新型金属离子光化学传感器的设计制备及其在生物体内的应用研究

发布时间：2018-03-09 11:56

本文选题：香豆素　切入点：萘　出处：《江苏大学》2017年硕士论文　论文类型：学位论文

【摘要】：自然界中有各种各样的金属,包括碱金属和碱土金属,过渡金属和重金属,这些金属在生物体中扮演着重要的角色。摄入过多或摄入不足会导致生理功能障碍,甚至导致疾病。因此,设计和合成一种可用于金属离子检测的荧光探针是非常重要的。本文设计合成了一系列新型小分子荧光探针分别用于Fe~(3+),Al~(3+),Zn~(2+)等离子的识别与检测。(1)设计合成了一种基于香豆素衍生物的Fe~(3+)荧光猝灭性小分子荧光探针7-二乙氨基香豆素-3-醛。当pH=7时,探针溶液本身荧光较强,考察一系列金属离子Pb~(2+),Ni~(2+),Mg~(2+),Cd~(2+),Co~(2+),Cu~(2+),Mg~(2+),Fe~(2+),Zn~(2+),K~+,Li~+,Na~+,Al~(3+),Fe~(3+),Cr~(3+)对探针的影响,发现仅仅与Fe~(3+)结合后荧光淬灭,由此建立了Fe~(3+)测定的新方法。本方法具有水溶性好、灵敏度高、选择性好等优点,检出限低至2.5×10-2μM。同时,本荧光探针可实现生物细胞Ramos内Fe~(3+)的检测,证明其在化学传感以及生物成像领域具有潜在的应用价值。(2)通过将D-葡萄糖胺盐酸盐与2-羟基-1-萘甲醛反应合成了新的萘席夫碱基荧光探针,即1-(C2-葡糖基-亚氨基-甲基)-萘-2-醇。它自身没有荧光,但是对Al~(3+)具有极强的荧光响应,而且在Pb~(2+),Mg~(2+),Cd~(2+),Co~(2+),Cu~(2+),Ni~(2+),Fe~(2+),Mn~(2+),Hg~(2+),K~+,Li~+,Na~+,Fe~(3+),Cr~(3+)和Zn~(2+)等15种乙醇溶液中仅对Al~(3+)具有极强的选择性。随着Al~(3+)的加入,在激发波长为427 nm处的荧光强度会增强50倍,这是由于Al~(3+)和探针之间的螯合增强(CHEF)作用。由Job曲线可以知道探针与Al~(3+)是1:1结合的,而且经计算得出探针与Al~(3+)的缔合常数为5.748×103 M-1。在0~25μM线性区间内,计算得到探针L2对Al~(3+)的检出限为2.83×10-3μM。此外,研究发现L-Al~(3+)络合物的荧光可以在相同体系中添加F-时猝灭,考察其它阴离子,包括Cl~-,Br~-,I~-,NO_2~-,NO_3~-,ClO_4~-,CO_3~(2-),HCO_3~-,SO_4~(2-),HSO_4~-,CH_3COO-等均无此现象。[L Al~(3+)]络合物与F-阴离子的结合通过不同的荧光滴定研究建立,在乙醇中的检测限为3.2 nM。本荧光探针能够实现细胞内Al~(3+)和F-的检测,在传感及生物成像领域具有潜在的实际应用价值。(3)设计合成了一种新颖的基于香豆素的荧光探针((4E-4-((7-羟基-4-甲基-2-氧代-2H-色烯-8-基亚甲基)肼基硫代酰胺)L3,可以在水环境中作为比色传感器来检测Fe~(3+),其通过在水环境中从无色到棕色的颜色变化来表现出对于Fe~(3+)的高选择性和灵敏性的识别。同时,探针L3也可以作为荧光探针在乙醇:水(8:2,v/v)的混合溶剂中显示出对Zn~(2+)的显著的荧光增强效应。Fe~(3+)或Zn~(2+)的选择性识别不受其它竞争性金属离子例如Pb~(2+),Cd~(2+),Mg~(2+),Fe~(2+),Co~(2+),Ni~(2+),Cu~(2+),Mn~(2+),Hg~(2+),K~+,Li~+,Na~+,Al~(3+),Cr~(3+)和Sr~(2+)等离子存在的干扰。此外,在这项研究中,细胞成像的结果表明这种新的探针可以用在生物体系中的Zn~(2+)检测。
[Abstract]:There are a variety of metals in nature, including alkali and alkaline earth metals, transition metals and heavy metals, which play an important role in organisms. And even cause disease. It is very important to design and synthesize a fluorescent probe which can be used for metal ion detection. In this paper, a series of novel small molecular fluorescent probes have been designed and synthesized for the identification and detection of Fe~(3 (Fe~(3). A Fe~(3 based on coumarin derivatives) fluorescence quenching small molecular fluorescence probe 7-diethylaminocoumarin -3-aldehyde. At pH = 7:00, The fluorescence of the probe solution itself is stronger. The effect of a series of metal ions, Pb~(2, Pb~(2, Pb~(2 and Pb~(2, on the probe is investigated. It is found that the probe is quenched only after it is combined with Fe~(3. A new method for the determination of Fe~(3 was established. The method has the advantages of good water solubility, high sensitivity and good selectivity. The detection limit is as low as 2.5 脳 10 ~ (-2) 渭 M. at the same time, the fluorescence probe can be used to detect Fe~(3 in the Ramos of biological cells. It is proved that it has potential application value in the field of chemical sensing and biological imaging. A new fluorescence probe of naphthalene Schiff base was synthesized by the reaction of D-glucosamine hydrochloride with 2-hydroxy-1-naphthalene formaldehyde. It has no fluorescence on its own, but it has a very strong fluorescence response to Al~(3. Moreover, in 15 kinds of ethanol solutions, such as Pb~(2, Al~(3, Al~(3, Al~(3), the fluorescence intensity at 427nm can be enhanced by 50 times with the addition of Al~(3. The fluorescence intensity at 427nm is increased by 50 times with the addition of the Al~(3, the fluorescence intensity is increased by 50 times at 427nm, and the fluorescence intensity at 427nm can be increased by 50 times with the addition of the Al~(3, and the fluorescence intensity is increased by 50 times in the 15 kinds of ethanol solutions, such as Pb~(2, Al~(3, and Zn~(2), and the fluorescence intensity at 427nm is enhanced by 50 times with the addition of Al~(3, and the fluorescence intensity is increased by 50 times at the excitation wavelength of 427nm, and the fluorescence intensity can be increased by 50 times at the excitation wavelength of 427nm. This is due to the chelation enhancement between Al~(3) and the probe. From the Job curve, we can know that the probe and Al~(3) are 1: 1 bound, and the association constant of the probe and Al~(3) is calculated to be 5.748 脳 103M-1.In the linear range of 0 ~ 25 渭 M, The detection limit of probe L2 for Al~(3 was calculated to be 2.83 脳 10-3 渭 M. in addition, it was found that the fluorescence of L-Alb3) complex could be quenched by adding F- in the same system, and other anions were investigated. There is no such phenomenon, including the Cl-OBr-Br-ti-tip-no _ 2- no _ 3- _ _ _. A novel coumarin-based fluorescence probe 4e-4-dihydroxy-4-methyl-2-oxo-2H-2-chromene-8-methylenehydrazide) thioamides L3 has been designed and synthesized in the field of sensing and biometric imaging. A colorimetric sensor used as a colorimetric sensor in water to detect Fe~(3, which exhibits a highly selective and sensitive recognition of Fe~(3 by changing its color from colorless to brown in the water environment. Probe L3 can also be used as a fluorescence probe in ethanol: water 8: 2 v / v) to show a significant fluorescence enhancement effect on Zn~(2) or selective recognition of Zn~(2) from other competitive metal ions such as Pb~(2. In addition, the presence of plasma in the presence of K and Sr~(2. In this study, cell imaging results suggest that the new probe can be used for Zn~(2 detection in biological systems.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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