罗丹明类ClO~-、常见金属离子荧光探针的设计合成及性能研究

发布时间：2018-07-07 20:09

本文选题：荧光探针 + 次氯酸根　；参考：《西北大学》2017年硕士论文

【摘要】：人体内的活性氧物质(ROS)是产生各种疾病的重要因素,次氯酸(HOC1),作为活性氧物质之一,与许多疾病的致病机制有着十分密切的关联。现如今,各种活性氧物质的识别与检测已经成为化学与生物学科发展中具有挑战性的非常重要的前沿课题。随着人类各种金属用品的使用以及环境污染的加剧,使生物体内金属离子(尤其是重金属离子)的含量都有所增加,并可能造成生物体各系统的紊乱,甚至会引起一系列疾病的发生,严重影响了生命体的健康。正是由于次氯酸和金属离子与人类的身体健康有着密切关联,因此发展高效、及时、灵敏的次氯酸和金属离子的检测方法显得尤为重要,并且对生命及环境科学具有是很重要的意义。罗丹明类衍生物具有优良的光学性能,在荧光分析中一直以来有着非常广泛的应用,是设计合成性质优良的荧光探针的一个良好平台。本论文设计合成了四大类(按功能划分)罗丹明螺环隐色体荧光探针(RBP和RBT,RBAI、RGAI和RGNC,BOS1-BOS7,BMS1-BMS5);对所有探针进行表征并通过研究光谱性质讨论了对受体的识别机理;探究了部分探针对活体细胞的毒性、细胞染色及生物活体标记,取得了比较好的结果。主要研究内容有:1.以罗丹明B结构为荧光发色团,二甲酰肼结构为C1O-的特异性氧化位点,设计合成了 2种C1O-荧光探针。通过光谱性质证明探针RBP和RBT对C1O-良好的检测能力。对识别机理进行了理论分析和HRMS(ESI)实验验证。将探针成功应用于L929活细胞及小鼠体内荧光成像,表明探针RBP和RBT具有较低细胞毒性,良好的细胞穿透性,可用于生物体内ClO-的检测及成像,在生物学检测方面具有潜在的应用价值。2.以罗丹明B及罗丹明6G结构为荧光发色团,进行修饰和改进,设计合成了 3种Hg2+荧光探针(RBAI、RGAI、RGNC)。通过光谱性质研究确定了探针对Hg2+的光学识别性能。获得了探针RBAI的单晶结构。对识别机理进行了理论剖析和HRMS(ESI)验证。将探针RBAI、RGAI拓展于吸附固体表面检测Hg2+,及成功用于L929活细胞及小鼠体内荧光成像,证明了它们在环境检测、生物染色方面的应用价值。3.以罗丹明B为荧光发色团,邻苯二胺为连接臂,N和O原子为金属离子主要结合位点,设计合成了 7种单一分子同时检测A13+、Cr3+、Zn2+、Cu2+的多功能探针BOS1-BOS7。该系列探针的紫外吸收及荧光发射光谱对上述四种金属离子,发光波段、发光强度均有所不同,且裸眼检测中可以明显观察到不同的颜色及荧光差异,从而达到多功能识别的效果。应用于SGC-7901活细胞成像,验证了探针的细胞染色效果。4.以罗丹明B为荧光发色团,间苯二胺为连接臂,N和O原子为金属离子主要结合位点,设计合成了 5种检测Al3+、Cr3+的探针BMS1-BMS5。光谱性质研究发现,探针可以在众多金属离子中选择性识别Al3+、Cr3+,并且可以实现裸眼检测。
[Abstract]:Reactive oxygen species (Ros) are important factors of various diseases. Hypochlorite (HOC1), as one of reactive oxygen species, is closely related to the pathogenesis of many diseases. Nowadays, the identification and detection of various reactive oxygen species has become a very important and challenging subject in the development of chemistry and biology. With the use of various metal supplies by human beings and the intensification of environmental pollution, the content of metal ions (especially heavy metal ions) in organisms has increased and may lead to the disruption of biological systems, It can even cause a series of diseases, seriously affecting the health of life. It is precisely because hypochlorite and metal ions are closely related to human health that the development of efficient, timely and sensitive methods for the detection of hypochlorite and metal ions is particularly important. And it is of great significance to the science of life and environment. Rhodamine derivatives have excellent optical properties and have been widely used in fluorescence analysis, which is a good platform for the design and synthesis of fluorescent probes with excellent properties. In this paper, four kinds of Rhodamine snail ring cryptosomal fluorescence probes (RBP and RBTX RBAIGai RGAI and RGNCN BBOS1-BOS7 BMS1-BMS5) were designed and synthesized, all the probes were characterized and the recognition mechanism of the receptors was discussed by studying the spectral properties. The toxicity of some probes to living cells, cell staining and biological in vivo labeling were investigated, and good results were obtained. The main research contents are: 1. Two kinds of C1O- fluorescent probes were designed and synthesized with rhodamine B as fluorescent chromophore and dimethylhydrazide as the specific oxidation site of C1O-. The detection ability of the probe RBP and RBT for C 1O-was proved by spectral properties. The recognition mechanism is analyzed theoretically and verified by HRMS (ESI) experiment. The probe was successfully applied to the fluorescence imaging of L929 living cells and mice. The results showed that the probe RBP and RBT had low cytotoxicity and good cell penetration, and could be used for the detection and imaging of ClO- in vivo. It has potential application value in biological detection. Using Rhodamine B and Rhodamine 6G as fluorescent chromophore, three Hg2 fluorescent probes (RBAIRGAIN RGNC) were designed and synthesized. The optical recognition performance of the probe to Hg _ 2 was determined by the study of spectral properties. The single crystal structure of probe RBAI was obtained. The recognition mechanism is analyzed theoretically and verified by HRMS (ESI). The probe RBAIRGAI was extended to adsorbed solid surface to detect Hg2, and was successfully used in fluorescence imaging of L929 living cells and mice, which proved their application value in environmental detection and biological staining. Using rhodamine B as fluorescent chromophore and o-phenylenediamine as the main binding site of metal ions, seven multifunctional probes BOS1-BOS7 were designed and synthesized for simultaneous detection of A13 Cr3Zn2 / Cu2. The UV absorption and fluorescence emission spectra of the probes are different in the luminescence band and luminescence intensity of the four metal ions mentioned above, and different colors and fluorescence differences can be observed in the naked eye detection. In order to achieve the effect of multi-function recognition. It was applied to SGC-7901 living cell imaging to verify the cell staining effect of the probe. 4. Using rhodamine B as fluorescent chromophore and resorcinenediamine as connecting arm N and O atoms as the main binding sites of metal ions, five probes BMS1-BMS5 were designed and synthesized for the detection of Al3 cr _ 3. It is found that the probe can selectively recognize Al3 and Cr3 in many metal ions, and can be used for naked eye detection.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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