Oxidation of linoleic acid in emulsions: Effect of substrate, emulsifier, and sugar concentration

Linoleic acid oxidation in oil-in-water emulsions stabilized by a nonionic surfactant (Tween-20) was studied. The emulsion composition was varied at a constant oil droplet size. Lipid oxidation was measured as a function of time in the presence of a catalyst (FeSO₄ corbic acid) by two methods: gas chromatographic determination of residual substrate and ultraviolet-visible spectrophotometric determination of conjugated dienes. Rate of oxidation was influenced by the emulsion composition (relative concentrations of substrate and emulsifier) and especially by the partition of the emulsifier between the interface and water phase. Concentrations of emulsifier exceeding the critical micelle concentration protected the fatty acid against oxidation. Excess surfactant formed micelles and mixed micelles with linoleic acid, which retarded oxidation by diluting the substrate or perhaps by replacing linoleic acid at the interface, making it less accessible to radical attack. The addition of sucrose also had a protective effect, but only up to a certain concentration, indicating the effect may involve factors other than viscosity.     

Structured phosphatidylcholine with elevated content of conjugated linoleic acid: Optimization by response surface methodology

Structured phosphatidylcholine was successfully produced by immobilized phospholipase A₁ catalyzed acidolysis of phosphatidylcholine and CLA. Response surface methodology was applied to optimize the reaction system using three process parameters: enzyme load, temperature, and substrates molar ratio. Optimal conditions obtained from the model were 15% enzyme load at 55°C for a 1:4 (PC/CLA) substrates molar ratio, which produced a yield of 85.8% of CLA incorporation. The total correlation coefficient (R²) was 0.92 and no lack of fit was detected. This suggests the fitness of the model obtained and it suggests that the model is sufficiently accurate to estimate the incorporation of CLA into PC. Practical applications: This study could contribute to process development for enzyme catalyzed phospholipid modification. By changing the fatty acid composition of lecithin, delivery of desired (beneficial) fatty acids could be better achieved. Additionally, emulsification properties of the phospholipids could open a wide area of applications in the food and cosmetic industries.     

Influence of native antioxidants on the formation of fatty acid hydroperoxides in model systems

The effect of alpha‐tocopherol (alpha‐T) and quercetin on the formation of hydroperoxides of linoleic and linolenic acids during autoxidation at 60 ± 1 °C was investigated. Three isomers of hydroperoxides were detected using HPLC. Of isomers of linoleic acid hydroperoxides, 13‐hydroperoxy‐octadecadienoic acid trans‐trans (13‐HPODE t‐t), 9‐HPODE cis‐trans (9‐HPODE c‐t) and 9‐HPODE trans‐trans (9‐HPODE t‐t) were identified, constituting 64, 19 and 17% of the total amount, respectively. For linolenic acid, the components 13‐hydroperoxy‐octadecatrienoic acid trans‐trans (13‐HPOTE t‐t), 9‐HPOTE c‐t and 9‐HPOTE t‐t contributed 7, 33 and 60% to the total, respectively. The different dominant hydroperoxide isomers detected in linoleic and linolenic acids during oxidation are related to their chemical structure and the microenvironment of emulsion droplets. The ratios between specific isomers for both fatty acid hydroperoxides did not change during oxidation with or without antioxidants. Alpha‐T effectively inhibited the oxidation of fatty acids and reduced the formation of hydroperoxides. The total amount of the hydroperoxides decreased along with the increase in the concentration of alpha‐T, 1–40 µM. Quercetin inhibited the oxidation of both fatty acids at similar efficiency only at 40 µM concentration. A synergistic antioxidant effect of quercetin with alpha‐T in a binary system on both fatty acids was observed.     

Synergistic antioxidative effects of tocopherol and ascorbic acid in fish oil/lecithin/water system

Individual and combined effects of ascorbic acid andδ-tocopherol on the autoxidation of fish oil have been evaluated with the induction period monitored by Rancimat. The antioxidative efficiency of them was found to increase with increasing concentration.δ-Tocopherol and ascorbic acid acted highly synergistic with each other. Whenδ-tocopherol content was varied at a fixed content of ascorbic acid, the synergistic efficiency was generally 100% or more. On the other hand, when ascorbic acid content was varied at a fixed content ofδ-tocopherol, the synergistic efficiency rose sigmoidally with increasing concentration. We concluded that at least 0.01–0.02% ascorbic acid is required to obtain a considerable synergistic effect withδ-tocopherol in stabilizing fish oil.     

硫氰酸铵-乙醇-水体系萃取浮选铜法间接测定抗坏血酸

微量Cu(II)被抗坏血酸还原成Cu(I)后可与SCN-生成CuSCN沉淀,在乙醇与水分相的过程中,CuSCN被浮选,且抗坏血酸用量和浮选率之间存在良好的线性关系。抗坏血酸的检出限为5×10-5mol/L。该方法简单、快速、干扰离子少,已成功应用于水果中抗坏血酸的检测。     

Lipid peroxidation in vivo is induced by exercise on a bicycle ergometer in athletes

There is a widely held belief that exercise leads to lipid peroxidation. Plasma hydroxy fatty acids originate from the diet and possibly from lipid peroxidation in vivo. We examined whether acute exercise (1 h at ∼76% of predicted maximal aerobic capacity) leads to an increase in plasma hydroxy fatty acids without the confounding influence of the diet in 7 male athletes. In addition, using a random‐sequence cross‐over design, we examined whether vitamin C supplementation of 1 g per day for 10 days prior to exercise could prevent exercise‐induced lipid peroxidation. Supplementation doubled the plasma vitamin C from 56.9 ? 3.4 to 112.7 ? 14.6 μM (P< 0.001) and lowered pre‐exercise plasma hydroxy fatty acids from 1.30 ? 0.18 to 1.03 ? 0.14 μM (P< 0.05). Plasma hydroxy fatty acid levels rose up to 3‐fold during exercise in some athletes on placebo and peak levels were reached after 20 min. The rise in plasma hydroxy fatty acid levels was delayed and remained lower after supplementation with vitamin C compared to placebo: 0.01 ? 0.07 vs. 0.63 ? 0.16 μM (P< 0.05). Vitamin C supplementation reduced pre‐exercise creatine kinase levels (193 ? 52 vs. 277 ? 68 U/L; P< 0.05) but its effect on exercise‐induced changes in creatine kinase did not reach statistical significance. In conclusion, large supplements of vitamin C reduced exercise‐induced lipid peroxidation in athletes. This small, but carefully controlled study illustrates the usefulness of plasma hydroxy fatty acid levels to monitor lipid peroxidation in vivo in acute studies.     

捕收剂的亚油酸/油酸比值对磷矿浮选的影响

探讨了几种脂肪酸皂类捕收剂的亚油酸/油酸(L)值对浮选温度和选别指标的影响。黄麦岭磷矿的浮选试 验表明,L值越大。综合指数K越高,选矿效果越好。温度较低时,应选用亚油酸含量较高的脂肪酸皂捕收剂。     

抗坏血酸对Fe2+/H2O2体系氧化NO的促进作用

采用实验方法研究了低成本环境友好型添加剂抗坏血酸(AA)对Fe²⁺/H₂O₂体系氧化NO气体及其对体系内H₂O₂分解的影响,分析了AA对体系氧化NO能力及H₂O₂分解的影响机制。研究结果表明:AA通过加速Fe³⁺向Fe²⁺的转化而促进Fe²⁺/H₂O₂体系对NO的氧化。[AA]₀:[Fe²⁺]₀对体系氧化NO的能力及H₂O₂的分解具有重要影响。综合考虑NO氧化脱除量及H₂O₂消耗量,合理的[AA]₀:[Fe²⁺]₀为1/3~1/2。AA的分次添加方式可大幅度提升体系氧化NO气体的能力。研究结果可望为发展基于H₂O₂为氧化剂的烟气NO绿色氧化技术提供理论基础。     

Monooxygenase system of Bacillus megaterium ALA2: Studies on linoleic acid epoxidation products

Bacillus megaterium ALA2 produces many oxygenated FA from linoleic acid: 12,13-dihydroxy-9(Z)-octadecenoic acid; 12,13,17-trihydroxy-9(Z)-octadecenoic acid; 12,13,16-trihydroxy-9(Z)-octadecenoic acid; 12-hydroxy-13,16-epoxy-9 (Z)-octadecenoic acid; and 12,17;13,17-diepoxy-16-hydroxy-9 (Z)-octadecenoic acid. Recently, we studied the monooxygenase system of B. megaterium ALA2 by comparing its palmitic acid oxidation products with those of the well-studied catalytically self-sufficient P450 monooxygenase of B. megaterium ATCC 14581 (NRRL B-3712) and of B. subtilis strain 168 (NRRI B-4219). We found that their oxidation products are identical, indicating that their monooxygenase systems (hydroxylation) are similar. Now, we report that strain ALA2 epoxidizes linoleic acid to 12,13-epoxy-9(Z)-octadecenoic acid and 9,10-epoxy-12 (Z)-octadecenoic acid, the initial products in the linoleic acid oxidation. The epoxidation enzyme did not oxidize specific double bond of the linoleic acid. The epoxidation activity of strain ALA2 was compared with the above-mentioned two Bacillus strains. These two Bacillus strain also produced 12,13-expoxy-9 (Z)-octadecenoic acid and 9,10-epoxy-12(Z)-octadecenoic acid, indicating that their epoxidation enzyme systems might be similar. The ratios of epoxy FA production by these three strains (A1 A2, NRRI B-3712, and NRRI B-4219) were, respectively, 5.56∶0.66∶0.18 for 12,13-epoxy-9(Z)-octadecenoic acid and 2.43∶0.41∶0.57 for 9,10-epoxy-12(Z)-octadecenoic acid per 50 mL medium per 48 h.     

亚油酸乳状液体系氧化模型与求解

研究了恒表面氧压静置式无限氧补偿条件下乳状液中亚油酸的氧化,通过综合考虑气液边界传质阻力、水相扩散、油水边界乳化剂膜边界层阻力、多不饱和脂肪酸(PUFA)自催化氧化反应动力学,建立了扩散-氧化数学模型。采用非对称正交配置法处理特殊边界,求解偏微分方程组,计算了氧化过程中乳状液中氧和亚油酸在垂直于液膜方向的浓度分布,计算方法快捷、有效;结合数学模拟试验和实验值,确定了气液界面氧的液膜传质系数和水相中氧的扩散系数。实验验证该模型能较好地拟合静置式无限氧补偿条件下乳状液中氧的扩散和亚油酸的氧化过程。     

Persulfate/ascorbic acid initiated synthesis of poly(acrylonitrile)‐grafted tamarind seed gum: A potential commercial gum

Acrylonitrile was grafted on to tamarind seed gum using persulfate/ascorbic acid redox initiator and a representative sample of the graft copolymer (Tm‐g‐PAN) was characterized using infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Grafting conditions were optimized where %G and %E were found to increase with the increase in the concentration of the monomer; initiator, and the reaction temperature, whereas increase in gum concentration decreased the %G in the concentration range of 4–12 g/L, The maximum % grafting (%G) and % efficiency (%E) achieved were 305 and 75%, respectively. Water/saline retention, gel forming ability, and the shelf life of the grafted gum solutions were also studied to explore the possibility of its commercial utilization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of initial slight oxidation on stability of polyunsaturated fatty acid/protein mixtures under controlled atmospheres

A mixture of unsaturated fatty acids (FA), mainly linolenic acid, and bovine serum albumin (BSA) was incubated under several different atmospheres to study the effect of these atmospheres on the stability of FA to oxidation. Four experiments were carried out simultaneously, which consisted of the incubation of the FA/BSA mixture under air, nitrogen, air in the presence of 200 ppm of butylated hydroxytoluene, and air for 6 h and then under nitrogen. The four experiments were tested for lipid oxidation and color changes by measuring absorbances at 234 and 270 nm, formation of thiobarbituric acid-reactive substances, and color differences and yellowness index. The samples that were oxidized with air before storage under nitrogen were the most stable against lipid peroxidation and exhibited the smallest color changes. These results suggest that a slight and controlled lipid oxidation improved the oxidative stability of FA/BSA mixtures.     

Effect of initial slight oxidation on stability of polyunsaturated fatty acid/protein mixtures under controlled atmospheres

A mixture of unsaturated fatty acids (FA), mainly linolenic acid, and bovine serum albumin (BSA) was incubated under several different atmospheres to study the effect of these atmospheres on the stability of FA to oxidation. Four experiments were carried out simultaneously, which consisted of the incubation of the FA/BSA mixture under air, nitrogen, air in the presence of 200 ppm of butylated hydroxytoluene, and air for 6 h and then under nitrogen. The four experiments were tested for lipid oxidation and color changes by measuring absorbances at 234 and 270 nm, formation of thiobarbituric acid-reactive substances, and color differences and yellowness index. The samples that were oxidized with air before storage under nitrogen were the most stable against lipid peroxidation and exhibited the smallest color changes. These results suggest that a slight and controlled lipid oxidation improved the oxidative stability of FA/BSA mixtures.     

Effect of salvianolic Acid B and paeonol on blood lipid metabolism and hemorrheology in myocardial ischemia rabbits induced by pituitruin

The purpose of this study was to determine the therapeutic effect of salvianolic acid b and paeonol on coronary disease. The ischemia myocardial animal model is induced by administering pituitrin (20 μg·kg(-1)) intravenously via the abdominal vein. A combination of salvianolic acid b and paeonol (CSAP) (5, 10 and 15 mg/kg BW) was administrated to experimental rabbits. Biochemical indices were evaluated during six weeks of intervention. We found that the compound of salvianolic acid b and paeonol (5, 10 and 15 mg/kg BW) can markedly and dose-dependently reduce fibrinogen and malonaldehyde levels, increase the HDL level, improve blood viscosity and plasma viscosity in rabbits. In addition, the medicine can still reduce the ratio of NO/ET and the contents of lactate dehydrogenase (LDH) and creatine phosphokinase (CPK) in a dose-dependent manner. This study demonstrates that compound of salvianolic acid b and paeonol (5, 10 and 15 mg/kg BW) can improve the blood hemorrheology, decrease oxidative injury and repair the function of blood vessel endothelium, and subsequently prevent the development of Coronary disease.     

Polymerization kinetics of acrylonitrile by oxidation: Reduction system using potassium persulfate/ascorbic acid in an aqueous medium

The kinetics of acrylonitrile polymerization initiated by free radicals formed in situ in a potassium persulfate/ascorbic acid redox system was investigated in an aqueous sulfuric acid medium in the temperature range of 40–70°C. The rate of polymerization and the rate of the disappearance of potassium persulfate were measured. A kinetic scheme involving the production of initiating radicals from the oxidation of ascorbic acid by potassium persulfate ions and termination exclusively by the interaction of chain radicals with persulfate ions is proposed. The effects of some water‐miscible organic solvents on the rate of polymerization were investigated. The temperature dependence of the rate was studied. A possible mechanism consistent with the experimental data is proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

乙醇-水体系3D纳/微米球形磷酸铁的制备与表征

提出了一种在温和条件下制备高振实密度球形磷酸铁的简单方法。制备过程中无需引入碱性物质调节pH和添加其他模板剂,仅以九水合硝酸铁[Fe（NO₃）·9H₂O]和磷酸（H₃PO₄）为原料,在乙醇-水体系中即可制备3D纳/微米球形磷酸铁（记为FPE）。采用扫描电镜（SEM）、激光粒度仪、X射线衍射仪（XRD）、热重-差式扫描量热仪（TG-DSC）、比表面积测试仪（BET）等对制备的磷酸铁进行表征分析。结果显示,制备的磷酸铁具有3D纳/微米球形结构,平均一次粒径为27.2 nm,二次粒径D₅₀为3.75 μm。FPE的组成为二水合磷酸铁（FePO₄·2H₂O）,纯度较高,具有介孔结构,平均孔径为2.75 nm,比表面积为22.41 cm ²/g,同时具有较高的振实密度（1.34 g/cm ³）。3D纳/微米球形磷酸铁制备方法简单,性能优异,以其为前驱体制备的磷酸铁锂（LiFePO₄/C）具有较高的振实密度（1.46 g/cm ³）,在0.2C倍率下的放电比容量为157.9 mA·h/g。     

Lipid peroxidative damage on Cisplatin exposure and alterations in antioxidant defense system in rat kidneys: a possible protective effect of selenium

Cisplatin (Cis-diamminedichloroplatinum II, CP) is an important chemotherapeutic agent, useful in the treatment of several cancers, but with several side effects such as nephrotoxicity. The present study investigated the possible protective effect of selenium (Se) against CP-induced oxidative stress in the rat kidneys. Male Wistar albino rats were injected with a single dose of cisplatin (7 mg CP/kg b.m., i.p.) and selenium (6 mg Se/kg b.m, as Na(2)SeO(3), i.p.), alone or in combination. The obtained results showed that CP increased lipid peroxidation (LPO) and decreased reduced glutathione (GSH) concentrations, suggesting the CP-induced oxidative stress, while Se treatment reversed this change to control values. Acute intoxication of rats with CP was followed by statistically significant decreased activity of antioxidant defense enzymes: superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GR) and glutathione-S-transferase (GST). Treatment with Se reversed CP-induced alterations of antioxidant defense enzyme activities and significantly prevented the CP-induced kidney damage.     

氯酚类有机物在超声波／零价铁体系中降解特性的研究

以2-氯酚、2,4-二氯酚、2,4,5-三氯酚、2,3,4,6-四氯酚及五氯酚等氯酚类化合物（CPs）为目标污染物,研究了CPs在超声波／零价铁联合体系中（US／Fe^0）的降解特性。结果表明,在同一条件下,苯环上的氯取代基越多,降解速率越大;当氯原子取代得越多,碳正离子的形成速度越快,反应活性越大;随着氯取代基增多,分子的（Elumo－Ehomo）^2减小,该分子越不稳定。