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基于分子印迹—碳纳米管的双酚A电化学传感器的制备

Preparation of Electrochemical Sensor for Bisphenol A Determination Based on Molecularly Imprinted-Carbon Nanotubes

【作者】 程红波

【导师】 赵慧敏;

【作者基本信息】 大连理工大学 , 环境工程, 2010, 硕士

【摘要】 双酚A(BPA)具有三致效应和内分泌干扰性,且在世界各地的水体中均有检出,被认为是一种典型的内分泌干扰物,BPA等环境激素的环境行为及风险评价是目前环境领域的研究热点。由于环境样品的复杂性或现场检测要求,具有快速、高灵敏性、高选择性特点的分析方法成为限制相关研究的关键问题。本研究基于碳纳米管独特的电子传导性和吸附性,以及分子印迹聚合物(MIPs)的特异性识别性能,使用热聚合方法在多壁碳纳米管(MWNTs)修饰的玻碳电极(GCE)表面合成BPA分子印迹膜,构建一种对水中BPA具有高灵敏性和高选择性响应的新型分子印迹电化学传感器,应用线性扫描伏安法(LSV)对水中BPA进行检测。通过测定印迹膜电极MIP/MWNTs/GCE和MIP/GCE对相同浓度BPA的响应,证实了MWNTs的加入有效地提高了传感器表面的电子传导速率,从而提高了传感器对目标分子识别的灵敏度。在优化条件下,LSV响应峰电流与BPA浓度成线性关系的浓度范围为0.1-10mg/L,检测限达到0.0242mg/L(S/N=3)。选取与BPA结构相似的酚类化合物,包括对硝基苯酚、苯酚、间苯二酚和对苯二酚作为干扰物质,在相同的条件下,印迹膜电极对BPA的LSV电流响应分别是干扰物质的46.5、25.0、14.4、16.1倍,显示了该电极具有良好的选择性。本研究首次将碳纳米管和分子印迹技术结合起来用以检测水体中的BPA,发展了一种BPA检测的新方法,将为水中的双酚A等环境内分泌干扰物的高灵敏度现场检测提供重要的技术支撑,对实现正确快速的环境风险评价、突发环境事件预警具有重要意义。

【Abstract】 Because of the teratogenic, carcinogenic, mutagenic and endocrine disrupting effects, as well as the detection in water around the world, bisphenol A (BPA) has been listed as a typical endocrine disruptor. Nowadays, the environmental behavior and risk assessment of environmental hormones such as BPA are focused in environment field. Owing to the complexity of environmental samples or requirements of field determination, rapid, highly sensitive and selective analysis methods become the key issues restricted related studies.Based on the unique electronic properties and high adsorption capacity of carbon nanotubes as well as the specific recognition ability of molecularly imprinted polymers (MIPs), a novel molecularly imprinted electrochemical sensor with high sensitivity and selectivity was constructed for detection of BPA in water. The sensor was fabricated by directly preparing molecularly imprinted membrane of BPA on a multi-wall carbon nanotubes (MWNTs) modified glassy carbon electrode (GCE). The linear sweep voltammogram (LSV) of BPA at this sensor exhibited a well-defined anodic peak which was used to determine BPA.Comparing to MIP/GCE, BPA exhibited much higher LSV current response at the MIP/MWNTs/GCE. It could be inferred that MWNTs can expand the current response signal by enhancing electron transfer on the surface of the sensor. Under optimum conditions, the oxidation current was linear to the concentration of BPA in the range from 0.1 to 10mg/L with correlation coefficient of 0.9989 and detection limit of 0.0242mg/L (S/N=3). At the same concentration, the LSV response current of BPA at MIP/MWNTs/GCE was 46.5、25.0、14.4 and 16.1 times that of p-nitrophenol, phenol, hydroxyphenol or hydroquinone respectively, which indicated that the MIP/MWNTs/GCE performed excellent selectivity.This is the first time to report the determination of BPA in water by utilizing molecular imprinting technology in combination with carbon nanotubes. This study will provide important technical support to rapid and highly sensitive field analysis of BPA in water, and has important significance for environmental risk assessment and early warning of environmental emergencies.

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