本文選題：多功能熒光傳感器 + 2　； 參考：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：熒光傳感器在環(huán)境污染監(jiān)測、生命科學(xué)、電子信息等領(lǐng)域扮演著非常重要的角色,并在最近十幾年里面取得了長足的發(fā)展。作為其中重要的一員,熒光化學(xué)傳感器由于具有高靈敏度、高選擇性、簡便易行以及實(shí)時(shí)檢測等優(yōu)點(diǎn)而備受關(guān)注。已有許多類型的熒光化學(xué)傳感器被設(shè)計(jì)合成并用于檢測陽離子、陰離子及氨基酸等分析物。但是大部分已報(bào)道的熒光化學(xué)傳感器的功能比較單一,只能對一種或兩種待分析物進(jìn)行檢測。通常來說制備這些傳感器比較繁瑣耗時(shí)。因此,設(shè)計(jì)一種能夠同時(shí)檢測多種不同待分析物的熒光化學(xué)傳感器就顯得非常有必要。和廣泛報(bào)道的熒光化學(xué)傳感器相比,熒光力傳感器(也被稱作力致變色材料)的發(fā)展還處在相對初級的階段。作為一種新的智能材料,熒光力傳感器因在很多領(lǐng)域具有潛在的應(yīng)用價(jià)值,比如說光學(xué)存儲、顯示、安全通信等,所以最近引起了研究學(xué)者的大量關(guān)注。目前,文獻(xiàn)中報(bào)道的這類材料在靈敏度、可回復(fù)性、熒光顏色變化的多樣性上還存在諸多問題。因此,開發(fā)新型的熒光力傳感器并賦予其以優(yōu)異的性能是非常有必要的。本論文的主要內(nèi)容及研究成果分為以下四個(gè)部分:1.通過Suzuki偶聯(lián)反應(yīng),設(shè)計(jì)、合成了兩種含有2,2'-聯(lián)咪唑單元的線形和支化共軛聚合物,并且研究了它們對金屬離子、氨基酸和酸性氣體的熒光傳感性能。結(jié)果發(fā)現(xiàn),這兩種聚合物的熒光都能夠通過光誘導(dǎo)電子轉(zhuǎn)移過程被Co2+有效地淬滅,表現(xiàn)出"關(guān)閉型"熒光響應(yīng)特性。其檢測過程不受Cu2+的干擾。聚合物對Ag+表現(xiàn)出"比率型"熒光變化。由于巰基對Ag+有很強(qiáng)的絡(luò)合作用,聚合物-Ag+配合物對半胱氨酸也表現(xiàn)出優(yōu)異的傳感性能。半光氨酸的線性檢測范圍可以通過改變配合物溶液中Ag+的當(dāng)量來方便的調(diào)節(jié)。此外,我們還發(fā)現(xiàn)當(dāng)聚合物溶液接觸HCl或NH3氣體時(shí),溶液的熒光顏色可以在綠色和藍(lán)色之間可逆的變化。相較于線形聚合物,支化聚合物具有更高的檢測靈敏度。這些結(jié)果說明這種基于2,2'-聯(lián)咪唑結(jié)構(gòu)單元的共軛聚合物可以用作一種性能優(yōu)異的多功能熒光化學(xué)傳感器。2.設(shè)計(jì)、合成了一種含2,2'-聯(lián)咪唑、苯并噻二唑及咔唑結(jié)構(gòu)單元的三元共軛聚合物P1。P1能夠在水溶液中形成形貌較為規(guī)整的球狀納米粒子。由于分子鏈中咔唑-聯(lián)咪唑和咔唑-苯并噻二唑單元之間存在非常明顯的熒光共振能量轉(zhuǎn)移效應(yīng),納米粒子表現(xiàn)出一定強(qiáng)度的橘黃色熒光(熒光量子產(chǎn)率為9%)。基于電荷轉(zhuǎn)移作用,該納米粒子能夠用于檢測缺電子的硝基化合物,并且對缺電子性最強(qiáng)的三硝基苯酚表現(xiàn)出最佳的靈敏度。其檢測過程不受各種金屬離子的干擾。我們還發(fā)現(xiàn)因?yàn)榧{米粒子的微相富集作用,對含水量高的納米粒子溶液來說具有更高的檢測靈敏度。3.設(shè)計(jì)、合成了兩種芘硼酸環(huán)狀酯化合物PPB和NPB,并對它們的固態(tài)熒光性質(zhì)進(jìn)行了研究。含有五元環(huán)狀硼酸酯的芘衍生物(PPB)表現(xiàn)出可逆的力致變色及氣致變色性質(zhì),并且在室溫下就具有很快地自回復(fù)能力(大約5分鐘)。而六元環(huán)狀硼酸酯化合物(NPB)卻并沒有表現(xiàn)出這一性質(zhì)。結(jié)果證明PPB和NPB的固態(tài)熒光性質(zhì)強(qiáng)烈地依賴于其分子的堆積結(jié)構(gòu)和固態(tài)塑性。相對更加柔軟的PPB晶體因?yàn)榇嬖诨泼?在受到剪切應(yīng)力的時(shí)候能夠通過分子滑移形成三明治夾心結(jié)構(gòu)的激基締合物。由于室溫下的回復(fù)速度很快,PPB可以用于制作具有自擦除能力的寫字板。4.基于羅丹明結(jié)構(gòu),我們設(shè)計(jì)、合成了一種新穎的力致變色彈性體。為了使第一重網(wǎng)絡(luò)分子鏈呈充分舒展?fàn)顟B(tài)以提高力響應(yīng)的靈敏度,彈性體經(jīng)過三次溶脹-光聚合反應(yīng)過程。結(jié)果表明最終的三重網(wǎng)絡(luò)彈性體顯示出非常獨(dú)特的性質(zhì)。在單軸連續(xù)拉伸及卸力期間,彈性體顯示出三種熒光顏色之間的變化。通過合理的調(diào)節(jié)拉伸比例,可以表現(xiàn)出多姿多彩的熒光顏色。這種新合成的力致變色基團(tuán)開環(huán)所形成的兩性離子熒光量子產(chǎn)率可以高達(dá)67%,這比廣泛使用的部花青素結(jié)構(gòu)高出近兩個(gè)數(shù)量級。另外,彈性體對力表現(xiàn)出很高的響應(yīng)靈敏度,其可檢測活化應(yīng)變值為0.24。因此可以用于偵測手指關(guān)節(jié)的相關(guān)運(yùn)動。彈性體的合成簡單、原料易得并且表現(xiàn)出很好的機(jī)械性能。這些因素都使其在實(shí)際應(yīng)用上非常具有優(yōu)勢。
[Abstract]:Fluorescence sensors have played a very important role in environmental pollution monitoring, life science, electronic information and other fields, and have made great progress in the last decade. As one of the important members, fluorescent chemical sensors have attracted much attention because of their advantages of high sensitivity, high selectivity, easy to use and real-time detection. There are many types of fluorescent chemical sensors designed to be synthesized and used to detect cations, anions and amino acids. But most of the reported fluorescent chemical sensors have a single function and can only detect one or two kinds of analytes. Generally, the preparation of these sensors is more time-consuming. Therefore, the design is designed. A fluorescent chemical sensor that can detect a variety of different analytes at the same time is necessary. Compared with the widely reported fluorescent chemical sensors, the development of a fluorescent force sensor (also called a force photochromic material) is still in a relatively primary stage. As a new intelligent material, the fluorescent force sensors are in a lot of collar. The domain has potential application value, such as optical storage, display, safe communication, and so on. So recently, a lot of attention has been paid to the researchers. At present, there are many questions on the variety of sensitivity, recoverability, and color change of the materials reported in the literature. Excellent performance is necessary. The main contents and research results of this paper are divided into four parts: 1. through the coupling reaction of Suzuki, two kinds of linear and branched conjugated polymers containing 2,2'- linimidazole are synthesized and their fluorescence sensing properties for metal ions, amino acids and acid gases are studied. It is found that the fluorescence of the two polymers can be effectively quenched by the photoinduced electron transfer process by Co2+, showing a "closed" fluorescence response characteristic. The detection process is not disturbed by Cu2+. The polymer shows a "ratio type" fluorescence change to Ag+. Because of the strong complexation of the sulfhydryl group to the Ag+, the polymer -Ag+ complex has the cysteamine. Acid also shows excellent sensing properties. The linear detection range of hemiparine can be easily regulated by changing the equivalent of Ag+ in the complex solution. In addition, we also find that when the polymer solution contacts the HCl or NH3 gas, the fluorescence color of the solution can be reversible in the green and blue between the green and the blue. These results show that the conjugated polymer based on the 2,2'- imidazole structural unit can be used as a multifunctional fluorescent chemical sensor.2. with excellent performance. The synthesis of a three element conjugated polymer containing 2,2'- imidazole, benzothiazole two azoles and carbazole junction units can be synthesized. Due to the obvious fluorescence resonance energy transfer effect between carbazole biazoles and carbazole benzothiazole two units in the molecular chain, the nanoparticles show a certain intensity of orange fluorescence (the fluorescence quantum yield is 9%). Based on the charge transfer effect, the nanoparticle is the nanoparticles. It can be used to detect nitro compounds lacking electrons and has the best sensitivity to the most electron deficient three nitrophenol. The detection process is not disturbed by various metal ions. We also found that the microphase enrichment of nanoparticles has a higher detection sensitivity.3. for the nanoparticles with high water content. Two kinds of pyrene borate cyclic ester compounds PPB and NPB were synthesized and their solid-state fluorescence properties were studied. The pyrene derivative (PPB) containing five membered ring borate (PPB) showed reversible photochromic and gas chromic properties, and at room temperature it had a fast self recovery capacity (about 5 minutes) and six membered ring borate ester. The compound (NPB) does not show this property. The results show that the solid-state fluorescence properties of PPB and NPB depend strongly on the stacking structure and solid plasticity of their molecules. The relatively softer PPB crystals can form the radical associates with sandwich sandwich structures at the time of shear stress, because of the existence of sliding surfaces. Because the recovery speed at room temperature is very fast, PPB can be used to make a self erasable writing board.4. based on the Luo Danming structure. We design a novel force photochromic elastomer. In order to make the first heavy network molecular chain fully stretches to improve the sensitivity of the force response, the elastomer passes three times of swelling photopolymerization. The results show that the final three heavy network elastomers show very unique properties. During the uniaxial continuous stretching and unloading, the elastomer shows the changes between the three kinds of fluorescent colors. By reasonable adjustment of the tensile ratio, the colorful fluorescent color can be displayed. This new synthetic force chromotropic group opens the ring. The fluorescence quantum yield of the amphoteric ion can be as high as 67%, which is nearly two orders of magnitude higher than that of the widely used anthocyanin structure. In addition, the elastic body has a high response sensitivity to the force, and it can detect the activation strain of 0.24. so that it can be used to detect the related motion of the finger joints. It also shows good mechanical properties. These factors make it very advantageous in practical applications.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O657.3
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本文編號：1832616