【摘要】：環(huán)境污染一直是當今社會的一個熱門話題,環(huán)境污染的檢測也引起了科學家的關注,并且已經(jīng)成為環(huán)境科學研究中的重要領域。一些金屬離子和陰離子過量都會造成生態(tài)環(huán)境的污染,并且對人體造成傷害,引起疾病。所以研究定性定量檢測金屬離子和陰離子的分析方法是有意義的。熒光傳感器技術在近幾年得到快速發(fā)展,因為熒光傳感器檢測具有選擇性好、靈敏度高、儀器設備簡單易操作、可即時性肉眼觀察識別等優(yōu)。可用于生態(tài)環(huán)境中離子檢測以及生物活性細胞成像技術,實際應用發(fā)揮著重要作用。本論文致力于設計合成了一系列基于有機熒光染料的新型小分子熒光探針用于環(huán)境中金屬陽離子以及陰離子的選擇性識別與檢測。(1)基于金屬離子能誘導羅丹明染料中酰胺螺環(huán)開環(huán)從而引起顏色及熒光顯著變化的原理設計合成了新型的熒光比色探針1。考察了探針1對一系列金屬陽離子的響應特性,發(fā)現(xiàn)該探針僅對Fe~(3+)和Cu~(2+)離子表現(xiàn)出了顏色變化和熒光增強、選擇性好、檢測限低、可逆等響應優(yōu)點。并采用理論和實驗相結合的方式,即利用紫外熒光滴定光譜、紅外光譜和密度泛函理論,對探針1選擇性響應Fe~(3+)和Cu~(2+)離子的響應機理進行了初步探討。然后通過簡單的試紙試驗成功將探針1用于環(huán)境樣品中Fe~(3+)和Cu~(2+)離子的檢測。(2)基于羅丹明染料獨特的內(nèi)酯結構和硫原子的強親合性的,設計合成了新型的Fe~(3+)離子的熒光比色探針2。探針2能在純水環(huán)境中只對Fe~(3+)離子表現(xiàn)出了顏色變化和熒光增強、靈敏度高、檢測限低等響應優(yōu)點。同樣,采用紫外熒光滴定光譜法初步探討了探針2高選擇性響應Fe~(3+)離子的響應機理。探針2成功用于活細胞中的Fe~(3+)離子檢測,表明該探針在化學傳感以及生物成像領域具有潛在的應用價值。(3)基于羥基香豆素染料能方便地利用羥基位點來控制熒光“開-光”和SO_3~(2-)離子能誘導乙酰丙�；Ｗo的羥基基團脫去保護的原理,設計合成了新穎的用于選擇性檢測SO_3~(2-)陰離子熒光紫外比值探針3。考察這個SO_3~(2-)熒光紫外比值探針的光譜性質(zhì),發(fā)現(xiàn)該探針在純水環(huán)境中對SO_3~(2-)陰離子表現(xiàn)出了熒光增強、紫外比值信號線性增加、靈敏度高、以及響應時間迅速的檢測優(yōu)點。并通過ESI-MS譜圖證明了探針3與SO_3~(2-)陰離子的響應機理。探針3成功用于活細胞中的SO_3~(2-)陰離子的檢測。該探針為開發(fā)更多的熒光紫外比值探針提供了平臺。(4)基于香豆素熒光基團設計合成的熒光探針4,選擇性檢測ClO~-陰離子。ClO~-陰離子與探針4上的酰胺反應,使酰胺發(fā)生水解生成6-羧基香豆素產(chǎn)生藍色熒光。探究了ClO~-熒光探針的光譜性質(zhì),發(fā)現(xiàn)探針4能夠在純水環(huán)境中對ClO~-陰離子表現(xiàn)出熒光紫外信號線性增強、靈敏度高、響應時間短等優(yōu)異的光譜性質(zhì)。通過檢測探針4與ClO~-陰離子反應后的溶液體系ESI-MS譜圖證明探針4與ClO~-陰離子的響應機理。探針4成功的應用于生物活細胞中熒光成像實驗。
[Abstract]:Environmental pollution has always been a hot topic in the society, and the detection of environmental pollution has also attracted the attention of scientists and has become an important area in environmental science research. The excess of some metal ions and anions can cause the pollution of the ecological environment and cause harm to the human body and cause the disease. Therefore, it is of great significance to study the analytical methods for the qualitative and quantitative detection of metal ions and anions. The fluorescence sensor technology has been developed rapidly in recent years, because the detection of the fluorescence sensor has the advantages of good selectivity, high sensitivity, simple and easy operation of the instrument and the like, and can be used to observe and recognize the real-time naked eye. can be used for ion detection in the ecological environment and the biological active cell imaging technology, and the practical application plays an important role. This paper is devoted to the design and synthesis of a series of new small molecular fluorescent probes based on organic fluorescent dyes for selective identification and detection of metal cations and anions in the environment. and (1) a novel fluorescent colorimetric probe 1 is designed and synthesized on the basis of the principle that metal ions can induce the ring-opening of the alicyclic amine in the rhodamine dye so as to cause a significant change of color and fluorescence. The response characteristics of the probe (1) to a series of metal cations were investigated. It was found that the probe only has the advantages of color change and fluorescence enhancement, good selectivity, low detection limit and reversible response to the Fe ~ (3 +) and Cu ~ (2 +) ions. The response mechanism of the selective response of the probe 1 to the Fe ~ (3 +) and Cu ~ (2 +) ions was discussed by means of the combination of theory and experiment. and then the probe 1 is successfully used for detecting the Fe ~ (3 +) and Cu ~ (2 +) ions in the environment sample through a simple test paper test. (2) The novel Fe ~ (3 +) ion-based fluorescent colorimetric probe 2 was designed based on the unique lactone structure of rhodamine dye and the strong affinity of the sulfur atom. in that pure wat environment, the probe 2 has the advantages of color change and fluorescence enhancement, high sensitivity, low detection limit and the like in the pure water environment. In the same way, the response mechanism of the high selectivity of the probe 2 in response to the Fe ~ (3 +) ion was studied by UV-fluorescence titration. The probe 2 is successfully used for the detection of Fe ~ (3 +) ions in living cells, which indicates that the probe has potential application value in the field of chemical sensing and biological imaging. (3) Based on the principle that the hydroxyl group can be conveniently used to control the deprotection of the hydroxyl group protected by the fluorescent 鈥渙pen-light鈥，

本文編號：2377586