荆条蜂胶化学成分的研究

本文对荆条蜂胶乙醇提取物的化学成分进行了研究,为进一步的活性评价及建立标准化模型提供基础数据。蜂胶原胶经65%乙醇溶液80℃加热得到蜂胶提取物,将提取物采用石油醚、乙酸乙酯、正丁醇进行逐级溶剂分配、硅胶色谱柱层析、重结晶、制备液相等方法进行分离和纯化,从乙酸乙酯部分分离得到31个化合物,通过对化学物理性质分析以及红外、紫外、质谱、核磁共振波谱的测定解析,确定了化合物结构。其中黄酮类化合物14个,肉桂酸衍生物7个,咖啡酸酯类化合物6个,其它类4个。     

空气氧化法制备肉桂酸

以银吸附在活性碳上作催化剂 ,用空气作氧化剂 ,将肉桂醛转化为肉桂酸 ,收率为 95 8%。     

荆条蜂胶化学成分分析

该文对荆条蜂胶乙醇提取物的化学成分进行了考察,蜂胶原胶经体积分数65%的乙醇于80℃加热得到蜂胶提取物,将提取物采用石油醚、乙酸乙酯、正丁醇进行逐级溶剂分配、硅胶色谱柱层析、重结晶、制备液相进行分离和纯化,从乙酸乙酯部分分离得到31个化合物,通过对化学物理性质分析以及红外、紫外、质谱、核磁共振波谱的测定解析,确定了化合物结构。其中,黄酮类化合物14个,肉桂酸衍生物7个,咖啡酸酯类化合物6个,其他类4个。     

Effect of evening primrose extracts on oxidative stability of sunflower and rapeseed oils

Antioxidative activities of evening primrose seed meal extracts in sunflower and rapeseed oils were compared with that of commercially used antioxidants, namely butylated hydroxytoluene (BHT), ascorbylpalmitate as well as Grindox‐118. The study was carried out under Schaal oven conditions at 60 °C and the weight gain was followed up by p‐anisidine value measurement following the oxidation. An Oxidograph apparatus monitored the oxidation of oils at 110 °C. Among the examined extracts, the ethyl acetate extract (0.2%), containing only 87 mg/g of total phenolics, exhibited a stronger antioxidant activity than BHT (0.01%) and effectively stabilised both oils. A strong antioxidative effect was also noted for the ethanol‐ethyl acetate extract (168 mg/g of total phenolics). The study showed that addition of ethyl acetate and ethanol‐ethyl acetate extracts could extend the sunflower and rapeseed oils shelf‐life by protecting oils from further decomposition that naturally occurs during thermal treatments.     

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.     

Studies on the enzymatic synthesis of lipophilic derivatives of natural antioxidants

The esterification of some natural antioxidants such as cinnamic acid derivatives and ascorbic acid in non-aqueous media, catalyzed by immobilized lipases from Candida antarctica and Rhizomucor miehei, was investigated. The alcohol chain length affected the rate of esterification of cinnamic acids by both lipases. Higher reaction rates were observed when the esterification was carried out with medium- or long-chain alcohols. The rate also depended on aromatic acid structure. The reactivity of the carboxylic function of the cinnamic acids was affected by electron-donating substituents in the aromatic ring. Higher yields were observed for the esterification of p-hydroxyphenylacetic acid (97%) catalyzed by C. antarctica lipase and for the esterification of cinnamic acid (59%) catalyzed by R. miehei lipase. Candida antarctica lipase was more suitable for producing ascorbic acid fatty esters, catalyzing with a relatively high yield (up to 65% within 24 h) the regioselective esterification of ascorbic acid with various fatty acids in 2-methyl-2-propanol. The reaction rate and yield depended on the fatty acid chain length and on the molar ratio of reactants. All ascorbic acid fatty esters produced by this procedure exhibited a significant antioxidant activity in a micellar substrate composed of linoleic acid.     

肉桂酸抑制酪氨酸酶催化反应的动力学研究

在30℃,pH=6.8的Na2HPO4-NaH2PO4缓冲体系中,采用酶动力学方法研究了肉桂酸对酪氨酸酶单酚酶和二酚酶活力的抑制动力学.实验结果表明,肉桂酸对酪氨酸酶单酚酶和二酚酶活性均有良好抑制作用,对单酚酶和二酚酶活力的相对抑制率达到50%的肉桂酸浓度(IC50)约分别为0.37 mmol.L-1和0.61 mmol.L-1,比熊果苷抑制二酚酶活性的IC50值5.3 mmol.L-1小得多.肉桂酸能明显延长单酚酶的迟滞时间,0.4 mmol.L-1肉桂酸能使迟滞时间由1.1 min延长至2.3 min.Lineweaver-Burk图显示肉桂酸对二酚酶的抑制作用表现为非竞争性抑制,表观米氏常数(Km)为0.68 mmol.L-1,抑制常数(Kl)为058 mmol.L-1.     

Effect of Steric Structure on the Mechanism of Antioxidant Activity of Alkyl Gallates in Soybean Oil Triacylglycerols—A Kinetic Approach

From an interfacial phenomena standpoint, the effect of the alkyl chain length is evaluated on the mechanism of antioxidant activity of gallic acid ester derivatives (methyl, propyl, octyl, dodecyl, and stearyl gallates) in bulk phase oil. A combinational kinetic model is used to estimate the oxidation kinetic parameters, such as induction period, the maximum concentration of lipid hydroperoxides, and critical reverse micelle concentration. These kinetic parameters are estimated much better with the combinational model compared to the tangent method. The nonlinear behavior is observed for inhibitory activities of homologous series of antioxidants in soybean triacylglycerols. In terms of different kinetics parameters, including antioxidant effectiveness and activity, methyl gallate has the highest inhibitory effect during lipid peroxidation. Gallic acid and alkyl gallates are able to protect bulk oils against peroxidation (induction period > 336 h) in terms of the extent of their participation in the main reaction of chain termination and pro-oxidative side reactions of chain initiation, and anti-oxidative side reactions of chain propagation. Practical Applications: This work explains the effect of the esterification in the inhibitory activity of alkyl gallates, mechanism action of alkyl gallates in bulk oil systems, antiradical potency as a function of the interfacial phenomena, and free radical chain mechanism, the impact of antioxidant activity on critical reverse micelle concentration of hydroperoxides. Moreover, in this study, it is confirmed that the combinational kinetic model can be employed as a reliable method for determining the oxidation kinetic parameters.     

肉桂酸及其衍生物的应用与开发

介绍了肉桂酸及其衍生物的应用和市场开发前景.为肉桂酸的综合利用提供参考.     

Oregano flavonoids as lipid antioxidants

Oregano (Origanum vulgare L.) leaves were successively extracted with hexane, ethyl ether, ethyl acetate and ethanol. The ethanol extract was reextracted in a separatory funnel with petroleum ether, ethyl ether, ethyl acetate and butanol. The ethyl ether layer was the most effective in stabilizing lard against oxidation, with activity equal to butylated hydroxytoluene. It also showed antioxidant activity when tested on vegetable oils under storage or frying conditions. The main antioxidant factors isolated from the ethyl ether layer consisted of flavonoids. Chromatographic and spectrophotometric analysis demonstrated the presence of the flavone apigenin, the flavanone, eriodictyol and the dihydroflavonols, dihydrokaempferol and dihydroquercetin.     

超临界水中乙酸氧化的研究进展

超临界水氧化技术是一种快速彻底降解废水中有机物质的新型处理技术。在超临界水氧化有机物中 ,乙酸被认为是一种中间产物 ,乙酸氧化是反应速率的控制步骤 ,其氧化动力学的研究对反应器设计具有重要意义。大部分研究都集中在动力学参数和反应条件如温度、压力、密度和停留时间上。最近的研究发现加入二氧化锰等催化剂 ,可缓和反应温度、压力条件 ,以达到高效节能的目的。综述了目前在超临界水氧化乙酸动力学方面的研究进展。对连续平推流或间歇反应器中实验数据用幂指数曲线拟合得到的动力学方程表明 ,乙酸氧化为一级反应     

间二甲苯液相催化氧化动力学研究

通过对四个不同初始反应物浓度下的实验数据拟合,得到反应动力学模型的动力学参数。利用此模型得到的180℃,185℃,190℃,195℃下的反应速率常数与Arrhenius方程相符合,得到180~195℃反应活化能40~76 kJ/mol,其中间羧基苯甲醛(3-CBA)氧化活化能最高,说明其受温度的影响最大,间甲基苯甲酸(MT)氧化活化能次之。MT氧化为3-CBA为反应控制步骤。