熒光聚合物的合成、性能及其對金屬離子和有機小分子的傳感作用
發(fā)布時間：2018-07-23 16:44
【摘要】：環(huán)境污染和安全問題一直是人們關(guān)注的焦點,尤其是金屬離子的污染和硝基芳香爆炸物的危害,引起了研究者的重點關(guān)注。熒光聚合物檢測金屬離子和有機小分子時,因具有靈敏度高、選擇性好、操作簡便以及實時在線檢測等優(yōu)點而被廣泛應(yīng)用。本論文主要針對聚合物合成過程繁瑣、單體復(fù)雜難得、熒光調(diào)色困難等問題,采用加熱回流這種簡單易行的方法,通過胺醛縮聚制備了一系列熒光聚合物,并將其應(yīng)用于金屬離子和硝基芳香爆炸物檢測領(lǐng)域中。主要研究內(nèi)容如下:首先,采用加熱回流法,選擇三聚氰胺和乙二醛等簡單易得的原料通過胺醛縮合得到藍光聚合物溶液,然后用丙酮溶劑沉積得到固體藍光材料。采用傅里葉變換紅外光譜(FT-IR)、固體核磁碳譜(13C-NMR)、X射線衍射(XRD)、熱重分析(TG-DTA)、熒光光譜(PL)、紫外吸收光譜及熒光壽命測試等表征方法分析了產(chǎn)物的結(jié)構(gòu)組成和性能。通過固體產(chǎn)物分散于水溶液中的PL熒光測定,以及各種金屬離子對溶液熒光的響應(yīng)情況,確定了該藍光聚合物對水溶液中的Cu2+有良好的選擇性、靈敏性和抗干擾性。并且隨著Cu2+濃度從5 n M到750μM的逐漸增加,熒光猝滅程度呈現(xiàn)上升趨勢�；诰酆衔锵鄬晒鈴姸菷0/F與Cu2+濃度之間的Stern-Volmer關(guān)系式,當Cu2+濃度處于低濃度0-100 nM范圍內(nèi)時,標準曲線呈現(xiàn)良好的線性關(guān)系,且線性相關(guān)系數(shù)為0.99226,檢出限LOD為16.2nM。根據(jù)EPA的數(shù)據(jù)顯示,飲用水中Cu2+的標準約為20μM,污水排放中的指標約為7.8μM,均在可檢測范圍之內(nèi)。由于該聚合物中含有豐富的N、O元素,而Cu2+又極易與含這些元素的物質(zhì)形成絡(luò)合物,故導(dǎo)致了藍光的猝滅從而達到檢測的目的。以上結(jié)果表明三聚氰胺-乙二醛藍光材料在銅離子熒光傳感領(lǐng)域具有潛在的應(yīng)用價值。其次,采用加熱回流法,以成本低、簡單易得的雙官能團對苯二甲醛和氨水為原料,分別用甲醇、DMF、DMSO作為溶劑,通過胺醛縮合制備了一系列新型的雙席夫堿共軛聚合物,且它們的熒光發(fā)生了由藍綠→綠色→黃綠色的轉(zhuǎn)變。通過13C-NMR,PXRD和FT-IR等表征手段,分析了該系列聚合物的結(jié)構(gòu)組成;分別通過FE-SEM測試,分析了它們的形貌特征;又通過TG-DTA探索了這系列共軛聚合物的熱穩(wěn)定性。通過該系列共軛聚席夫堿懸浮液的熒光強度和激發(fā)發(fā)射波長穩(wěn)定性,以及形貌和熱穩(wěn)定性對比分析,發(fā)現(xiàn)甲醇為溶劑合成的聚合物具有良好的熱穩(wěn)定性和均勻的粒子形態(tài),故選擇此共軛聚合物P-meth來檢測有機小分子爆炸物硝基苯。本文探索了各種有機小分子對懸浮液熒光的響應(yīng)情況,發(fā)現(xiàn)硝基苯對懸浮液熒光近乎完全猝滅,通過聚合物P-meth檢測硝基苯的選擇性、競爭性和靈敏性實驗,發(fā)現(xiàn)此共軛聚合物對硝基苯的檢測濃度可低至10 ppm,且在低濃度10-250 ppm范圍內(nèi),熒光猝滅效率與硝基苯濃度之間的曲線呈現(xiàn)良好的線性關(guān)系,且線性相關(guān)系數(shù)為0.9953。在檢測過程中,由于電子發(fā)生了從富電子的共軛聚席夫堿向吸電子硝基苯的轉(zhuǎn)移,故導(dǎo)致了熒光的猝滅。目前共軛聚席夫堿的應(yīng)用多局限于金屬離子的檢測,對小分子爆炸物的檢測鮮有報道,因此,本章中將熒光共軛聚席夫堿應(yīng)用于硝基苯(NB)的檢測具有十分重要的意義。
[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.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3
本文編號：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.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3
【參考文獻】
相關(guān)期刊論文 前2條
1 陳云;邵亞;范麗娟;;共軛高分子材料熒光顏色的調(diào)節(jié)機理及方法[J];化學(xué)進展;2014年11期
2 武照強;孟令芝;;熒光聚合物研究進展[J];化學(xué)進展;2007年09期
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