Antioxidant activities of six natural phenolics against lipid oxidation induced by Fe2+ or ultraviolet light

The mechanisms and antioxidant activities of six natural phenolics against lipid oxidation induced by ultraviolet (UV) radiation or Fe²⁺ were studied. An oil emulsion was prepared with flax oil and the thiobarbituric acid-reactive substances (TBARS) method was used to determine lipid oxidation. The antioxidant activities of the six phenolics against UV-induced lipid oxidation were as follows: quercetin > rutin = caffeic acid = ferulic acid = sesamol > catechin. The inhibitory concentrations (IC₅₀) showed that the effectiveness of these antioxidants against Fe²⁺-induced lipid oxidation was in the order quercetin (1.7 μM) > rutin (10.3 μM) > catechin (14.9 μM) > sesamol (18.5 μM) > caffeic acid (19 μM) > ferulic acid (>250 μM), and quercetin was more efficient than butylated hydroxytoluene (BHT) (2.9 μM). Quercetin and rutin had absorption maxima at the UV-A (320–380 nm) region, while the other phenolics tested had absorption maxima near (catechin, 278 nm) or at the UV-B (280–320 nm) region. The stoichiometric ratios of quercetin, rutin, catechin, and caffeic acid to Fe²⁺ were 3:1, 2:1, 1:1, and 1:1, respectively. Although free-radical scavenging capability of antioxidants was the most critical, UV absorption and/or Fe²⁺-chelation properties of natural phenolics also contributed significantly to the control of lipid oxidation induced by UV or Fe²⁺ in oil systems.     

Inhibition of lipid oxidation by carnosine

The antioxidant activity of carnosine, a β-alanine-histidine dipeptide found in skeletal muscle, was investigated. Carnosine (25 mM) inhibited the catalysis of lipid oxidation by iron, hemoglobin, lipoxidase and singlet oxygen from 35–96% suggesting that the antioxidant mechanism of carnosine is not solely due to metal chelation. Heating the carnosine at 100°C for 15 min had no effect on its ability to inhibit these lipid oxidation catalysts, and the activity of carnosine was not affected over the pH range of 5.1–7.1. Studies using tocopherol-containing liposomes suggest that carnosine and tocopherol do not act synergistically to inhibit lipid oxidation. These data indicate that carnosine has excellent potential for use as a natural antioxidant in processed foods. This paper (90-5-5) is published with the approval of the Director of the University of Kentucky Agricultural Experiment Station.     

Effect of lipid unsaturation on the antioxidative activity of some phenolic acids

Antioxidative properties ofp-hydroxybenzoic, vanillic, syringic, 3,4-dihydroxybenzoic,p-coumaric, ferulic, sinapic and caffeic acids were studied in the concentration range 0.02–0.20 wt% during autoxidation at 100°C of lard and sunflower oil methyl esters (MEL and MESO, respectively). In both lipid systems, the derivatives of benzoic acid had weaker inhibiting properties than did the corresponding analogues of cinnamic acid. The effectiveness and strength of the antioxidative action were considerably lower in the lipid system MESO, which was rich in linoleic acid and was more easily oxidized. Thep-hydroxybenzoic, vanillic, syringic andp-coumaric acids in this system exercised no inhibiting effect. We established that the molecules of the investigated phenolic acids initiated the chain radical process of autoxidation, and the formed antioxidant radicals propagated the chains as a result of the reaction with the lipid substrate. These reactions proceeded at a higher rate in MESO than in MEL.     

活化过硫酸盐氧化法降解酚类污染物的研究进展

活化过硫酸盐氧化法因具有经济、高效、环保、安全稳定等优势,近年来在酚类污染物的降解中备受关注。目前活化过硫酸盐降解酚类污染物的方法主要包含外加能量活化和外加催化剂活化两大类。其中单一的热活化、光活化、超声活化、电化学活化、等离子体活化等外加能量活化过程能量消耗较大,且对酚类污染物不易达到满意的降解效果。过渡金属活化和碳质材料活化等外加催化剂活化方式,由于环境污染小、操作成本低、降解率高等优点,越来越受到科研工作者的重视。为了提高对酚类污染物的降解率,不同的过硫酸盐活化方式不断融合,逐渐形成多种耦合活化方式,例如,碳质材料与过渡金属的耦合活化、电化学与过渡金属催化剂的耦合活化以及光与外加催化剂的耦合活化等。本文论述了活化过硫酸盐氧化法降解酚类污染物的研究进展,概述了活化过硫酸盐的影响因素,分析了活化过硫酸盐降解酚类污染物存在的问题,展望了活化过硫酸盐降解酚类污染物的发展方向。     

Inhibition of lipid peroxidation in UVA‐treated skin fibroblasts by luteolin and its glucosides

Ultraviolet A (UVA) radiation causes oxidative damage to human skin cells. This damage may be reduced or prevented using plant compounds as photoprotectants. To investigate the relationship between chemical structure and UVA‐protective activity, three structurally related flavonoids, namely luteolin, luteolin‐7‐O‐glucoside (both present in artichoke) and luteolin‐4'‐O‐glucoside (present in wild carrot), were studied. Human skin fibroblasts exposed to UVA (250 and 500 kJ/m²) were treated with each flavonoid (30 µM) for 18 h prior to irradiation. The extent of lipid peroxidation in the cellular extracts was assessed as lipid peroxides and malondialdehyde (MDA). Luteolin and luteolin‐7‐O‐glucoside both prevented a significant increase in lipid peroxides at 250 kJ/m², but at 500 kJ/m² their effectiveness was clearly attenuated. Contrastingly, luteolin‐4'‐O‐glucoside was pro‐oxidant at both radiation doses. Measurements of MDA levels highlighted that luteolin was clearly more effective than the two glucosides at both 250 and 500 kJ/m². Overall, these results show clear differences between the three flavonoids and suggest that the B ring 3',4'‐dihydroxy group, lacking in luteolin‐4'‐O‐glucoside, may be particularly important. Flavonoid: transition metal ion chelation studies confirmed the influence of the 3',4'‐dihydroxy group, which is also relevant to the quenching of singlet oxygen. These features as well as the greater lipophilic nature of luteolin together explain the superior activity of this flavonoid which may be potentially useful as a supplement in photoprotective skin preparations.     

Antioxidant activity of Magnolol, honokiol, and related phenolic compounds

The antioxidant activity of 10 Japanese and Chinese crude drugs (Kampo drugs) was determined in vitro. Extract of Magnolia cortex, which had the highest antioxidant activity, contained phenolic compounds magnolol and honokiol. However, inhibitory effects of these compounds on lipid oxidation were weaker than that of α-tocopherol as measured by thiobarbituric acid assay. The structure-activity relationship of phenolic compounds showed that antioxidant activities were in the order 4-allyl-2,6-dimethoxyphenol ≥ p,p′-biphenol > eugenol > 2-allyl-6-methylphenol > honokiol > magnolol > caffeic acid > p-ethylphenol > guaiacol. As expected, these results showed that an electron donor and/or bulky groups at the ortho- or para-position of the phenol were required for inhibition of lipid oxidation. Electron spin resonance spin trapping experiments showed that phenol compounds with an allyl substituent on their aromatic rings directly scavenged superoxide (O ₂ ⁻ ), and that only eugenol trapped hydroxyl radicals. These findings suggest that phenolic compounds that contain allyl groups may be effective antioxidants because of the scavenging ability of O ₂ ⁻ or hydroxyl radical, whereas other phenols, without an allyl moiety such as α-tocopherol, may play a role in the termination of free radical chain reactions.     

非均相Fenton催化降解酚类化合物的研究进展

非均相Fenton催化法是去除水中难降解有机污染物的一种重要高级氧化技术,近些年以其效率高、污染少、材料来源广泛而受到人们更多的重视。介绍了现今主要的非均相Fenton催化降解酚类化合物的催化剂研究进展,包括零价铁、Fe3O4、Fe2O3、以碳、黏土、柱撑黏土、沸石、介孔二氧化硅等为载体的催化剂。最后提出了三个非均相Fenton反应的研究方向。     

Analysis of nonvolatile lipid oxidation products in vegetable oils by normal-phase high-performance liquid chromatography with mass spectrometric detection

Nonvolatile triacylglyceride (TAG) oxidation products play an important role in the oxidative degradation of lipids. They serve as a reservoir of oxygen-containing species and hence can act as off-flavor precursors or as initiators for further oxidation reactions. Possible nonvolatile lipid oxidation products are TAG with a hydroperoxy, hydroxy, epoxy, or oxo (ketone or aldehyde) group or combination of these groups. The breakdown of TAG hydroperoxides yields nonvolatile glyceride species with two intact fatty acid chains and one short chain mostly ending in an aldehyde or hydroxy group (2 1/2 glycerides). By means of normal-phase high-performance liquid chromatography (HPLC) with mass spectrometric (MS) detection, non-volatile lipid oxidation products can be separated according to polarity. This results in separation into classes of TAG oxidation products, such as epoxy-TAG, oxo-TAG, hydroperoxy-TAG, hydroxy-TAG and 2 1/2 glycerides, which can be identified using selected ion chromatograms. The retention times of TAG oxidation products on the normal-phase HPLC system and the signal intensity of the MS detector are stable enough to enable quantitative analysis based on external calibration. The normal-phase HPLC-MS method is very suitable for the characterization and quantitation of nonvolatile TAG oxidation products in oxidized TAG reference compounds as well as in real oils or oil phases isolated from emulsions, spreads, or other fat-based food products. This method can give detailed information for the study of lipid oxidation mechanisms. Presented at the 15th Montreux Symposium on Liquid Chromatography/Mass Spectrometry, Montreux, Switzerland, November 9–10, 1998.     

A novel quasi-dimeric oxidation product of (+)-catechin from lipid peroxidation

A novel quasi-dimeric oxidation product of (+)-catechin, formed during the radical-scavenging reaction that prevents lipid peroxidation, was isolated by chromatography, and its structure was elucidated by infrared, ultraviolet and¹H and¹³C nuclear magnetic resonance spectra and mass spectrometry. It was 5′-[3-[3,4-(3′,5′-dihydroxy) benzo-8-oxo-2,7-dioxabicyclo [4.4.0] deca-3,9-dien-10-yl]acryloyl]-(+)-catechin. It is an unusual type of dimer of flavan-3-ol derivatives, which is different from the naturally formed dimer, procyanidin.     

多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解

漆酶是一种多铜氧化酶,在空气条件下即可催化氧化多胺、多酚类有机物,被认为是水处理及土壤修复领域的绿色催化剂。纳米酶是一种具有酶催化活性的纳米材料,因其具有多功能性、低成本、高稳定性等优点,近年来引起广泛关注。因此,本文以尿素水解过程中产生的异氰酸根离子为模板剂,与Cu(NO₃)₂溶液反应制备具有漆酶活性的多级结构羟基硝酸铜[H-Cu₂(OH)₃NO₃]纳米酶。其催化活性是传统Cu(NO₃)₂与尿素水解法制备的羟基硝酸铜的1.85倍,其最大反应速率是漆酶的1.27倍。H-Cu₂(OH)₃NO₃纳米酶在不同pH、温度、储存时间和盐浓度条件下体现良好的催化稳定性。在重复利用12次后,保持58%的催化活性,体现出良好的重复利用性。而且H-Cu₂(OH)₃NO₃纳米酶具有降解土壤与地下水中常见的2,4-二氯苯酚、对...     

Interaction between amino acid degradation,sensory attributes and lipid peroxidation in wheat rolls

The influence of lipid peroxidation and heating duration on the amino acid pattern of wheat rolls was assessed in a model baking test. Therefore, three different types of dough were prepared including dough without any fat and two doughs with fat. To estimate the impact of lipid peroxidation products on the amino acid pattern, the two doughs containing fat were both made with rapeseed oil, one with fresh oil, the other with oxidised rapeseed oil. All kinds of dough were baked for three different duration times (18, 24 and 30 min). The lipid peroxidation status of both rapeseed oils was measured with the peroxide value and the p‐anisidine value of the unbaked fat. The amino acid content was analysed by HPLC after acid and alkaline hydrolysis. Besides determining water content and protein content, a sensory analysis was performed. Whereas the amino acid content in the dough without fat was only affected by the baking time, the doughs with rapeseed oil additionally showed a significant increase in amino acid degradation caused by lipid peroxidation products. Especially in the dough prepared with oxidised rapeseed oil, the amino acid content was partly decreased in raw dough without any heating influence. Confirming the influence of lipid peroxidation products in dough prepared with oxidised rapeseed oil, sensory analysis also showed the significantly worst overall score.     

Inhibition of lipid peroxidation and nonlipid oxidative damage by carnosine

The antioxidant effects of carnosine on lipids and nonlipids, including liposomes, carbohydrates, and proteins, were investigated. Carnosine exhibited a remarkable antioxidant effect in liposome and deoxyribose model systems. Carnosine at high amounts (50 mg/mL) was effective in protecting protein against oxidation. The correlation coefficients between reducing ability and the inhibition of liposome, albumin, and deoxyribose oxidation were r=0.92, 0.83, and 0.41, respectively. Carnosine exhibited metal-binding ability and scavenging ability for hydroxyl radicals generated by photolysis of H₂O₂ with UV light. The correlation coefficients between hydroxyl radical scavenging and the inhibitory effect on deoxyribose, liposome, and albumin oxidative damage were r=0.97, 0.60, and 0.29, respectively. These properties may explain how carnosine protects lipids and non-lipids against oxidative damage.     

电化学诱发羟基自由基降解水中酚类污染物

DMPO（5,5-dimethyl-1-pyrroline-N-oxide）为自旋捕集剂,采用电子自旋共振技术（electron spin resonance spectroscopy,ESR）直接证实了经氟树脂改性的β PbO₂阳极和不锈钢网阴极构成的电化学体系中产生的羟基自由基（·OH）。通过电化学氧化水中含酚类及其前驱体污染物,发现环状结构化合物受电化学产生的羟基自由基攻击而发生开环反应产生易生物降解的有机酸,如反丁烯二酸和草酸,直至完全矿化为CO₂和水分子,苯醌是酚类污染物开环前产生的共同稳态中间体。该类污染物的电化学降解共性规律为电化学氧化技术的工业化应用和提高其处理工艺的经济性提供了理论依据。     

Behavior of phenolic antioxidants in a partitioned medium: Focus on linoleic acid peroxidation induced by iron/ascorbic acid system

The peroxidation of linoleic acid was induced by the Fe²⁺/ascorbic acid system in a micellar medium, and the kinetics of the produced conjugated dienes to a weak level (0.7 μM) in order to initiate only the sequential oxidative reactions without superimposed antioxidant activity. Other conditions were established to obtain a simple kinetic profile. With a linoleic acid/Fe²⁺ ratio of 10 and an Fe²/ascorbic acid ratio of 23 in the medium emulsified by Tween and saturated in oxygen, no limiting effect of substrates was observed for several hours. Fe²⁺ disappeared in less than 5 min, while a linear propagation rate was reached after 1 h for up to 15 h. Two parameters were chosen to quantify the level of the oxidation: the slope of the linear phase, and the extrapolated absorbance of this step at zero time. These two parameters were used in order to compare the antioxidant power of different phenolic compounds in this partitioned medium.     

Near‐infrared spectroscopy for the determination of lipid oxidation in cereal food products

The present study was aimed at determining the ability of near‐infrared (NIR) spectroscopy to in situ describe fat oxidation kinetics in three different cereal‐based products: salted crackers (20% saturated palm oil and lauric oil, sprayed on surface); healthy crackers (10% unsaturated rapeseed oil, homogeneously distributed inside the product matrix); and moist pasteurised Asian noodles (1.5% unsaturated rapeseed oil, sprayed on surface). Products were stored under accelerated oxidation conditions at 40 °C. Lipid oxidation rates were determined from peroxide value (PV) measurements. We observed no significant changes in PV for the dry crackers (3 meq/kg after 60 days), a slight linear increase in PV for the healthy crackers (40 meq/kg after 60 days), and a rapid increase for the Asian noodles (80 meq/kg after 20 days). The NIR spectra were recorded between 1000 and 2500 nm by using a Fourier Transform NIR spectrometer, using an external probe. Measurements were done directly in situ on the product, on the ground samples, and on the extracted fat phase. The analysis of NIR spectral data by PLS statistical methods demonstrated some correlation trends (R² = 0.575–0.897; RMSEC = 17–55%) for the products having a significant increase in PV. It was not possible to propose predictive models to calculate the oxidation rate.     

Accelerated ageing of polypropylene stabilized by phenolic antioxidants under high oxygen pressure

Polypropylene (PP) samples stabilized by a hindered phenol (Irganox 1010) were submitted to thermal ageing at 80°C in air at atmospheric pressure or in pure oxygen at 5.0 MPa pressure. Both the polymer oxidation and the stabilizer consumption were monitored by Infrared spectrometry and thermal analysis. The stabilizer efficiency, as assessed by the ratio induction time/stabilizer concentration is almost constant at atmospheric pressure even when the stabilizer concentration is higher than its solubility limit in PP (0.4% or 24 × 10^?3 mol L^?1). In contrast, at high pressure, the efficiency decreases almost hyperbolically with the stabilizer concentration when this latter is higher than 6.0 × 10^?3 mol L^?1. The results indicate the existence of a direct phenol‐oxygen reaction negligible at low oxygen pressure but significant at 5.0 MPa pressure. The reality of this reaction has been proved on the basis of a study of the thermal oxidation of a phenol solution in a nonoxidizable solvent. A kinetic model of PP oxidation in which stabilization involves three reactions has been proposed. It simulates correctly the effect of oxygen pressure and stabilizer concentration on carbonyl build‐up and stabilizer consumption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The synthesis of oxime reagents from natural and semi‐synthetic phenolic lipid and alkanoic acid resources for the solvent recovery of copper(II)

In a study of the relationship between structure and efficiency towards recovery of copper(II) by chelation/solvent extraction, a series of homologous aldoximes has been synthesised from natural phenolic lipidic, and fatty lipidic renewable sources, for comparison with commercial reagents prepared from petrochemical sources. From cardanol, in technical cashew nut‐shell liquid, isoanacardic aldoxime, [2‐hydroxy‐4‐pentadec(en)yl]aldoxime, and from the natural phenolic lipid, anacardic acid, the isomer, 2‐hydoxy‐6‐pentadec(en)ylaldoxime, have been synthesised. A C₁₁ analogue of anacardic aldoxime from Anacardium giganteum has been prepared. The isomeric n‐octyl aldoximes have been synthesised, the o‐ and p‐isomers from the readily available fatty acid n‐octanoic acid and the m‐isomer from cardanol. Related m‐aldoximes have been prepared from the ketonic intermediates methyl isoamyl and methyl amyl ketones. The solvent extraction properties for copper(II) of the synthesised aldoximes have been compared with those of a current commercial reagent, 2‐hydroxy‐5‐t‐nonylbenzaldoxime (Acorga 5100, Cytec), and two former extractants, 2‐hydroxy‐5‐t‐nonylacetophenone ketoxime (SME 529, Shell) and 2‐hydroxy‐5‐t‐nonylbenzophenone ketoxime (LIX 65N, Henkel). All the aldoximes possessed useful properties in extraction efficiency, notably the isoanacardic and the C₈ aldoximes with the C₈o‐isomer, 2‐hydroxy‐3‐n‐octylbenzaldoxime, exhibited optimal extraction, stripping and phase separation characteristics. Copyright © 2005 Society of Chemical Industry     

Kinetics of lipid oxidation in the presence of cinnamic acid derivatives

The effects of seven (prenyl‐ and methoxy‐) derivatives of cinnamic acid (0.1 mM) on the kinetics of lipid (sunflower oil triacylglycerols, TGSO) bulk phase oxidation at 80 °C have been compared. Synthesis of prenyl cinnamic acid derivatives: 3‐prenyl‐4‐hydroxy‐cinnamic acid (PHC), 3,5‐diprenyl‐4‐hydroxy‐cinnamic acid (DPHC), 2,2‐di‐methyl‐6‐carboxy‐ethenyl‐2H‐benzopyran (DMCB), 2,2‐dimethyl‐6‐carboxy‐ethenyl‐8‐prenyl‐2H‐benzopyran (DCEPB) present in Brazilian propolis has been performed. The monoprenyl derivative (PHC) has been found to exert a higher antioxidant activity as compared to the diprenyl derivative (DPHC). However, cinnamic acid derivatives DMCB and DCEPB have caused no change in the kinetics of TGSO oxidation. The results obtained have been compared with those on related compounds containing a cinnamic acid moiety as a structural feature, such as 4‐hydroxy‐cinnamic (p‐coumaric), 3‐methoxy‐4‐hydroxy‐cinnamic (ferulic) and 3,5‐dimethoxy‐4‐hydroxy‐cinnamic (sinapic) acids, as well as with data on butylated hydroxytoluene (BHT) and α‐tocopherol (αToc). PHC has shown a stronger antioxidant efficiency than BHT, p‐coumaric and ferulic acid, but a weaker antioxidant efficiency than α‐Toc and sinapic acid. The observed antioxidant effect of DPHC was stronger than that of p‐coumaric and ferulic acids and weaker than that of α‐Toc, BHT and sinapic acid.     

催化臭氧化处理酚类化合物的研究进展与机理解析

催化臭氧化技术具有操作简单、氧化效率高、二次污染小等特点,在水中酚类化合物的去除方面具有较大的技术优势。本文以酚类化合物的催化臭氧化处理为切入点,介绍了均相催化臭氧化（二价铁离子）和非均相催化臭氧化（金属型、硅基负载型、碳基负载型、铝基负载型）处理不同浓度梯度酚类化合物的研究进展。然后,基于上述研究进展,根据污染物氧化过程的探针实验结果、催化剂表征特性和有机物转化规律,阐述了苯酚等酚类化合物的催化臭氧化机理。最后,从新型催化剂的再开发、酚类化合物的广谱催化和催化氧化机理的进一步探讨方面对催化臭氧化处理酚类化合物进行了展望。