Degradation, under non-oxygen-mediated autooxidation, of carotenoid profile present in paprika oleoresins with lipid substrates of different fatty acid composition

A heat-induced degradation was carried out over two crude paprika oleoresins diluted with high oleic or high linoleic oil. Occurrence of oxygen was avoided, and changes in individual carotenoids were followed over time. Degradation rate constants were not significantly different, so that carotenoid stability was not linked with unsaturation degree of the oily system. A parallel reaction to degradation, trans to cis carotenoid isomer conversion, was also denoted during the thermal treatment, and it initially showed a higher rate than degradation of cis-isomers. Both processes (isomerization and cis-isomers degradation) were finally compensated, and their development was also unaffected by the nature of the lipid profile. Under the reaction conditions, oleic and linoleic fatty acids showed the same reactivity and induced degradative reactions, equally affecting the carotenoid profile. An enhanced stability of carotenoid content and provitamin A value was not achieved with a decrease in the unsaturation level of the oily system.     

Kinetic model for studying the effect of quercetin on cholesterol oxidation during heating

Inhibition of the heat-induced cholesterol oxidation at 150 degrees C by incorporation of quercetin was kinetically studied. Results showed that without quercetin, the cholesterol oxidation products (COPs) concentration increased with increasing heating time. A low amount (0.002%, w/w) of quercetin was effective in inhibiting the formation of COPs during the initial heating period (< or =30 min) at 150 degrees C. However, after prolonged heating (30-120 min), a low antioxidant activity was observed because of the degradation of quercetin. When using nonlinear regression models for kinetic study of cholesterol oxidation in the absence of quercetin, the epoxidation showed the highest rate constant (h(-1) = 683.1), followed by free radical chain reaction (h(-1) = 453.5), reduction (h(-1) = 290.3), dehydration (h(-1) = 155.5), triol dehydrogenation (h(-1) = 5.35), dehydrogenation (h(-1) = 0.68), thermal degradation (h(-1) = 0.66), and triol formation (h(-1) = 0.38). However, in the presence of quercetin, the reaction rate constants (h(-1)) for epoxidation (551.4), free radical chain reaction (111.7), and thermal degradation (0.28) were reduced greatly. The kinetic model developed in this study can be used to predict the inhibition of COPs by quercetin during the heating of cholesterol.     

Copper Oxide Nanoparticle-Coated Quartz Sand as a Catalyst for Degradation of an Organic Dye in Water

Copper oxide nanoparticles were immobilized on quartz sand and their catalytic activity for the degradation of an organic dye was investigated. The use of nanoparticles as catalysts for non photo-induced oxidation of water contaminants is relatively new. The CuO catalyst has shown promising results when suspended in free form in batch systems. Because heterogeneous catalysis is often the preferred mode of operation for application of catalytic technology, we studied the effect of immobilization of the nanoparticles on quartz sand in a flow-through system and its implication for the catalytic process. The coated sand was packed in a column and its catalytic activity for the degradation of an organic dye was investigated in a series of flow-through experiments with hydrogen peroxide as the oxidant. Control experiments with uncoated sand were also performed for comparison. The coated sand demonstrated high catalytic ability, achieving complete oxidation of the dye. During the reaction, CO₂ was produced, leading to a decrease in the water saturation in the column and reduced contact surface between the nano-CuO catalysts and the dye solution. The degradation was improved by enabling a longer residence time of the dye in the column, yielding up to 85% degradation of the dye. These results suggest that CuO nanoparticle-coated sand is an efficient catalyst for complete degradation of the organic dye.     

土壤中的氧化锰对酚类化合物的氧化降解作用

本文研究了砖红壤和红壤中的氧化锰对１０种有毒酚化合物的氧化降解作用及氧化锰与酚化合物之间的氧化还原动力学，结果表明，土壤中氧化锰对某些有毒酚化合物具有氧化降解作用，各种酚化合物氧化降解的难易与其本身性质和分子结构有关。土壤中的氧化锰的还原溶解和氢醌的卖化均符合一级反应动力学方程。介质ｐＨ的降低有利于反应的进行，两种土壤中的氧化锰不溶解反应对（Ｈ＾＋）的级数为０．１６，氢醌除与氧化锰发生氧化还原反应     

Ability of surface-active antioxidants to inhibit lipid oxidation in oil-in-water emulsion

Lipid oxidation in dispersed lipids is prevalent at the oil-water interface where lipid hydroperoxides are decomposed into free radicals by transition metals. Free radical scavenging antioxidants are believed to be most effective in lipid dispersions when they accumulate at the oil-water interface. The surface activity of antioxidants could be increased by their conjugation to hydrocarbon chains. In this study, p-hydroxyphenylacetic acid (HPA) was conjugated with either a butyl or dodecyl group. The HPA conjugates were more effective at decreasing interfacial tension than unconjugated HPA, indicating that they were able to adsorb at lipid-water interfaces. However, free HPA was a more effective antioxidant than butyl and dodecyl conjugates in Menhaden oil-in-water emulsions as determined by both lipid hydroperoxides and thiobarbituric acid reactive substances. The increased antioxidant activity of free HPA could be due to its more effective free radical scavenging activity and its higher concentration in the lipid phase of oil-in-water emulsions in the presence of surfactant micelles where it can act as a chain-breaking antioxidant.     

Antioxidative activity of urate in bovine milk

The antioxidative effects of urate on peroxidase-induced protein oxidation and light-induced riboflavin degradation and lipid oxidation in whole milk were studied. In addition, experiments using ascorbate were conducted to directly compare the antioxidative activity of urate and ascorbate. The presence of urate and/or ascorbate (10-30 mg/L) lowered peroxidase-induced formation of dityrosine by 44-96% in unpasteurized whole milk. No synergistic effect of urate and ascorbate on peroxidase-induced dityrosine formation was registered, but merely an additive effect. Light exposure of pasteurized whole milk showed that ascorbate was oxidized at the expense of urate, which indicated ascorbate-mediated recycling of the urate radical. Moreover, both urate and ascorbate (30 mg/L) retarded light-induced lipid oxidation in pasteurized whole milk as measured by formation of lipid hydroperoxides with urate being the most effective (28% reduction in lipid hydroperoxides) compared with ascorbate (14%). Finally, addition of urate or ascorbate (300 mg/L) to pasteurized whole milk showed a slight protective effect against light-induced degradation of riboflavin with urate being the most effective.     

The Effect of Polyethylene Glycol (PEG) Modification on Fe Dispersal and the Catalytic Degradation of Phenol Wastewater

Modification of a catalyst with polyethylene glycol (PEG) created a dramatic increase in the catalytic activity for the degradation of phenol wastewater. The Fe/PEG-modified γ-Al₂O₃ catalyst was prepared by an impregnation method. The as-prepared catalyst was characterized by X-ray photoelectron spectroscopy, wide- and small-angle X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and N₂ adsorption-desorption experiments, and the results showed that the Fe species were highly dispersed on the surface of the PEG-modified support. At the same time, the PEG modification resulted in an increase in the Brunauer-Emmett-Teller surface area and pore volume. The catalytic activity test showed that the Fe/PEG-modified γ-Al₂O₃ catalyst exhibited a superior performance for the degradation of phenol wastewater in this study, and the phenol and COD removal values reached 94.1 and 88.9%, respectively, within 60 min. The results clearly show that PEG modification is a promising methodology for the preparation of a catalyst with good dispersal of the active component on the support.     

Quantitative HPLC determination of the antioxidant activity of capsaicin on the formation of lipid hydroperoxides of linoleic acid: a comparative study against BHT and melatonin.

The antioxidant activity of capsaicin, as compared to BHT and melatonin, was determined by the direct measurement of lipid hydroperoxides formed upon linoleic acid autoxidation initiated by AIBN. The formation of four isomeric lipid hydroperoxides was detected after reverse-phase HPLC separation. Data from three detectors, UV absorption, glassy carbon electrode electrochemical detection, and postcolumn chemiluminescence using luminol, were compared. Capsaicin was more effective than melatonin in suppressing the formation of lipid hydroperoxides but not as effective as BHT. The formation of capsaicin and BHT dimers was observed during oxidation, and the dimers were characterized using APCI MS(n).     

Degradation of chloroacetanilide herbicides by anodic fenton treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.     

粘土矿物固定化微生物对土壤中阿特拉津的降解研究

以粘土矿物为载体,采用吸附挂膜法对已筛选的阿特拉津降解菌株进行固定化,并应用固定化微生物降解土壤中的阿特拉津。结果表明,该菌株在粘土矿物上生长良好,根据菌种生理生化特性、环境扫描电镜图片以及16S rDNA基因的相似性分析初步鉴定该菌株为Ochrobactrum sp.。接种降解菌能明显加快阿特拉津在土壤中的降解速率,粘土矿物固定化微生物的降解效果要明显优于游离菌,粘土矿物粒径越小,固定化微生物的降解效果越好,纳米粘土矿物固定化微生物的降解效果要好于原粘土矿物。用一级动力学方程描述阿特拉津在土壤中的降解过程,不同土壤中阿特拉津的降解速率不同。阿特拉津在红壤、砂姜黑土、黄褐土中的降解半衰期（t1/2）分别为36.9、49.1、55.0 d,投加纳米蒙脱石固定化降解菌后的半衰期则分别为16.3、25.3、21.7 d。     

Cancer chemopreventive and antioxidant activities of pterostilbene,a naturally occurring analogue of resveratrol

Pterostilbene, a natural methoxylated analogue of resveratrol, was evaluated for antioxidative potential. The peroxyl-radical scavenging activity of pterostilbene was the same as that of resveratrol, having total reactive antioxidant potentials of 237 +/- 58 and 253 +/- 53 microM, respectively. Both compounds were found to be more effective than Trolox as free radical scavengers. Using a plant system, pterostilbene also was shown to be as effective as resveratrol in inhibiting electrolyte leakage caused by herbicide-induced oxidative damage, and both compounds had the same activity as alpha-tocopherol. Pterostilbene showed moderate inhibition (IC50 = 19.8 microM) of cyclooxygenase (COX)-1, and was weakly active (IC50 = 83.9 microM) against COX-2, whereas resveratrol strongly inhibited both isoforms of the enzyme with IC50 values of approximately 1 microM. Using a mouse mammary organ culture model, carcinogen-induced preneoplastic lesions were, similarly to resveratrol, significantly inhibited by pterostilbene (ED50 = 4.8 microM), suggesting antioxidant activity plays an important role in this process.     

Organics Wastewater Degradation by a Mesoporous Chromium-Functionalized γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with H<Subscript>2</Subscript>O<Subscript>2</Subscript> Assistance

In this study, a mesoporous chromium-functionalized γ-Al₂O₃ (Cr/γ-Al₂O₃) catalyst was prepared by an impregnation method, and the catalytic activity was evaluated by the degradation of organics wastewater. The prepared catalyst was characterized by X-ray photoelectron spectroscopy, X-ray diffraction, nitrogen adsorption-desorption experiments, and scanning electron microscopy. The characterization results confirmed that the pores in the Cr/γ-Al₂O₃ catalyst distributed broadly in the mesoporous region, and the active chromium species were highly dispersed on the catalyst surface. The catalytic activity tests showed that the Cr/γ-Al₂O₃ catalyst exhibited a superior performance for the degradation of organics wastewater with H₂O₂ assistance. And the methylene blue (MB) disappeared within 20 min and the COD removal reached 76.5% within 40 min for the MB-simulated wastewater; for the phenol-simulated wastewater, the phenol removal was above 95% and the corresponding COD removal reached 71% within 40 min. Such an excellent catalytic performance demonstrates that the Cr/γ-Al₂O₃ catalyst has a potential application in the degradation of complex organics wastewater simultaneously.     

玉米草（Zea Mexicana）与海藻寡糖联合修复石油烃污染土壤的研究

采用玉米草及海藻寡糖联合修复技术研究了石油污染土壤的修复效果,对修复过程中酶活性变化进行了测定,并采用变性梯度凝胶电泳（DGGE）技术测定了土壤中微生物群落的变化。结果表明,种植玉米草可以有效提高土壤中石油烃的降解,与对照相比石油烃降解率增加了11%;加入不同浓度海藻寡糖进一步增加了石油烃的降解效果,降解率最高达到28.6%。种植植物及加入海藻寡糖可以有效提高多酚氧化酶、脱氢酶及尿酶的活性。PCR-DGGE结果表明植物种植及海藻寡糖的加入增加了土壤中微生物数量,其微生物群落结构与未种植植物及修复前土壤相比发生了较大的变化。     

Modeling evaluation of carbaryl degradation in a continuously stirred tank reactor by anodic fenton treatment

Anodic Fenton treatment (AFT) has been shown to be effective in removing pesticides from aqueous solution in batch reactors with the formation of less toxic and more biodegradable products. To facilitate practical application of AFT, carbaryl degradation in a continuously stirred tank reactor (CSTR) by AFT was investigated under different experimental conditions, such as carbaryl inlet concentration, Fenton reagent concentration/ratio, and carbaryl feeding flow rate. A higher Fe2+ delivery rate and H2O2 to Fe2+ ratio (H2O2:Fe2+) were found to favor the carbaryl degradation process, whereas flow rate was shown to be a much less significant factor to influence the degradation rate under the evaluated experimental conditions. A kinetic-based semiempirical model was developed to simulate the experimental data, and a very good fit between the model and the raw data was found (R2 > 0.99). A dimensionless parameter (k/q2) was found to be a good indicator of the degradation rate; that is, the higher the k/q2value is, the faster the degradation process is. The rate parameter (k) can be used to evaluate the degradation rate when the flow rate is invariant for a given pesticide. The shape parameter (beta) is most likely related to the availability and reactivity of Fenton reagents and hydroxyl radicals. To compare the degradation rate of different pesticides, more information other than k/q2, k, and beta values, such as the instantaneous degradation rate vs time relationship, needs to be considered.     

Model studies on the degradation of phenylalanine initiated by lipid hydroperoxides and their secondary and tertiary oxidation products

The reaction of methyl 13-hydroperoxyoctadeca-9,11-dienoate (MeLOOH), methyl 13-hydroperoxyoctadeca-9,11,15-trienoate (MeLnOOH), methyl 13-hydroxyoctadeca-9,11-dienoate (MeLOH), methyl 13-oxooctadeca-9,11-dienoate (MeLCO), methyl 9,10-epoxy-13-hydroxy-11-octadecenoate (MeLEPOH), and methyl 9,10-epoxy-13-oxo-11-octadecenoate (MeLEPCO) with phenylalanine was studied to determine the comparative reactivity of primary, secondary, and tertiary lipid oxidation products in the Strecker degradation of amino acids. All assayed lipids were able to degrade the amino acid to a high extent, although the lipid reactivity decreased slightly in the following order: MeLEPCO > or = MeLCO > MeLEPOH > or = MeLOH > MeLOOH approximately = MeLnOOH. These data confirmed the ability of many lipid oxidation products to degrade amino acids by a Strecker-type mechanism and suggested that, once the lipid oxidation is produced, a significant Strecker degradation of surrounding amino acids should be expected. The contribution of different competitive mechanisms to this degradation is proposed, among which the conversion of the different lipid oxidation products assayed into the most reactive MeLEPCO and the fractionation of long-chain primary and secondary lipid oxidation products into short-chain aldehydes are likely to play a major role.     

红枣汁中维生素C热降解的动力学研究(简报)

为了了解加热温度对红枣汁中维生素C含量变化的影响,降低红枣汁在加工过程中维生素C的损失,该文以红枣澄清汁为材料,采用可逆的一级反应模型研究了不同加热温度下还原型维生素C(AA)的降解规律并推导出氧化型维生素C(DHAA)含量变化的数学模型.在此基础上利用Arrhenius方程计算得到AA和DHAA的降解反应活化能.结果表明,在303,313,323,333,343 K温度条件下,可逆的一级反应模型适用于表达红枣汁中AA的降解规律,非线性回归决定系数γ2均大于0.98.DHAA的数学模型也能较好地预测DHAA在红枣汁中的含量变化规律.在不同的加热温度下,AA与DHAA均能发生降解反应,但DHAA的降解速率较AA低,DHAA的降解主要发生在AA的降解反应达到平衡之后.AA热降解反应活化能较低,表明红枣汁中的AA对热处理较敏感.该研究为优化红枣汁的加工工艺、提高红枣汁的品质提供理论依据.     

Broccoli processing wastes as a source of peroxidase

A peroxidase isozyme (BP) was purified to homogeneity from broccoli stems ( Brassica oleraceae var. maraton) discarded from industrial processing wastes. BP specific activity was 1216 ABTS [2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid)] units/mg, representing 466-fold that of crude extract. BP is a monomeric glycoprotein containing 16% carbohydrates, with a molecular mass of 49 kDa and an isoelectric point close to 4.2. From kinetic data it showed a two-substrate ping-pong mechanism, and the catalytic efficiency measured as the rate-limiting step of free BP regeneration was 3.4 x 10(6) M(-1) s(-1). The ABTS K m value was 0.2 mM, which was about 20 times lower than that reported for acidic commercial horseradish peroxidase (HRP). Assessment of BP secondary structure showed 30% helical character, similar to HRP and cytochrome c peroxidase. BP lost only 25% activity after 10 min of heating at 55 degrees C and pH 6; it was stable in the pH range from 4 to 9 and showed an optimum pH of 4.6 using ABTS as substrate. BP was active on substrates normally involved in lignin biosynthesis, such as caffeic and ferulic acids, and also displayed good catechol oxidation activity in the presence of hydrogen peroxide. Reverse micellar extraction was successfully used as potential large-scale prepurification of broccoli peroxidase, achieving a purification factor of 7, with 60% activity yield. Stems from the broccoli processing industry have a high potential as an alternative for peroxidase purification.     

铝铁柱撑黏土活化单过硫酸盐降解邻苯二甲酸二乙酯的研究

邻苯二甲酸二乙酯(DEP)是地表水和土壤环境中一种常见的有机污染物,研究DEP的去除方法对于人体健康和环境安全具有十分重要的意义。蒙脱土是一种廉价易得的粘土矿物,通过将铝铁聚合阳离子引入蒙脱土的层间域可得到比表面积大和催化活性高的环境友好型催化材料-铝铁柱撑粘土(Al/Fe-PILCs)。利用XRD、BET、FTIR及HRTEM等手段对材料的理化性质进行表征,并研究了其活化单过硫酸盐(PMS)对DEP的去除效果。结果表明：在Al/Fe-PILCs活化PMS体系中,反应24 h后DEP的降解率约为92%,且反应后的溶液中未检测到溶解性Fe离子。体系中产生的强氧化性.OH是DEP降解的主要原因。同时,环境中常见的阴离子(Cl_^-, NO_3^-和CO_3^2-)不能完全抑制DEP降解。因此,在实际水体和土壤环境中Al/Fe-PILCs作为活化PMS的催化材料,具有一定的应用潜力。     

Proteolytic activation of latent Paraguaya peach PPO. Characterization of monophenolase activity

The kinetics of the activation process of latent peach PPO by trypsin was studied. By coupling this activation process to the oxidation of 4-tert-butylcatechol (TBC) to its corresponding quinone, it was possible to evaluate the specific rate constant of active PPO formation, k(3), which showed a value of 0.04 s(-1). This proteolytic activation of latent peach PPO permitted us to characterize the monophenolase activity of peach PPO for the first time using p-cresol as substrate, and it showed the characteristic lag period of the kinetic mechanism of monophenols hydroxylation, which depended on the enzyme and substrate concentration, the pH and the presence of catalytic amounts of o-diphenol (4-methylcatechol). The enzyme activation constant, k(act), was 2 microM.     

哈夫尼菌降解毒死蜱条件的优化及动力学模型建立

利用响应面法优化哈夫尼菌降解毒死蜱的条件,并建立了降解模型。采用Box-Behnken设计试验,以响应面法进行优化,结果表明,哈夫尼菌降解毒死蜱的最优条件为：蔗糖浓度0.31%,毒死蜱初浓度51.33mg·L-1,培养温度30.7℃,在该条件下理论预测毒死蜱降解率可达74.7%。通过假设和验证,得出哈夫尼菌降解毒死蜱为一级动力学模型,哈夫尼菌能水解毒死蜱P-O键,属一级酶促反应。