【摘要】：近年來,具有聚集態(tài)熒光增強(qiáng)效應(yīng)(AIE)和機(jī)械壓制熒光變色(MFC)的化合物越來越受到科學(xué)研究者們的關(guān)注。它們可以應(yīng)用于生物探針、壓力傳感器等器件中。本文主要研究了一類V-型分子以及相應(yīng)X-型分子的光物理性質(zhì),建立了初步的性能與結(jié)構(gòu)之間的構(gòu)效關(guān)系;同時設(shè)計(jì)開發(fā)了一種新穎的基于AIE效應(yīng)機(jī)制的、具有V-型分子結(jié)構(gòu)的關(guān)閉-開啟”型氰根離子探針,對其響應(yīng)性能進(jìn)行了測定。主要研究內(nèi)容如下:1、合成了一種具有V-型分子結(jié)構(gòu)的熒光化合物,即(E)-2'-[2-(苯并[d]噻唑-2-基)乙烯基]-N,N-二甲基-4-(1,1'-聯(lián)苯基胺)及其線形異構(gòu)體,并對它們的熒光性質(zhì)進(jìn)行了測定。由于HOMO與LOMO軌道電子云密度的獨(dú)立分布,使其在不同極性溶劑中表現(xiàn)出強(qiáng)烈的ICT效應(yīng)。研究表明,該分子在高水含量的乙醇/水混合液中具有強(qiáng)烈的熒光源于其在高濃度條件下的聚集態(tài)誘導(dǎo)發(fā)光效應(yīng)(AIE),其線性異構(gòu)體則沒有此現(xiàn)象。由于化合物扭曲的空間結(jié)構(gòu)和疏松的分子堆積模式,使得其受到外界壓力刺激情況下能發(fā)生明顯的機(jī)械壓制熒光變色(MFC)現(xiàn)象,而線性異構(gòu)體的堆積較為緊密則沒有MFC性質(zhì)。此外,由于其對三氟乙酸具有獨(dú)特的加和能力,該化合物可以應(yīng)用于一種加密和解密程序非常簡單的安全墨水的開發(fā)。2、合成了上述V-型分子的一些類似物和相應(yīng)的部分X-型分子,并對它們的熒光性質(zhì)進(jìn)行了測定,建立了初步的性能與結(jié)構(gòu)之間的構(gòu)效關(guān)系。與V-型分子相比,X-型分子由于較大的π共軛效應(yīng)使其在溶液和固態(tài)中顯示出更長的熒光發(fā)射。研究表明,給電子官能團(tuán)的能力越大使其在極性溶劑中ICT效應(yīng)越明顯。在聚集態(tài)時,由于苯基核上的兩個取代基的鄰位排列導(dǎo)致分子具有高度扭曲的構(gòu)象和松散的分子堆積,使得它們能表現(xiàn)出現(xiàn)強(qiáng)烈地固體熒光發(fā)射。同時給電子官能團(tuán)為N,N-二甲氨基的化合物具有機(jī)械熒光變色(MFC)性質(zhì),對周圍的pH變化敏感,遇到三氟乙酸后導(dǎo)致氫鍵的消失和晶格的塌陷。能夠發(fā)生MFC現(xiàn)象V-型化合物都具有松散的分子堆積和扭曲的分子構(gòu)象,X-型分子雖然也具有此結(jié)構(gòu),但是由于其分子體系過大導(dǎo)致超結(jié)晶而不能發(fā)現(xiàn)MFC現(xiàn)象。3、合成了一種具有V-型分子結(jié)構(gòu)的新型氰根離子探針,即2-[2-[4-(二甲基氨基)苯基]苯基]-1,3,3-三甲基-3H-吲哚摀碘化物探針,并對其性質(zhì)進(jìn)行了測定。研究表明,該探針的響應(yīng)機(jī)制源于其與氰根離子作用后加合物的AIE效應(yīng)。同時該探針顯示出了相較于文獻(xiàn)報(bào)道的其他氰根離子探針更低的檢測限(55 nM)和更快的響應(yīng)時間(15-20 s)。除了磷酸根與碳酸根離子對其產(chǎn)生微弱的干擾之外,其他20余中常見陰離子的共存對其檢測性能無任何影響。此外,我們將該探針吸附于濾紙上開發(fā)成為一種即用即拋型的探針試紙,可方便的用于氰根離子的現(xiàn)場快速檢測。
[Abstract]:In recent years, compounds with aggregated fluorescence enhancement effect (AIE) and mechanical suppression of fluorescent discoloration (MFC) have attracted more and more attention from scientific researchers. They can be used in biological probes, pressure sensors and other devices. In this paper, the photophysical properties of a class of V-type molecules and their corresponding X- molecules are studied, and the structure-activity relationship between the properties and structures is established, and a novel mechanism based on the AIE effect is designed and developed. The response properties of the closed-open type cyanoion probe with V-type molecular structure were determined. The main contents of this study are as follows: 1. A novel fluorescent compound with V- type molecular structure, (E)-2-[2- (benzo [d] thiazolyl) vinyl]-N- N- dimethyl-4- (1h1-diphenyl amine) and its linear isomers were synthesized and their fluorescence properties were determined. Because of the independent distribution of electron cloud density between HOMO and LOMO orbitals, they exhibit strong ICT effect in different polar solvents. The results show that the strong fluorescence of the molecule in ethanol / water mixture with high water content is due to the aggregation state induced luminescence effect of the molecule at high concentration (AIE), and its linear isomer does not have this phenomenon. Due to the distorted spatial structure of compounds and loose molecular stacking mode, obvious mechanical suppression of fluorescent discoloration (MFC) can occur under external pressure stimulation, while the stacking of linear isomers has no MFC property. In addition, due to its unique additive capacity for trifluoroacetic acid, The compound can be used in the development of a very simple encryption and decryption procedure for the development of safe ink. Some analogues of the V- type molecules and some corresponding X- type molecules have been synthesized and their fluorescence properties have been determined. A preliminary structure-activity relationship between properties and structures was established. Compared with the V- type molecule, the X- type molecule exhibits longer fluorescence emission in solution and solid state due to the larger 蟺 conjugation effect. It is shown that the greater the ability of giving electron functional groups, the more obvious the ICT effect in polar solvents. Due to the orthoalignment of the two substituents on the phenyl nucleus, the molecules have highly distorted conformation and loose molecular stacking, which makes them exhibit strong solid fluorescence emission. At the same time, the compounds with N ~ (2 +) N-dimethylamino have the properties of (MFC), which are sensitive to the pH change of the surroundings, and lead to the disappearance of hydrogen bond and the collapse of lattice after encountering trifluoroacetic acid. V- type compounds have loose molecular stacking and distorted molecular conformation although they also have this structure. However, a new cyanide ion probe, 2- [2- [4- [4- (dimethyl amino) phenyl] -1n (3) trimethyl -3H-indole-containing iodide probe, was synthesized because its molecular system was too large to lead to supercrystallization and the phenomenon of MFC could not be found. Its properties were determined. It is shown that the response mechanism of the probe is due to the AIE effect of the adduct after it acts with cyanide ion. The probe also shows a lower detection limit (55nm) and a faster response time (15-20 s).) than other cyanide probes reported in the literature. In addition to the weak interference of phosphate and carbonate ions, the coexistence of other common anions in more than 20 years had no effect on their detection performance. In addition, the probe is adsorbed on filter paper and developed into a kind of disposable probe test paper, which can be used for rapid detection of cyanide ions in situ.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3

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