【作者】 胡美华；

【导师】 吴芳英；

【作者基本信息】 南昌大学 ， 分析化学， 2006， 硕士

【摘要】 以分子识别为基础的主-客体化学已经成为当今研究的热点，它包括对中性分子、阳离子和阴离子的识别。其中阴离子识别较前两者发展相对缓慢，亟待丰富和发展新型识别体系。阴离子能通过静电作用、氢键作用、疏水作用等与主体分子作用。依据基态电荷转移理论，筛选特异性识别阴离子的生色离子载体，建立了系列灵敏度高、选择性好的阴离子光化学传感体系，实现了“裸眼”检测阴离子。本学位论文共分五章介绍阴离子识别的发展状况，阐述本论文所建立的各类阴离子光化学传感体系及相关理论模型。 第一章文献综述，简要介绍了阴离子识别的发展现状，分析其发展缓慢的根源，概述己建立的阴离子识别体系，包括（1）阴离子的结构特点：（2）阴离子识别研究中所涉及的分子间相互作用力；（3）阴离子识别研究中所涉及的方法。 第二章设计合成了对硝基苯偶氮酚类化合物，比较了α-萘酚、8-羟基喹啉和苯酚等三类偶氮硝基苯衍生物的吸收光谱及其阴离子配合物稳定性的差异。研究表明，α-萘酚、8-羟基喹啉和苯酚等三个含酚羟基的偶氮硝基苯化合物均可识别阴离子客体，产生显著的光谱和颜色变化，实现了裸眼检测阴离子。就同一个主体分子而言，主-客体配合物的稳定常数大小依次为AcO^-＞F^-＞H₂PO₄^-＞Cl^-，与阴离子碱性强弱顺序一致；而不同主体分子对同一阴离子亲和力的大小顺序为：α-萘酚＞8-羟基喹啉＞苯酚，亲和力的大小与主体分子中电子供体的给电子能力和主体分子共轭体系的大小相关。 第三章应用吸收光谱滴定法研究了茜素与阴离子间的识别行为，比较了主体分子结构对阴离子配合物稳定性的影响。研究结果表明：在乙腈中，茜素通过氢键与F^-和AcO^-分别形成1∶2和1∶1型稳定的阴离子配合物，在长波长563nm和553nm处分别出现电荷转移吸收带，溶液由无色变为紫红色或浅紫色，其它的阴离子如H₂PO₄^-，HSO₄^-，ClO₄^-Cr^-及Br^-等未引起明显的光谱及溶液颜色的变化。同时考察了2,4-二羟基苯甲酸和3,4-二羟基苯甲酸对阴离子的识别作用，发现：F^-对上述两个化合物吸收光谱影响相似，无明显差异；而AcO^-对两者的光谱影响差别较大。因此，我们认为茜素对F^-和AcO^-具有选择性识别作用，取决于阴离子的碱性和主体分子的空间结构。 第四章设计合成了偶氮苯二酚类化合物，比较了不同取代基的偶氮间苯二酚化合物的吸收光谱及其阴离子配合物稳定性的差异，同时还比较了羟基个数和位置对阴离子配合物稳定性的差异。研究表明：偶氮间苯二酚衍生物、对硝基苯偶氮邻苯二酚和对硝基苯偶氮苯酚等偶氮苯化合物均可识别阴离子客体，产生明显的光谱和颜色变化，实现了裸眼检测阴离子。对于偶氮间苯二酚衍生物，除甲基取代基外，主-客体配合物的最大吸收峰位置随取代基的拉电子能力增强而向长波移动。就对硝基苯偶氮间苯二酚而言，主-客体配合物的稳定常数大小依次为F^-＞AcO^-＞H₂PO₄^-，该变化是由于F^-离子半径较更多还原

【Abstract】 Host-guest chemistry based on molecular recognition has been a hot topic of current research in supramolecular chemistry. And supramolecular chemistry includes sensing of neutral molecular, cations and anions. A anion coordination chemistry is less developed compared with the former ones. It is therefore necessary to construct novel anion receptors. Anions can form typical inclusion complexes with many receptors via various interactions, such as electrostatic, hydrogen-bonding, hydrophobic. In this thesis, we constructed chromophores with ground-state charge transfer. Several highly selective and sensitive sensors for anions were developed. And naked-eye detection came true. The thesis consists of five chapters.In Chapter 1, there is literature review. Researches in the development of anion recognition were briefly summarized. The coordination chemistry of anions has received little attention before compared to that devoted to coordination chemistry of cations. However, anion sensors play key roles in many fields. Therefore a number of anion recognition systems have been reported. The content of this chapter includes: （1） structural characters of anions. （2） noncovalent interactions existed in anion coordination, （3） methods in anion recognition.In Chapter 2, compounds based on p-nitrobenzene azophenol were designed and synthesized. The properties of absorption spectra and association constants of complexes between hosts and anions were investigated and compared. The results indicated that the three compounds, which are l-naphthol-4-azo-4’-nitrobenzene, 8-hydroxyl-quinoline-5-azo - 4’ -nitrobenzene and l-phenol-4-azo-4"-nitrobenzene, respectively, could act as efficient chromogenic reagents for the anion sensing. Upon addition of various anions, the spectra, profiles and color of the solution of hosts changed significantly. The affinity of hosts for anions was measured by UV-vis spectroscopic titration experiments. For the same host, the. association constants followed the order of AcO^- >F^- >H-2PO₄^- >>Cl^-, which was i（?）. agreement with the basicity order of anions. And for the same anions such as AcO^-, the association constants followed the order of 3 （a-naphthol） >2 （8-hydroxyl-quinoline） >I （phenol）, which is attributed to electronic withdrawing effect of substituents and the conjugated system of host cmpounds.In Chapter 3, a selevtive colorimetric assay for fluoride and acetate anion based on alizarin was developed. The effect of hydroxyl configuration to anionic complex formation was investigated by UV-vis spectra titration. Results indicated that 1:2 complex between alizarin and fluoride was formed in acetonitrile. However, 1:1 complex formed between更多还原