植物多酚对皮革中Cr（Ⅵ）的防治机理及防治作用研究
|
摘要
Cr(VI)由于具有致癌作用,而引起人们对皮革中Cr(VI)的高度关注。研究证明皮革存在的微量Cr(VI)是在皮革中不饱和油脂氧化的过程中,受协同效应影响,由作为鞣剂的皮革中的Cr(Ⅲ)转变而来的。而铬鞣暂时无可替代的,如何防止Cr(Ⅲ)转变为Cr(VI)成为皮革行业的一道坎。
大量研究的基础上,我们发现植物多酚具有对上述转变的抑制作用。我们对植物多酚的抗氧化性和对皮革中Cr(VI)的防治作用进行了深入的研究,合成了一种专门解决Cr(VI)问题的防治助剂,并应用于生产实际中。
具体研究内容包括:
研究酚羟基化合物中最基本的几种单环多羟基酚对皮革中油脂氧化和Cr(Ⅲ)氧化为Cr(VI)的抑制作用。为了克服皮革结构和皮革中各种化合物对试验的影响,特用海绵模拟皮革体系,成分单一的油酸模拟不饱和加脂剂,让铬液、油脂和酚类物质等化学物质在海绵这种载体上进行反应。并定期测定油酸的过氧化值、碘值及Cr(VI)含量,从而研究不同结构的几种多羟基单酚与其对油酸抗氧化性能和Cr(VI)防治作用的关系。同时,辅助IR和GC/MS对反应的过程进行了监测。试验结果表明单环多羟基酚对油酸过氧化有明显的抑制作用,可以很好的减缓油酸的过氧化速度,降低油酸中的过氧化物的产出量。同时多羟基单酚也可以减缓和抑制油酸中的双键被氧化。各种不同的单环多羟基酚对油酸体系过氧化的抑制作用是不同的,基本上是三羟基酚大于二羟基酚,即随羟基数目的增加,酚的抗氧化作用加强;邻位羟基大于对位羟基;羟基对位的羧基具有吸收电子的能力,会削弱酚对氧化作用的抑制能力。Cr(Ⅲ)被氧化为Cr(VI)的可能性与体系中的过氧化值密切相关,过氧化值高,被氧化为Cr(Ⅲ)被氧化为Cr(VI)的量大,反之亦然。当体系中存在着酚类物质时,油脂的过氧化反应受到抑制,Cr(Ⅲ)被氧化为Cr(VI)的反应也受到抑制。在油脂氧化产生的各自由基对Cr(VI)生成的影响上,羟基自由基是Cr(VI)生成的主要自由基,而羟基自由基的生成是从α-H自氧化引发造成的一系列自由基反应造成的,因此,在Cr(VI)防治上抑制α-H的活性是Cr(VI)防治的关键,清除羟基自由基的能力是决定Cr(VI)防治最终效果的一个重要的衡量指标。
在研究了单环多羟基酚的基础上,我们对多环多羟基酚进一步研究,研究没食子单宁橡椀和塔拉及其小分子单宁酸没食子酸和鞣花酸的还原性、抗氧化性与其对Cr(Ⅲ)氧化为Cr(VI)防治作用的相关性。鉴于植物多酚的酚羟基数目直接影响其抗氧化性和还原性,本文对四种样品的测试全部在总酚值相同的情况下进行的。实验在样品总酚值相同的浓度条件下,采用铁氰化钾还原光度法表征其还原性的强弱,连苯三酚红褪色光度法测其对羟基自由基的清除率,连苯三酚比色光度法测其对过氧阴离子自由基的清除率。样品对Cr(Ⅲ)氧化为Cr(VI)的防治能力测试:用油酸模拟不饱和加脂剂,将其与铬液、四种等酚值的样品分别混合于聚酯海绵中,然后将海绵放于温度55℃,相对湿度17%的恒温恒湿箱中加热,每隔三天测海绵中Cr(VI)的含量,共测试14天。
主要结论:实验中所用的没食子类单宁及其水解单体由于其活性酚羟基的存在,具有还原性和抗氧化性,及对DPPH自由基、羟基自由基、超氧阴离子自由基、脂质过氧自由基的清除能力,因而对皮革中的三价铬转变为Cr(VI)的反应具有一定的抑制作用。没食子酸类单宁对皮革中Cr(VI)的防治作用,不仅与其还原性、抗氧化性及对DPPH自由基、羟基自由基、超氧阴离子自由基、脂质过氧自由基的清除能力相关而且与其对Cr(Ⅲ)的络合能力也密切相关。在四个体系中,没食子酸二内酯鞣花酸体系对Cr(VI)的抑制作用最好,这不仅是其具有较好的还原性、较好的抗氧化性及自由基清除能力而且对Cr(Ⅲ)具有较好的络合作用决定的。没食子酸类单宁对Cr(VI)的抑制机理不仅是通过邻位酚羟基失氢,捕捉自由基,成为更加稳定的半醌结构,而且在其失氢后,与Cr(Ⅲ)络合,进而形成螯合物,减少游离Cr(Ⅲ)的数量,从而达到防治Cr(VI)产生的作用。没食子酸类丹宁在皮革Cr(VI)防治中具体应用时,在考虑其具有一定的还原性,抗氧化性的基础上,慎重考虑其与Cr(Ⅲ)的络合能力才是决定其对皮革Cr(VI)最终防治效果的决定因素。
在选择了鞣花酸作为最佳抗氧化剂以后,我们以鞣花酸为研究对象,研究了明胶对鞣花酸抗羟基自由基,DPPH自由基,超氧阴离子自由基,脂质过氧自由基的影响,采取以海绵模拟皮革环境,油酸模拟加脂剂,胶原模拟皮革纤维,用铬液、油酸、鞣花酸、明胶在海绵内进行老化试验,优化鞣花酸的用量,同时进一步研究在皮革模拟体系中,在胶原存在的情况下,鞣花酸对Cr(VI)的防治作用。试验结果表明:鞣花酸本身具有较强羟基自由基捕捉能力、过氧阴离子自由基清除能力和脂质过氧自由基清除能力,因此,其对Cr(VI)有较好的防治作用。胶原本身对羟基自由基、脂质过氧自由基有一定的清除作用,这种作用是与其对金属离子的络合作用紧密相关。当鞣花酸和胶原等质量作用时,其二者对羟基自由基、过氧阴离子自由基、脂质过氧自由基的抗氧化作用会大大减弱,对皮革中Cr(VI)防治效果最差。
鉴于鞣花酸价格昂贵,成本大;鞣花酸使用量过大后皮革显绿色,影响皮革染色;水溶性差,使用在生产中皮革吸收率低;鞣花酸与皮革加脂剂的相容性差,不能在油脂中大量分散,难以保证它对油脂抗氧化的长期性。鉴于此,研究对鞣花酸进行改性,在保证它抗氧化效果的基础上,提高它的水溶、油溶性,淡化它的颜色,同时试验采用以价格便宜、原料广泛、富含鞣花酸的橡椀为原料，对其进行先水解后酯化改性;对改性后的产品进行抗氧化性测试,采用红外吸收光谱、HPLC和核磁共振对其进行表征。
试验结果表明通过对比醇的种类、催化剂的种类、带水剂的种类对橡椀单宁酯化改性的影响，以羟基自由基清除率、总酚值、产率为考察指标,优选出了最优的酯化剂为异丙醇、最优的带水剂为环己烷,最优的催化剂为硫酸氢钠。通过对酯化剂用量、催化剂用量、反应温度、反应时间、带水剂用量进行正交试验,以羟基自由基清除率、总酚值、产率为考察指标,以橡椀单宁的质量为计，得出最佳改性条件为酯化剂异丙醇用量为8:1、催化剂硫酸氢钠的用量为1:10、试验反应温度为80℃、试验反应时间12h、带水剂环己烷用量4:5,在此条件下,橡椀单宁改性产物对羟基自由基的清除率为80%、总酚值为55%、产率为13%。
最后,我们将合成出来的六价铬专用防治助剂应用于皮革的不同复鞣工序,采用同工艺对比实验改变用量比,最终在80℃的烘箱中和紫外光照老化条件下,对比其Cr(VI)含量优化出Cr(VI)防治助剂的最优应用工艺条件。试验结果表明:在六价铬专用防治助剂的应用生产工艺中,其用量0.3%为最佳用量,在加脂中或加脂后1小时固定前加入,均可达到控制Cr(VI)含量低于3mg/Kg的要求。
Along with the Cr (VI) is as carcinogenic, more and more people pay high attention to Cr (VI) in leather. Studies have shown the existence of the micro Cr (VI) in leather come from the oxidation of Cr (Ⅲ) by the synergistic effect of the oxidation process of unsaturated fatliquoring. As a temporary irreplaceable chrome tanning, how to solve the high Cr(VI) content has become a difficult problem in leather industry.
Based on extensive research, we found the hydroxybenzene have inhibitory effects on these oxidations. our team study on the antioxidant of hydroxybenzene and its prevention on Cr(VI) in leather deeply, synthesize a special agent to prevent Cr(VI) and address the issue of control hexavalent chromium additives, and apply it in leather.
Our studies include:
Breaking down the oxidation of unsaturated oil by hydroxybenzene so as to prevent Cr(Ⅲ) from oxidizing into Cr(VI)was investigated. PVC sponge was used as a reacting carrier, taking the advantage of the sponge’s porous character similarly to the leather. The oleic acid, chrome liquid and different phenols such as pyrocatechin, hydroquinone, gallic acid and pyrogallicoleic acid were absorbed by sponge and then put in box with invariableness temperature and humidity to oxidize deeply. The iodine value, peroxide value of oils and the contents of the Cr(VI) were determined in regular intervals also. The structure change of oleic acid was analysis by IR and GC-MS at different time.
The results showed that the mono cyclic polyhydroxy phenol has inhibitory effect on the oxidation of oleic acid caused byα-H in both speed and output and also on oxidation of double bound synchronously. The different mono cyclic polyhydroxy phenol has the different inhibitory effect on the oxidation of the oleic acid. In generally speaking, the ability to inhibit oxidation ranks decreasingly as follow: trihydroxy phenol, dihydroxy phenol, single hydroxyl phenol, when with same number of hydroxyl, the o-hydroxy phenol, the p-hydroxy phenol, but when the carboxyl, the electron-absorbing group, opposite to the hydroxyl, the ability of polyhydroxy phenol with one ring in oxidation resistance would be weaken. The oxidation possibility of Cr(Ⅲ) into Cr(VI) is closely related to peroxide value. The higher the peroxide value is, the much the quantity of Cr(Ⅲ) oxidized to Cr(VI) is, and vice versa. When the system contains phenol the peroxide of unsaturated lipid could be inhibited and resulted in inhibition of oxidation of Cr(Ⅲ) into Cr(VI). The hydroxyl radical is the main free radical in the effect on Cr(VI) formation by free radicals after lipid oxidation. And the hydroxyl radicals are caused by a series of radical reaction fromα-H autoxidation. Therefore, control activity ofα-H determine the Cr (VI) formation, and the clearance rate of hydroxyl radical is an important indicator on the final Cr (VI) prevention.
Base on the study on the monocyclic polyhydroxy phenol with one ring, our team study further on the polycyclic polyhydroxy phenol. Vegetable extracts, the Valonia, Tara, and the main components of vegetable extracts, the gallic acid, ellagic acid, as test samples are studied to explore the relationship between reducibility antioxidation of these materials and ability to prevent Cr(Ⅲ) from oxidation into Cr(VI).
Abilities of these materials to eliminate free radical were measured by the following tests: Given quantities of materials above on the base of equivalent phenolic value were taken to ascertain reducibility by absorbency method of K3Fe(CN)6 reduce, eliminating ability against hydroxyl free radical by absorbency method of pyrogallol-red fading, eliminating ability against superoxide anion free radical by the absorbency method of pyrogallol autoxidation. These parameters were considered as the index of ability to prevent Cr(Ⅲ) from being oxidized into Cr(VI).
The prevention of samples to Cr(Ⅲ) from being oxidized into Cr(VI) was measured. PVC sponge was used as a reacting carrier, the oleic acid, chrome liquid and different phenols were absorbed by sponge and then put in thermostat/ humidistat at 55℃and 17% relative humidity for 14 days with interval determination the quantity of Cr(VI) against one piece of sponge in groups by first time after two days and then every three days.
Main results: Gallic acid, Tara, ellagic acid and Valonia all have preventive effects on the oxidation of Cr(Ⅲ) in leather because of its active phenolic hydroxyls which have reducibility, antioxidation, the clearance ability of DPPH radical, hydroxyl radical, superoxide anion radical, lipid peroxy radical. The effect to prevent Cr(Ⅲ) from Cr(VI) by vegetable extracts such as members of gallic acid family is closely related to their reducibility, antioxidation and also abilityb of complex with Cr(Ⅲ). All of the four samples, ellagic acid system is best in preventing Cr(Ⅲ) from Cr(VI),which is attributed to stronger antioxidation and reducibility, also to greater ability of complex with Cr(Ⅲ). The mechanism to prevent Cr(Ⅲ) from Cr(VI) by vegetable extracts such as members of gallic acid family is forming semi-quinone structure of ortho-phenolic hydroxyl, releasing the free hydrogen, capturing free radicals and meanwhile complexing with Cr(Ⅲ), forming chelates to reduce free Cr(Ⅲ) in the system. Based on study of mechanism above, when the chemicals with ability to prevent Cr(Ⅲ) from Cr(VI) is designed it should be taken into consideration: reducibility, antioxidation, the complexation with Cr(Ⅲ).
After ellagic acid was selected as the best antioxidant, our team studied on the effect of gelatin on the clearance ability of ellagic acid against hydroxyl radical, DPPH radical, superoxide anion radical, lipid peroxy radicals. The experiment used PVC sponge as leather environment, oleic acid as fatliquoring, gelatin as collagen fibers. The sponge with chromium solution, oleic acid, ellagic acid was taken in aging test to optimize the adding amount of ellagic acid and study the complexation of ellagic acid, free Cr(VI) and gelation.
The results showed that: ellagic acid has a strong clearance ability to hydroxyl radical, superoxide anion radical, lipid peroxy radical and also the prevention of Cr(VI) formation. Collagen itself has certain clearance effect on hydroxyl radical, lipid peroxy radical through the complex with metal ions. When the Ellagic acid and collagen proportional mix, the clearance effect on hydroxyl radical, superoxide anion radical, lipid peroxy radicals will be greatly weakened, and also the prevention of Cr(VI) formation.
In view of ellagic acid is expensive, makes the leather green after excessive using, causes the problem in dyeing, has poor water solubility and low absorption in the leather processing, has poor compatibility with fatliquoring and can not be dispersed in oil largely which is disadvantage to its long-term antioxidant effect. So ellagic acid need be modified to ensure its antioxidant effect and improve its water-soluble oil-soluble, make its color pale. The experiment used the Valonia with cheap, raw materials extensive, rich in ellagic acid as subject. Then the Valonia was first hydrolyzed and next esterified, meanwhile the modified products were tested by antioxidation test and analyzed by IR, HPLC and NMR.
The results show that: by comparing the effect of types of alcohol, catalyst, water-carrying agent on the Valonia modification, standard by hydroxyl radical scavenging, total phenol value, the yield, isopropyl alcohol is the best esterification agent, the best water-carrying agent is cyclohexane, the best catalyst is sodium bisulfate. The valonia extract hydrolysis-esterification modified condition were confined through by single-factor test and orthogonal experiment. Results revealed that the optimum modified conditions were as follow: according to the quality of valonic extract, alcohol consumption 8:1, the amount of catalyst 1:10, reaction temperature 80℃, reaction time 12h, the dosage of water entrainer 4: 5. Under this condition, the phenol content and the hydroxyl radical scavenging rate of modified product were highest, and the yelled was at 13%. Finally, The modified product was used in leather retanning process with different procedure and amount. The application process was optimized in Cr(VI) prevention at ageing of 80℃and UV irradiation conditions.The results show that: the best application amount of the modified product is 0.3%, the best adding time is 1 hour after adding fatliquoring. And adding in fatliquoring and 1 hour after fatliquoring both can make the Cr(VI) Content Less than 3mg/Kg.
大量研究的基础上,我们发现植物多酚具有对上述转变的抑制作用。我们对植物多酚的抗氧化性和对皮革中Cr(VI)的防治作用进行了深入的研究,合成了一种专门解决Cr(VI)问题的防治助剂,并应用于生产实际中。
具体研究内容包括:
研究酚羟基化合物中最基本的几种单环多羟基酚对皮革中油脂氧化和Cr(Ⅲ)氧化为Cr(VI)的抑制作用。为了克服皮革结构和皮革中各种化合物对试验的影响,特用海绵模拟皮革体系,成分单一的油酸模拟不饱和加脂剂,让铬液、油脂和酚类物质等化学物质在海绵这种载体上进行反应。并定期测定油酸的过氧化值、碘值及Cr(VI)含量,从而研究不同结构的几种多羟基单酚与其对油酸抗氧化性能和Cr(VI)防治作用的关系。同时,辅助IR和GC/MS对反应的过程进行了监测。试验结果表明单环多羟基酚对油酸过氧化有明显的抑制作用,可以很好的减缓油酸的过氧化速度,降低油酸中的过氧化物的产出量。同时多羟基单酚也可以减缓和抑制油酸中的双键被氧化。各种不同的单环多羟基酚对油酸体系过氧化的抑制作用是不同的,基本上是三羟基酚大于二羟基酚,即随羟基数目的增加,酚的抗氧化作用加强;邻位羟基大于对位羟基;羟基对位的羧基具有吸收电子的能力,会削弱酚对氧化作用的抑制能力。Cr(Ⅲ)被氧化为Cr(VI)的可能性与体系中的过氧化值密切相关,过氧化值高,被氧化为Cr(Ⅲ)被氧化为Cr(VI)的量大,反之亦然。当体系中存在着酚类物质时,油脂的过氧化反应受到抑制,Cr(Ⅲ)被氧化为Cr(VI)的反应也受到抑制。在油脂氧化产生的各自由基对Cr(VI)生成的影响上,羟基自由基是Cr(VI)生成的主要自由基,而羟基自由基的生成是从α-H自氧化引发造成的一系列自由基反应造成的,因此,在Cr(VI)防治上抑制α-H的活性是Cr(VI)防治的关键,清除羟基自由基的能力是决定Cr(VI)防治最终效果的一个重要的衡量指标。
在研究了单环多羟基酚的基础上,我们对多环多羟基酚进一步研究,研究没食子单宁橡椀和塔拉及其小分子单宁酸没食子酸和鞣花酸的还原性、抗氧化性与其对Cr(Ⅲ)氧化为Cr(VI)防治作用的相关性。鉴于植物多酚的酚羟基数目直接影响其抗氧化性和还原性,本文对四种样品的测试全部在总酚值相同的情况下进行的。实验在样品总酚值相同的浓度条件下,采用铁氰化钾还原光度法表征其还原性的强弱,连苯三酚红褪色光度法测其对羟基自由基的清除率,连苯三酚比色光度法测其对过氧阴离子自由基的清除率。样品对Cr(Ⅲ)氧化为Cr(VI)的防治能力测试:用油酸模拟不饱和加脂剂,将其与铬液、四种等酚值的样品分别混合于聚酯海绵中,然后将海绵放于温度55℃,相对湿度17%的恒温恒湿箱中加热,每隔三天测海绵中Cr(VI)的含量,共测试14天。
主要结论:实验中所用的没食子类单宁及其水解单体由于其活性酚羟基的存在,具有还原性和抗氧化性,及对DPPH自由基、羟基自由基、超氧阴离子自由基、脂质过氧自由基的清除能力,因而对皮革中的三价铬转变为Cr(VI)的反应具有一定的抑制作用。没食子酸类单宁对皮革中Cr(VI)的防治作用,不仅与其还原性、抗氧化性及对DPPH自由基、羟基自由基、超氧阴离子自由基、脂质过氧自由基的清除能力相关而且与其对Cr(Ⅲ)的络合能力也密切相关。在四个体系中,没食子酸二内酯鞣花酸体系对Cr(VI)的抑制作用最好,这不仅是其具有较好的还原性、较好的抗氧化性及自由基清除能力而且对Cr(Ⅲ)具有较好的络合作用决定的。没食子酸类单宁对Cr(VI)的抑制机理不仅是通过邻位酚羟基失氢,捕捉自由基,成为更加稳定的半醌结构,而且在其失氢后,与Cr(Ⅲ)络合,进而形成螯合物,减少游离Cr(Ⅲ)的数量,从而达到防治Cr(VI)产生的作用。没食子酸类丹宁在皮革Cr(VI)防治中具体应用时,在考虑其具有一定的还原性,抗氧化性的基础上,慎重考虑其与Cr(Ⅲ)的络合能力才是决定其对皮革Cr(VI)最终防治效果的决定因素。
在选择了鞣花酸作为最佳抗氧化剂以后,我们以鞣花酸为研究对象,研究了明胶对鞣花酸抗羟基自由基,DPPH自由基,超氧阴离子自由基,脂质过氧自由基的影响,采取以海绵模拟皮革环境,油酸模拟加脂剂,胶原模拟皮革纤维,用铬液、油酸、鞣花酸、明胶在海绵内进行老化试验,优化鞣花酸的用量,同时进一步研究在皮革模拟体系中,在胶原存在的情况下,鞣花酸对Cr(VI)的防治作用。试验结果表明:鞣花酸本身具有较强羟基自由基捕捉能力、过氧阴离子自由基清除能力和脂质过氧自由基清除能力,因此,其对Cr(VI)有较好的防治作用。胶原本身对羟基自由基、脂质过氧自由基有一定的清除作用,这种作用是与其对金属离子的络合作用紧密相关。当鞣花酸和胶原等质量作用时,其二者对羟基自由基、过氧阴离子自由基、脂质过氧自由基的抗氧化作用会大大减弱,对皮革中Cr(VI)防治效果最差。
鉴于鞣花酸价格昂贵,成本大;鞣花酸使用量过大后皮革显绿色,影响皮革染色;水溶性差,使用在生产中皮革吸收率低;鞣花酸与皮革加脂剂的相容性差,不能在油脂中大量分散,难以保证它对油脂抗氧化的长期性。鉴于此,研究对鞣花酸进行改性,在保证它抗氧化效果的基础上,提高它的水溶、油溶性,淡化它的颜色,同时试验采用以价格便宜、原料广泛、富含鞣花酸的橡椀为原料，对其进行先水解后酯化改性;对改性后的产品进行抗氧化性测试,采用红外吸收光谱、HPLC和核磁共振对其进行表征。
试验结果表明通过对比醇的种类、催化剂的种类、带水剂的种类对橡椀单宁酯化改性的影响，以羟基自由基清除率、总酚值、产率为考察指标,优选出了最优的酯化剂为异丙醇、最优的带水剂为环己烷,最优的催化剂为硫酸氢钠。通过对酯化剂用量、催化剂用量、反应温度、反应时间、带水剂用量进行正交试验,以羟基自由基清除率、总酚值、产率为考察指标,以橡椀单宁的质量为计，得出最佳改性条件为酯化剂异丙醇用量为8:1、催化剂硫酸氢钠的用量为1:10、试验反应温度为80℃、试验反应时间12h、带水剂环己烷用量4:5,在此条件下,橡椀单宁改性产物对羟基自由基的清除率为80%、总酚值为55%、产率为13%。
最后,我们将合成出来的六价铬专用防治助剂应用于皮革的不同复鞣工序,采用同工艺对比实验改变用量比,最终在80℃的烘箱中和紫外光照老化条件下,对比其Cr(VI)含量优化出Cr(VI)防治助剂的最优应用工艺条件。试验结果表明:在六价铬专用防治助剂的应用生产工艺中,其用量0.3%为最佳用量,在加脂中或加脂后1小时固定前加入,均可达到控制Cr(VI)含量低于3mg/Kg的要求。
Along with the Cr (VI) is as carcinogenic, more and more people pay high attention to Cr (VI) in leather. Studies have shown the existence of the micro Cr (VI) in leather come from the oxidation of Cr (Ⅲ) by the synergistic effect of the oxidation process of unsaturated fatliquoring. As a temporary irreplaceable chrome tanning, how to solve the high Cr(VI) content has become a difficult problem in leather industry.
Based on extensive research, we found the hydroxybenzene have inhibitory effects on these oxidations. our team study on the antioxidant of hydroxybenzene and its prevention on Cr(VI) in leather deeply, synthesize a special agent to prevent Cr(VI) and address the issue of control hexavalent chromium additives, and apply it in leather.
Our studies include:
Breaking down the oxidation of unsaturated oil by hydroxybenzene so as to prevent Cr(Ⅲ) from oxidizing into Cr(VI)was investigated. PVC sponge was used as a reacting carrier, taking the advantage of the sponge’s porous character similarly to the leather. The oleic acid, chrome liquid and different phenols such as pyrocatechin, hydroquinone, gallic acid and pyrogallicoleic acid were absorbed by sponge and then put in box with invariableness temperature and humidity to oxidize deeply. The iodine value, peroxide value of oils and the contents of the Cr(VI) were determined in regular intervals also. The structure change of oleic acid was analysis by IR and GC-MS at different time.
The results showed that the mono cyclic polyhydroxy phenol has inhibitory effect on the oxidation of oleic acid caused byα-H in both speed and output and also on oxidation of double bound synchronously. The different mono cyclic polyhydroxy phenol has the different inhibitory effect on the oxidation of the oleic acid. In generally speaking, the ability to inhibit oxidation ranks decreasingly as follow: trihydroxy phenol, dihydroxy phenol, single hydroxyl phenol, when with same number of hydroxyl, the o-hydroxy phenol, the p-hydroxy phenol, but when the carboxyl, the electron-absorbing group, opposite to the hydroxyl, the ability of polyhydroxy phenol with one ring in oxidation resistance would be weaken. The oxidation possibility of Cr(Ⅲ) into Cr(VI) is closely related to peroxide value. The higher the peroxide value is, the much the quantity of Cr(Ⅲ) oxidized to Cr(VI) is, and vice versa. When the system contains phenol the peroxide of unsaturated lipid could be inhibited and resulted in inhibition of oxidation of Cr(Ⅲ) into Cr(VI). The hydroxyl radical is the main free radical in the effect on Cr(VI) formation by free radicals after lipid oxidation. And the hydroxyl radicals are caused by a series of radical reaction fromα-H autoxidation. Therefore, control activity ofα-H determine the Cr (VI) formation, and the clearance rate of hydroxyl radical is an important indicator on the final Cr (VI) prevention.
Base on the study on the monocyclic polyhydroxy phenol with one ring, our team study further on the polycyclic polyhydroxy phenol. Vegetable extracts, the Valonia, Tara, and the main components of vegetable extracts, the gallic acid, ellagic acid, as test samples are studied to explore the relationship between reducibility antioxidation of these materials and ability to prevent Cr(Ⅲ) from oxidation into Cr(VI).
Abilities of these materials to eliminate free radical were measured by the following tests: Given quantities of materials above on the base of equivalent phenolic value were taken to ascertain reducibility by absorbency method of K3Fe(CN)6 reduce, eliminating ability against hydroxyl free radical by absorbency method of pyrogallol-red fading, eliminating ability against superoxide anion free radical by the absorbency method of pyrogallol autoxidation. These parameters were considered as the index of ability to prevent Cr(Ⅲ) from being oxidized into Cr(VI).
The prevention of samples to Cr(Ⅲ) from being oxidized into Cr(VI) was measured. PVC sponge was used as a reacting carrier, the oleic acid, chrome liquid and different phenols were absorbed by sponge and then put in thermostat/ humidistat at 55℃and 17% relative humidity for 14 days with interval determination the quantity of Cr(VI) against one piece of sponge in groups by first time after two days and then every three days.
Main results: Gallic acid, Tara, ellagic acid and Valonia all have preventive effects on the oxidation of Cr(Ⅲ) in leather because of its active phenolic hydroxyls which have reducibility, antioxidation, the clearance ability of DPPH radical, hydroxyl radical, superoxide anion radical, lipid peroxy radical. The effect to prevent Cr(Ⅲ) from Cr(VI) by vegetable extracts such as members of gallic acid family is closely related to their reducibility, antioxidation and also abilityb of complex with Cr(Ⅲ). All of the four samples, ellagic acid system is best in preventing Cr(Ⅲ) from Cr(VI),which is attributed to stronger antioxidation and reducibility, also to greater ability of complex with Cr(Ⅲ). The mechanism to prevent Cr(Ⅲ) from Cr(VI) by vegetable extracts such as members of gallic acid family is forming semi-quinone structure of ortho-phenolic hydroxyl, releasing the free hydrogen, capturing free radicals and meanwhile complexing with Cr(Ⅲ), forming chelates to reduce free Cr(Ⅲ) in the system. Based on study of mechanism above, when the chemicals with ability to prevent Cr(Ⅲ) from Cr(VI) is designed it should be taken into consideration: reducibility, antioxidation, the complexation with Cr(Ⅲ).
After ellagic acid was selected as the best antioxidant, our team studied on the effect of gelatin on the clearance ability of ellagic acid against hydroxyl radical, DPPH radical, superoxide anion radical, lipid peroxy radicals. The experiment used PVC sponge as leather environment, oleic acid as fatliquoring, gelatin as collagen fibers. The sponge with chromium solution, oleic acid, ellagic acid was taken in aging test to optimize the adding amount of ellagic acid and study the complexation of ellagic acid, free Cr(VI) and gelation.
The results showed that: ellagic acid has a strong clearance ability to hydroxyl radical, superoxide anion radical, lipid peroxy radical and also the prevention of Cr(VI) formation. Collagen itself has certain clearance effect on hydroxyl radical, lipid peroxy radical through the complex with metal ions. When the Ellagic acid and collagen proportional mix, the clearance effect on hydroxyl radical, superoxide anion radical, lipid peroxy radicals will be greatly weakened, and also the prevention of Cr(VI) formation.
In view of ellagic acid is expensive, makes the leather green after excessive using, causes the problem in dyeing, has poor water solubility and low absorption in the leather processing, has poor compatibility with fatliquoring and can not be dispersed in oil largely which is disadvantage to its long-term antioxidant effect. So ellagic acid need be modified to ensure its antioxidant effect and improve its water-soluble oil-soluble, make its color pale. The experiment used the Valonia with cheap, raw materials extensive, rich in ellagic acid as subject. Then the Valonia was first hydrolyzed and next esterified, meanwhile the modified products were tested by antioxidation test and analyzed by IR, HPLC and NMR.
The results show that: by comparing the effect of types of alcohol, catalyst, water-carrying agent on the Valonia modification, standard by hydroxyl radical scavenging, total phenol value, the yield, isopropyl alcohol is the best esterification agent, the best water-carrying agent is cyclohexane, the best catalyst is sodium bisulfate. The valonia extract hydrolysis-esterification modified condition were confined through by single-factor test and orthogonal experiment. Results revealed that the optimum modified conditions were as follow: according to the quality of valonic extract, alcohol consumption 8:1, the amount of catalyst 1:10, reaction temperature 80℃, reaction time 12h, the dosage of water entrainer 4: 5. Under this condition, the phenol content and the hydroxyl radical scavenging rate of modified product were highest, and the yelled was at 13%. Finally, The modified product was used in leather retanning process with different procedure and amount. The application process was optimized in Cr(VI) prevention at ageing of 80℃and UV irradiation conditions.The results show that: the best application amount of the modified product is 0.3%, the best adding time is 1 hour after adding fatliquoring. And adding in fatliquoring and 1 hour after fatliquoring both can make the Cr(VI) Content Less than 3mg/Kg.
引文
[1]张淑华.技术性贸易壁垒对我国皮革行业的影响及对策[J].陕西科技大学学报,2004,22(3):1-4.
[2] Ausar S F, Beltramo D M, Castagna L F, et al. Treatment of theumatoid arthritis by oral administration of bovine tracheal type(Ⅱ): collagen. Rbeumatol Int, 2001, 20: 138-144.
[3] Maria Eugenia Maciel , Gerardo Daniel Castro,Jose Alberto Castro.Inhibition of the Rat Breast Cytosolic Bioactivation of Ethanol to Acetaldehyde by Some Plant Polyphenols and Folic Acid[J]. Nutrition and Cancer, 2004, 49(1): 94-99.
[4]陈春添.皮革中Cr(VI)的成因及其检测[J].皮革化工,2003,20(4):24-26.
[5]刘素英,丁绍兰等.聚焦皮革中的六价铬及其测定方法[J].中国皮革,2002,31(5):28-33.
[6] IARC: IARC monographs on the evaluation of carciongenic risks to humans, chromium nickel and welding lyon[Z]. France, IARC, 1990, 49:187.
[7]易超,于素芳.六价铬化合物致肺癌机制的研究进展[J].中国公共卫生,2006,22(4):497-498.
[8] Maria Eugenia Maciel, Gerardo Daniel Castro, Jose Alberto Castro. Inhibition of the Rat Breast Cytosolic Bioactivation of Ethanol to Acetaldehyde by Some Plant Polyphenols and Folic Acid[J]. Nutrition and Cancer, 2004, 49(1):94-99.
[9] Stephane George, Pierre Brat, pascaline Alter, etal. Rapid Determination of Polyphenols and Vitamin C in Plant-Derived Products[J]. Agricultutal and Food Chemistry, 2005, 53(5):1370-1373.
[10]戴伯初.关于皮革中的六价铬[J].中国皮革,2000,29(19):23.
[11] ZHANG Yu-ping, JIANG Shou-wei, YIN Zhong-wei. Genetic Algorithms to the Nesting Problem in Leather Manufacturing Industry[J]. Journal of Donghua University, 2005, 22(1): 90-95.
[12] Apostolis Agalias, Prokopios Magiatis, Alexios Leandros Skaltsounis, etal. A New Process for the Management of Olive Oil Mill Waste Water and Recovery of Natural Antioxidants[J]. Agricultutal and Food Chemistry, 2007, 55(7): 2671-2676.
[13] Donghee Park, Yeoung Sang Yun, Jong Moon Park. Reduction of Hexavalent Chromium with the Brown Seaweed Ecklonia Biomass[J]. Enviroumental Science and Technology, 2004, 38(18): 4860-4864.
[14] Chunming Su, Ralph D. Ludwig. Treatment of Hexavalent Chromium in Chromite Ore Processing Solid Waste Using a Mixed Reductant Solution of Ferrous Sulfate and Sodium Dithionite[J]. Enviroumental Science and Technology, 2005, 39(16): 6208-6212.
[15] L. Dupont, E. Guillon. Removal of Hexavalent Chromium with a Lignocellulosic Substrate Extracted from Wheat Bran[J]. Enviroumental Science and Technology, 2003, 37(18): 4235-4241.
[16]孙根行,俞从正,曹洁,等.坚木栲胶对皮革中六价铬预防作用的研究[J].中国皮革,2003,32(1):6-9.
[17]宋立江,狄莹等.植物多酚研究与利用的意义及发展趋势[J].化学进展,2000,12(2):161-170.
[18]石碧,狄莹.植物多酚[M].北京:科学出版社,2000:1-20.
[19] Amita Kaul, Krishan Khanduja. Plant Polyphenols Inhibit Benzoyl Peroxide-Induced Superoxide Anion Radical Production and Diacylglyceride Formation in Murine Peritoneal macrophages[J]. Nutrition and Cancer, 2000, 35(2): 207-211.
[20] Wim Broothaerts, Joan Mc Pherson, Baochun Li, etal. Fast Apple(Malus-domestica)and Tobacco (Nicotiana tobacum)Leaf Polyphenol Oxidase Activity Assay for Screening Transgenic Plants[J]. Agricultutal and Food Chemistry, 2000, 48(12): 5924-5928.
[21] Nadejzda Haider, Sigbritt Karlsson. Kinetics of Migration of Antioxidants from Polyolefins in Natural Environments as a Basis for Bioconversion Studies[J]. BiomacromLecules, 2000, 1(3): 481-487.
[22] B. N. Shyamala, M. Madhava Naidu, G. Sulochanamma, etal. Studies on the Antioxidant Activities of Natural Vanilla Extract and Its Constituent Compounds through in Vitro Models[J]. Agricultutal and Food Chemistry, 2007, 55(19): 7738-7743.
[23]中国林业科学研究院科技情报研究所.国外栲胶技术[M].北京:中国林业科学出版社,1981:1-4.
[24] K. Indira Priyadarsini, Sujata M. Khopde, S. Santosh Kumar, etal. FreeRadical Studies of Ellagic Acid, a Natural Phenolic Antioxidant[J]. Agricultutal and Food Chemistry, 2002, 50(7): 2200-2206.
[25] Claude Alain Calliste, Patrick Trouillas, Daovy Paulette Allais, etal. Castanea sativa Mill. Leaves as New Sources of Natural Antioxidant: An Electronic Spin Resonance Study[J]. Agricultutal and Food Chemistry, 2005, 53(2): 282-288.
[26] Nagendran Balasundram, Kalyana Sundram,Samir Samman.Phenolic compounds in plants and agri-industrial by-products:Antioxidant activity, occurrence, and potential uses [J].Food Chemistry,2005,5:1-13.
[27] Haslam E. Plant Polyp henols—Vegetable Tannins Revisited[D]. Cambridge University Press, Cambridge, 1989: 170.
[28] Foo Y, Porter L. Vegetable Tannins[J]. Appita, 1986, 39(6): 477-480.
[29]贺近恪,布朗A.黑荆树及其利用[J].中国林业出版社,北京,1991,261.
[30] Hemingway R, Laks P. Plant Polyphenols[M]. New York: Plenum Press, 1992: 421-436.
[31]邢淑婕,刘开华,刘学彦.植物多酚对脂肪酸合酶活性抑制作用的研究[J].食品研究与开发,2007,128(6):37-39.
[32]哈本JB.黄酮类化合物[M].北京:科学出版社,1983:51-56.
[33]杨华祥,马建中,杨宗邃等.栲胶改性研究综述[J].皮革化工,1997,4:11-16.
[34]杨宗邃.鞣制化学[M].西北轻工业学院,1994,(59):86.
[35] Dikmelik Y. Faculty of Agriculture Bornova-Izmir[D]. Greece,Aegean University, 2003.
[36] Ismet Hakimoglu.橡椀栲胶的应用[J].中国皮革,2006,35(17): 7-8.
[37]黄文,石碧等.植物单宁的生物降解[J].化学通报,2002,5: 321-325.
[38] Jeffrey De Graft Johnson, Krzysztof Kolodziejczyk, Maciej Krol, etal. Ferric-Reducing Ability Power of Selected Plant Polyphenols and Their Metabolites: Implications for Clinical Studies on the Antioxidant Effects of Fruits and Vegetable Consumption[J]. Basic and Clinical Pharmacology and Toxicology, 2007, 100: 345-352.
[39] Sweetie R. Kanatt, Ramesh Chander, P. Radhakrishna, etal. Potato Peel Extractsa Natural Antioxidant for Retarding Lipid Peroxidation in Radiation Processed Lamb Meat[J]. Agricultutal and Food Chemistry, 2005, 53(5):1499-1504.
[40] E. Grant Jones, Lori M. Balster. Interaction of a Synthetic Hindered-Phenol with Natural Fuel Antioxidants in the Autoxidation of Paraffins[J]. Energy and Fuels, 2000, 14(3): 640-645.
[41]刘运荣,胡键华.植物多酚的研究进展[J].武汉工业学院学报,2005,12:63-65.
[42] Reed J. Cranberry Flavonoids: Atherosclerosis and Cardiovascular Health[J]. Crit Rev Food Scinutr, 2002, 42(301): 16.
[43] Monica Leopoldini, Nino Russo, Marirosa Toscano. Gas and Liquid Phase Acidity of Natural Antioxidants[J]. Agricultutal and Food Chemistry, 2006, 54(8): 3078-3085.
[44] Aurora Napolitano, Vincenzo Fogliano, Alessio Tafuri, etal. Natural Occurrence of Ochratoxin A and Antioxidant Activities of Green and Roasted Coffees and Corresponding Byproducts[J]. Agricultutal and Food Chemistry, 2007, 55(25): 10499-10504.
[45]陈曾三.植物多酚功能性及其开发利用[J].粮食与油脂,2000,3:40-41.
[46]赵扬帆,郑宝东.植物多酚类物质及其功能学研究进展[J].福建轻纺,2006,11:107-108.
[47] Alberto Macone, Mirella Nardini, Antonio Antonucci, etal. Identification of Aminoethylcysteine Ketimine Decarboxylated Dimer, a Natural Antioxidant, in Dietary Vegetables[J]. Agricultutal and Food Chemistry, 2002, 50(7): 2169-2172.
[48]王建新.天然活性化妆品[M].北京:中国轻纺工业出版社, 1997 :303-307.
[49] Hui Xiang, Su Hua pan. Studies on Human Feal Lens Crystallins under Oxidative Stress and Protective Effects of Tea Polyphenols[J].眼科学报, 1998, 14(3): 170-175.
[50]何有节,狄节,赵宇.等黑荆树皮单宁降解产物的抑菌性能[J].林产化学与工业,1999 ,19(2):1-7.
[51] A Bcress, Wassermamn, T Bruhn. A new Procedure for the isolation of anti-HIV compounds (polysaccharides and polyphenols) from the marine alga Fucus vesicnlosus[J]. Journal of Natural Products, 1993,56(4):478-488.
[52]张国营,李彦勇,何丽娜,等.绿茶及茶多酚抗人轮状病毒的实验[J].茶叶科学,1994, 14: 166-168.
[53]曹进.茶儿茶素影响细胞外糖合成和变异链球菌附着的研究[J].茶叶科学,1996, 16, 57-60.
[54]周丽珠.用栲胶的新型木工胶粘剂的研制[J].林产化工通讯, 2002,36(4):6-8.
[55]王晓东,郎春燕,梁明启.水泥回转窑水冷喷嘴加药防垢方法[J].工业水处理,2002,22(7):51-52.
[56]刘运荣,胡健华.植物多酚的研究进展[J].武汉工业学院学报,2005,24(4):63-65.
[57] Isabel Medina, Isabel Tombo, M. Teresa Satuea Gracia, etal. Effects of Natural Phenolic Compounds on the Antioxidant Activity of Lactoferrin in Liposomes and Oil-in-Water Emulsions[J]. Agricultutal and Food Chemistry, 2002, 50(8): 2392-2399.
[58] Bisanda E T N,Ogola W O,Tesha J V. Characterisation of tannin resin blends for particle applications [J]. Cenment & Concrete Composites. 2003, 25: 593-598.
[59] Lee W. J,Lan W. C.Properties of resorcinol-tannin-formaldehyde copolymer resins prepared from the bark extract of Taiwan acacia and China fir [J]. Bioresource Technology ,2006,97:257-264.
[60]黄占华,方桂珍等.植物单宁的应用及研究进展[J].林产化工通讯,2005,39,(5):39-42.
[61] MatamalaG.Comparison of steel anticorrosive protection formulated with natural tannins extracted from acacia and from pine bark [J]. Corrosion Science, 2000, 42 :1351-1362.
[62]叶秀菁等.石材专用清洗剂[P].中国专利:200410019228.1, 2004-10-01.
[63] Bisanda E T N,Ogola W O,Tesha J V. Characterisation of tannin resin blends for particle applications [J]. Cenment & Concrete Composites. 2003, 25: 593-598.
[64] Lee W. J,Lan W. C.Properties of resorcinol-tannin-formaldehyde copolymer resins prepared from the bark extract of Taiwan acacia and China fir [J]. Bioresource Technology ,2006,97:257-264.
[65]黄占华,方桂珍等.植物单宁的应用及研究进展[J].林产化工通讯,2005,39,(5):39-42.
[66] MatamalaG.Comparison of steel anticorrosive protection formulated with natural tannins extracted from acacia and from pine bark [J].Corrosion Science, 2000, 42 :1351-1362.
[67]叶秀菁等.石材专用清洗剂[P].中国专利:200410019228.1,2004-10-01.
[68]付美云,周立祥.植物多酚在环境保护与农业生产中的应用[J].应用生态学报,2004,15(9):1673-1676.
[69] Ma He-wei, Liao Xue-pin, Liu Xin. Recovery of Platinum(Ⅳ)and Palladium(Ⅱ)by Bayberry Tannin Immobilized Collagen Fiber Membtane From Solution[J]. Journal of Membrane Science, 2006, 278(2): 373-380.
[70]葛学贵,黄少云,马广伟,等.环境矿物SAP化学固沙浆材综合治理荒漠初探[J].岩石矿物学杂志,2001,20(4):511-514.
[71] Canbolat O, Ozkan C. O, Kamalak A. Effects of NaOH Treatment On Condensed Tannin Contents And Gas Production Kinetics of Tree Leaves[J]. Animal Feed Science And Technology, 2007, 138(2): 189-194.
[72] Beauchemin K. A, McGinn S. M, Martinez T. F. Use of Condensed Tannin Extract From Quebracho Trees To Reduce Methane Emissions From Cattle[J]. Journal of Animal Science, 2007, 85(9): 1990-1996.
[73]奚长生,龙来寿,罗翠环,等.栲胶法提取镓的研究[J].湖南有色金属,2004,10(1):11-13.
[74] Kaal. Joeri, Nierop. Klaas G. J, Verstraten. Jacobus M. Interactions Between Tannins And Goethite-or Ferrihydrite-Coated Quartz Sand: Influence of pH And Evaporation[J]. Geoderma, 2007, 139(4): 379-387.
[75] Toth Bela. Use of Vegetable Tannins in Non-Leather-Releted Industries[J]. Bor-Cipotech, 1994, 44(1): 8-11.
[76] Dr.Christiane Hauber. FORMATION, PREVENTION&DETERMINATION OF Cr(VI) IN LEATHER[J]. UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION, 2000, 9: 1-7.
[77] Wolf, G. and B. Wegner. Avoiding Cr(VI) in leather manufacture[J]. World Leather, 2000, 5: 39.
[78] Chen Hui, Shan Zhihua. Influence of fatliquoring components on Cr(VI) levels[J]. JSLTC, 2005, 89(6): 257-259.
[79] Angelika R, Ronald E W, Ellagic acid content of red raspberry juice as influenced by cultivar, processing, and environmental factors [J]. Agric.Food Chem.,1993, 41:1951-1960.
[80] John L M , Gene J G, Ellagic acid , an anticarcinogen in fruits, especially in stawberries : a review[J]. Hortscience, 1991 , 26 :10-14.
[81] Dixit R,Teel R W,Daniel F B et al.Inhibition of benzo(a)pyrene and benzo(a)pyrene-trans-7,8-diol metabolism and DNA binding in mouse lung explants by ellagic acid[J]. Cancer Res.,1985, 45: 2951-2956.
[82] Teel R W, Dixit R, Stoner G D. The effect of ellagic acid on the uptake, persistence, metabolism and DNA-binding of benzo(a)pyrene in cultured explants of strain A/J mouse lung[J]. Carcinogenesis, 1985, 6:391-195.
[83] Mandal S, Ahuja A, Shivapurkar N M et al. Inhibition of aflatoxin B, mutagenesis in Salmonella typhimurium and DNA damage in cultured rat and human tracheobronchial tissues by ellagic acid[J]. Carcinogenesis, 1987, 8:1651-1656.
[84] Mandal S, Shivapurkar N M, Galati A J et al. Inhibition of N-nitrosoben-zylmet- hylamine metabolism and DNA binding in cultured rat esophagus by ellagic acid[J]. Carcinogenesis, 1988, 9: 1313-1316.
[85] Das M, Bickers D R, Mukhtar H. Effect of ellagic acid on hepatic and pulmonary xenobiotic metabolism in mice: studies on the mechanism of its anticarcinogenic action[J]. Carcinogenesis, 1985, 6:1409-1413.
[86] Sayer J M ,Yaji H ,Wood A W et al. Extremely facile reaction between the ultimate carcinogen benzo (a) pyrene-7, 8-diol 9 ,10-epoxide and ellagic acid[J]. J. A mer. Chem. Soc., 1982, 104: 5562-5564.
[87] Dixit R, Gold BB. Inhibition of N-methyl-N-nitrosourea-in-duced mutagenicity and DNA methylation by ellagic acid[J]. Proc. N atl. A cad. Sci. (USA), 1986, 83: 8039-8043.
[88] Teel R W. Ellagic acid binding to DNA as a possible mechanism for its antimutagenic and anticarcinogenic action[J]. Cancer Lett., 1986, 30: 329-336.
[89] De Flora S, Ramel C. Mechanisms of inhibitors of mutagenesis and carcinogenesis classification and overview[J]. Mutation Res., 1988, 202: 285-306.
[90] Hayatsu H, Arinoto S, Nnegishi T. Dietary inhibitors of mutagenesis and carcinogenesis[J]. M utation Res., 1988, 202: 429-446.
[91] Stoner G D. Ellagic acid: A naturally occurring inhibitor of chemically induced cancer[J]. Proc.1989 Ann. Mtg. Amer. Strawberry Growers Assn., 1989, 20-34.
[92] Take Y, Imouye Y, Nakamura S et al. Comparative studies of the inhibitory properties of antibiotics on human immunodeficiency virus and avian myeloblastosis virus reverse transcriptases and cellular DNA polymerases[J]. J.A ntibioti xs, 1989, 42:107-115.
[93] Asanaka M, Kubayashi T, Okuda T et al. Inhibitors of HIV-1 replication that inhibit HIV integrase. Fourth Intl. Conf. Immunnopharma-cology., May 1988, Osaka, Japan.
[94]李庆,姚开等.新型天然抗氧化剂——鞣花酸[J].四川食品与发酵,2001,37(4):10-14.
[95]丁运生,孙小虎,李有桂等.鞣花酸及其衍生物研究进展[J].合肥工业大学学报(自然科学版),2008,31(11):1809-1812.
[96]李素琴,袁其朋,徐健梅.鞣花酸的生理功能及工艺开发研究现状[J].天然产物的研究与开发,2001,13(5):71-74.
[97] Dziedzic S Z, Hudson B J F, Phenolic acids and related compounds as antioxidant for edible oils [J]. Food Chem., 1984, 14: 45-51.
[98] Kurechi T, Kunugi A. Studies on the antioxidants, XVⅡ: photooxidation products of concomitantly used butylate hydroxyanisole [J]. J.A mer. Oil Chem. Soc. , 1983, 60: 109-113.
[99] Okuda T, Kimura Y, Yoshida T et al. Ellagitannins as active constituents of medicinal plants[J]. Planta Med., 1989, 55:117-122.
[100] Takuo K, Ishida H, Yokota M et al.Studies on antihemorrhagic substances in herbs classified as hemostatics in Chinese medicineⅢon the antihemorrhagic principle in sanguisorba officinallis L, Chem Pharm. Bull., 1984, 32: 4478-4481.
[101] Chemeng K A,Schwender C F, Fu K P et al. DNA gyrase inhibitory and antibacterial activity of some flavones(1) [J]. Bioorg. Med. Chem. Lett., 1993, 3(2): 225-230.
[102] Damas J, Remade V G, Ther thrombopenic effect of ellagic acid in the rat, another model of platelet stimulation in vivo[J]. Thromn.Res., 1987, 45: 153-163.
[103] Jurd L, Plant polyphenols. I. the polyphenolic constituents of the pellicle of the walnut (Juglans regia) [J]. J. Am. Chem. Soc. 1956, 78: 3445-3448.
[104] Khac D D, Van S T, Marth A et al. Ellagic compounds from diplopanax stachyanthus[J]. Phytochemistry, 1990, 29 (1):251-256.
[105] Mishra N C, Gold B, Synthesis of 13 C-and 14C-labeled ellagic acid[J]. Journal of Labelled Compounds and Radiopharm aceuticals, 1990.XXV III (8): 927-941.
[106] Mayer W, Hoffmann E H, Losch N et al. Dehydrierungs reaktionen mit gallussaureestern[J]. Liebigs Ann. Chem., 1984, 929-938.
[107] Nara O, Effective purification of ellagic acid by successive automatic recrystallization and absolute determination of purity by absorptivity ratio[J]. A nalytic Chemical Acta, 1997, 338:247-253.
[108]邵航,刘芸,刘春祥等.具有抗癌作用靴花酸的合成[J].现代应用药学,1995,12(2):27.
[109]李玉华,马培华,张前军等.鞣花酸-2-乙基己酸酯的合成条件探讨[J].毕节师范高等专科学校学报, 2004,22(1):93-96.
[110]杨泽方,冯海燕,傅洵.由五倍子萃取液中的单宁酸制取鞣花酸的液相色谱分析[J].山东化工,2004,33(2):29-30.
[111]王静,周昕,王姝等.由五倍子制取鞣花酸[J].青岛化工学院学报,2002,23(3):8-11.
[112]陈笳鸿,吴冬梅,汪咏梅等.紫外分光光度法测定鞣花酸含量的研究[J].生物质化学工程,2007,41(3):18-20.
[113]郭金彩.高效液相色谱法测定鞣花酸含量[J].河北化工,2006,29(9):51-52.
[114]周本宏,吴振华,刘春等.高效液相色谱法测定石榴皮中鞣花酸的含量[J].广东药学院学报,2005,21(6):693-694.
[115]王应红,孔虹等.植物多酚作还原剂制备铬鞣剂及应用研究[J].中国皮革,2004,33(11):7-9.
[116]陈武勇,王应红等.铬-橡椀复鞣剂的制备及应用研究[J].中国皮革,2005,34(17):20-29.
[117] ISMET HAKIMOGLU.橡椀栲胶的应用[J].中国皮革,2006,35(17):7-8.
[118]汪建根,杨宗邃等.微波辐照促进橡椀栲胶改性的研究[J].中国皮革,2006,35(19):8-13.
[119] Vaquero I, Marcobala,et al. Tannase activity by lactic acid bacteria isolated from grape must and wine[J]. Int J FoodMicro-biol,2004, 96: 199-204.
[120] Saxena S, Saxena R K. Statistical optimization of tannase production from Penicillum variable using fruits (Chebulic myrobalan) of Terminalia chebula[J]. Biotechnol Appl Biochem, 2004, 39: 99-106.
[121]黄文,石碧等.植物单宁的生物降解[J].化学通报,2002,5:321-325.
[122]孙根行,蔡祥等.TiO2光催化降解橡椀栲胶的研究[J].皮革科学与工程,2006,16(2):18-21.
[123]李琳,冯易君等.橡椀单宁去除水中有毒重金属离子的研究[J].环境工程,1997,15(5):14-16.
[124]黄文,石碧,李庆等.橡椀单宁生物降解动力学研究[J].林产化学与工业, 2001,5(4):7-10.
[125]黄文,石碧,李庆等.利用多菌种共培养降解橡惋单宁制备蹂花酸[J].林产化学与工业,2002,26(1):21-24.
[126]汪建根张新强.微波作用对改性橡椀栲胶分子结构的影响[J].材料导报,2007,S2:19
[127]吕远平,姚开,李庆.可降解橡碗单宁产鞣花酸的菌种筛选[J].食品与发酵工业,2003,29(2):38-41.
[128] Ausar S F, Beltramo D M, Castagna L F, etal. Treatment of theumatoid arthritis by oral administration of bovine tracheal type(Ⅱ) [J]. Collagen,Rbeumatol Int,2001,20:138-144.
[129]于义.我国皮革中六价铬含量水平[J].皮革化工,2003,20(3):16.
[130]张汉池,张继军,刘峰.铬的危害与防治[J] .内蒙古石油化工,2003,30:72 - 73.
[131]朱建华,王莉莉.不同价态铬的毒性及其对人体的影响[J].环境与开发,1997,12(3):46-48.
[132]谭西顺.危害人体健康的杀手-六价铬[J].劳动保护,2003,(1):16.
[133]戴伯初.关于皮革中的六价铬[J].中国皮革,2000,29(19):23-24.
[134]赵红兵,赵集民.关于皮革中六价铬问题的制革过程分析与实践控制[J].中国皮革,2004,33(9):46-47.
[135]俞从正,孙根行.皮革中六价铬成因初探[J].中国皮革,2002,31(3):25-29.
[136]吕生华,孙根行,俞从正.两性皮革加脂剂的合成及性能研究[J].中国皮革,2003,32(13):1-3.
[137]俞从正,孙根行,彭晓凌等.皮革中Cr(VI)的产生原因及预防研究[J].陕西科技大学学报,2003,21(2):1-5.
[138]陈春添.皮革中Cr(VI)的成因及其检测[J].皮革化工,2003,20(4):24-27.
[139]孙根行,俞从正.皮革中六价铬的研究进展[J].中国皮革,2002,31(7):35-39.
[140]陈慧,单志华,邵双嘉等.皮革中Cr(VI)的测定及影响因素[J].皮革科学与工程,2004,14(3):11-15.
[141]俞从正,刘鹏杰,孙根行.储存条件对皮革中六价铬含量的影响[J],中国皮革,2004,33(19):36-40.
[142] Font J, Cuadros R M, Lalueza J, etal. Presence of Cr(VI) in sheepskins: influence of tannery processe[J].JSLTC: 1999: 83~91.
[143] Font J, Cuadros R M, Reyes M R. Influence of Various facrors on chromium Cr(VI) formation by photo-aging[J]. JSLTC,1999,83:300-306.
[144] D. Graf, Dr.Boehme. The influence of the relative humidity of air during storage on the formation lowering of Cr(VI) in chrome tanned leather[J]. World Leather , 2000 , 13(5) : 38～39.
[145] Dieter Graf &Dr. Th.Boeheme KG. Formation of Cr(VI) Traces in Chrome - Tanned Leather: Causes, Prevention & Latest Findings [J]. JALCA, 2001, 96(4) : 169 -177.
[146]俞从正,孙根行,郭生伟.皮革中六价铬成因初探[J].中国皮革,2002,31(3):25～29.
[147]俞从正,杨红敏等.不同碘值的油脂对三价铬氧化为六价铬的影响[J].中国皮革,2009,38(5):7-11.
[148]杨子超.基础无机化学理论[M].西安:陕西人民出版社, 1982: 666-668.
[149]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[150] IUC-18, standard of the IULICS[S]. JSLTC, 1995, 79: 57.
[151]赵红兵,赵集民.关于皮革中六价铬问题的制革过程分析与实践控制[J].中国皮革,2004,33(9):46-47.
[152] Sung Wook Jeen, John L. Jambor, David W. Blowes, etal. Precipitates on Granular Iron in Solutions Containing Calcium Carbonate with Trichloroethene and Hexavalent Chromium[J]. Enviroumental Science and Technology, 2007, 41(6): 1989-1994.
[153]赵勇.皮革中六价铬的成因及预防[J].中国皮革,2005,34(7):11-12.
[154]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[155]张玲,俞从正,杨红敏等.羟基自由基对皮革中Cr(Ⅲ)氧化为Cr(VI)作用的研究[J].中国皮革,2010,39(5):20-23.
[156]张玲,俞从正.氢过氧化物对皮革中Cr(Ⅲ)转化为Cr(VI)的影响[J].中国皮革,2009,38(19):11-14.
[157]易宗俊,马兴元,俞从正,等.杨梅栲胶的极性分离物与皮革中六价铬的抑制[J].中国皮革,2008,37(17):8-12.
[158]马兴元,易宗俊,徐小波,等.塔拉单宁的极性分离及抗氧化性研究[J].皮革科学与工程,2008,18(6):12-15.
[159]易宗俊,马兴元,俞从正,等.栲胶改性及其应用研究进展[J].皮革与化工,2008,25(6):23-31.
[160]易宗俊,马兴元,俞从正,等.皮革中六价铬的综合防治[J].皮革与化工,2009,26(2):25-29.
[161]马兴元,易宗俊,俞从正,等.杨梅栲胶的改性及其对六价铬防治作用的研究[J].皮革化工,2007,24(6):1-4.
[162]王希安,付丽红等.蓝湿革乳酸脱铬的研究[J].中国皮革,2009,38(1): 14-17.
[163]马兴元等.六价铬专用防治PC助剂的应用研究[J].中国皮革,2005,34(9):19-23.
[164]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[165]孙根行,俞从正等.荆树皮栲胶对皮革中六价铬预防作用的研究[J].皮革化工,2002,19(6):26-31.
[166]王瑞,马兴元等.荆树皮栲胶的两性改性及其对皮革中Cr6+的防治作用[J] .中国皮革,2007,36(23):1-7.
[167] CHEN Chun-tian.Causes of Chromium(VI)in Leather and Its Determining Methods [J]. Leather Chemicals, 2003, 20(4): 24~26.
[168] Yu Congzheng, Liu Pengjie . Exploring in the oxidation approach of chromium (III) into chromium (VI) by unsatured lipoids in leather. 28th IULTCS.
[169] National Standards of P.R.C. Oils and fats-Determination of peroxide value[S].GB/T5532-85, 1985: 168~169.
[170] National Standards of P.R.C. Methods of Food Hygienic Analysis-physical and chemical section [S].GB/T500936~1996.
[171] Yu Congzheng, Ding Shaolan, Sun Genxing, . The Analysis and Test Technology of Leather [M].Bei Jing: Chemical Industry Press, 2005, 4.
[172] A.E.Shilov, Xu Jiqing.Activation of Saturated Hydrocarbons by Transition Metal Complexes [M].Bei Jing: Science Press, 1998, 81~82.
[173] ZHOU Hua--long, XU Jia--kuan, LIU Chang.Study of the Limitation in Oxidative Mechanism of Oils and Fats [J].Westleacher, 2006, 6: 35~38.
[174] Bao Zhi-yong.The Progress of Phenolic Antioxidant [J].Plastics Additives, 2000, 3: 1~5.
[175] LIU Jie, WANG Bo-chu, PENG Liang.Structure-activity Relationship of Flavonoids Antioxidants [J] . Journal of Chongqing University(Natural Science Edition), 2004, 27(2): 120~124.
[176] Li qinghua, Guo xue yang.Technology for the Preparation of Fatliquor from Rape Oil [J].Guangdong Chemical Industry.1999, (6): 26~27.
[177] Li Jianhua.The Quantitative Study on the Correlation Between the Self - Ignition Behavior and the Iodine Value of Plant Esters[J].FIRE SAFETY SCIENCE, 1999, 8(19): 14~20.
[178]张友杰,李念平.有机波谱教程.武汉:华中师范大学出版社. 1990,55-57.
[179] Zhang Youjie, Li Nianping. A Courrse in Organic Spectrometry[M]. Wu Han: Central China Normal Univercity Press. 1990, 55-57.
[180] Yu, Congzheng; Ma, Xingyuan; Liu, Pengjie; et, al. Exploring the oxidation of chromium(III) to chromium(VI) by unsaturated lipids in leather[J]. Journal of the Society of Leather Technologies and Chemists, 2007, 91(3): 116-122.
[181] Silvina B Lotito; Balz Freis. Relevance of apples polyphenols as antioxidants in human plasma: contrasting vitro and in vivo effects [J]. Free Radical Biology & Medicine, 2004, 36(2): 201-211
[182] Yenhun He; Fereidoom Shahidi. Antioxidant activity of green tea and its catechins in a fish meat system[J]. Agric Food Chem, 1997, 45: 4262-4266.
[183] Guo Yali; Li Cong; Ou Lingcheng and et, al. Studies on the resistancecapability to oxidation of natural antioxidants by three photometric methods [J]. Chinese Journal of Analysis Laboratory, 2004, 23(10): 43-48.
[184] Cheng Yuhong; Li Zhirong; Fu Qi. Study on the Eradicating Effect of Oxygen Free Radicals by Ginkgo-Biloba Extract [J]. Anyang Normal University Journal, 2007, 2: 80-82.
[185] Shela Gorinstein, Marina Zemser,Ratiporn Haruenkit, et al. Comparative content of total polyphenols and dietary fiber in tropical fruits and persimmon [J]. J Nutr Biochem, 1999(10): 368.
[186] Silvina B Lotito , Balz Frei. Relevance of apple polyphenols as antioxidants in human plasma: contrasting vitro and in vivo effects [J]. Free Radical Biology & Mechicine, 2004, 36(2): 201-211.
[187] Singleton V L, Rossi J A. Colorimetry of total phenolics with phosphomolybdic-phosphotungstic acid reagents[J]. Am J Enol Vitic. 1965. 16:144-158.
[188]曹炜,索志荣. Folin-Ciocalteu比色法测定蜂蜜中总酚酸的含量[J].食品与发酵工业,2003,29(12):80-82.
[189]郭娟,艾志录,崔建涛等.苹果渣中多酚物质的福林法测定[J].食品工业科技,2006,(2):178-180.
[190]马亚军,杨秉勤,郎惠高.铁盐-铁氰化钾分光光度法测定葡萄籽原花青素的含量[J].西部粮油科技,2003,(1):60-61.
[191]陆曦,王磊,魏红等.黄酮类化合物抗氧化活性的构效关系[J].食品科学,2006,27(12):233-237.
[192]魏红,丰帆,陈旭丹等. 4种中药黄酮提取物清除自由基活性的研究[J].天津师范大学学报(自然科学版),2008,28(2):14-17.
[193] Majhenic L J, Kerget M S, Knez Z E. Antioxidant and antimicrobial activity of guarana seed extracts[J]. Food Chemistry, 2007, 104(3): 1258-1268.
[194]卢聪聪,邵卫梁,杭晓敏等.两种茶多酚化学改性制备的脂溶性茶多酚抗氧化性能研究[J].安徽医药,2008,12(3):201-204.
[195]郑晶泉.抗氧化剂抗氧化实验研究进展[J].国外医学卫生学分册,2000,27(1):37-41.
[196]郭亚力,李聪,欧灵澄等. 3种分光光度法对天然抗氧化物质抗自由基性能的分析检测[J].分析试验室,2004,23(10):43-47.
[197]李益新,方允中.超氧化物歧化酶活力测定的新方法——化学发光法[J].生物化学与生物物理进展,1983,2:59-62.
[198]胡敏,袁津玮,张声华.银杏叶提取物的抗氧化性能研究[J].华中农业大学学报,1998,17(4):409-412.
[199]邓碧玉,袁勤生,李文杰.改良的连苯三酚自氧化测定超氧化物歧化酶活性的方法[J].生物化学与生物物理进展,1991,18(2):163.
[200]张海生,陈锦屏.蜂蛹黄酮的提取及体外抗氧化作用的研究[J].食品科学, 2008,29(2):158-162.
[201] Kishida KT, Hoeffer CA, Hu D, Pao M, Holland SM, Klann E. Synaptic plasticity deficits and mild memory impairments in mouse models of chronic granulomatous disease[J]. Mol Cell Biol, 2006, 26: 5908–5920.
[202]栾霞,祖丽亚,樊铁.食用油脂中p-茴香胺值的测定[J].中国油脂,2006,31(11):38-40.
[203]林谦,张汉洪等.磁性固体超强酸SO42 - /TiO2 - Fe3O4催化合成柠檬酸三辛酯[J].广州化工,2009,37(5):103-105.
[2] Ausar S F, Beltramo D M, Castagna L F, et al. Treatment of theumatoid arthritis by oral administration of bovine tracheal type(Ⅱ): collagen. Rbeumatol Int, 2001, 20: 138-144.
[3] Maria Eugenia Maciel , Gerardo Daniel Castro,Jose Alberto Castro.Inhibition of the Rat Breast Cytosolic Bioactivation of Ethanol to Acetaldehyde by Some Plant Polyphenols and Folic Acid[J]. Nutrition and Cancer, 2004, 49(1): 94-99.
[4]陈春添.皮革中Cr(VI)的成因及其检测[J].皮革化工,2003,20(4):24-26.
[5]刘素英,丁绍兰等.聚焦皮革中的六价铬及其测定方法[J].中国皮革,2002,31(5):28-33.
[6] IARC: IARC monographs on the evaluation of carciongenic risks to humans, chromium nickel and welding lyon[Z]. France, IARC, 1990, 49:187.
[7]易超,于素芳.六价铬化合物致肺癌机制的研究进展[J].中国公共卫生,2006,22(4):497-498.
[8] Maria Eugenia Maciel, Gerardo Daniel Castro, Jose Alberto Castro. Inhibition of the Rat Breast Cytosolic Bioactivation of Ethanol to Acetaldehyde by Some Plant Polyphenols and Folic Acid[J]. Nutrition and Cancer, 2004, 49(1):94-99.
[9] Stephane George, Pierre Brat, pascaline Alter, etal. Rapid Determination of Polyphenols and Vitamin C in Plant-Derived Products[J]. Agricultutal and Food Chemistry, 2005, 53(5):1370-1373.
[10]戴伯初.关于皮革中的六价铬[J].中国皮革,2000,29(19):23.
[11] ZHANG Yu-ping, JIANG Shou-wei, YIN Zhong-wei. Genetic Algorithms to the Nesting Problem in Leather Manufacturing Industry[J]. Journal of Donghua University, 2005, 22(1): 90-95.
[12] Apostolis Agalias, Prokopios Magiatis, Alexios Leandros Skaltsounis, etal. A New Process for the Management of Olive Oil Mill Waste Water and Recovery of Natural Antioxidants[J]. Agricultutal and Food Chemistry, 2007, 55(7): 2671-2676.
[13] Donghee Park, Yeoung Sang Yun, Jong Moon Park. Reduction of Hexavalent Chromium with the Brown Seaweed Ecklonia Biomass[J]. Enviroumental Science and Technology, 2004, 38(18): 4860-4864.
[14] Chunming Su, Ralph D. Ludwig. Treatment of Hexavalent Chromium in Chromite Ore Processing Solid Waste Using a Mixed Reductant Solution of Ferrous Sulfate and Sodium Dithionite[J]. Enviroumental Science and Technology, 2005, 39(16): 6208-6212.
[15] L. Dupont, E. Guillon. Removal of Hexavalent Chromium with a Lignocellulosic Substrate Extracted from Wheat Bran[J]. Enviroumental Science and Technology, 2003, 37(18): 4235-4241.
[16]孙根行,俞从正,曹洁,等.坚木栲胶对皮革中六价铬预防作用的研究[J].中国皮革,2003,32(1):6-9.
[17]宋立江,狄莹等.植物多酚研究与利用的意义及发展趋势[J].化学进展,2000,12(2):161-170.
[18]石碧,狄莹.植物多酚[M].北京:科学出版社,2000:1-20.
[19] Amita Kaul, Krishan Khanduja. Plant Polyphenols Inhibit Benzoyl Peroxide-Induced Superoxide Anion Radical Production and Diacylglyceride Formation in Murine Peritoneal macrophages[J]. Nutrition and Cancer, 2000, 35(2): 207-211.
[20] Wim Broothaerts, Joan Mc Pherson, Baochun Li, etal. Fast Apple(Malus-domestica)and Tobacco (Nicotiana tobacum)Leaf Polyphenol Oxidase Activity Assay for Screening Transgenic Plants[J]. Agricultutal and Food Chemistry, 2000, 48(12): 5924-5928.
[21] Nadejzda Haider, Sigbritt Karlsson. Kinetics of Migration of Antioxidants from Polyolefins in Natural Environments as a Basis for Bioconversion Studies[J]. BiomacromLecules, 2000, 1(3): 481-487.
[22] B. N. Shyamala, M. Madhava Naidu, G. Sulochanamma, etal. Studies on the Antioxidant Activities of Natural Vanilla Extract and Its Constituent Compounds through in Vitro Models[J]. Agricultutal and Food Chemistry, 2007, 55(19): 7738-7743.
[23]中国林业科学研究院科技情报研究所.国外栲胶技术[M].北京:中国林业科学出版社,1981:1-4.
[24] K. Indira Priyadarsini, Sujata M. Khopde, S. Santosh Kumar, etal. FreeRadical Studies of Ellagic Acid, a Natural Phenolic Antioxidant[J]. Agricultutal and Food Chemistry, 2002, 50(7): 2200-2206.
[25] Claude Alain Calliste, Patrick Trouillas, Daovy Paulette Allais, etal. Castanea sativa Mill. Leaves as New Sources of Natural Antioxidant: An Electronic Spin Resonance Study[J]. Agricultutal and Food Chemistry, 2005, 53(2): 282-288.
[26] Nagendran Balasundram, Kalyana Sundram,Samir Samman.Phenolic compounds in plants and agri-industrial by-products:Antioxidant activity, occurrence, and potential uses [J].Food Chemistry,2005,5:1-13.
[27] Haslam E. Plant Polyp henols—Vegetable Tannins Revisited[D]. Cambridge University Press, Cambridge, 1989: 170.
[28] Foo Y, Porter L. Vegetable Tannins[J]. Appita, 1986, 39(6): 477-480.
[29]贺近恪,布朗A.黑荆树及其利用[J].中国林业出版社,北京,1991,261.
[30] Hemingway R, Laks P. Plant Polyphenols[M]. New York: Plenum Press, 1992: 421-436.
[31]邢淑婕,刘开华,刘学彦.植物多酚对脂肪酸合酶活性抑制作用的研究[J].食品研究与开发,2007,128(6):37-39.
[32]哈本JB.黄酮类化合物[M].北京:科学出版社,1983:51-56.
[33]杨华祥,马建中,杨宗邃等.栲胶改性研究综述[J].皮革化工,1997,4:11-16.
[34]杨宗邃.鞣制化学[M].西北轻工业学院,1994,(59):86.
[35] Dikmelik Y. Faculty of Agriculture Bornova-Izmir[D]. Greece,Aegean University, 2003.
[36] Ismet Hakimoglu.橡椀栲胶的应用[J].中国皮革,2006,35(17): 7-8.
[37]黄文,石碧等.植物单宁的生物降解[J].化学通报,2002,5: 321-325.
[38] Jeffrey De Graft Johnson, Krzysztof Kolodziejczyk, Maciej Krol, etal. Ferric-Reducing Ability Power of Selected Plant Polyphenols and Their Metabolites: Implications for Clinical Studies on the Antioxidant Effects of Fruits and Vegetable Consumption[J]. Basic and Clinical Pharmacology and Toxicology, 2007, 100: 345-352.
[39] Sweetie R. Kanatt, Ramesh Chander, P. Radhakrishna, etal. Potato Peel Extractsa Natural Antioxidant for Retarding Lipid Peroxidation in Radiation Processed Lamb Meat[J]. Agricultutal and Food Chemistry, 2005, 53(5):1499-1504.
[40] E. Grant Jones, Lori M. Balster. Interaction of a Synthetic Hindered-Phenol with Natural Fuel Antioxidants in the Autoxidation of Paraffins[J]. Energy and Fuels, 2000, 14(3): 640-645.
[41]刘运荣,胡键华.植物多酚的研究进展[J].武汉工业学院学报,2005,12:63-65.
[42] Reed J. Cranberry Flavonoids: Atherosclerosis and Cardiovascular Health[J]. Crit Rev Food Scinutr, 2002, 42(301): 16.
[43] Monica Leopoldini, Nino Russo, Marirosa Toscano. Gas and Liquid Phase Acidity of Natural Antioxidants[J]. Agricultutal and Food Chemistry, 2006, 54(8): 3078-3085.
[44] Aurora Napolitano, Vincenzo Fogliano, Alessio Tafuri, etal. Natural Occurrence of Ochratoxin A and Antioxidant Activities of Green and Roasted Coffees and Corresponding Byproducts[J]. Agricultutal and Food Chemistry, 2007, 55(25): 10499-10504.
[45]陈曾三.植物多酚功能性及其开发利用[J].粮食与油脂,2000,3:40-41.
[46]赵扬帆,郑宝东.植物多酚类物质及其功能学研究进展[J].福建轻纺,2006,11:107-108.
[47] Alberto Macone, Mirella Nardini, Antonio Antonucci, etal. Identification of Aminoethylcysteine Ketimine Decarboxylated Dimer, a Natural Antioxidant, in Dietary Vegetables[J]. Agricultutal and Food Chemistry, 2002, 50(7): 2169-2172.
[48]王建新.天然活性化妆品[M].北京:中国轻纺工业出版社, 1997 :303-307.
[49] Hui Xiang, Su Hua pan. Studies on Human Feal Lens Crystallins under Oxidative Stress and Protective Effects of Tea Polyphenols[J].眼科学报, 1998, 14(3): 170-175.
[50]何有节,狄节,赵宇.等黑荆树皮单宁降解产物的抑菌性能[J].林产化学与工业,1999 ,19(2):1-7.
[51] A Bcress, Wassermamn, T Bruhn. A new Procedure for the isolation of anti-HIV compounds (polysaccharides and polyphenols) from the marine alga Fucus vesicnlosus[J]. Journal of Natural Products, 1993,56(4):478-488.
[52]张国营,李彦勇,何丽娜,等.绿茶及茶多酚抗人轮状病毒的实验[J].茶叶科学,1994, 14: 166-168.
[53]曹进.茶儿茶素影响细胞外糖合成和变异链球菌附着的研究[J].茶叶科学,1996, 16, 57-60.
[54]周丽珠.用栲胶的新型木工胶粘剂的研制[J].林产化工通讯, 2002,36(4):6-8.
[55]王晓东,郎春燕,梁明启.水泥回转窑水冷喷嘴加药防垢方法[J].工业水处理,2002,22(7):51-52.
[56]刘运荣,胡健华.植物多酚的研究进展[J].武汉工业学院学报,2005,24(4):63-65.
[57] Isabel Medina, Isabel Tombo, M. Teresa Satuea Gracia, etal. Effects of Natural Phenolic Compounds on the Antioxidant Activity of Lactoferrin in Liposomes and Oil-in-Water Emulsions[J]. Agricultutal and Food Chemistry, 2002, 50(8): 2392-2399.
[58] Bisanda E T N,Ogola W O,Tesha J V. Characterisation of tannin resin blends for particle applications [J]. Cenment & Concrete Composites. 2003, 25: 593-598.
[59] Lee W. J,Lan W. C.Properties of resorcinol-tannin-formaldehyde copolymer resins prepared from the bark extract of Taiwan acacia and China fir [J]. Bioresource Technology ,2006,97:257-264.
[60]黄占华,方桂珍等.植物单宁的应用及研究进展[J].林产化工通讯,2005,39,(5):39-42.
[61] MatamalaG.Comparison of steel anticorrosive protection formulated with natural tannins extracted from acacia and from pine bark [J]. Corrosion Science, 2000, 42 :1351-1362.
[62]叶秀菁等.石材专用清洗剂[P].中国专利:200410019228.1, 2004-10-01.
[63] Bisanda E T N,Ogola W O,Tesha J V. Characterisation of tannin resin blends for particle applications [J]. Cenment & Concrete Composites. 2003, 25: 593-598.
[64] Lee W. J,Lan W. C.Properties of resorcinol-tannin-formaldehyde copolymer resins prepared from the bark extract of Taiwan acacia and China fir [J]. Bioresource Technology ,2006,97:257-264.
[65]黄占华,方桂珍等.植物单宁的应用及研究进展[J].林产化工通讯,2005,39,(5):39-42.
[66] MatamalaG.Comparison of steel anticorrosive protection formulated with natural tannins extracted from acacia and from pine bark [J].Corrosion Science, 2000, 42 :1351-1362.
[67]叶秀菁等.石材专用清洗剂[P].中国专利:200410019228.1,2004-10-01.
[68]付美云,周立祥.植物多酚在环境保护与农业生产中的应用[J].应用生态学报,2004,15(9):1673-1676.
[69] Ma He-wei, Liao Xue-pin, Liu Xin. Recovery of Platinum(Ⅳ)and Palladium(Ⅱ)by Bayberry Tannin Immobilized Collagen Fiber Membtane From Solution[J]. Journal of Membrane Science, 2006, 278(2): 373-380.
[70]葛学贵,黄少云,马广伟,等.环境矿物SAP化学固沙浆材综合治理荒漠初探[J].岩石矿物学杂志,2001,20(4):511-514.
[71] Canbolat O, Ozkan C. O, Kamalak A. Effects of NaOH Treatment On Condensed Tannin Contents And Gas Production Kinetics of Tree Leaves[J]. Animal Feed Science And Technology, 2007, 138(2): 189-194.
[72] Beauchemin K. A, McGinn S. M, Martinez T. F. Use of Condensed Tannin Extract From Quebracho Trees To Reduce Methane Emissions From Cattle[J]. Journal of Animal Science, 2007, 85(9): 1990-1996.
[73]奚长生,龙来寿,罗翠环,等.栲胶法提取镓的研究[J].湖南有色金属,2004,10(1):11-13.
[74] Kaal. Joeri, Nierop. Klaas G. J, Verstraten. Jacobus M. Interactions Between Tannins And Goethite-or Ferrihydrite-Coated Quartz Sand: Influence of pH And Evaporation[J]. Geoderma, 2007, 139(4): 379-387.
[75] Toth Bela. Use of Vegetable Tannins in Non-Leather-Releted Industries[J]. Bor-Cipotech, 1994, 44(1): 8-11.
[76] Dr.Christiane Hauber. FORMATION, PREVENTION&DETERMINATION OF Cr(VI) IN LEATHER[J]. UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION, 2000, 9: 1-7.
[77] Wolf, G. and B. Wegner. Avoiding Cr(VI) in leather manufacture[J]. World Leather, 2000, 5: 39.
[78] Chen Hui, Shan Zhihua. Influence of fatliquoring components on Cr(VI) levels[J]. JSLTC, 2005, 89(6): 257-259.
[79] Angelika R, Ronald E W, Ellagic acid content of red raspberry juice as influenced by cultivar, processing, and environmental factors [J]. Agric.Food Chem.,1993, 41:1951-1960.
[80] John L M , Gene J G, Ellagic acid , an anticarcinogen in fruits, especially in stawberries : a review[J]. Hortscience, 1991 , 26 :10-14.
[81] Dixit R,Teel R W,Daniel F B et al.Inhibition of benzo(a)pyrene and benzo(a)pyrene-trans-7,8-diol metabolism and DNA binding in mouse lung explants by ellagic acid[J]. Cancer Res.,1985, 45: 2951-2956.
[82] Teel R W, Dixit R, Stoner G D. The effect of ellagic acid on the uptake, persistence, metabolism and DNA-binding of benzo(a)pyrene in cultured explants of strain A/J mouse lung[J]. Carcinogenesis, 1985, 6:391-195.
[83] Mandal S, Ahuja A, Shivapurkar N M et al. Inhibition of aflatoxin B, mutagenesis in Salmonella typhimurium and DNA damage in cultured rat and human tracheobronchial tissues by ellagic acid[J]. Carcinogenesis, 1987, 8:1651-1656.
[84] Mandal S, Shivapurkar N M, Galati A J et al. Inhibition of N-nitrosoben-zylmet- hylamine metabolism and DNA binding in cultured rat esophagus by ellagic acid[J]. Carcinogenesis, 1988, 9: 1313-1316.
[85] Das M, Bickers D R, Mukhtar H. Effect of ellagic acid on hepatic and pulmonary xenobiotic metabolism in mice: studies on the mechanism of its anticarcinogenic action[J]. Carcinogenesis, 1985, 6:1409-1413.
[86] Sayer J M ,Yaji H ,Wood A W et al. Extremely facile reaction between the ultimate carcinogen benzo (a) pyrene-7, 8-diol 9 ,10-epoxide and ellagic acid[J]. J. A mer. Chem. Soc., 1982, 104: 5562-5564.
[87] Dixit R, Gold BB. Inhibition of N-methyl-N-nitrosourea-in-duced mutagenicity and DNA methylation by ellagic acid[J]. Proc. N atl. A cad. Sci. (USA), 1986, 83: 8039-8043.
[88] Teel R W. Ellagic acid binding to DNA as a possible mechanism for its antimutagenic and anticarcinogenic action[J]. Cancer Lett., 1986, 30: 329-336.
[89] De Flora S, Ramel C. Mechanisms of inhibitors of mutagenesis and carcinogenesis classification and overview[J]. Mutation Res., 1988, 202: 285-306.
[90] Hayatsu H, Arinoto S, Nnegishi T. Dietary inhibitors of mutagenesis and carcinogenesis[J]. M utation Res., 1988, 202: 429-446.
[91] Stoner G D. Ellagic acid: A naturally occurring inhibitor of chemically induced cancer[J]. Proc.1989 Ann. Mtg. Amer. Strawberry Growers Assn., 1989, 20-34.
[92] Take Y, Imouye Y, Nakamura S et al. Comparative studies of the inhibitory properties of antibiotics on human immunodeficiency virus and avian myeloblastosis virus reverse transcriptases and cellular DNA polymerases[J]. J.A ntibioti xs, 1989, 42:107-115.
[93] Asanaka M, Kubayashi T, Okuda T et al. Inhibitors of HIV-1 replication that inhibit HIV integrase. Fourth Intl. Conf. Immunnopharma-cology., May 1988, Osaka, Japan.
[94]李庆,姚开等.新型天然抗氧化剂——鞣花酸[J].四川食品与发酵,2001,37(4):10-14.
[95]丁运生,孙小虎,李有桂等.鞣花酸及其衍生物研究进展[J].合肥工业大学学报(自然科学版),2008,31(11):1809-1812.
[96]李素琴,袁其朋,徐健梅.鞣花酸的生理功能及工艺开发研究现状[J].天然产物的研究与开发,2001,13(5):71-74.
[97] Dziedzic S Z, Hudson B J F, Phenolic acids and related compounds as antioxidant for edible oils [J]. Food Chem., 1984, 14: 45-51.
[98] Kurechi T, Kunugi A. Studies on the antioxidants, XVⅡ: photooxidation products of concomitantly used butylate hydroxyanisole [J]. J.A mer. Oil Chem. Soc. , 1983, 60: 109-113.
[99] Okuda T, Kimura Y, Yoshida T et al. Ellagitannins as active constituents of medicinal plants[J]. Planta Med., 1989, 55:117-122.
[100] Takuo K, Ishida H, Yokota M et al.Studies on antihemorrhagic substances in herbs classified as hemostatics in Chinese medicineⅢon the antihemorrhagic principle in sanguisorba officinallis L, Chem Pharm. Bull., 1984, 32: 4478-4481.
[101] Chemeng K A,Schwender C F, Fu K P et al. DNA gyrase inhibitory and antibacterial activity of some flavones(1) [J]. Bioorg. Med. Chem. Lett., 1993, 3(2): 225-230.
[102] Damas J, Remade V G, Ther thrombopenic effect of ellagic acid in the rat, another model of platelet stimulation in vivo[J]. Thromn.Res., 1987, 45: 153-163.
[103] Jurd L, Plant polyphenols. I. the polyphenolic constituents of the pellicle of the walnut (Juglans regia) [J]. J. Am. Chem. Soc. 1956, 78: 3445-3448.
[104] Khac D D, Van S T, Marth A et al. Ellagic compounds from diplopanax stachyanthus[J]. Phytochemistry, 1990, 29 (1):251-256.
[105] Mishra N C, Gold B, Synthesis of 13 C-and 14C-labeled ellagic acid[J]. Journal of Labelled Compounds and Radiopharm aceuticals, 1990.XXV III (8): 927-941.
[106] Mayer W, Hoffmann E H, Losch N et al. Dehydrierungs reaktionen mit gallussaureestern[J]. Liebigs Ann. Chem., 1984, 929-938.
[107] Nara O, Effective purification of ellagic acid by successive automatic recrystallization and absolute determination of purity by absorptivity ratio[J]. A nalytic Chemical Acta, 1997, 338:247-253.
[108]邵航,刘芸,刘春祥等.具有抗癌作用靴花酸的合成[J].现代应用药学,1995,12(2):27.
[109]李玉华,马培华,张前军等.鞣花酸-2-乙基己酸酯的合成条件探讨[J].毕节师范高等专科学校学报, 2004,22(1):93-96.
[110]杨泽方,冯海燕,傅洵.由五倍子萃取液中的单宁酸制取鞣花酸的液相色谱分析[J].山东化工,2004,33(2):29-30.
[111]王静,周昕,王姝等.由五倍子制取鞣花酸[J].青岛化工学院学报,2002,23(3):8-11.
[112]陈笳鸿,吴冬梅,汪咏梅等.紫外分光光度法测定鞣花酸含量的研究[J].生物质化学工程,2007,41(3):18-20.
[113]郭金彩.高效液相色谱法测定鞣花酸含量[J].河北化工,2006,29(9):51-52.
[114]周本宏,吴振华,刘春等.高效液相色谱法测定石榴皮中鞣花酸的含量[J].广东药学院学报,2005,21(6):693-694.
[115]王应红,孔虹等.植物多酚作还原剂制备铬鞣剂及应用研究[J].中国皮革,2004,33(11):7-9.
[116]陈武勇,王应红等.铬-橡椀复鞣剂的制备及应用研究[J].中国皮革,2005,34(17):20-29.
[117] ISMET HAKIMOGLU.橡椀栲胶的应用[J].中国皮革,2006,35(17):7-8.
[118]汪建根,杨宗邃等.微波辐照促进橡椀栲胶改性的研究[J].中国皮革,2006,35(19):8-13.
[119] Vaquero I, Marcobala,et al. Tannase activity by lactic acid bacteria isolated from grape must and wine[J]. Int J FoodMicro-biol,2004, 96: 199-204.
[120] Saxena S, Saxena R K. Statistical optimization of tannase production from Penicillum variable using fruits (Chebulic myrobalan) of Terminalia chebula[J]. Biotechnol Appl Biochem, 2004, 39: 99-106.
[121]黄文,石碧等.植物单宁的生物降解[J].化学通报,2002,5:321-325.
[122]孙根行,蔡祥等.TiO2光催化降解橡椀栲胶的研究[J].皮革科学与工程,2006,16(2):18-21.
[123]李琳,冯易君等.橡椀单宁去除水中有毒重金属离子的研究[J].环境工程,1997,15(5):14-16.
[124]黄文,石碧,李庆等.橡椀单宁生物降解动力学研究[J].林产化学与工业, 2001,5(4):7-10.
[125]黄文,石碧,李庆等.利用多菌种共培养降解橡惋单宁制备蹂花酸[J].林产化学与工业,2002,26(1):21-24.
[126]汪建根张新强.微波作用对改性橡椀栲胶分子结构的影响[J].材料导报,2007,S2:19
[127]吕远平,姚开,李庆.可降解橡碗单宁产鞣花酸的菌种筛选[J].食品与发酵工业,2003,29(2):38-41.
[128] Ausar S F, Beltramo D M, Castagna L F, etal. Treatment of theumatoid arthritis by oral administration of bovine tracheal type(Ⅱ) [J]. Collagen,Rbeumatol Int,2001,20:138-144.
[129]于义.我国皮革中六价铬含量水平[J].皮革化工,2003,20(3):16.
[130]张汉池,张继军,刘峰.铬的危害与防治[J] .内蒙古石油化工,2003,30:72 - 73.
[131]朱建华,王莉莉.不同价态铬的毒性及其对人体的影响[J].环境与开发,1997,12(3):46-48.
[132]谭西顺.危害人体健康的杀手-六价铬[J].劳动保护,2003,(1):16.
[133]戴伯初.关于皮革中的六价铬[J].中国皮革,2000,29(19):23-24.
[134]赵红兵,赵集民.关于皮革中六价铬问题的制革过程分析与实践控制[J].中国皮革,2004,33(9):46-47.
[135]俞从正,孙根行.皮革中六价铬成因初探[J].中国皮革,2002,31(3):25-29.
[136]吕生华,孙根行,俞从正.两性皮革加脂剂的合成及性能研究[J].中国皮革,2003,32(13):1-3.
[137]俞从正,孙根行,彭晓凌等.皮革中Cr(VI)的产生原因及预防研究[J].陕西科技大学学报,2003,21(2):1-5.
[138]陈春添.皮革中Cr(VI)的成因及其检测[J].皮革化工,2003,20(4):24-27.
[139]孙根行,俞从正.皮革中六价铬的研究进展[J].中国皮革,2002,31(7):35-39.
[140]陈慧,单志华,邵双嘉等.皮革中Cr(VI)的测定及影响因素[J].皮革科学与工程,2004,14(3):11-15.
[141]俞从正,刘鹏杰,孙根行.储存条件对皮革中六价铬含量的影响[J],中国皮革,2004,33(19):36-40.
[142] Font J, Cuadros R M, Lalueza J, etal. Presence of Cr(VI) in sheepskins: influence of tannery processe[J].JSLTC: 1999: 83~91.
[143] Font J, Cuadros R M, Reyes M R. Influence of Various facrors on chromium Cr(VI) formation by photo-aging[J]. JSLTC,1999,83:300-306.
[144] D. Graf, Dr.Boehme. The influence of the relative humidity of air during storage on the formation lowering of Cr(VI) in chrome tanned leather[J]. World Leather , 2000 , 13(5) : 38～39.
[145] Dieter Graf &Dr. Th.Boeheme KG. Formation of Cr(VI) Traces in Chrome - Tanned Leather: Causes, Prevention & Latest Findings [J]. JALCA, 2001, 96(4) : 169 -177.
[146]俞从正,孙根行,郭生伟.皮革中六价铬成因初探[J].中国皮革,2002,31(3):25～29.
[147]俞从正,杨红敏等.不同碘值的油脂对三价铬氧化为六价铬的影响[J].中国皮革,2009,38(5):7-11.
[148]杨子超.基础无机化学理论[M].西安:陕西人民出版社, 1982: 666-668.
[149]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[150] IUC-18, standard of the IULICS[S]. JSLTC, 1995, 79: 57.
[151]赵红兵,赵集民.关于皮革中六价铬问题的制革过程分析与实践控制[J].中国皮革,2004,33(9):46-47.
[152] Sung Wook Jeen, John L. Jambor, David W. Blowes, etal. Precipitates on Granular Iron in Solutions Containing Calcium Carbonate with Trichloroethene and Hexavalent Chromium[J]. Enviroumental Science and Technology, 2007, 41(6): 1989-1994.
[153]赵勇.皮革中六价铬的成因及预防[J].中国皮革,2005,34(7):11-12.
[154]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[155]张玲,俞从正,杨红敏等.羟基自由基对皮革中Cr(Ⅲ)氧化为Cr(VI)作用的研究[J].中国皮革,2010,39(5):20-23.
[156]张玲,俞从正.氢过氧化物对皮革中Cr(Ⅲ)转化为Cr(VI)的影响[J].中国皮革,2009,38(19):11-14.
[157]易宗俊,马兴元,俞从正,等.杨梅栲胶的极性分离物与皮革中六价铬的抑制[J].中国皮革,2008,37(17):8-12.
[158]马兴元,易宗俊,徐小波,等.塔拉单宁的极性分离及抗氧化性研究[J].皮革科学与工程,2008,18(6):12-15.
[159]易宗俊,马兴元,俞从正,等.栲胶改性及其应用研究进展[J].皮革与化工,2008,25(6):23-31.
[160]易宗俊,马兴元,俞从正,等.皮革中六价铬的综合防治[J].皮革与化工,2009,26(2):25-29.
[161]马兴元,易宗俊,俞从正,等.杨梅栲胶的改性及其对六价铬防治作用的研究[J].皮革化工,2007,24(6):1-4.
[162]王希安,付丽红等.蓝湿革乳酸脱铬的研究[J].中国皮革,2009,38(1): 14-17.
[163]马兴元等.六价铬专用防治PC助剂的应用研究[J].中国皮革,2005,34(9):19-23.
[164]俞从正,刘鹏杰,段力民等.储存条件对皮革中六价铬含量的影响[J].中国皮革,2004,33(19):36-40.
[165]孙根行,俞从正等.荆树皮栲胶对皮革中六价铬预防作用的研究[J].皮革化工,2002,19(6):26-31.
[166]王瑞,马兴元等.荆树皮栲胶的两性改性及其对皮革中Cr6+的防治作用[J] .中国皮革,2007,36(23):1-7.
[167] CHEN Chun-tian.Causes of Chromium(VI)in Leather and Its Determining Methods [J]. Leather Chemicals, 2003, 20(4): 24~26.
[168] Yu Congzheng, Liu Pengjie . Exploring in the oxidation approach of chromium (III) into chromium (VI) by unsatured lipoids in leather. 28th IULTCS.
[169] National Standards of P.R.C. Oils and fats-Determination of peroxide value[S].GB/T5532-85, 1985: 168~169.
[170] National Standards of P.R.C. Methods of Food Hygienic Analysis-physical and chemical section [S].GB/T500936~1996.
[171] Yu Congzheng, Ding Shaolan, Sun Genxing, . The Analysis and Test Technology of Leather [M].Bei Jing: Chemical Industry Press, 2005, 4.
[172] A.E.Shilov, Xu Jiqing.Activation of Saturated Hydrocarbons by Transition Metal Complexes [M].Bei Jing: Science Press, 1998, 81~82.
[173] ZHOU Hua--long, XU Jia--kuan, LIU Chang.Study of the Limitation in Oxidative Mechanism of Oils and Fats [J].Westleacher, 2006, 6: 35~38.
[174] Bao Zhi-yong.The Progress of Phenolic Antioxidant [J].Plastics Additives, 2000, 3: 1~5.
[175] LIU Jie, WANG Bo-chu, PENG Liang.Structure-activity Relationship of Flavonoids Antioxidants [J] . Journal of Chongqing University(Natural Science Edition), 2004, 27(2): 120~124.
[176] Li qinghua, Guo xue yang.Technology for the Preparation of Fatliquor from Rape Oil [J].Guangdong Chemical Industry.1999, (6): 26~27.
[177] Li Jianhua.The Quantitative Study on the Correlation Between the Self - Ignition Behavior and the Iodine Value of Plant Esters[J].FIRE SAFETY SCIENCE, 1999, 8(19): 14~20.
[178]张友杰,李念平.有机波谱教程.武汉:华中师范大学出版社. 1990,55-57.
[179] Zhang Youjie, Li Nianping. A Courrse in Organic Spectrometry[M]. Wu Han: Central China Normal Univercity Press. 1990, 55-57.
[180] Yu, Congzheng; Ma, Xingyuan; Liu, Pengjie; et, al. Exploring the oxidation of chromium(III) to chromium(VI) by unsaturated lipids in leather[J]. Journal of the Society of Leather Technologies and Chemists, 2007, 91(3): 116-122.
[181] Silvina B Lotito; Balz Freis. Relevance of apples polyphenols as antioxidants in human plasma: contrasting vitro and in vivo effects [J]. Free Radical Biology & Medicine, 2004, 36(2): 201-211
[182] Yenhun He; Fereidoom Shahidi. Antioxidant activity of green tea and its catechins in a fish meat system[J]. Agric Food Chem, 1997, 45: 4262-4266.
[183] Guo Yali; Li Cong; Ou Lingcheng and et, al. Studies on the resistancecapability to oxidation of natural antioxidants by three photometric methods [J]. Chinese Journal of Analysis Laboratory, 2004, 23(10): 43-48.
[184] Cheng Yuhong; Li Zhirong; Fu Qi. Study on the Eradicating Effect of Oxygen Free Radicals by Ginkgo-Biloba Extract [J]. Anyang Normal University Journal, 2007, 2: 80-82.
[185] Shela Gorinstein, Marina Zemser,Ratiporn Haruenkit, et al. Comparative content of total polyphenols and dietary fiber in tropical fruits and persimmon [J]. J Nutr Biochem, 1999(10): 368.
[186] Silvina B Lotito , Balz Frei. Relevance of apple polyphenols as antioxidants in human plasma: contrasting vitro and in vivo effects [J]. Free Radical Biology & Mechicine, 2004, 36(2): 201-211.
[187] Singleton V L, Rossi J A. Colorimetry of total phenolics with phosphomolybdic-phosphotungstic acid reagents[J]. Am J Enol Vitic. 1965. 16:144-158.
[188]曹炜,索志荣. Folin-Ciocalteu比色法测定蜂蜜中总酚酸的含量[J].食品与发酵工业,2003,29(12):80-82.
[189]郭娟,艾志录,崔建涛等.苹果渣中多酚物质的福林法测定[J].食品工业科技,2006,(2):178-180.
[190]马亚军,杨秉勤,郎惠高.铁盐-铁氰化钾分光光度法测定葡萄籽原花青素的含量[J].西部粮油科技,2003,(1):60-61.
[191]陆曦,王磊,魏红等.黄酮类化合物抗氧化活性的构效关系[J].食品科学,2006,27(12):233-237.
[192]魏红,丰帆,陈旭丹等. 4种中药黄酮提取物清除自由基活性的研究[J].天津师范大学学报(自然科学版),2008,28(2):14-17.
[193] Majhenic L J, Kerget M S, Knez Z E. Antioxidant and antimicrobial activity of guarana seed extracts[J]. Food Chemistry, 2007, 104(3): 1258-1268.
[194]卢聪聪,邵卫梁,杭晓敏等.两种茶多酚化学改性制备的脂溶性茶多酚抗氧化性能研究[J].安徽医药,2008,12(3):201-204.
[195]郑晶泉.抗氧化剂抗氧化实验研究进展[J].国外医学卫生学分册,2000,27(1):37-41.
[196]郭亚力,李聪,欧灵澄等. 3种分光光度法对天然抗氧化物质抗自由基性能的分析检测[J].分析试验室,2004,23(10):43-47.
[197]李益新,方允中.超氧化物歧化酶活力测定的新方法——化学发光法[J].生物化学与生物物理进展,1983,2:59-62.
[198]胡敏,袁津玮,张声华.银杏叶提取物的抗氧化性能研究[J].华中农业大学学报,1998,17(4):409-412.
[199]邓碧玉,袁勤生,李文杰.改良的连苯三酚自氧化测定超氧化物歧化酶活性的方法[J].生物化学与生物物理进展,1991,18(2):163.
[200]张海生,陈锦屏.蜂蛹黄酮的提取及体外抗氧化作用的研究[J].食品科学, 2008,29(2):158-162.
[201] Kishida KT, Hoeffer CA, Hu D, Pao M, Holland SM, Klann E. Synaptic plasticity deficits and mild memory impairments in mouse models of chronic granulomatous disease[J]. Mol Cell Biol, 2006, 26: 5908–5920.
[202]栾霞,祖丽亚,樊铁.食用油脂中p-茴香胺值的测定[J].中国油脂,2006,31(11):38-40.
[203]林谦,张汉洪等.磁性固体超强酸SO42 - /TiO2 - Fe3O4催化合成柠檬酸三辛酯[J].广州化工,2009,37(5):103-105.