【作者】 王小亮；

【导师】 姜世梅；

【作者基本信息】 吉林大学 ， 物理化学， 2011， 硕士

【摘要】 分子识别是超分子化学研究的核心内容。分子识别包括阳离子识别、阴离子识别和中性分子识别。近年来人们将分子识别运用到分子逻辑上,在未来的微电子学和信息技术上有很大的发展空间。水杨醛类西佛碱分子可以与多种阴阳离子作用,其离子识别性质在分子逻辑上有广阔的应用前景。本论文的主体思想是设计并合成新颖的水杨醛类西佛碱分子,进而详细研究其对阴阳离子的识别性质,并尝试将其运用到分子逻辑电路中。本论文开展了以下几个方面的研究:1、利用一系列含有推电子基团、拉电子基团和不同共轭程度的六种水杨醛分子分别与对苯二胺和2-苯基-3-（对胺基苯）丙烯腈通过简单的醛胺缩合反应得到两大类水杨醛西佛碱分子。2、利用含氯原子取代水杨醛西佛碱B2分子（3,5-二氯水杨醛与2-苯基-3-（对胺基苯）丙烯腈）反应得到)研究其阴离子识别性质。发现该分子在THF溶液中通过荧光光谱可选择性识别CN^￣,在THF溶液和THF与水的混合溶液（4:1, v/v）中通过紫外光谱可选择性识别CN^￣,同时可以达到“裸眼”识别的效果。3、利用含胺基取代水杨醛西佛碱B5分子（3,5-二叔丁基水杨醛与2-苯基-3-（对胺基苯）丙烯腈）反应得到)研究其在THF溶液中对阴阳离子的识别性质。研究表明B5分子通过紫外和荧光光谱可以选择性地识别Zn²⁺、Cu²⁺、F^-和CN^￣,同时可以“裸眼”识别Cu²⁺、F^-和CN^￣,其中Cu²⁺的识别对于其它阳离子有很好地抗干扰能力。4、基于B5分子与阴阳离子作用的性质以及各种离子加入顺序的不同产生的荧光光谱结果,通过设定合适的逻辑阈值,我们构建了两个NOR门,一个XNOR门,两个INHIBIT门。同时依据加入10倍当量CN^￣和3倍当量Cu²⁺顺序不同时产生不同的荧光输出信号,成功构建一个具有逻辑存储功能的分子键盘。更多还原

【Abstract】 Supramolecular chemistry is“the chemistry beyond the molecule”, as opposed to molecular chemistry based on covalent bonds between atoms, supramolecular chemistry is based on weak intermolecular interaction. There is a need for more intermolecular binding sites and interaction to form strong intermolecular forces. Molecular recognition is one of the cores for molecular recognition, it includes cation recognition, anion recognition and neutral molecular recogniton. Molecular recognition is applied to molecuar logic function recently, there are excellent application prospects for microelectronics and information technology in the future. There are C = N bond and hydroxyl group on the benzene ring for the structure of salicylidene Schiff bases, which makes salicylidene Schiff bases can chelate with a variety of cations, while salicylaldehyde Schiff bases react with a lot of anions through nucleophilic addition reactions and intermolecular hydrogen bonding, so it is possible for salicylaldehyde Schiff bases to recognize the ions selectively and be used in molecular logic circuits. Therefore, the design and synthesis for new salicylaldehyde Schiff bases with ion recognition are great significance. We designed a series of salicylidene Schiff bases in order to research the selective recognition for ions and use them in molecular logic circuit.The work in this thesis mainly includes five parts as follow:First, we used six salicylaldehyde molecules with donating electron groups, withdrawing electron groups and different conjugated level’s goups to react with p- phenylenediamine and 2-phenyl-3-（p-aminophenyl）acrylonitrile by condensation reaction between aldehyde group and amine group, and the molecules’ purity were verified by NMR spectra.Second, we used three molecules with slightly different structures, namely, B1, B2 and C, to study the anion recognition ability by UV and fluorescence spectroscopy and found that only salicylidene Schiff base with chlorine atoms （B2） can selectively recognize CN^- better. Among the seven anions （10 equiv.） tested in THF solution, the UV-vis and fluorescence spectral changes for B2 upon addition of CN^-, AcO^￣and H₂PO₄^- were same, while there were no changes for spectroscopy adding Cl￣, Br￣and I￣into solution of B2. Unlike spectral changes of the six aions above, UV-vis and fluorescence spectra had a large change upon addition of CN^-, so B2 can recognize CN^- through spectral changes, and the naked eye observation also showed that only CN^- can result in colorless, orange to violet color changes. Andthen the corresponding color changes under a UV lamp were brown, red and blue. Moreover the absorbance spectra change of B2 with the addition of cyanide in THF-H2O （4:1, v/v） solution was large, and the color of the solution could also changed from colorless to yellow in the meantime. However, the addition of other anions including F^-, AcO^- and H₂PO₄^- didn’t promote any change of the absorbance spectra. Therefore cyanide could be detected by both the absorbance change and the naked-eye color change even in aqueous media.Third, we used salicylidene Schiff base with amino group （B5） in THF to study the cation recognition ability through adding eihgteen kinds of cations （3 equiv.） by UV-vis and fluorescence spectra and found that molecule B5 can selectively recognize Cu²⁺ and Zn²⁺ better. Then upon addition of Zn²⁺, the fluorescence emission intensity of B5 increased largely, while the fluorescence emission intensity quenched by adding CU2+ into the solution of B5, at the same time, the addition of other cations promoted no change of the fluorescence spectra or slightly decrease of the fluorescence intensity. So B5 can recognize Cu²⁺ and Zn²⁺ through fluorescence spectral changes, andthen the emission profiles of the B5/ Cu²⁺ complexes were unperturbed in the presence of other metal ions. In addition, B5 can only recognize Cu²⁺ through absorption spectral changes, and the absorption band centered at 423 nm gradually decreased with a light blue shift of the absorption band, moreover, the naked eye observation also showed that Cu²⁺ can bring about yellow to light yellow color changes.Fourth, we used salicylidene Schiff base with amino group （B5） in THF to study the anion recognition ability through adding seven anions （10 equiv.） by UV-vis and fluorescence spectra and found that molecule B5 can selectively recognize F^- and CN^- better. And upon addition of CN^-, the band centered at 543 nm gradually decreased with a new peak emerged at 470 nm, while the fluorescence emission intensity increased largely by adding F^- into the solution of B5, what is more, the addition of other ations didn?t promote any change of the fluorescence spectra. So B5 can recognize CN^- and F^- through fluorescence spectral changes. Andthen, B5 can recognize CN^- and F^- through absorption spectral changes, also ,the naked eye observation indicated that F^- and CN^- can bring about yellow to sepia and claybank changes respectively.Fifth, based on properties that B5 reacted with ions and changes of the fluorescence emission intensity by adding ions into B5 with different order, we successfully constructed two NOR gates, one XNOR gate and two INHIBIT gates by setting logic threshold reasonably. In addition, the chemical inputs of CN^- （10equiv.） and Cu²⁺ （3equiv.） in a sequential manner generated an output which mimicked the functions of a security keypad lock.更多还原