamin E in the human diet. Although this vitamin is readily available, independent nutritional surveys have shown that human populations do not consume enough vitamin E, and suffer from mild to severe deficiency. Tocochromanols are mostly produced by plants, algae, and some cyanobacteria. Tocochromanol metabolism has been mainly studied in higher plants that produce tocopherols, tocotrienols, plastochromanol-8, and tocomonoenols. In contrast to the tocochromanol biosynthetic pathways that are well characterized, our understanding of the physiological and molecular mechanisms regulating tocochromanol biosynthesis is in its infancy. Although it is known that tocochromanol biosynthesis is strongly conditioned by the availability in homogentisate and polyprenyl pyrophosphate, its polar and lipophilic biosynthetic precursors, respectively, the mechanisms regulating their biosyntheses are barely known. This review summarizes our current knowledge of tocochromanol biosynthesis in plants, and highlights future challenges regarding the understanding of its regulation.

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The profile of lipophilic antioxidants in different vegetative parts (leaves, shoots, buds and berries) was studied in sea buckthorn (Hippophae rhamnoides L.) male and female plants collected in the end of spring. Five lipophilic compounds, i.e. three tocopherol homologues (α, ß and γ), plastochromanol-8 and ß-carotene, were identified in each vegetative part of male and female sea buckthorn plants at the following concentrations: 7.25-35.41, 0.21-2.43, 0.41-1.51, 0.19-1.79 and 4.43-24.57 mg/100 g dry weight basis. Additionally, significant amounts of α-tocotrienol (1.99 mg/100 g dry weight basis) were detected in buds. The α-tocopherol and ß-carotene were predominant lipophilic antioxidants in each vegetative part, accounting for 78.3-97.0% of identified compounds. The greatest amounts of lipophilic antioxidants were found in leaves, especially of female plants. Nevertheless, apart from leaves, also shoots of plants of both sexes seem to be a good source of α-tocopherol and ß-carotene.

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The objective of this study is to compare the influence of genotype, environmental conditions and processing methods after maturation and harvesting of four varieties of flaxseed (Altess, Biltstar, Niagara and Oliwin) on the levels of tocochromanols, carotenoids and chlorophyll in flaxseed oil. Samples were produced by cold pressing of dry seeds and seeds heated for 30 min at 60 °C. Temperature, sunshine and rainfall were primary environmental conditions included. Grand mean of mass fraction of γ-tocopherol was (522±29), of plastochromanol-8 (305±2) and total tocochromanols (831±3) mg per kg of oil. The highest levels of these compounds and strongest antioxidant activity were found in cold- -pressed oil of Biltstar variety. During seed maturation, levels of γ-tocopherol and plastochromanol-8 increased with average temperature and total sunshine and decreased with total rainfall. Fifth week after flowering was identified as the maturation period with best climate conditions to achieve optimal tocochromanol content. Grand mean of mass fraction of carotenoids expressed as ß-carotene was (1.83±0.01) and of chlorophyll expressed as pheophytin a (0.43±0.10) mg per kg of oil. Altess variety had the highest levels of pigments. Antioxidant activity decreased with the increase of chlorophyll, while correlations with carotenoids were not determined. Generally, oil obtained by cold pressing had higher levels of tocochromanols and lower levels of pigments but similar antioxidant activity to the oil after seed conditioning. The results of this study contribute to identifying the flaxseed variety that is the best for oil production with the highest antioxidant activity and nutritive value, and provide better understanding of tocochromanol biosynthesis depending on different climate conditions.

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Plastochromanol-8 (PC-8) is an antioxidant that, together with tocopherols and tocotrienols, belongs to the group of tocochromanols. Plastochromanol-8 has been found to occur in several plant species, including mosses, and lichens. PC-8 is found in seeds, leaves and other organs of higher plants. In leaves, PC-8 is restricted to chloroplasts. The identification of tocopherol cyclase (VTE1) as the key enzyme in the biosynthesis of PC-8 suggests that plastoglobules are the primary site of its biosynthesis. Other enzymes related with PC-8 biosynthesis in plastoglobules include: NDC1 and the ABC1-like kinase ABC1K3. The antioxidant properties of PC-8 are similar to those of other chloroplastic antioxidants in polar solvents but considerably they are enhanced in hydrophobic environments, suggesting that the unsaturated side chain performs some quenching activity. As a result of a non-enzymatic reaction, singlet oxygen can oxidize any of the 8 double bonds in the side chain of PC-8, giving at least eight hydroxy-PC-8 isomers. This review summarizes current evidence of a widespread distribution of PC-8 in photosynthetic organisms, as well as the contribution of PC-8 to the pool of lipid-soluble antioxidants in both leaves and seeds.

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