本文選題：重金屬識(shí)別　切入點(diǎn)：熒光化學(xué)傳感器　出處：《西南大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：工業(yè)作為經(jīng)濟(jì)騰飛的重要支柱,在世界經(jīng)濟(jì)發(fā)展的同時(shí),所導(dǎo)致的環(huán)境污染問題也日益嚴(yán)重。重金屬污染由于其處理難度大、周期長(zhǎng),成為一個(gè)嚴(yán)重的污染問題。汞因其特殊的物理化學(xué)性質(zhì),它的環(huán)境污染特性呈現(xiàn)高毒性、遷移性、持久性和生物積蓄性等顯著特點(diǎn),不僅會(huì)威脅生物健康,還會(huì)對(duì)整個(gè)環(huán)境造成持久的污染,儼然已成為全球最關(guān)注的污染物之一。隨著人們對(duì)環(huán)境問題重視程度的提高,水環(huán)境中重金屬離子的檢測(cè)識(shí)別及分離去除也備受關(guān)注。熒光化學(xué)傳感器能依外部環(huán)境的變化而改變自身熒光性能,使其能感知環(huán)境中存在的某種特定物質(zhì)的信息。BODIPY(氟硼二吡咯)為母體的熒光染料因其具有較強(qiáng)的熒光發(fā)射強(qiáng)度和良好的穩(wěn)定性而受到研究者們的重視。將BODIPY小分子熒光探針與大分子結(jié)合,制備具有重金屬離子識(shí)別功能的熒光高分子材料也是近幾年的研究熱點(diǎn)之一。本文制備了幾種能夠識(shí)別檢測(cè)重金屬離子汞離子(Hg~(2+))、鐵離子(Fe~(3+))和鉻離子(Cr~(3+))的BODIPY基小分子熒光探針,并將其中三種(B3a、B3b和B3c)小分子熒光探針接入聚氨酯制備出聚氨酯基大分子熒光傳感器,通過紫外-可見光譜和熒光光譜等分析方法研究了這幾種熒光探針對(duì)于重金屬離子的識(shí)別性能。具體研究如下:(1)利用核磁共振氫譜(1H-NMR)、傅里葉紅外光譜(FTIR)、質(zhì)譜(MS)等確認(rèn)了BODIPY小分子熒光探針的結(jié)構(gòu)。(2)通過控制反應(yīng)物的加入比例,可得到一個(gè)分子中分別含有一個(gè)和兩個(gè)熒光基元的小分子OS11和OS21。小分子OS11和OS21在純?nèi)軇┲?OS21的熒光強(qiáng)度是OS11熒光強(qiáng)度的兩倍,這是因?yàn)橐粋�(gè)OS11分子中只含有一個(gè)熒光團(tuán),而一個(gè)OS21分子中含有兩個(gè)熒光團(tuán)。分子中熒光基元越多,熒光強(qiáng)度越高。并且OS11和OS21在識(shí)別Hg~(2+)和Fe~(3+)時(shí),表現(xiàn)為熒光猝滅。而B3a、B3b和B3c能夠增強(qiáng)熒光強(qiáng)度識(shí)別Hg~(2+)、Fe~(3+)和Cr~(3+)。(3)實(shí)驗(yàn)表明,OS11能在pH為3.65-11.09的緩沖液中穩(wěn)定存在,OS21能在pH為3.16-11.88的緩沖液中穩(wěn)定存在。當(dāng)OS11和OS21與含有Hg~(2+)或Fe~(3+)的水溶液作用時(shí),OS11和OS21表現(xiàn)為熒光強(qiáng)度減弱,而OS21小分子溶液的熒光強(qiáng)度比OS11小分子溶液的熒光強(qiáng)度減弱的程度要大很多。同時(shí)OS11和OS21小分子溶液的顏色由玫紅色變?yōu)榈S色。工作曲線滴定實(shí)驗(yàn)表明,OS11和Fe~(3+)的絡(luò)合比為1:2,OS11和Hg~(2+)的絡(luò)合比為1:1,OS21與Fe~(3+)的絡(luò)合比為1:3,OS21與Hg~(2+)的絡(luò)合比為1:1。并且OS21小分子探針能夠識(shí)別Hg~(2+)濃度為0.5μmol/L。(4)B3a、B3b和B3c與Hg~(2+)、Fe~(3+)和Cr~(3+)溶液作用后,表現(xiàn)為熒光強(qiáng)度增強(qiáng)且顏色改變。B3a、B3b和B3c的小分子溶液由紅色變?yōu)辄S色。同時(shí),能識(shí)別濃度為2.5×10-6mol/mL的鐵離子溶液。當(dāng)將B3a、B3b和B3c引入到聚氨酯上制成聚氨酯膜(PU-B3a、PU-B3b和PU-B3c)后,小分子對(duì)金屬離子的選擇識(shí)別作用依然保持。小分子B3a、B3b和B3c的熒光峰出現(xiàn)在510nm左右,大分子聚氨酯膜的熒光峰在580nm附近出現(xiàn)了一個(gè)新峰。原子吸收實(shí)驗(yàn)表明,大分子聚氨酯膜PU-B3a單位時(shí)間內(nèi)可以吸收84mg/g Hg~(2+),PU-B3b的吸收值為80mg/g Hg~(2+),PU-B3c的吸收值為76mg/g Hg~(2+)。
[Abstract]:As an important pillar industry of economic development, economic development in the world at the same time, the problem of environmental pollution caused by heavy metal pollution is increasingly serious. Because of its difficulty, long period, become a serious pollution problem. Mercury due to its special physical and chemical properties, environmental pollution characteristics that showed high toxicity, mobility obviously, persistence and biological accumulation, not only threatens the health of living will cause persistent pollution to the whole environment, has become one of the world's most concerned pollutants. As people improve the degree of attention to environmental issues, detection and identification and separation of heavy metal ions in water to remove the fluorescent chemical is also of concern. The sensor can change their fluorescence properties according to changes in the external environment, so that it can be a specific material existence in the environment of information.BODIPY (fluorboric two pyrrole) as matrix. Light dye attention of researchers because of its strong fluorescence emission intensity and good stability. The BODIPY small molecule fluorescent probes and fluorescent molecules, to prepare polymer materials with metal ion recognition function is one of the research hotspot in recent years. This paper prepared several can identify the detection of heavy metal ions mercury ion (Hg~ (2+)), iron (Fe~ (3+)) and chromium (Cr~ (3+)) BODIPY based small molecule fluorescent probe, and three of them (B3a, B3b and B3c) small molecule fluorescent probe access prepared polyurethane based polyurethane macromolecular fluorescent sensor, by UV the visible spectrum and fluorescence spectrum analysis method to study the recognition performance of fluorescent probes for metal ions. The specific studies are as follows: (1) using nuclear magnetic resonance spectroscopy (1H-NMR), Fourier transform infrared spectroscopy (FTIR), mass spectrometry (MS) confirmed BODIPY small 瀛愯崸鍏夋帰閽堢殑緇撴瀯.(2)閫氳繃鎺у埗鍙嶅簲鐗╃殑鍔犲叆姣斾緥,鍙緱鍒頒竴涓垎瀛愪腑鍒嗗埆鍚湁涓，

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