新型5-meso-修饰尾式卟啉的合成及光谱性能研究

发布时间：2018-01-03 00:29

本文关键词：新型5-meso-修饰尾式卟啉的合成及光谱性能研究　出处：《湖南科技大学》2016年硕士论文　论文类型：学位论文

【摘要】：卟啉化合物卟啉是高度共轭的?电子体系,它具有大的刚性平面芳香环结构,环内电子流动性好,且在可见光区具有极强的吸收和优良的供电子特性,此外卟啉化合物还具有许多独特的理化性质。由于卟啉化合物环平面具有易修饰的特点,因此通过对其进行一系列选择性的修饰,可以得到在光动力化学药物治疗、生物荧光探针和生物成像等方面有广泛应用前景的新尾式卟啉化合物。本论文主要开展了以下两方面的研究:1.由于3,4-二氢嘧啶酮及其衍生物(DHPM)是一种重要的药物中间体,具有特殊的治疗性质和药理活性,根据药物设计拼合原理,设计将DHPM及其衍生物修饰卟啉环5-meso位,将DHPM衍生物以二溴烷烃为桥连接到卟啉上,以达到提高光动力化学药物治疗中光敏剂药物活性的目的。本文合成了10个新型DHPM修饰的尾式卟啉及其金属锌配合物。通过单晶衍射,证实了尾式锌卟啉配合物中尾端的活性基团DHPM与锌配位,我们推测由于配位键的拉伸作用,使卟啉环发生了扭曲;并通过1H NMR、13C NMR、HR-MS、IR等方法对所有的新化合物结构进行了表征。2.由于卟啉具有良好的细胞组织穿透性,而且是一种天然荧光团;设计利用光诱导电子转移机理以强吸电子基团2,4-二硝基苯磺酰基修饰卟啉5-meso位,制备了一种可用于硫离子检测的新型2,4-二硝基苯磺酰基修饰的尾式卟啉荧光探针。该探针能对硫离子实行高灵敏度、高选择性的荧光检测且已被成功地应用于活细胞中S2-的成像。与现有的有机小分子荧光探针相比,该荧光探针具有较长的荧光发射波长(λem650nm),可在近红外区实现对微量硫离子的高灵敏度、高选择性、高时效性检测,在生物和环境检测领域有着巨大的应用前景。
[Abstract]:Porphyrins are highly conjugated? The electronic system has a large rigid planar aromatic ring structure, good electron fluidity in the ring, strong absorption and excellent electron supply characteristics in the visible region. In addition, porphyrin compounds also have many unique physicochemical properties. Because porphyrins have the characteristics of easy modification, they are modified by a series of selective modification. New tail porphyrin compounds with wide application prospect in photodynamic chemotherapeutic therapy, biofluorescence probe and biological imaging can be obtained. In this paper, the following two aspects of research are mainly carried out: 1. 4-dihydropyrimidinone and its derivative DHPMs are important drug intermediates with special therapeutic properties and pharmacological activities. DHPM and its derivatives were designed to modify the 5-meso position of porphyrin ring, and the DHPM derivatives were bridged to porphyrins with dibromoalkanes. In order to improve the drug activity of Guang Min in photodynamic chemotherapeutic therapy, ten novel DHPM modified tail porphyrin and its metal zinc complexes were synthesized by single crystal diffraction. The coordination of DHPM with zinc in the tail zinc porphyrin complex was confirmed. We speculated that the porphyrin ring was distorted due to the stretching of the coordination bond. The structures of all new compounds were characterized by 1H NMR-13C NMR-HR-MSIR. 2. Because porphyrin has good cell tissue penetration. And it is a kind of natural fluorescence group; Using photoinduced electron transfer mechanism to modify the 5-meso site of porphyrin with strong electron-absorbing group 2n 4- dinitrobenzene sulfonyl group, a new type of 2 can be prepared for sulfur ion detection. A tail porphyrin fluorescence probe modified with 4-dinitrobenzene sulfonyl group was developed, which can be highly sensitive to sulfur ions. Highly selective fluorescence detection has been successfully used in the imaging of S2- in living cells, compared with the existing organic small molecular fluorescence probes. The fluorescence probe has a long fluorescence emission wavelength (位 em650nm) and can be used to detect trace sulfur ions with high sensitivity, selectivity and timeliness in near infrared region. It has great application prospect in the field of biological and environmental detection.
【学位授予单位】：湖南科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

【参考文献】