Effects of quenching mechanisms of carotenoids on the photosensitized oxidation of soybean oil

The effects of 0, 1.0 × 10”⁻⁵, 2.5 × 10⁻⁵, and 5.0 × 10⁻⁵ M β-apo-8'-carotenal, β-carotene, and canthaxanthin on the photooxidation of soybean oil in methylene chloride containing 3.3 × 10⁻⁹ M chlorophyll b were studied by measuring peroxide values and conjugated diene content. β-Apo-8'-carotenal, β-carotene, and canthaxanthin contain 10,11, and 13 conjugated double bonds, respectively. The peroxide values and conjugated diene contents of oils containing the carotenoids were significantly lower (P<0.05) than those of control oil containing no carotenoid. As the number of conjugated double bonds of the carotenoids increased, the peroxide values of soybean oils decreased significantly (P<0.05). The quenching mechanisms and kinetics of the carotenoids in the photosensitized oxidation of soybean oil were studied by measuring peroxide values. The steady-state kinetics study showed that carotenoids quenched singlet oxygen to reduce chlorophyll-sensitized photooxidation of soybean oil. The singlet-oxygen quenching rate constants ofβ- apo-8'-carotenal, β-carotene, and canthaxanthin were 3.06 × 10⁹, 4.60 × 10⁹, and 1.12 × 10¹⁰ M⁻¹sec⁻¹, respectively.     

角黄素合成新工艺

1,3-二双键十五碳膦酸酯直接缩合法合成β-胡萝卜素,β-胡萝卜素选择性催化氧化合成角黄素.用单因素实验、均匀实验设计和单纯形寻优法研究β-胡萝卜素催化氧化工艺.1,3-二双键十五碳膦酸酯和2,7-二甲基-2,4,6-辛三烯-1,8-二醛缩合合成β-胡萝卜素,收率68%;催化氧化反应合适工艺条件：β-胡萝卜素6.8 g,复合催化剂0.45 g,二氯甲烷250 ml,饱和次氯酸钠溶液50 ml,CO₂作酸碱调节剂和惰性气体, -5℃下反应40 min,角黄素收率89.6%.β-胡萝卜素和角黄素粗产物用重结晶方法提纯.     

β-Carotene and lipid oxidation

The relevant recent literature regarding the antioxidant properties of β-carotene as a radical scavenger and singlet oxygen quencher in lipid oxidation is presented and discussed. In this connection, a brief information about the biological activity of β-carotene is also given. As the antioxidative behaviour of β-carotene is closely related to its own oxidation, the rate and mechanism of oxidative degradation of β-carotene at different conditions are also presented. Taking into account the results of the papers discussed in this review, further investigations of the cooperative action of β-carotene with other natural antioxidants, e.g., non-toxic flavonoids, phenolic acids, coumarins, etc., should be carried out. This is recommended in view to obtain new types of edible fats and lipid containing products with high oxidation stability, which, at the same time, could serve as functional foods with positive effects on our nutrition and health.     

Catalytic wet air oxidation of butyric acid solutions using carbon-supported iridium catalysts

Aqueous solutions of butyric acid were treated by catalytic wet air oxidation using carbon-supported iridium catalysts in a stirred reactor. Under the operating conditions of 6.9 bar of oxygen partial pressure and 200 °C of temperature, conversions up to 52.9% after 2 h were obtained depending on the type of catalyst used. The effects of butyric acid initial concentration, loading of catalyst, oxygen partial pressure and temperature were investigated and the empirical rate law for acid conversion is presented. Oxidation intermediates such as propionic and acetic acid were identified. The heterogeneous catalyzed free-radical oxidation of butyric acid is discussed.     

Carotinoide in der Gesamtnahrung–Bestimmung der täglichen Zufuhrmenge an individuellen Derivaten

Carotenoids in the Total Diet — Determination of the Daily Intake of Individual Derivatives In the past, special attention was focused on β-carotene (provitamin A) when it came to determining and evaluating carotene in foods of vegetable origin. Nowadays the other earotenoids (carotenes and xanthophylls) are also attracting interest, since they have been accredited with the same antioxidative characteristics (ability to capture radieals) which were previously only attributed to the antioxidative vitamins A, C and E. These three vitamins and the carotenoids are currently the subject of attention, as studies have suggested that they are able to reduce the risk of various types of cancer. The necessary or recommended daily intake is thought to be at least 2 mg of β-carotene. The present studies were designed to show to what extent a diet consisting of a balanced mixture of foodstuffs prepared using normal household methods can contribute to achieving the desired intake. The individual carotenoids in the total diet samples were qualitatively and quantitatively determined using HPLC. In addition to β-carotene, α-carotene, lycopene, lutein, anthcraxanthin, zcaxanthin, β-cryptoxanthin, α-cryptoxanthin. violaxanthin and neoxanthin were quantified.     

Antioxidant activity of β-carotene-related carotenoids in solution

The effect of the antioxidant activity of β-carotene and related carotenoids on the free radical-oxidation of methyl linoleate in solution was examined by measuring the production of methyl linoleate hydroperoxides. Canthaxanthin and astaxanthin which possess oxo groups at the 4 and 4′-positions in the β-inonone ring retarded the hydroperoxide formation more efficiently than β-carotene and zeaxanthin which possess no oxo groups. The rates of autocatalytic oxidation of canthaxanthin and astaxanthin were also slower than those of β-carotene and zeaxanthin. These results suggest that canthaxanthin and astaxanthin are more effective antioxidants than β-carotene by stabilizing the trapped radicals.     

Peroxidase-catalyzed oxidation of β-carotene in HL-60 cells and in model systems: Involvement of phenoxyl radicals

Recent studies provide extensive evidence for the importance of carotenoids in protecting against oxidative stress associated with a number of diseases. In particular, reactions of carotenoids with phenoxyl radicals generated by peroxidasecatalyzed one-electron metabolism of phenolic compounds may represent an important antioxidant function of carotenoids. To further our understanding of the antioxidant mechanisms of carotenoids, we used in the present work two different phenolic compounds, phenol and a polar homologue of vitamin E (2,2,5,7,8-pentamethyl-6-hydroxychromane, PMC), as representatives of two different types of phenols to study reactions of their respective phenoxyl radicals with carotenoids in cells and in model systems. We found that phenoxyl radicals of PMC did not oxidize β-carotene in either HL-60 cells or in model systems with horseradish peroxidase (HRP)/H₂O₂. In contrast, the phenoxyl radicals generated from phenol (by native myeloperoxidase in HL-60 cells or HRP/H₂O₂ in model systems) effectively oxidized β-carotene and other carotenoids (canthaxanthin, lutein, lycopene). One-electron reduction of the phenoxyl radical by ascorbate (assayed by electron spin resonance-detectable formation of semidehydroascorbyl radicals) prevented HRP/H₂O₂-induced oxidation of β-carotene. PMC, but not phenol, protected β-carotene against oxidation induced by a lipid-soluble azo-initiator of peroxyl radicals. No adducts of peroxidase/phenol/H₂O₂-induced β-carotene oxidation intermediates with phenol were detected by high-performance liquid chromatography-mass spectrometry analysis of the reaction mixture. Since carotenoids are essential constituents of the antioxidant defenses in cells and biological fluids, their depletion through the reaction with phenoxyl radicals formed from endogenous, nutritional and environmental phenolics, as well as phenolic drugs, may be an important factor in the development of oxidative stress.     

Antioxidants and stabilizers. LXV. Contribution to the investigation of sensitized photooxidation of phenolic antioxidants. Quenching of singlet oxygen with stilbenequinoid compounds

The photooxidation of 2,6-di-tert-butyl-4-methylphenol (I) and 2,2′-methylene-bis(4-methyl-6-tert-butylphenol) (II) sensitized with methylene blue in dichloromethane was investigated. The oxidation of phenol I proceeds at a reduced rate, but otherwise similar to the oxidation in methanol, that is, with the formation of 2,6-di-tert-butyl-4-methyl-4-hydroperoxy-2,5-cyclohexadiene-1-one (III, R = tert-butyl). On the other hand, bisphenol II remains almost unoxidized in dichloromethane. This is due to the formation of stilbenequinoid derivatives of type VI which slow down the oxidation even at insignificant concentrations. The effect approaches that of β-carotene. Phenol I has a much weaker tendency towards the formation of an analogous derivatives, i.e. 3,5,3′,5′-tetra-tert-butylstil-benequinone (VIII), which however is also an active retarder of oxidation. A more detailed study carried out with VIII indicates that the mechanism of its effect is the same as for β-carotene, that is, the quenching of singlet oxygen. Stilbenequinone VIII used in a fourfold concentration has almost the same effect as β-carotene, but unlike the latter it is much more stable towards oxidation. The activity of VI lies between that of stilbenequinone VIII and β-carotene.     

Experimental measurement and correlation of solubility of β-carotene in pure and ethanol-modified subcritical water

For the first time, the solubility of β-carotene in pure and ethanol-modified subcritical water (SW) using the static method was determined. The experimental runs were performed at a temperature ranging from 298.15 to 403.15 K and 0–10% (w/w) of ethanol as a modifier at a constant pressure of 5 MPa. Samples were analyzed by UV–vis spectrophotometer. The solubility of β-carotene was found to range from 1.084 × 10⁻⁸ to 227.1 × 10⁻⁸ mol fractions in the subcritical water in above mentioned conditions. The obtained β-carotene solubility data were correlated using the linear model and modified Apelblat model. The obtained results showed the modified Apelblat model was better for estimating the solubility of β-carotene in SW. The values of the root-mean-square deviation (RMSD) between experimental and correlated data were calculated and used as the index of validity and accuracy for the model. Also, thermodynamic properties of the solution such as the Gibbs free energy of solution, enthalpy, and entropy of solution were estimated.     

Experimental measurement and correlation of solubility of β-carotene in pure and ethanol-modified subcritical water

For the first time, the solubility of β-carotene in pure and ethanol-modified subcritical water (SW) using the static method was determined. The experimental runs were performed at a temperature ranging from 298.15 to 403.15 K and 0-10% (w/w) of ethanol as a modifier at a constant pressure of 5 MPa. Samples were analyzed by UV-vis spectrophotometer. The solubility of β-carotene was found to range from 1.084×10^-8 to 227.1×10^-8 mol fractions in the subcritical water in above mentioned conditions. The obtained β-carotene solubility data were correlated using the linear model and modified Apelblat model. The obtained results showed the modified Apelblat model was better for estimating the solubility of β-carotene in SW. The values of the rootmean-square deviation (RMSD) between experimental and correlated data were calculated and used as the index of validity and accuracy for the model. Also, thermodynamic properties of the solution such as the Gibbs free energy of solution, enthalpy, and entropy of solution were estimated.     

Purified Canola Lutein Selectively Inhibits Specific Isoforms of Mammalian DNA Polymerases and Reduces Inflammatory Response

In the screening of DNA polymerase (pol) inhibitor, we isolated lutein, a carotenoid, from the crude (unrefined) pressed oil of canola (low erucic acid rapeseed, Brassica napus L.). Commercially prepared carotenoids such as lutein (1), zeaxanthin (2), β-cryptoxanthin (3), astaxanthin (4), canthaxanthin (5), β-carotene (6), lycopene (7), capsanthin (8), fucoxanthin (9) and fucoxanthinol (10), were investigated for the inhibitory activities of pols. Compounds 1, 2 and 8 exhibited strong inhibition of the activities of mammalian pols β and λ, which are DNA repair- and/or recombination-related pols. On the other hand, all carotenoids tested had no influence on the activity of a mammalian pol α, which is a DNA replicative pol. Lutein (1) was the strongest pol inhibitor of mammalian pols β and λ in the prepared ten carotenoids tested, but did not influence of the activities of mammalian pols α, γ, δ and ε. The tendency for pols β and λ inhibition by these carotenoids showed a positive correlation with the suppression of TPA (12-O-tetradecanoylphorbol-13-acetate)-induced inflammation. These results suggest that cold pressed unrefined canola/rapeseed oil, or other oils with high levels of lutein and other carotenoids, may be useful for their anti-inflammatory properties.     

Singlet oxygen quenching ability of naturally occurring carotenoids

The singlet oxygen quenching ability of various naturally occurring carotenoids was examined by measuring toluidine blue-sensitized photooxidation of linoleic acid. To assess quenching, the oxidation of linoleic acid was followed by measuring oxygen consumption and ultraviolet absorbance at 235 nm. We found that oxygen quenching increased as the number of conjugated double bonds in the carotenoids increased, but quenching varied with chain structure and functional groups. Acyclic carotenoids enhanced quenching more than did cyclic carotenoids. Conjugated keto groups and the presence of a cyclopentane ring stimulated quenching, while hydroxy, epoxy and methoxy groups showed lesser effects. The photosynthetic bacterial carotenoids, spirilloxanthin and rhodopin, were found to be most effective as quenchers, followed by the cayenne carotenoid, capsorbin.     

The influence of carotenoids and tocopherols on the stability of safflower seed oil during heat-catalyzed oxidation

The stability and antioxidant effects of carotenoids and tocopherols in safflower seed oil were evaluated under thermal (75°C) and oxidative conditions and the oxidative stability index (OSI) determined. The antioxidant capability of butylated hydroxytoluene (BHT) was also compared with that of β-carotene in a model system. Lycopene and β-carotene (1 to 2000 ppm) were heated (75°C) and exposed to air (2.5 psi) in an oxidative stability instrument. β-Carotene had no antioxidant effect at concentrations below 500 ppm, because it did not alter the induction time. Lycopene increased the induction time only slightly at low concentrations. However, at concentrations greater than 500 ppm, both β-carotene and lycopene acted as prooxidants, significantly decreasing the induction period. At the highest concentration, 2000 ppm, lycopene was more prooxidative than β-carotene. α- and γ-Tocopherol (concentration, 1000 ppm) delayed the induction time by 16 and 26 h, respectively. There was no cooperative interaction between α-tocopherol and β-carotene in delaying the onset of oxidation. Furthermore, BHT was significantly more antioxidative than β-carotene. Thus, under thermal and oxidative conditions, β-carotene could not delay the onset of oxidation. The tocopherols and BHT were effective in suppressing the onset of oxidation, as determined by the oxidative stability measurement.     

Substrate contribution on carotenoids production in Blakeslea trispora cultivations

The present report gives an insight into the specific changes in the three main carotenoids (lycopene, γ-carotene and β-carotene) occurring in Blakeslea trispora cultures, with regard to medium composition. Various carbon sources and refined natural vegetable oils as co-substrates were used. The different carbon sources greatly affect the final composition of carotenoids, with lactose medium to preferentially accumulate the all-trans-β-carotene. Furthermore, the use of lactose and starch as carbon sources, respectively, gives a first indication that B. trispora is able to metabolise various homo- and hetero-saccharides, thus leading to different carotenoid percentages. The presence of oils as co-substrates resulted in enhanced fungus growth and subsequent higher carotenoid production. Substrates containing linoleic acid or other oils rich in it led to less lycopene accumulation. The data showed that the biosynthesis of lycopene, γ-carotene and β-carotene starts in most cases simultaneously in the early growth phase even in trace amounts and thus may play a role also as antioxidants for the B. trispora cells.     

Pro-Oxidant Effects of β-Carotene During Thermal Oxidation of Edible Oils

β-Carotene is one of the most important fat soluble pigments with well-known antioxidant and pro-vitamin A activity. It is used in industries as a food colorant and a source of vitamin A. The thermal induced degradation during processing of wide varieties of carotenoid-rich foods leads to color and properties losses. The thermal stability of edible oils is thus of great importance to food manufacturers. Corn oil, rapeseed, and sunflower oils were fortified with 50–300 μg/g of β-carotene and oxidized using a Rancimat apparatus (air flow rate 20 L/h) at 110 °C for 14 h. β-Carotene degradation was measured using high performance thin layer chromatography and confirmed by HPLC–DAD–MS. Triacylglycerols and polar compounds (PC) were determined using LC–ESI–MS. Results showed that most of the β-carotene was degraded during the first 5 h of the thermal oxidation. It was found that the addition of β-carotene produces significant effects (P < 0.05) on the peroxide index, free fatty acid values and radical scavenging activity of the three oils. Triacylglycerols containing high amounts of oleic acid show higher stability toward thermal oxidation and β-carotene treatment. Among the oils, rapeseed oil was the most stable oil in terms of the formation of polar compounds (PC), followed by corn oil, while sunflower oil was more prone to oxidation and thus higher amounts of PC were formed.     

Lipid deterioration: β-Carotene destruction and oxygen evolution in a system containing lactoperoxidase,hydrogen peroxide and halides

A model system containing lactoperoxidase/H₂O₂/halide decomposed β-carotene in a reaction greatly affected by the concentration of H₂O₂. The optimal concentrations of H₂O₂ for activation of iodide and bromide were 2 mM and 10 μM, respectively. The oxidation of chloride by a lactoperoxidase, using β-carotene destruction as a sensitive method to determine the activity of the enzyme, is reported herein. In the presence of optimal amounts of H₂O₂, the rate of β-carotene destruction increases slowly until a critical concentration of the halides, followed by a rapid increase in the rate when halide concentrations were furthere increased. A lactoperoxidase/H₂O₂/iodide and/or bromide system generates oxygen in the presence of high H₂O₂ and halide concentrations. β-Carotene inhibited the evolution of oxygen. A possible mechanism of β-carotene destruction and triplet unexcited oxygen evolution by a lactoperoxidase/H₂O₂/halide system are proposed.     

Supercritical Carbon Dioxide Extraction of Carotenoids from Pumpkin (Cucurbita spp.): A Review

Carotenoids are well known for their nutritional properties and health promoting effects representing attractive ingredients to develop innovative functional foods, nutraceutical and pharmaceutical preparations. Pumpkin (Cucurbita spp.) flesh has an intense yellow/orange color owing to the high level of carotenoids, mainly α-carotene, β-carotene, β-cryptoxanthin, lutein and zeaxanthin. There is considerable interest in extracting carotenoids and other bioactives from pumpkin flesh. Extraction procedures able to preserve nutritional and pharmacological properties of carotenoids are essential. Conventional extraction methods, such as organic solvent extraction (CSE), have been used to extract carotenoids from plant material for a long time. In recent years, supercritical carbon dioxide (SC-CO₂) extraction has received a great deal of attention because it is a green technology suitable for the extraction of lipophylic molecules and is able to give extracts of high quality and totally free from potentially toxic chemical solvents. Here, we review the results obtained so far on SC-CO₂ extraction efficiency and quali-quantitative composition of carotenoids from pumpkin flesh. In particular, we consider the effects of (1) dehydration pre-treatments; (2) extraction parameters (temperature and pressure); the use of water, ethanol and olive oil singularly or in combination as entrainers or pumpkin seeds as co-matrix.     

Precipitation and encapsulation of β-carotene in PHBV using carbon dioxide as anti-solvent

The main objective of this work was to investigate the application of supercritical carbon dioxide as anti-solvent for the encapsulation of β-carotene in poly(hydroxybutirate-co-hydroxyvalerate) (PHBV) with dichloromethane as organic solvent using the Solution Enhanced Dispersion by Supercritical fluids (SEDS) technique. For the precipitation experiments with pure compounds the parameters investigated were the concentration of β-carotene (4 and 8 mg mL⁻¹) and PHBV (30 mg mL⁻¹) in the organic solution, pressure (from 80 to 200 bar), solution flow rate fixed at 1 mL min⁻¹, anti-solvent flow rate at 40 mL min⁻¹ and constant temperature of 313 K. Pure β-carotene precipitation indicates that an increase in pressure led in most cases to particles with larger sizes, while the opposite trend was verified for pure PHBV precipitation. The morphology of precipitated PHBV particles was spherical and was not influenced by increasing pressure. The morphology of β-carotene microparticles changed from plate-like to leaf-like particles when raising operational pressure, but was not influenced by its concentration in the organic solution as verified by micrographs of scanning electronic microscopy (SEM). For the co-precipitation experiments it was evaluated the effect of β-carotene concentration (2-30 mg mL⁻¹) in the organic solution, at fixed parameters: PHBV concentration (30 mg mL⁻¹) in organic solution, temperature at 313 K, pressure at 80 bar, solution flow rate at 1 mL min⁻¹ and anti-solvent flow rate at 40 mL min⁻¹. The encapsulation data showed that increasing the concentration of β-carotene, keeping fixed the PHBV content, results in higher percentage of solute encapsulated, increasing the encapsulation efficiency.     

The contribution of singlet oxygen to the photofading of triphenylmethane and related dyes

The contribution of singlet oxygen (¹Δ_gO₂) to the photofading of Crystal Violet in some solvents is examined. The rates of photofading in dichloromethane or acetone are accelerated in the presence of singlet oxygen sensitizers, e.g. Methylene Blue. The rates are retarded by adding effective singlet oxygen quenchers such as β-carotene or nickel dimethyldithiocarbamate. It seem shtat Crystal Violet is mainly photooxidized to give Michler's ketone and p-dimethylaminophenol via the reaction with singlet oxygen, which can be generated by the dye itself or by an added sensitizer. The effect of various singlet oxygen quenchers on the photostability of coloured materials derived from colour formers, such as Crystal Violet Lactone and 3-diethylamino-6-methyl-7-anilinofluoran, is examined also on silica gel.     

Insight into the strong antioxidant activity of deinoxanthin, a unique carotenoid in deinococcus radiodurans

Deinoxanthin (DX) is a unique carotenoid synthesized by Deinococcus radiodurans, one of the most radioresistant organisms known. In comparison with other carotenoids, DX was proven to exhibit significantly stronger reactive oxygen species (ROS)-scavenging activity, which plays an important role in the radioresistance of D. radiodurans. In this work, to gain deeper insights into the strong antioxidant activity of DX, the parameters characterizing ROS-scavenging potential were calculated by means of quantum chemical calculations. It was found that DX possesses lower lowest triplet excitation energy for its unique structure than other carotenoids, such as β-carotene and zeaxanthin, which endows DX strong potential in the energy transfer-based ROS-scavenging process. Moreover, the H-atom donating potential of DX is similar to zeaxanthin according to the theoretical homolytic O-H bond dissociation enthalpy. Thus, the large number of conjugated double bonds should be crucial for its strong antioxidant activity.