Antioxidant vs. Prooxidant Properties of the Flavonoid,Kaempferol, in the Presence of Cu(II) Ions: A ROS-Scavenging Activity,Fenton Reaction and DNA Damage Study

Kaempferol is a flavonoid that occurs in tea and in many vegetables and fruits, including broccoli, cabbage, beans, grapes, apples, and strawberries. The efficacy of Kaempferol has been demonstrated in the treatment of breast, esophageal, cervical, ovarian, and liver cancers and leukemia, which very likely arises from its prooxidant properties and the activation of pro-apoptotic pathways. Indeed, this matter has already been the focus of a number of published studies and reviews. The aim of the present study was to elucidate the antioxidant vs. prooxidant properties of flavonoids in the presence of the redox-active metal, copper (II) ion, by means of the Fenton reaction. The specific motivation of this work is that, since an increased level of Cu(II) ions is known to be associated with many disease states such as neurological conditions (Alzheimer’s disease) and cancer, any interaction between these ions and flavonoids might affect the outcome of therapeutic uses of the latter. The structure of the Cu-kaempferol complex in DMSO was investigated by means of low temperature EPR spectroscopy, which confirmed the existence of at least two distinct coordination environments around the copper (II) ion. UV vis-spectra of kaempferol and its Cu(II) complex in DMSO revealed an interaction between the 5-OH (A ring) group and the 4-CO (C ring) group of kaempferol with Cu(II) ions. An ABTS assay confirmed that kaempferol acted as an effective radical scavenger, and that this effect was further enhanced in the form of the Cu(II)-kaempferol complex. Quantitative EPR spin trapping experiments, using DMPO as the spin trap, confirmed suppression of the formation of a mixture of hydroxyl, superoxide, and methyl radicals, in a Fenton reaction system, upon coordination of kaempferol to the redox-active Cu(II) ions, by 80% with respect to the free Cu(II) ions. A viscometric study revealed a better DNA-intercalating ability of the Cu-kaempferol complex than for free kaempferol, essential for conferring anticancer activity of these substances. The results of the viscometric measurements were compared with those from a DNA damage study of Cu-kaempferol complexes in a Fenton reaction system, using gel electrophoresis. At low concentrations of kaempferol (Cu–kaempferol ratios of 1:1 and 1:2), a very weak protective effect on DNA was noted, whereas when kaempferol was present in excess, a significant DNA-protective effect was found. This can be explained if the weakly intercalated kaempferol molecules present at the surface of DNA provide protection against attack by ROS that originate from the Fenton reaction involving intercalated Cu(II)-kaempferol complexes. Following the application of ROS scavengers, L-histidine, DMSO, and SOD, gel electrophoresis confirmed the formation of singlet oxygen, hydroxyl radicals, and superoxide radical anions, respectively. We propose that the prooxidant properties of Cu-kaempferol complexes may provide anticancer activity of these substances. When present in excess, kaempferol displays antioxidant properties under Cu-Fenton conditions. This suggests that kaempferol might prove a suitable candidate for the prevention or treatment of oxidative stress related medical conditions that involve a disturbed metabolism of redox metals such as copper, for example, Menkes disease, and neurological disorders, including Alzheimer’s disease. For the potential use of kaempferol in clinical practice, it will be necessary to optimize the dose size and critical age of the patient so that this flavonoid may be beneficial as a preventive drug against cancer and neurological disorders.     

Inhibition of oxidation in 10% oil-in-water emulsions by β-carotene with α- and γ-tocopherols

The effects of low concentrations of β-carotene, α-, and γ-tocopherol were evaluated on autoxidation of 10% oil-in-water emulsions of rapeseed oil triacylglycerols. At concentrations of 0.45, 2, and 20 μg/g, β-carotene was a prooxidant, based on the formation of lipid hydroperoxides, hexanal, or 2-heptenal. In this emulsion, 1.5, 3, and 30 μg/g of γ-tocopherol, as well as 1.5 μg/g of α-tocopherol, acted as antioxidants and inhibited both the formation and decomposition of lipid hydroperoxides. Moreover, at a level of 1.5 μg/g, γ-tocopherol was more effective as an antioxidant than α-tocopherol. At levels of 0.5 μg/g, both α- and γ-tocopherol significantly inhibited the formation of hexanal but not the formation of lipid hydroperoxides. Oxidation was effectively retarded by combinations of 2 μg/g β-carotene and 1.5 μg/g γ- or α-tocopherol. The combination of β-carotene and α-tocopherol was significantly better in retarding oxidation than α-tocopherol alone. While γ-tocopherol was an effective antioxidant, a synergistic effect between β-carotene and γ-tocopherol could not be shown. The results indicate that there is a need to protect β-carotene from oxidative destruction by employing antioxidants, such as α- and γ-tocopherol, should β-carotene be used in fat emulsions.     

黄酮类化合物促进氧化作用的研究

本文综述了国外一些学者对几种黄酮类化合物作为促氧化剂,在体外实验中促进氧化作用的表现及与其结构的关系。     

Prooxidative and antioxidative effects of phospholipids on milk fat

The effects of dipalmitoylphosphatidylethanolamine (DPE) and dipalmitoylphosphatidylcholine (DPC) on milk fat oxidation was examined at 50°C and 95°C under various conditions by monitoring oxygen uptake and fatty acid composition. DPE strongly inhibited milk fat oxidation both at 50°C and 95°C in the absence of water. DPC was less effective than DPE. In aqueous systems, the reverse was observed. DPE accelerated milk fat oxidation at both 50°C and 95°C. DPC accelerated the oxidation at 50°C, but inhibited it at 95°C. The free amino group in DPE may be responsible for its inhibiting effect in the dry system. The accelerating activity of DPE in the aqueous system is probably due to the formation of a more dispersed structure with better oxygen accessibility.     

The effects of extraction methods on sesame oil stability

The oxidative stability of sesame oil, as measured by the Rancimat test, was shown to be dependent on extraction methods and seed pre-treatment. Oils extracted from whole seeds were more stable than those extracted from dehulled seeds by the same method. Extraction of the same seeds with polar solvents and effective seed crushing yielded more-stable oils (16.7–21.3 Rancimat hours) compared with extraction with nonpolar solvents and coarsely crushed or pressed seeds (4.5–6.4 Rancimat hours). Heptane-isopropanol (3:1, vol/vol) provided slightly more stable oils thann-hexane by the same method. Results are discussed in relation to some of the major anti- and prooxidants present in the oils.     

Evaluation of Equol Function on Anti- or Prooxidant Status in vivo

ABSTRACT:  The present study was performed to investigate the effects of equol on oxidative stress and the antioxidant defense system in the livers of mice. Mice were orally administered equol at either 5 or 25 mg/kg body weight/day for 1, 3, or 7 wk. Equol administration significantly inhibited biomarkers of oxidative stress (thiobarbituric acid-reactive substances value, carbonyl content, and serum 8-OH-dG) at all doses and for all durations of administration, and this phenomenon was most pronounced at 3 wk. Moreover, catalase and total superoxide dismutase (SOD) activities and their mRNA expression were significantly increased by equol. Although equol increased the glutathione peroxidase (GSH-px) activity in mice treated with equol for 1 wk, long-term administration of equol (7 wk) caused a decrease in the ratio of reduced/oxidized glutathione (GSH/GSSG) and the activities of GSH-px and glutathione reductase (GR). Taken together, these results suggest that equol may act as an antioxidant through an inhibition of oxidative stress and stimulation of catalase and SOD, but can also cause prooxidant effects such as reduction of the GSH/GSSG ratio, depending on the treatment period.     

Stability of α-, γ-, or δ-Tocopherol during Soybean Oil Oxidation

ABSTRACT:  The decomposition of α-, γ-, or δ-tocopherol in soybean oil during 24 d of storage at 50 °C was determined by high performance liquid chromatography (HPLC). The initial contents of α-, γ-, and δ-tocopherol in soybean oil were 53, 750, and 268 ppm, respectively. The degradation rates of α-, γ-, and δ-tocopherol for the first 10 d were 5.6%, 1.2, and 0.5% per day, respectively. The α-tocopherol was completely destroyed in 16 d. The destructions of γ- and δ-tocopherol were 28% and 17% after 24 d. The induction period of soybean oil determined by headspace oxygen, conjugated diene, and peroxide value was 8 d. As the degradations of α-, γ-, and δ-tocopherol increased, the headspace oxygen disappearance, conjugated diene formation, and peroxide value of soybean oil increased. The correlation coefficient between the degradation of tocopherols and the oxidation of soybean oil was about 0.95. The degradation of tocopherols in soybean oil during storage was due to the oxidation.     

Anti- and Prooxidant Properties of Carotenoids

Carotenoids can be effective singlet oxygen quenchers and inhibit free-radical induced lipid peroxidation. A remarkable property of β-carotene ( 1a ) is the change from an antioxidant to a prooxidant depending on oxygen pressure and concentration. In the present study a considerable number of carotenoids ( 1a , 2c , 2d , 2e , 3a , 4a , 5a , 6a , 7a , 8a , 8h , 8i , 8j , 9f , 10a , 11a , 12g ) was investigated using two independent approaches: 1. Comparison of their effects on inhibition of the free-radical oxidation of methyl linoleate, and 2. The direct study of the effect of oxygen partial pressure upon their rates of oxidation. It is shown that some carotenoids ( 7a , 8a ) are even more effective than the well-known compounds β-carotene ( 1a ) and astaxanthin ( 5a ) and are powerful antioxidants without any prooxidative property. Different carotenoids display different behaviour depending on chain length and end groups. The influence of these functional groups on the antioxidative reactivity is discussed.     

Accelerated and environmental weathering studies on polyethylene–starch blend films

Biodegradable polymers are desirable for a variety of applications, such as in packaging, agriculture, and medicine. Polyethylene (PE) blended with starch is already found to be a potential candidate to replace nondegradable thermoplastics in the areas of packaging. Films of polyethylene (PE)–starch blends with and without vegetable oil as a compatibilizer were prepared. The degradation of the films under thermooxidative treatment, ultraviolet light exposure, high temperature, high humidity, and natural ambience (soil burial) were monitored. It is seen that vegetable oil as an additive has a dual role: as a plasticizer, it improves the film quality; as a prooxidant, it accelerates degradation of the film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2251–2257, 1998