儿童玩具中内分泌干扰物及异噻唑啉酮类物质的电化学及色谱检测方法研究

发布时间：2018-12-09 11:55

【摘要】：婴幼儿童在生活中玩耍时可通过呼吸、舔食和皮肤接触玩具等行为,将一些有毒有害物质摄入体内。本文以影响生殖发育和身心健康的有毒有害成分作为研究对象,探讨了(1)炭黑纳米粒子(CBNPs)与离子液体(IL)复合材料修饰电极对儿童玩具中双酚A的测定;(2)新型硅烷化试剂用于儿童玩具中内分泌干扰物质的GC-MS/MS检测分析;(3)高效液相色谱法检测造型黏土中的防腐剂。为玩具的安全性评价、标准完善和儿童健康防护提供了一定的数据和资料。一.CBNPs/IL/DTAB修饰玻碳电极对儿童玩具中双酚A的电化学测定在儿童玩具中双酚A的检测研究中用到了快速、灵敏、可微型化的电化学分析方法,其中炭黑纳米粒子作为修饰电极材料具有诸多优势,如价格便宜、导电性能好、吸附能力强、比表面积大等;被人们誉为“绿色溶剂”的离子液体也有独特的功能,如化学和热稳定性高,低可燃性、高离子电导率、稳定的电化学窗口等。把离子液体引入纳米材料可以将他们的优越特性结合起来,从而提高他们在电化学和传感器中的性能。二.新型硅烷化试剂用于儿童玩具中内分泌干扰物质的GC-MS/MS检测分析作为双酚A(BPA)的替代品,即双酚S(BPS),双酚F(BPF)和双酚B(BPB)等,它们具有与BPA类似的结构,辛基苯酚(OP)和壬基苯酚(NP)同样有内分泌干扰作用。实验中参考文献合成了一种有趣的新型衍生化试剂用于与内分泌干扰物质反应,生成的衍生化产物用于气质联用进行检测分析。实验结果显示该衍生化试剂有诸多优势且检测结果也令人满意。三.高效液相色谱法测定造型黏土中的防腐剂造型黏土是一类很受婴幼儿童青睐的益智类玩具,造型黏土产品可在两年或更久的时间里保持不变质等现象说明了产品可能添加了某些防腐剂,这些防腐剂被科学家认为是具有致敏性的,若添加过量,孩子长期接触或误食易对身体健康造成潜在危害。目前,EN71-9:2007《玩具安全—第9部分有机化合物限值要求》中对异噻唑啉酮类防腐剂已经有明确的限值要求,而国内至今对造型黏土中所使用的防腐剂的类别及含量均未做出明确规定。基于此,本实验建立了一种用于对造型黏土中的异噻唑啉酮类物质进行检测的项目,通过建立色谱检测方法、优化实验条件等步骤,结果显示实验方法简便、分析数据准确,为我国建立此类标准检测方法的提供了一定数据和经验。
[Abstract]:Infant children can breathe, lick and touch toys when they play in life, and take some toxic and harmful substances into the body. In this paper, the toxic and harmful components affecting reproductive development and physical and mental health were studied. (1) the determination of bisphenol A in children's toys by carbon black nano-particle (CBNPs) and ionic liquid (IL) composite modified electrode; (2) the new silane reagent was used to detect endocrine disrupting substances in children's toys by GC-MS/MS, and (3) high performance liquid chromatography (HPLC) was used to detect preservatives in molded clay. It provides some data and information for toy safety evaluation, standard improvement and child health protection. 1. Electrochemical determination of bisphenol A in children's toys with CBNPs/IL/DTAB modified glassy carbon electrode has been applied to the detection of bisphenol A in children's toys by using a rapid, sensitive and miniaturized electrochemical analysis method. Carbon black nanoparticles as modified electrode materials have many advantages, such as low price, good conductivity, strong adsorption ability, large specific surface area and so on. Ionic liquids known as "green solvents" also have unique functions, such as high chemical and thermal stability, low flammability, high ionic conductivity, stable electrochemical window and so on. The introduction of ionic liquids into nanomaterials can combine their superior properties to improve their performance in electrochemistry and sensors. II. The new silane reagent was used for the detection of endocrine disrupting substances in children's toys by GC-MS/MS. As a substitute for bisphenol A (BPA), such as bisphenol S (BPS), bisphenol F (BPF) and bisphenol B (BPB), etc. They have similar structures as BPA, and octylphenol (OP) and nonylphenol (NP) also have endocrine disrupting effects. An interesting new derivative reagent was synthesized for reaction with endocrine disrupting substances, and the derived products were used for GC-MS analysis. The experimental results show that the derivative reagent has many advantages and the detection results are satisfactory. Three Determination of preservative clay in moulding clay by HPLC is a kind of educational toys favored by infants and children. The fact that molded clay products can remain intact for two years or more suggests that some preservatives may have been added to the product, which scientists consider to be sensitized, if added in excess, Children's long-term contact or misuse of food is likely to cause potential health hazards. At present, the limits for isothiazolinone preservatives in EN71-9:2007 "Toy Safety-part 9" organic compounds have been specified. However, the types and contents of preservatives used in moulding clay have not been clearly defined in China. Based on this, an item was established to detect isothiazolinone in clay. The method of chromatographic detection was established and the experimental conditions were optimized. The results showed that the experimental method was simple and the analysis data was accurate. It provides some data and experience for establishing this kind of standard detection method in our country.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS958.07;O657

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