硅基荧光表面印迹复合材料的制备及其靶向检测环境中拟除虫菊酯的研究

发布时间：2018-01-17 21:26

本文关键词：硅基荧光表面印迹复合材料的制备及其靶向检测环境中拟除虫菊酯的研究　出处：《江苏大学》2017年硕士论文　论文类型：学位论文

【摘要】：在工业和农业生产生活中,拟除虫菊酯杀虫剂(Pyrethroid pesticides,PPs)的滥用已导致其在水体中残留含量严重超标,危害人体健康和生态平衡。研究表明在使用PPs防治靶向害虫的同时,还会对非靶向生物带来较大的危害,如鱼、虾、蟹等水生物,甚至对蜜蜂也会带来巨大的伤害,部分PPs残留会影响到人类神经系统和生殖系统。针对复杂环境中识别痕量PPs残留问题,探索新型、快速有效、灵敏的检测方法已经成为当务之急。本课题以荧光识别技术为基础结合分子印迹技术的特异选择性,建立了一种新型选择性识别特定目标物的荧光分析技术。选择窄发射谱、高荧光量子产率的有机荧光染料作为荧光团,选用无机纳米颗粒为载体,在载体表面上包覆上印迹层,构建了一类具有稳定性好、快速高效、选择识别性荧光印迹复合材料,来实现复杂环境中三种残留PPs(三氟氯氰菊酯LC、高效氟氯氰菊酯BC、氟胺氰菊酯FL)的选择性识别。本课题主要开展的工作如下:(1)设计并使用沉淀聚合制备一种荧光印迹复合材料来选择性识别环境水样中痕量的LC。本研究以纳米SiO_2颗粒为基体材料,将荧光单体FITC通过硅烷偶联剂APTS接枝到SiO_2颗粒表面,分别加入模板分子(LC)、功能单体(AM)、交联剂(DVB)、引发剂(AIBN),用沉淀聚合法制备了SiO_2@FITC-APTS@MIPs荧光印迹复合材料。分别用红外波谱(FT-IR),热失重仪器(TGA),扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征手段来对这种荧光复合材料进行测试。测试分析显示这种荧光复合材料呈现均匀球形形貌,并具有明显的核-壳结构(壳厚约为100 nm)。通过Stern-Volmer公式,建立了荧光强度F与LC浓度C之间的线性关系,并得到了线性回归方程F0/F-1=0.0162C+0.0272,检出限LOD为9.17 nM。(2)采用沉淀聚合法,以KH570修饰的SiO_2为载体材料,模板分子(BC)、荧光功能单体(AF)、交联剂(TRIM)、引发剂(AIBN)在加热的条件下制备出荧光印迹复合材料用于选择性识别农产品水样中的BC。通过FT-IR、SEM和TEM等手段对其形貌特征进行了表征,结果发现此荧光印迹复合材料拥有较好的单分散性,以及较薄的印迹聚合层(约50 nm),通过荧光检测和选择性实验分析该荧光印迹复合材料具有良好的选择识别性能,在10.11-80 n M范围内具有良好的线性关系,线性回归方程为F0/F-1=0.0213C+0.0859,相关系数R2=0.9919,LOD=10.11 nM。(3)利用沉淀聚合法在SiO_2-KH570纳米粒子表面包覆上一层具有选择识别性能的表面分子印迹聚合物层,在反应体系中分别加入模板分子(FL)、荧光单体(AF)、功能单体(AM)、交联剂(TRIM),在AIBN引发聚合得到SiO_2-KH570@FL-FMIPs复合材料用于环境水样中痕量FL检测识别。运用各种表征手段检测展示了其较好的单分散性、稳定性和荧光特性,该荧光印迹复合材料展现了优异的选择识别能力。通过荧光识别技术和选择性实验分析了荧光强度F与FL浓度C在浓度为12.145-120 nM内具有良好的线性关系,并建立了线性回归方程F0/F-1=0.0164C-0.0067,相关系数为0.9975,LOD=12.145 nM。
[Abstract]:In the industrial and agricultural production and life, pyrethroid insecticides (Pyrethroid pesticides PPs) has led to the abuse of residues in water content exceed the standard seriously, endanger human health and ecological balance. The study showed that in the use of PPs control target pests at the same time, but also on the non target biology bring harm, such as fish. Shrimp, crab and other aquatic organisms, and even will bring great harm to the bees, part of the PPs residue will affect the human nervous system and reproductive system. According to the PPs identification in the complex environment of trace residues, to explore a new, rapid and effective, sensitive detection method has become a pressing matter of the moment. A specific and selective subject to the fluorescence based recognition technique combination of molecular imprinting technique, a fluorescent target identification new selective analysis technology. Selection of narrow emission spectra, high fluorescence quantum yield of organic fluorescent dyes as The fluorophore, using the inorganic nanoparticles as the carrier, on the imprinted layer coated on the surface of carrier, constructed a kind of good stability, fast and efficient, selective recognition of fluorescent imprinted composite materials, to achieve three kinds of residual PPs in complex environment (three cyfluthrin LC, Cyhalothrin BC, amine fluoride cypermethrin FL) selective recognition. The main work is as follows: (1) the design and use of polymerization to prepare a fluorescent imprinted composite material to selective recognition of trace LC. in environmental water samples in this study, nano SiO_2 particles as the base material of precipitation, fluorescent monomer FITC by silane coupling agent APTS was grafted to SiO_2 the particle surface, were added to the template molecule (LC), functional monomer (AM), crosslinking agent (DVB), initiator (AIBN), SiO_2@FITC-APTS@MIPs fluorescent imprinted materials were prepared by precipitation polymerization. By using infrared spectroscopy (FT-IR), thermogravimetric instrument (T GA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization methods to test the fluorescent composites. The test analysis showed that the fluorescent composite showed uniform spherical morphology, and has a clear core-shell structure (the shell thickness is about 100 nm). By using the Stern-Volmer formula, a linear the relationship between the fluorescence intensity and the concentration of LC F C, and obtained the F0/F-1=0.0162C+0.0272 linear regression equation, the detection limit is 9.17 nM. (2 LOD) by precipitation polymerization, modified by KH570 SiO_2 as the carrier material, the template molecule (BC), fluorescent functional monomer (AF), crosslinking agent, initiator (TRIM) (AIBN) prepared by fluorescence imprinted materials for selective recognition of agricultural products in water samples by BC. FT-IR under the condition of heating, its morphology is characterized by SEM and TEM methods. Results showed that the fluorescence of imprinted materials has a good single Dispersion, and thin MIP (about 50 nm), by fluorescence detection and selective experiment analysis of the fluorescence imprinted composite material has good recognition ability, has a good linear relationship in the range of M 10.11-80 n, the linear regression equation was F0/F-1=0.0213C+ 0.0859, the correlation coefficient R2=0.9919, LOD=10.11 (3) by nM. polymerization in coated SiO_2-KH570 nanoparticles on the surface layer has the recognition performance of surface imprinted polymer layer deposition, the template molecules were added in the reaction system (FL), fluorescent monomer (AF), functional monomer (AM), crosslinking agent, initiator (TRIM) SiO_2-KH570@FL-FMIPs composites for trace FL sample detection and recognition in AIBN. Using various characterization methods of detection showed its good monodispersity, stability and fluorescence, the fluorescence imprinted materials displayed an excellent selection of knowledge Other abilities. Through fluorescence recognition technology and selective experiment, the fluorescence intensity F and FL concentration C have a good linear relationship in the concentration of 12.145-120 nM, and a linear regression equation F0/F-1=0.0164C-0.0067 is established, the correlation coefficient is 0.9975, LOD=12.145 nM..

【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X830.2;O631.3

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