Vitamin E is recognized as an essential vitamin since its discovery in 1922. Most vegetable oils contain a mixture of tocopherols and tocotrienols in the vitamin E composition. Structurally, tocopherols and tocotrienols share a similar chromanol ring and a side chain at the C-2 position. Owing to the three chiral centers in tocopherols, they can appear as eight different stereoisomers. Plant sources of tocopherol are naturally occurring in the form of RRR while synthetic tocopherols are usually in the form of all-racemic mixture. Similarly, with only one chiral center, natural tocotrienols occur as the R-isoform. In this review, we aim to discuss a few chromatographic methods that had been used to separate the stereoisomers of tocopherols and tocotrienols. These methods include high performance liquid chromatography, gas chromatography and combination of both. The review will focus on method development including selection of chiral columns, detection method and choice of elution solvent in the context of separation efficiency, resolution and chiral purity. The applications for separation of enantiomers in vitamin E will also be discussed especially in terms of the distinctive biological potency among the stereoisoforms.
In the present study, tocotrienol rich fraction (TRF) nanoemulsions were produced as an alternative approach to improve solubility and absorption of tocotrienols. In the present study, droplet size obtained after 10 cycles of homogenization with increasing pressure was found to decrease from 120 to 65.1 nm. Nanoemulsions stabilized with Tween series alone or emulsifier blend Brij 35:Span 80 (0.6:0.4 w/w) homogenized at 25,000 psi and 10 cycles, produced droplet size less than 100 nm and a narrow size distribution with a polydispersity index (PDI) value lower than 0.2. However blend of Tween series with Span 80 produced nanoemulsions with droplet size larger than 200 nm. This work has also demonstrated the amount of tocols losses in TRF nanoemulsion stabilized Tweens alone or emulsifier blend Brij 35:Span 80 (0.6:0.4 w/w) ranged between 3%-25%. This can be attributed to the interfacial film formed surrounding the droplets exhibited different level of oxidative stability against heat and free radicals created during high pressure emulsification.
Syrian Golden hamsters have been widely used as a experimental model for the investigation of the aetiology and development of atherosclerosis and cardiovascular disease. The responses of the hamster to dietary fat manipulations are in many ways similar to that observed in humans. The lipidaemic effect of a tocotrienol rich fraction (TRF) from palm oil on human trials has not been consistent. In this study, the cholesterolaemic effect of tocotrienols and tocopherols were differentiated by using pure tocotrienols (that were isolated from palm oil fatty acid distillate) and pure commercial tocopherols and squalene. A palm oil triacylglycerol fraction (POTG), free of all unsaponifiable matter, was used as the dietary fat in different feeding experiments. Tocotrienols added at 162 ppm to POTG (POTG-T3L) significantly (p<0.05) lowered serum total cholesterol (TC) level as compared to that of the POTG group; but the serum LDL-C , HDL-C and TG levels of the POTG-T3L group were not significantly lower than that of the POTG group (P>0.05). Increasing the level of tocotrienol supplementation to the diet (POTG-T3H) appeared to raise rather then reduce the serum TC, LDL-C and HDL-C levels as compared to that of POTG-T3L group. This observation that lower level of tocotrienol supplementation appeared to exhibit stronger hypocholesterolaemic effect than a higher level of tocotrienol supplementation is interesting; but its explanation is not yet forthcoming. When tocopherols were supplemented at 72 ppm to the POTG diet it was observed that the serum TC, LDL-C and HDL-C levels were all somewhat increased when compared to that of the POTG group. These results suggest that tocotrienols and tocopherols may have opposite cholesterolaemic effects in the hamster, and further experiments need to clarify the mode of action of these vitamin E isomers. In our second series of experiments the cholesterolaemic effects of tocotrienols and tocopherols were studied in the presence of squalene, a key intermediate in the cholesterol synthesis pathway and a controversial cholesterol lowering agent. Squalene added to the diet at 0.1% level significantly lowered (p<0.05) serum TC level when compared to that of the POTG group. The LDL-C, HDL-C and TG levels appeared to be lowered by the squalene supplementation also but the differences between the POTG-SQ and POTG groups were not statistically significant (P>0.05). When tocotrienols or tocopherols were added to the squalene-containing POTG diets, the serum TC and LDL-C levels were further reduced (p<0.01) when compared to that of the POTG and POTG-SQ groups. The HDL-C and TG levels were not affected by tocotrienol or tocopherol supplementation in the presence of squalene. These results indicate that in the presence of tocotrienols and squalene POTG exhibit hypocholesterolaemic action whereas tocopherols may have a hypercholesterolaemic effect in the hamster.
This study was carried out to characterize phenolic compounds, carotenoids, vitamins and the antioxidant activity of selected wild edible plants. Plant extracts were purified, and phenolic compounds comprising 11 phenolic acids (hydroxybenzoic acid and hydrocinnamic acid) and 33 flavonoids (including catechin, glycosides and aglycones) were analysed using High Performance Liquid Chromatography - Diode Array Detector (HPLC-DAD). Furthermore, the contents of ascorbic acid and tocopherol ((α and γ tocopherol) and carotenoids (lutein and β-carotene) were also determined. The major phenolics identified consisted of glycosides of flavones (apigenin and luteolin) and flavonols (kaempferol and quercetin). Among the phenolic acids identified after hydrolysis, coumaric acid was the predominant phenolic acid in all the extracts of wild plants. Ascorbic acid [53.8 mg/100 g fresh weight (FW)] and β-carotene (656.5 mg/100 g FW) showed the highest content in the leaf of Heckeria umbellatum. In conclusion, the leaves of H. umbellatum, Aniseia martinicensis and Gonostegia hirta have excellent potential in the future to emerge as functional ingredients.
Roselle is an annual botanical plant that widely planted in different countries worldwide. Its different parts, including seeds, leaves, and calyces, can offer multi-purpose applications with economic importance. The present review discusses the detailed profile of bioactive compounds present in roselle seeds, leaves, and calyces, as well as their extraction and processing, to explore their potential application in pharmaceutical, cosmetic, nutraceutical, food and other industries. Roselle seeds with high phenolics, fiber, and protein contents, which are suitable to use in functional food product development. Besides, roselle seeds can yield 17-20% of roselle seed oil with high content of linoleic acid (35.0-45.3%) and oleic acid (27.1- 36.9%). This unique fatty acid composition of roselle seed oil makes it suitable to use as edible oil to offer the health benefits of essential fatty acid. Moreover, high contents of tocopherols, phenolics, and phytosterols were detected in roselle seed oil to provide nutritional, pharmaceutical, and therapeutic properties. On the other hand, roselle leaves with valuable contents of phenols, flavonoids, organic acid, and tocopherols can be applied in silver nanoparticles, food product development, and the pharmaceutical industry. Roselle calyces with high content of anthocyanins, protocatechuic acids, and organic acids are widely applied in food and colorant industries.
Rice (Oryza sativa L.) is a principal food for more than half of the world's people. Rice is predominantly consumed as white rice, a refined grain that is produced during the rice milling process which removes the bran and germ and leaves the starchy endosperm. Rice bran is a by-product produced from the rice milling process, which contains many bioactive compounds, for instance, phenolic compounds, tocotrienols, tocopherols, and γ-oryzanol. These bioactive compounds are thought to protect against cancer, vascular disease, and type 2 diabetes. Extraction of rice bran oil also generates various by-products including rice bran wax, defatted rice bran, filtered cake, and rice acid oil, and some of them exert bioactive substances that could be utilized as functional food ingredients. However, rice bran is often utilized as animal feed or discarded as waste. Therefore, this review aimed to discuss the role of rice bran in metabolic ailments. The bioactive constituents and food product application of rice bran were also highlighted in this study. Collectively, a better understanding of the underlying molecular mechanism and the role of these bioactive compounds exerted in the rice bran would provide a useful approach for the food industry and prevent metabolic ailments.
Palm oil, unlike many other dietary oils, does not increase the yield of chemically-induced mammary tumors in rats when fed at high levels in the diet. This difference appears to be due to the vitamin E fraction of palm oil, which is rich in tocotrienols, since palm oil stripped of this fraction does increase tumor yields. Experiments in our laboratory have shown that tocotrienols inhibit proliferation and growth of both MDA-MB-435 and MCF-7 cells in culture much more effectively than a-tocopherol. In addition, it was found that combinations of tocotrienols with Tamoxifen, a drug widely used for treatment of breast cancer, inhibit these cells more effectively than either tocotrienols or Tamoxifen alone. The present studies have now shown synergistic effects between tocotrienols and a number of other flavonoids from various plant sources, including citrus fruits, in the inhibition of both MDA-MB-435 and MCF-7 cells (IC50s 0.05-25 and 0.02-5 μg/mL respectively). In the MCF-7 cells, 1:1:1 combinations of tocotrienols, flavonoids and Tamoxifen were even more effective, with the best combination being d-tocotrienol, hesperetin and Tamoxifen (IC50 0.0005 μg/mL). These results suggest that diets containing palm oil may reduce the risk of breast cancer, particularly when eaten with other plant foods containing flavonoids, and may also enhance the effectiveness of Tamoxifen for treatment of breast cancer.
A sensitive and rapid reversed-phase ultra performance liquid chromatographic (UPLC) method for the simultaneous determination of tocopherols (α-, β-, γ-, δ-), tocotrienols (α-, β-, γ-, δ-), α-tocopherol acetate and α-tocopherol nicotinate is described. The separation was achieved using a Kinetex pentafluorophenyl (PFP) column (150 × 2.1mm, 2.6 µm) with both photodiode array (PDA) and fluorescence (FL) detectors that were connected in series. Column was thermostated at 42°C. Under a gradient system consisting of methanol and water at a constant flow rate of 0.38 mL min(-1), all the ten analytes were well separated in less than 9.5 min. The method was validated in terms of linearity, limits of detection and quantitation, precision and recoveries. Calibration curves of the ten compounds were well correlated (r(2)>0.999) within the range of 100 to 25,000 μg L(-1) for α-tocopherol acetate and α-tocopherol nicotinate, 10 to 25,000 μg L(-1) for α-tocotrienol and 5 to 25,000 μg L(-1) for the other components. The method is simple and sensitive with detection limits (S/N, 3) of 1.0 to 3.0 μg L(-1) (FL detection) and 30 to 74 μg L(-1) (PDA detection). Relative standard deviations for intra- and inter-day retention times (<1%) and peak areas (≤ 4%) were obtained. The method was successfully applied to the determination of vitamin E in vegetable oils (extra virgin olive, virgin olive, pomace olive, blended virgin and refined olive, sunflower, soybean, palm olein, carotino, crude palm, walnut, rice bran and grape seed), margarines and supplements.
The concentration of vitamin E isomers, namely, alpha-tocopherol (alpha-T), alpha-tocotrienol, gamma-tocotrienol, and delta-tocotrienol in palm mesocarp at 4, 8, 12, 16, and 20 wk after anthesis (WAA) were quantified using HPLC coupled with fluorescence detection. alpha-T was detected throughout the palm fruits' maturation process, whereas unsaturated tocotrienols were found only in ripe palm fruits. These developmental results indicate that tocotrienols are synthesized between 16 and 20 WAA.
Crude palm oil contains 600 to 1000 ppm of tocols in the form of tocopherols and tocotrienols. These palm tocols have been isolated and analyzed in the past by various chromatographic techniques such as open column chromatography, high-performance liquid chromatography, as well as thin-layer chromatography. Supercritical fluid chromatography (SFC) has emerged as a more advanced chromatographic technique in recent years. The tocols present in palm oil are successfully isolated using SFC. Identification of these tocols is supported by various spectroscopic techniques such as 1H NMR, 13C NMR, and mass spectrometry.
Herein we examine the characteristics of date seed oil extracted from Chamaerops humilis L. var. humilis seeds (HSO) cultivated in a gardening zone in Tunisia. Its physicochemical properties, fatty acid composition, and thermal and antioxidant properties were evaluated and compared with those of seed oil from another variety of Chamaerops humilis. The results showed that HSO possessed higher contents of oleic (44%) and linoleic (20%) acids than the other seed oil. The total tocopherol and tocotrienol content was 88 mg/100 g oil, where α-tocotrienol (64%) was the major isomer. The total phenolic (91 μg/g oil) and flavonoid contents (18 μg/g oil) of the HSO were determined, and its antioxidant capacities, measured in terms of ABTS and DPPH radical-scavenging capacities, were 210 µM TEAC/g DW and 4.3 mM TEAC/g DW, respectively. The oxidative stability index (OSI) of the oil was 16 h at 110 °C. Furthermore, the OSI of soybean oil was significantly enhanced upon blending with HSO. HSO exhibited higher thermal stability than the other oils and significantly different thermal behavior. The determination of fatty acid composition, physicochemical properties, bioactive content, oxidative stability, and thermal behavior of HSO demonstrated that this renewable resource can be used for edible purposes.
An optimal ratio of omega-6 to omega-3 (ω-6/ω-3) polyunsaturated fatty acids (PUFA) in the diet prevents the pathogenesis of many inflammatory diseases. This study aimed to synthesize and characterize ternary oil blends with optimal ω-6/ω-3 ratios using olive (OL), sunflower (SU), and cress (CR) oils. The oxidative stability, thermal profile, fatty acid (FA) and tocopherol compositions, and the physicochemical properties of the blends were used to determine their quality. Oil mixtures were prepared with 2, 3, 4, and 5 ω-6/ω-3 ratios. FA composition and tocopherol content were the most important factors affecting the oxidation and thermal stabilities of the oils. All oil mixtures showed good quality indices. Thus, synthetized oil blends with high oxidative stability, high antioxidant content, optimal ω-6/ω-3 ratios, and recommended FA compositions can influence human health. The composition of healthy oil blends with optimal ω-6/ω-3 ratios was expressed mathematically and depicted graphically in a ternary diagram.
Studies were conducted to assess the percutaneous absorption of the triacyglycerols (TAGs), tocols and carotenoids present in crude and refined palm oil. In vitro experiments using upright Franz diffusion cells were employed to investigate the permeability of these compounds across full thickness human skin and into the receptor solution. Cetrimide, a cationic surfactant was chosen to be used as a solubilising agent in the receptor phase with an optimum concentration of 3.0 mg/mL and was able to provide sink conditions throughout the permeation. TAGs, tocols and carotenoids all permeated human skin from crude palm oil (CPO), whereas only TAGs permeated when refined palm oil (RPO) was used. Of the TAGs, oleic acid-containing TAGs was preferentially absorbed despite palmitic acid being the most prevalent fatty acid (FA) in TAGs. Tocols in the form of α-T3 showed the highest permeation followed by γ-T3, α-T and the lowest permeation was observed for δ-T3. Carotenoids (α-carotene and β-carotene) also showed an appreciable amount of permeation from CPO.
In the present work, the influence of microwave power and heating times on the quality
degradation of corn oil was evaluated. Microwave heating test was carried out using a domestic
microwave oven for different periods at low- and medium-power settings for the corn oil sample.
The changes in physicochemical characteristics related to oil degradation of the samples during
heating were determined by standard methods. In this study, refractive index, free fatty acid
content, peroxide value, p-anisidine value, TOTOX value, viscosity and total polar compound
of the oils all increased with increasing heating power and time of exposure. In GLC analysis,
the percentage of linoleic acid tended to decrease, whereas the percentage of palmitic, stearic
and oleic acids increased. The C18:2/C16:0 ratio decreased in all oil samples with increasing
heating times. Exposing the corn oil to various microwave power settings and heating periods
caused the formation of hydroperoxides and secondary oxidation products. The heating reduced
the various tocopherol isomers in corn oil and highest reduction was detected in γ-tocopherol.
Longer microwave heating times resulted in a greater degree of oil deterioration. Microwave
heating caused the formation of comparatively lower amounts of some degradative products in
the oil samples heated at low-power setting compared to medium-power setting. The present
analysis indicated that oil quality was affected by both microwave power and heating time.