新颖V-型荧光分子的合成、性能与应用研究
发布时间：2018-07-28 09:10
【摘要】：近年来,具有聚集态荧光增强效应(AIE)和机械压制荧光变色(MFC)的化合物越来越受到科学研究者们的关注。它们可以应用于生物探针、压力传感器等器件中。本文主要研究了一类V-型分子以及相应X-型分子的光物理性质,建立了初步的性能与结构之间的构效关系;同时设计开发了一种新颖的基于AIE效应机制的、具有V-型分子结构的关闭-开启”型氰根离子探针,对其响应性能进行了测定。主要研究内容如下:1、合成了一种具有V-型分子结构的荧光化合物,即(E)-2'-[2-(苯并[d]噻唑-2-基)乙烯基]-N,N-二甲基-4-(1,1'-联苯基胺)及其线形异构体,并对它们的荧光性质进行了测定。由于HOMO与LOMO轨道电子云密度的独立分布,使其在不同极性溶剂中表现出强烈的ICT效应。研究表明,该分子在高水含量的乙醇/水混合液中具有强烈的荧光源于其在高浓度条件下的聚集态诱导发光效应(AIE),其线性异构体则没有此现象。由于化合物扭曲的空间结构和疏松的分子堆积模式,使得其受到外界压力刺激情况下能发生明显的机械压制荧光变色(MFC)现象,而线性异构体的堆积较为紧密则没有MFC性质。此外,由于其对三氟乙酸具有独特的加和能力,该化合物可以应用于一种加密和解密程序非常简单的安全墨水的开发。2、合成了上述V-型分子的一些类似物和相应的部分X-型分子,并对它们的荧光性质进行了测定,建立了初步的性能与结构之间的构效关系。与V-型分子相比,X-型分子由于较大的π共轭效应使其在溶液和固态中显示出更长的荧光发射。研究表明,给电子官能团的能力越大使其在极性溶剂中ICT效应越明显。在聚集态时,由于苯基核上的两个取代基的邻位排列导致分子具有高度扭曲的构象和松散的分子堆积,使得它们能表现出现强烈地固体荧光发射。同时给电子官能团为N,N-二甲氨基的化合物具有机械荧光变色(MFC)性质,对周围的pH变化敏感,遇到三氟乙酸后导致氢键的消失和晶格的塌陷。能够发生MFC现象V-型化合物都具有松散的分子堆积和扭曲的分子构象,X-型分子虽然也具有此结构,但是由于其分子体系过大导致超结晶而不能发现MFC现象。3、合成了一种具有V-型分子结构的新型氰根离子探针,即2-[2-[4-(二甲基氨基)苯基]苯基]-1,3,3-三甲基-3H-吲哚摀碘化物探针,并对其性质进行了测定。研究表明,该探针的响应机制源于其与氰根离子作用后加合物的AIE效应。同时该探针显示出了相较于文献报道的其他氰根离子探针更低的检测限(55 nM)和更快的响应时间(15-20 s)。除了磷酸根与碳酸根离子对其产生微弱的干扰之外,其他20余中常见阴离子的共存对其检测性能无任何影响。此外,我们将该探针吸附于滤纸上开发成为一种即用即抛型的探针试纸,可方便的用于氰根离子的现场快速检测。
[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.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
[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.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
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