2，2'，4，4'-四溴联苯醚紫外光解及DNA损伤毒性研究
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摘要
溴系阻燃剂由于具有良好的阻燃性质,广泛应用于塑料、电子、建筑、纺织等材料与产品中。多溴联苯醚(PBDEs)是目前使用广泛的溴系阻燃剂。研究表明：环境中的PBDEs会对生态环境及人体健康造成危害,如对动物肝脏、甲状腺、生殖和发育、神经系统和免疫系统等都具有毒性作用或潜在的健康危害。目前各种环境介质和生物体内都检测出了PBDEs,而且在人体脂肪和母乳中也检出不同浓度水平的PBDEs。迄今的研究结果发现,BDE-47(2,2’,4,4’-四溴联苯醚)是目前分布最广、生物样品中含量最高、对生物和人体毒性最强的多溴联苯醚同系物之一,而光化学反应是BDE47在环境中的主要降解途径。因此,研究BDE47的光化学反应和BDE47的DNA损伤毒性有着重要的意义。
本论文的工作包括两个部分：
第一部分是BDE47的光化学反应研究。首先,根据研究工作的需要,完成了BDE47的合成。然后分别用4种溶剂和加入2种添加剂进行了BDE47的光化学反应研究。结果表明：①BDE47在4种溶剂中的光化学反应均为一级反应；反应速率大小顺序为正己烷>乙腈>DMSO>甲醇,光解速率大小与溶剂极性呈反向相关关系,极性小的溶剂有利于BDE47的光解反应,极性大的溶剂则不利于光解的发生。②BDE47在添加CuO和Cu2O的乙腈溶液中光解速率均下降,表明氧化剂和还原剂不利于BDE47光解反应的发生。BDE47的光解反应主要为连续脱溴反应,生成溴代数目更少的多溴联苯醚,各溶剂中产物丰度的差异反映出溶剂对光解反应的影响。
第二部分是BDE47对DNA损伤的研究。实验中选择小鼠淋巴细胞作为研究对象,采用单细胞凝胶电泳(彗星分析)的方法,对BDE47及光照产物的细胞毒性进行了研究。结果显示：①BDE47导致了小鼠淋巴细胞损伤,具有细胞毒性；而且随着BDE47的浓度增加而增加。②BDE47光照后的光解产物也导致了小鼠淋巴细胞损伤,具有细胞毒性；而且光解产物损伤作用大于BDE47,其中BDE1的细胞毒性最大。
Brominated flame retardants are widely used in plastics, electronics, construction, textiles and other materials and products due to their good flame-retardant property. PBDE is currently one of the most popular flame retardents. Studies have shown that, PBDEs is harmful to the ecological environment and human body, such as toxic effects or potential health hazard to animal liver, thyroid, reproductivity and development, neurology and immune systems and so on. In recent years, PBDEs have been detected in various environmental media and living organisms, also in human fat and breast milk for different concentration levels. So far, BDE-47 (2,2',4,4'-tetrapolybrominated diphenyl ether) is currently the most widely distributed, the highest concentrations of biological samples, one of the most toxic polybrominated diphenyl ether congeners in living organisms and human beings, thus photochemical reaction is the main degradation pathway of BDE47 in the environment. Therefore, it is of great significance to study the photochemical reaction of BDE47 and its DNA damage toxicity.
The work of this paper consists of two parts:
The first part is the photochemical reaction studies of BDE47. BDE47 sample is prepared in our lab.,and the photochemical reactions of it were conducted in 4 different solvents and acetonitrile with two kinds of additives, respectively. The results show that, photochemical reactions of BDE47 in four different solvents followed the rule of first order reaction and photolysis rate order in four different solvents is:hexane> acetonitrile>DMSO>methanol. There is an inverse correlation between photolysis rate and solvent polarity, the less polar solvents favor BDE47 photolysis reaction. Photodegradation rate of BDE47 decreased in the acetonitrile adding CuO and Cu2O, indicating that oxidant and reductant are negative to the occurrence of photolysis. The photolysis reaction of BDE47 is mainly consecutive debromination reaction, producing a number of lower-brominated diphenyl ethers, the abundance of photoproducts in various solvents reflect the solvent effect to the photodissociation pathway.
The second part is BDE47's DNA damage toxicity studies. In this study, cytotoxicity of mice lymphocytes induced by BDE47 and its' photoproducts is test by single cell gel electrophoresis (comet analysis) method. The results showed that:①BDE47 is of cytotoxicity and induced DNA damage of mice lymphocytes; the cytotoxicity increase with the concentration of BDE47.②The photoproducts of BDE47 induce DNA damage of mice lymphocytes more than BDE47, and BDE1 is the most tocxic one of them.
本论文的工作包括两个部分：
第一部分是BDE47的光化学反应研究。首先,根据研究工作的需要,完成了BDE47的合成。然后分别用4种溶剂和加入2种添加剂进行了BDE47的光化学反应研究。结果表明：①BDE47在4种溶剂中的光化学反应均为一级反应；反应速率大小顺序为正己烷>乙腈>DMSO>甲醇,光解速率大小与溶剂极性呈反向相关关系,极性小的溶剂有利于BDE47的光解反应,极性大的溶剂则不利于光解的发生。②BDE47在添加CuO和Cu2O的乙腈溶液中光解速率均下降,表明氧化剂和还原剂不利于BDE47光解反应的发生。BDE47的光解反应主要为连续脱溴反应,生成溴代数目更少的多溴联苯醚,各溶剂中产物丰度的差异反映出溶剂对光解反应的影响。
第二部分是BDE47对DNA损伤的研究。实验中选择小鼠淋巴细胞作为研究对象,采用单细胞凝胶电泳(彗星分析)的方法,对BDE47及光照产物的细胞毒性进行了研究。结果显示：①BDE47导致了小鼠淋巴细胞损伤,具有细胞毒性；而且随着BDE47的浓度增加而增加。②BDE47光照后的光解产物也导致了小鼠淋巴细胞损伤,具有细胞毒性；而且光解产物损伤作用大于BDE47,其中BDE1的细胞毒性最大。
Brominated flame retardants are widely used in plastics, electronics, construction, textiles and other materials and products due to their good flame-retardant property. PBDE is currently one of the most popular flame retardents. Studies have shown that, PBDEs is harmful to the ecological environment and human body, such as toxic effects or potential health hazard to animal liver, thyroid, reproductivity and development, neurology and immune systems and so on. In recent years, PBDEs have been detected in various environmental media and living organisms, also in human fat and breast milk for different concentration levels. So far, BDE-47 (2,2',4,4'-tetrapolybrominated diphenyl ether) is currently the most widely distributed, the highest concentrations of biological samples, one of the most toxic polybrominated diphenyl ether congeners in living organisms and human beings, thus photochemical reaction is the main degradation pathway of BDE47 in the environment. Therefore, it is of great significance to study the photochemical reaction of BDE47 and its DNA damage toxicity.
The work of this paper consists of two parts:
The first part is the photochemical reaction studies of BDE47. BDE47 sample is prepared in our lab.,and the photochemical reactions of it were conducted in 4 different solvents and acetonitrile with two kinds of additives, respectively. The results show that, photochemical reactions of BDE47 in four different solvents followed the rule of first order reaction and photolysis rate order in four different solvents is:hexane> acetonitrile>DMSO>methanol. There is an inverse correlation between photolysis rate and solvent polarity, the less polar solvents favor BDE47 photolysis reaction. Photodegradation rate of BDE47 decreased in the acetonitrile adding CuO and Cu2O, indicating that oxidant and reductant are negative to the occurrence of photolysis. The photolysis reaction of BDE47 is mainly consecutive debromination reaction, producing a number of lower-brominated diphenyl ethers, the abundance of photoproducts in various solvents reflect the solvent effect to the photodissociation pathway.
The second part is BDE47's DNA damage toxicity studies. In this study, cytotoxicity of mice lymphocytes induced by BDE47 and its' photoproducts is test by single cell gel electrophoresis (comet analysis) method. The results showed that:①BDE47 is of cytotoxicity and induced DNA damage of mice lymphocytes; the cytotoxicity increase with the concentration of BDE47.②The photoproducts of BDE47 induce DNA damage of mice lymphocytes more than BDE47, and BDE1 is the most tocxic one of them.
引文
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