离子响应型智能超分子有机凝胶的设计合成及性能研究

发布时间：2018-11-10 09:43

【摘要】：本论文在总结了一些近些年来国内刺激响应性有机凝胶的一些研究进展和本课题组在离子刺激响应型超分子有机凝胶研究工作的基础上,设计合成了几个系列的基于长烷氧基链和芳酰腙的超分子有机凝胶因子。这些凝胶因子的设计思想是:在凝胶因子中同时引入长烷基链间的强范德华力、芳环间的π-π堆积作用和酰胺之间的多重氢键作用,从而得到具有多重自组装驱动力的凝胶因子,这种凝胶因子比只具有单一自组装驱动力的凝胶因子有更强的自组装能力。另外,为了实现对特定阴离子的专一选择性刺激响应,在引入自组装位点时,我们有选择的引入萘环、芳腙等这些既可以作为氢键自组装位点、又可以作为离子结合位点的官能团。为了实现专一荧光识别阴离子,我们引入萘、羟基萘、硝基苯等共轭的荧光基团。更重要的是,在同一超分子凝胶体系中,引入两种不同的金属离子和凝胶因子及阴离子竞争配位来控制刺激响应型超分子凝胶的荧光信号和客体识别性质。为了实现对特定离子的荧光选择性刺激响应,我们提供了一种‘‘竞争配位控制凝聚态荧光的模型’’来指导合成基于凝胶态的超分子化学传感器的新颖设计方案。因此,我们报道了一种基于双金属竞争配位控制阴离子的刺激响应型超分子凝胶的灵巧设计方法。为了证明此方法,基于多重自组装驱动力的凝胶因子G1被合成。凝胶因子G1和Ca2+配位形成凝聚态荧光很强的金属凝胶CaG1。在CaG1中加入Cu2+后,形成CaCuG1的金属凝胶,并且CaG的凝聚态荧光淬灭。CaCuG1通过CN-和Cu2+竞争配位,Ca2+再一次和G1配位,从而专一选择性的荧光检测CN-。因此,CaCuG可充当CN-的检测组件,还可用做可重复书写的安全显示材料。这种方法为设计新颖的刺激响应型超分子凝胶提供了广阔的思路。同理,在同一超分子凝胶体系中合理的引入Ca2+和Fe3+制备了CaFeG1双金属凝胶。CaFe G1能在凝胶状态下通过Ca2+和Fe3+与凝胶因子G1以及H2PO4-之间的竞争配位实现对H2PO4-的荧光可逆专一性识别。因此,CaFeG1不仅能够用于H2PO4-的检测组件,而且还可用做可擦写的安全显示材料。另外,我们合理的只引入一种金属离子制得金属凝胶来控制离子刺激响应性能。为了证明此方法,我们设计合成了凝胶因子G2,G2和Fe3+配位形成的金属凝胶Fe G2能荧光检测CN-。
[Abstract]:In this paper, some recent advances in the research of stimulus-responsive organic gels in China and the research work of our team on ionic stimulation-responsive supramolecular organic gels are summarized. Several series of supramolecular organic gel factors based on long alkoxy chain and aroylhydrazone were designed and synthesized. The design ideas of these gel factors are that the strong van der Waals force between long alkyl chains, 蟺-蟺 stacking between aromatic rings and multiple hydrogen bonds between amides are introduced simultaneously into the gel factors. Therefore, a gel factor with multiple self-assembly driving forces is obtained, which has stronger self-assembly ability than that with a single self-assembly driving force. In addition, in order to achieve the specific selective stimuli response to certain anions, when we introduce self-assembly sites, we can selectively introduce naphthalene ring, aryl hydrazone and so on, which can be used as hydrogen bond self-assembly sites. It can also be used as the functional group of ion binding sites. In order to realize specific fluorescence recognition of anions, conjugated fluorescent groups such as naphthalene, hydroxy naphthalene and nitrobenzene were introduced. More importantly, in the same supramolecular gel system, two different metal ions and gel factors and anion competitive coordination are introduced to control the fluorescence signals and guest recognition properties of stimulus-responsive supramolecular gels. In order to achieve a selective fluorescence response to specific ions, we provide a 'competitive coordination controlled condensed matter fluorescence model' to guide the novel design of a supermolecular chemosensor based on gel state. Therefore, we report a smart design method for stimulus-responsive supramolecular gels based on bimetallic competitive coordination control anions. In order to prove this method, the gel factor G1 based on multiple self-assembly driving force is synthesized. Coordination of Gel Factor G1 with Ca2 to form a Metal Gel CaG1. with strong fluorescence in Condensed matter After the addition of Cu2 to CaG1, the metal gels of CaCuG1 were formed, and the condensed matter fluorescence of CaG was quenched. CaCuG1 coordinated with Cu2 by CN- and Cu2, and Ca2 again coordinated with G1 to detect CN-. selectively. Therefore, CaCuG can be used as a detection component for CN- and as a security display material for repeatable writing. This method provides a broad idea for the design of novel stimuli-responsive supramolecular gels. In the same way, CaFeG1 bimetallic gels were prepared by introducing Ca2 and Fe3 into the same supramolecular gel system. CaFe G1 can recognize H _ 2PO _ 4- by competitive coordination of Ca2 and Fe3 with G _ 1 and H _ 2PO _ 4-. Therefore, CaFeG1 can be used not only for H _ 2PO _ 4-detection components, but also for erasable and safe display materials. In addition, we only introduce one kind of metal ions to prepare metal gel to control the response of ion stimulation. To prove this method, we have designed and synthesized the metal gel Fe G2, which is formed by the coordination of G2G 2 and Fe3, which can detect CN-. by fluorescence.
【学位授予单位】：西北师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O648.17

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