【作者】 岳强；

【导师】 周建科；

【作者基本信息】 河北大学 ， 分析化学， 2006， 硕士

【摘要】 环境雌激素可以干扰动物和人类正常的内分泌功能，造成生殖障碍、发育异常、某些免疫系统疾病。环境雌激素污染物对人类和动物的不良影响已引起社会的普遍关注，建立快速有效的降解及检测方法，对于此类污染物的监测和治理具有重要意义。 本文对近年来国内外环境雌激素研究进展进行了综述，介绍了环境雌激素的定义、特性、分类、降解途径及检测方法。建立了分离测定2，4-二氯酚、2，6-二氯酚、3，4-二氯酚、4-壬基酚的气相色谱法和雌二醇、雌三醇、雌酮、己烯雌酚、炔诺酮、甲羟孕酮、黄体酮的高效液相色谱法，考察了色谱柱、柱温、流动相、检测波长等条件对分离和检测的影响情况。利用所建立的色谱法，研究了以二氯酚异构体、4-壬基酚和己烯雌酚为代表的典型酚类雌激素的光降解情况和影响因素。实验表明，3种二氯酚异构体在紫外光照射下均可较快降解，它们单独降解和混合降解时的速率不同，但降解趋势基本一致；混晶型的纳米TiO₂对于4-壬基酚的紫外光降解催化效果显著，在最佳降解条件下，光照60min其降解率可达90％以上，初始浓度、催化剂用量、pH值、光照距离等因素对降解有较大影响；纳米TiO₂、ZnO和TiO₂-ZnO均可以作为光催化剂有效的催化降解水中的己烯雌酚，TiO₂-ZnO复合材料能够快速转移光致电子，使电子与空穴有效分离而具有更高的光催化效率，己烯雌酚的光降解反应遵从动力学一级反应。此外，利用所建立的高效液相色谱法测定了牛奶及牛肌肉样品中雌二醇、雌三醇、己烯雌酚、甲羟孕酮等雌性激素，考察了多种样品前处理方法。结果表明，使用乙腈可以在沉淀牛奶中蛋白质的同时萃取雌激素，操作简单，引入杂质较少；牛肌肉与无水硫酸钠研磨均质后，用甲醇超声萃取雌激素也是简单可行的方法；设定波长程序可使各组分在其最佳波长下检测，减小样品中杂质吸收，提高检测灵敏度。对从超市购买的实际样品进行测定时，牛奶样品中有少量雌三醇和己烯雌酚检出，牛肌肉样品中没有雌激素检出，方法具有一定的实用价值。更多还原

【Abstract】 Environmental estrogens can interference normal endocrine action of animals and human beings. It has been demonstrated that environmental estrogens are related to reproductive difficulty, abnormal development and diseases of immune system. The problem of environmental estrogens has become a global focus problem. It’s meaningful to develop a fast and efficient method for degradation and determination of environmental estrogens.In the paper, the recent progress of environmental estrogens has been reviewed, including definition, characteristic, classify of environmental estrogens, and the method of degradation and determination. Methods for separation and determination of 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 4-nonylphenol, estradiol, estriol, estrone, diethylstilbestrol, norethisterone, medroxy progesterone acetate and progesterone using gas chromatography （GC） and high performance liquid chromatography （HPLC） have been developed. The chromatographic conditions, including column temperature, mobile phase and detection wavelength were investigated.Isomers of dichlorophenol, 4-nonylphenol and diethylstilbestrol were degradation under the irradiation of UV. Three dichlorophenol isomers all degraded rapidly under the irradiation of UV. The difference of their photodegradatic percentage under the same conditions when single component and a mixture degradation was investigated with GC method. Photodegradation characters of 4-nonylphenol in water using TiO₂ as catalysis was researched. Under the optimized condition, the degradation percentage of 4-nonylphenol in simulated water sample could be up to 90 % when photodegradatic time higher than 60 min. The degradation rate was strongly influenced by the initial concentration, TiO₂ amount, pH value and lightsource distance. Photocatalytic degradation of diethylstilbestrol was carried out in the presence of nanosized TiO₂, ZnO and TiO₂-ZnO with UV, and the photodegradation reactions were found to follow the first order kinetics law. Compared with TiO₂ and ZnO, nano-TiO₂-ZnO was more efficient for degradation of diethylstilbestrol. The enhancement of更多还原