【作者】 童丁毅；

【导师】 林英杰；

【作者基本信息】 吉林大学 ， 有机化学， 2014， 博士

【摘要】 随着有机合成方法的不断推陈出新，人们开发出多种多样性能优良的有机荧光染料，而这些染料在军用和民用多个领域发挥着重要的作用。近年来，有机荧光染料也被经常用于化学传感和分子逻辑门。荧光传感器是以有机荧光染料为探针，利用分子识别原理来实现对待测物质的检测，具有灵敏度高、响应快速、试样量小等特点。而分子逻辑门则是将传统集成电路功能实现在分子尺度的新兴科学，广泛应用于生物传感与诊断，药物传输与释放，分子计算机等领域。芘和8-羟基喹啉就是其中被广泛修饰的荧光母核之一。因此，我们希望通过一些简单的有机反应修饰上一些特定的官能团，从而制备出性能优良的荧光染料，检测效果好的荧光探针和功能复杂的分子逻辑门。1.我们制备了六个芘基噻唑荧光染料分子，并进行了相应的紫外和荧光光谱表征，发现苯环的引入对其光谱性质影响很大，而甲基的引入影响甚微。在对其的荧光量子产率测定中，我们发现随着溶剂极性的增加，荧光量子产率随之提高。但是在乙醇中因为乙醇可以与之形成氢键而出现反常的小幅下降。接下来，我们在其单晶结构中发现了苯-噻唑堆积而不是像其他芘衍生物那样的芘-芘堆积，分析原因可能是由于这样的排列方式更利用空间。最后我们进行了理论化学计算，解释了之前测定的光谱性能，并发现染料分子内存在着一定程度上的分子内电荷转移。2.而后，我们合成了芘基查尔酮荧光染料分子，发现该染料具有集聚诱导缔合发光增强的特性。利用这个特性，我们设计了一种水溶性的荧光探针，经测试，其对聚阴离子（聚丙烯酸钠和DNA)和生物硫醇（半胱氨酸）有优良的传感性能。然后，我们根据这两种不同传感方式可以导致不同颜色的“Tunr-on”荧光信号，设计出一个新型的2-4分子译码器。这个分子译码器可以在水环境下工作，颜色变化可以被裸眼识别，对环境友好不使用有毒物质（氰根等）和重金属离子（汞离子等）。而据我们所知，查尔酮结构在集聚诱导缔合发光增强材料和分子译码器之前都未曾报道，未来我们也将拓展这类材料在更多领域上的应用。3.我们根据药物化学的相关文献，合成了基于芘基酰亚胺的分子逻辑门。我们发现其在不同pH环境下可以选择性识别汞离子和银离子，其它金属离子不会对此产生干扰，这与之前报道的只能对汞离子识别的茈酰亚胺探针和萘酰亚胺探针有很大的不同。为此，我们进行了深入的研究，发现由于分子共轭效应，胸腺嘧啶和胞嘧啶功能被集成到一个有机小分子里。之后，我们设计了以氢离子、银离子、汞离子和硫离子为输入端的分子逻辑门，该分子逻辑门拥有16种不同的输入组合和3个逻辑元件（INHIBITOR，OR和IMPLICATION)。然后，我们将该分子逻辑门制作成荧光纸，用于加密文字，首次将分子逻辑门应用于密码学领域。4.我们将酰亚胺结构嫁接在8-羟基喹啉上，设计成一个分子逻辑门。该分子逻辑门可以在水：乙醇比例为96:4的溶液中工作，能选择性与锌离子，镉离子，钇离子和镧离子结合成荧光配合物，之后我们筛选出铜离子作为前四种输入端的INHIBITOR,组成一个五输入的分子逻辑门。5.我们利用Vilsmeier-Haack-Arnold反应，Corey-link反应和Corey-Fuchs反应，以最简单的苯环来替代芘，蒽，菲等稠环芳香烃，从原料苯乙酮出发进行了炔类化合物的合成探索，用以探索从芳烃出发的一条有机染料合成新路线。更多还原

【Abstract】 With the innovation of organic synthesis methods, a vairety of organic fluorescentdyes have been developed that play an important role in various areas of military andcivilian. In recent years, organic fluorescent dyes have been also often used inchemosensing and molecular logic gates. Fluorescent chemosensors combine molecularrecognition with some form of reporter. And the presence of target can be detected withorganic fluorescence dyes as the indicator. It is simple, fast, sensitive, and inexpensive.Molecular logic gates are an emerging interdiscipline, utilizing integrated circuits inelectronics on a molecular scale. And they have been widely applied in biosensing anddiagnostics, prodrug activation and drug delivery/release, intelligent mateirals andmolecular computers.The pyrene and8-hydroxy quinoline (8-HQ) are two of important fluorescent dyes.Therefore, we would prepare many fluorescent dyes with good fluorescence propertiesfrom these two dyes, and develop their applications in sensing and logic gates.1. We developed new fluorescent dyes based on pyrenylthiazoles and studied thefluorescence and UV/Vis properties of these dyes. The introduction of the phenylgroup could cause significant change and the effect of the methyl group was notobvious in fluorescence emission. From the single crystal data, we found anarrangement of benzene-thiazole stacking rather than pyrene-pyrene stacking. And thetheoretical (TD-DFT) calculations were carried out and the intramolecular chargetransfer was observed in these dyes. The theoretical calculations are in good agreementwith the expeirmental data. 2. We synthesized an aggregation-enhanced excimer emission (AEEE) fluorophore byintroducing chalcone into pyrene. Then we designed a probe with good watersolubility based on pyrenylchalcone for polyanion (Polyacrylic acid sodium salt andDNA) detection in aqueous media. Moreover, we found that the addition of biothiol(Cysteine) could lead to another different "Turn-on" change in fluorescence. And wemade this AEEE-active probe into a2-to-4molecular decoder. Our molecular decodercould work in pure water and be observed by naked eyes. And it wasenvironmentally-friendly (Instead of heavy metal ions and poisons, such as mercuryand cyanide). To our knowledge, the chalcone for AEEE-designing and itsapplications in the molecular decoder have not been reported before. This class ofAEEE-active luminophore is expected to be applied in more area in future.3.By using the new method in medicinal chemistry, we developed a new molecular logicgate that utilized a succinic imide labelled pyrene probe as the signal responser.Different from perylenebisimide and naphthalimide probes, this new logic gate canhandle both A+2+gand Hg in different pH without interference from other metal ions.After further investigating, owing to its molecular conjugative effect, we found thatthe functions of cytosine and thymine were integrated into an organic molecular. Thenwe desi+gn a molecular logic gate for H+, A+g，H22g and S" which has16kinds of inputcombinations and3different kinds of gate symbols (INHIBITOR，OR andIMPLICATION). Moreover，this molecular logic gate could be made into fluorescentpapers and firstly applied in the field of cryptography.4.We introduced the imide structure into8-HQ and made this new molecular logic gatef23or Zn++, Cd2+，Y and La)+selectively. Then we designed a five-input molecularlo2+gic gate by another input of Cu as INHIBITOR.5.We used the Vilsmeier-Haack-Arnold reaction, Corey-link reaction and Corey-Fuchsreaction to explore a new synthesis route of organic dyes from aromatic compounds.更多还原