荧光聚合物的合成、性能及其对金属离子和有机小分子的传感作用
发布时间：2018-07-23 16:44
【摘要】：环境污染和安全问题一直是人们关注的焦点,尤其是金属离子的污染和硝基芳香爆炸物的危害,引起了研究者的重点关注。荧光聚合物检测金属离子和有机小分子时,因具有灵敏度高、选择性好、操作简便以及实时在线检测等优点而被广泛应用。本论文主要针对聚合物合成过程繁琐、单体复杂难得、荧光调色困难等问题,采用加热回流这种简单易行的方法,通过胺醛缩聚制备了一系列荧光聚合物,并将其应用于金属离子和硝基芳香爆炸物检测领域中。主要研究内容如下:首先,采用加热回流法,选择三聚氰胺和乙二醛等简单易得的原料通过胺醛缩合得到蓝光聚合物溶液,然后用丙酮溶剂沉积得到固体蓝光材料。采用傅里叶变换红外光谱(FT-IR)、固体核磁碳谱(13C-NMR)、X射线衍射(XRD)、热重分析(TG-DTA)、荧光光谱(PL)、紫外吸收光谱及荧光寿命测试等表征方法分析了产物的结构组成和性能。通过固体产物分散于水溶液中的PL荧光测定,以及各种金属离子对溶液荧光的响应情况,确定了该蓝光聚合物对水溶液中的Cu2+有良好的选择性、灵敏性和抗干扰性。并且随着Cu2+浓度从5 n M到750μM的逐渐增加,荧光猝灭程度呈现上升趋势。基于聚合物相对荧光强度F0/F与Cu2+浓度之间的Stern-Volmer关系式,当Cu2+浓度处于低浓度0-100 nM范围内时,标准曲线呈现良好的线性关系,且线性相关系数为0.99226,检出限LOD为16.2nM。根据EPA的数据显示,饮用水中Cu2+的标准约为20μM,污水排放中的指标约为7.8μM,均在可检测范围之内。由于该聚合物中含有丰富的N、O元素,而Cu2+又极易与含这些元素的物质形成络合物,故导致了蓝光的猝灭从而达到检测的目的。以上结果表明三聚氰胺-乙二醛蓝光材料在铜离子荧光传感领域具有潜在的应用价值。其次,采用加热回流法,以成本低、简单易得的双官能团对苯二甲醛和氨水为原料,分别用甲醇、DMF、DMSO作为溶剂,通过胺醛缩合制备了一系列新型的双席夫碱共轭聚合物,且它们的荧光发生了由蓝绿→绿色→黄绿色的转变。通过13C-NMR,PXRD和FT-IR等表征手段,分析了该系列聚合物的结构组成;分别通过FE-SEM测试,分析了它们的形貌特征;又通过TG-DTA探索了这系列共轭聚合物的热稳定性。通过该系列共轭聚席夫碱悬浮液的荧光强度和激发发射波长稳定性,以及形貌和热稳定性对比分析,发现甲醇为溶剂合成的聚合物具有良好的热稳定性和均匀的粒子形态,故选择此共轭聚合物P-meth来检测有机小分子爆炸物硝基苯。本文探索了各种有机小分子对悬浮液荧光的响应情况,发现硝基苯对悬浮液荧光近乎完全猝灭,通过聚合物P-meth检测硝基苯的选择性、竞争性和灵敏性实验,发现此共轭聚合物对硝基苯的检测浓度可低至10 ppm,且在低浓度10-250 ppm范围内,荧光猝灭效率与硝基苯浓度之间的曲线呈现良好的线性关系,且线性相关系数为0.9953。在检测过程中,由于电子发生了从富电子的共轭聚席夫碱向吸电子硝基苯的转移,故导致了荧光的猝灭。目前共轭聚席夫碱的应用多局限于金属离子的检测,对小分子爆炸物的检测鲜有报道,因此,本章中将荧光共轭聚席夫碱应用于硝基苯(NB)的检测具有十分重要的意义。
[Abstract]:Environmental pollution and safety problems have always been the focus of attention, especially the pollution of metal ions and the harm of nitro aromatic explosives, which have attracted the attention of researchers. When detecting metal ions and small organic molecules, fluorescent polymers have the advantages of high sensitivity, good selectivity, simple operation and real-time on-line detection. It is widely used. This paper is mainly aimed at the complicated process of polymer synthesis, complex and difficult monomers and difficult fluorescent color adjustment. A series of fluorescent polymers are prepared by the condensation polymerization of amino aldehyde by heating reflux. The main research contents are as follows. First, the simple and easy materials, such as melamine and acetaldehyde, are selected by condensation of melamine and acetaldehyde to obtain blue light polymer solution by condensation of melamine and acetaldehyde, and then the solid blue light materials are deposited by acetone solvent. Fourier transform infrared spectroscopy (FT-IR), solid state carbon spectroscopy (13C-NMR), X ray diffraction (XRD), thermogravimetric analysis (TG-DTA), and fluorimetry are used. The structure and properties of the products were analyzed by PL, UV absorption spectroscopy and fluorescence lifetime test. By the PL fluorescence determination of solid products in aqueous solution and the response of various metal ions to the fluorescence of the solution, the blue photoluminescence was determined to have good selectivity for Cu2+ in aqueous solution. And with the increasing of Cu2+ concentration from 5 N M to 750 M, the degree of fluorescence quenching showed an upward trend. Based on the Stern-Volmer relation between the relative fluorescence intensity of F0/F and the concentration of Cu2+, the standard curve showed a good linear relationship when the concentration of Cu2+ was in the low concentration of 0-100 nM, and the linear relationship was in the linear phase relationship. The number is 0.99226 and the detection limit of LOD is 16.2nM. according to EPA data. The standard of Cu2+ in drinking water is about 20 mu M, and the target of sewage discharge is about 7.8 mu M, which is within the range of detectable. Because the polymer contains rich N, O elements, and Cu2+ is very easy to form complex with the substance containing these elements. The above results show that melamine B two aldehyde blue material has potential application value in the field of copper ion fluorescence sensing. Secondly, using the heating reflux method, with low cost, simple and easy difunctional groups of benzaldehyde and ammonia water as raw materials, methanol, DMF, DMSO as solvents, the preparation of amino aldehyde condensation. A series of new double schiff base conjugated polymers, and their fluorescence changes from blue to green to yellowish green, were analyzed by means of 13C-NMR, PXRD and FT-IR, and their morphologies were analyzed by FE-SEM test, and the series of conjugated polymers were explored by TG-DTA. By comparing the fluorescence intensity of the Conjugated Poly Schiff base suspension, the stability of the excited emission wavelength and the contrast analysis of the morphology and thermal stability, it is found that the polymers synthesized by the methanol to the solvent have good thermal stability and uniform particle morphology. Therefore, this conjugated polymer P-meth is selected to detect small organic molecules. Detonation of nitrobenzene. In this paper, the response of various organic small molecules to the fluorescence of the suspension was explored. It was found that nitrobenzene was almost completely quenched by the fluorescence of the suspension. The selectivity, competition and sensitivity of the nitrobenzene was detected by the polymer P-meth, and the detection concentration of the conjugated polymer to nitrobenzene could be as low as 10 ppm, and it was low concentration. In the range of 10-250 ppm, the fluorescence quenching efficiency has a good linear relationship with the concentration of nitrobenzene, and the linear correlation coefficient is 0.9953. in the detection process. Due to the electron transfer from the Conjugated Poly Schiff base to the absorption of the nitrobenzene, the fluorescence quenching is caused. The application of the Conjugated Poly Schiff base at present. It is limited to the detection of metal ions and is rarely reported for the detection of small molecular explosives. Therefore, the application of fluorescent conjugated Schiff base to the detection of nitrobenzene (NB) is of great significance in this chapter.
【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】：O657.3
本文编号：2140016
[Abstract]:Environmental pollution and safety problems have always been the focus of attention, especially the pollution of metal ions and the harm of nitro aromatic explosives, which have attracted the attention of researchers. When detecting metal ions and small organic molecules, fluorescent polymers have the advantages of high sensitivity, good selectivity, simple operation and real-time on-line detection. It is widely used. This paper is mainly aimed at the complicated process of polymer synthesis, complex and difficult monomers and difficult fluorescent color adjustment. A series of fluorescent polymers are prepared by the condensation polymerization of amino aldehyde by heating reflux. The main research contents are as follows. First, the simple and easy materials, such as melamine and acetaldehyde, are selected by condensation of melamine and acetaldehyde to obtain blue light polymer solution by condensation of melamine and acetaldehyde, and then the solid blue light materials are deposited by acetone solvent. Fourier transform infrared spectroscopy (FT-IR), solid state carbon spectroscopy (13C-NMR), X ray diffraction (XRD), thermogravimetric analysis (TG-DTA), and fluorimetry are used. The structure and properties of the products were analyzed by PL, UV absorption spectroscopy and fluorescence lifetime test. By the PL fluorescence determination of solid products in aqueous solution and the response of various metal ions to the fluorescence of the solution, the blue photoluminescence was determined to have good selectivity for Cu2+ in aqueous solution. And with the increasing of Cu2+ concentration from 5 N M to 750 M, the degree of fluorescence quenching showed an upward trend. Based on the Stern-Volmer relation between the relative fluorescence intensity of F0/F and the concentration of Cu2+, the standard curve showed a good linear relationship when the concentration of Cu2+ was in the low concentration of 0-100 nM, and the linear relationship was in the linear phase relationship. The number is 0.99226 and the detection limit of LOD is 16.2nM. according to EPA data. The standard of Cu2+ in drinking water is about 20 mu M, and the target of sewage discharge is about 7.8 mu M, which is within the range of detectable. Because the polymer contains rich N, O elements, and Cu2+ is very easy to form complex with the substance containing these elements. The above results show that melamine B two aldehyde blue material has potential application value in the field of copper ion fluorescence sensing. Secondly, using the heating reflux method, with low cost, simple and easy difunctional groups of benzaldehyde and ammonia water as raw materials, methanol, DMF, DMSO as solvents, the preparation of amino aldehyde condensation. A series of new double schiff base conjugated polymers, and their fluorescence changes from blue to green to yellowish green, were analyzed by means of 13C-NMR, PXRD and FT-IR, and their morphologies were analyzed by FE-SEM test, and the series of conjugated polymers were explored by TG-DTA. By comparing the fluorescence intensity of the Conjugated Poly Schiff base suspension, the stability of the excited emission wavelength and the contrast analysis of the morphology and thermal stability, it is found that the polymers synthesized by the methanol to the solvent have good thermal stability and uniform particle morphology. Therefore, this conjugated polymer P-meth is selected to detect small organic molecules. Detonation of nitrobenzene. In this paper, the response of various organic small molecules to the fluorescence of the suspension was explored. It was found that nitrobenzene was almost completely quenched by the fluorescence of the suspension. The selectivity, competition and sensitivity of the nitrobenzene was detected by the polymer P-meth, and the detection concentration of the conjugated polymer to nitrobenzene could be as low as 10 ppm, and it was low concentration. In the range of 10-250 ppm, the fluorescence quenching efficiency has a good linear relationship with the concentration of nitrobenzene, and the linear correlation coefficient is 0.9953. in the detection process. Due to the electron transfer from the Conjugated Poly Schiff base to the absorption of the nitrobenzene, the fluorescence quenching is caused. The application of the Conjugated Poly Schiff base at present. It is limited to the detection of metal ions and is rarely reported for the detection of small molecular explosives. Therefore, the application of fluorescent conjugated Schiff base to the detection of nitrobenzene (NB) is of great significance in this chapter.
【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】：O657.3
【参考文献】
相关期刊论文 前2条
1 陈云;邵亚;范丽娟;;共轭高分子材料荧光颜色的调节机理及方法[J];化学进展;2014年11期
2 武照强;孟令芝;;荧光聚合物研究进展[J];化学进展;2007年09期
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