稀土配位聚合物的制备及其传感应用研究

发布时间：2018-01-25 01:26

本文关键词： 稀土配位聚合物荧光探针核酸 Hg~(2+) pH 环丙沙星　出处：《郑州大学》2017年硕士论文　论文类型：学位论文

【摘要】：稀土配位聚合物荧光探针具有荧光寿命长、大的斯特克位移、尖锐的发射峰等特点,基于此发展起来的高灵敏度时间分辨荧光分析技术已经在生物监测领域得到了广泛的应用。在本论文的研究中,分别设计、合成及表征了三种新型具有特异性识别与传感功能的稀土配合物荧光探针。主要研究内容:(一)水溶性汞离子(Hg2+)具有生物降解差和通过食物链进行生物聚积的性质,是汞中最稳定的无机形式之一。即使在非常低的浓度下,它也会破坏人的大脑,肾脏和神经系统。因此,灵敏检测Hg2+是具有研究意义的。本论文设计了灵敏的Tb-CIP/AMP LCP探针{(CIP,环丙沙星)(AMP,单磷酸腺苷)},通过运用镧系离子作为金属节点,CIP作为配体分子,AMP作为桥联分子和识别单元来检测Hg2+。由于AMP的存在,从而阻碍水分子与Tb3+的配位,同时也屏蔽了由于O-H振动的猝灭效应使Tb3+荧光淬灭。随后加入Hg2+,由于AMP和Hg2+之间特定的配位作用会强烈猝灭Tb-CIP/AMP的荧光。作为检测Hg2+的荧光传感器,该探针对Hg2+展示出优秀的选择性和0.16 n M的低检出限。此外,该探针具有长达毫秒的荧光寿命,并已经运用于检测饮用水和尿样中的Hg2+,其结果令人满意。我们设想,以LCP为基础的高敏感性时间分辨发光检测的设计将会扩展到生物介质和生物医学成像方面。(二)人血清的正常p H值是在7.35-7.45之间,而p H值的异常主要与许多疾病相关,如癌症和阿尔茨海默病。因此,设计简单的p H探针并在生物流体中有效地把它用于一些疾病的诊断很有价值。在复杂的生物介质中,由于背景和散射荧光的干扰难以消除,始终存在着很大的挑战。稀土配位聚合物对此类分析物具有很好灵敏性和选择性。稀土配位聚合物(LCP)由于它们独特的结构和性质,已经成为广受关注的材料。在这项工作中,我们利用水溶性的生物分子鸟苷-5'-单磷酸(GMP)作为桥接连接物,镧系元素铽离子(Tb3+)作为金属节点,以及银离子(Ag+)作为增敏剂,合成对p H具有响应的稀土荧光配位聚合物探针,即Tb/GMP/Ag。该探针由于Ag+的感光作用使得其具有很强的荧光。然而在碱性溶液中,Tb/GMP/Ag中的Ag+立即与OH-结合,形成Ag2O沉淀并导致Tb/GMP/Ag的荧光明显猝灭。该探针对OH-显示出高选择性,进而具有更广的p H检测范围,其检测范围为7.0-13.0。此外,基于Tb/GMP/Ag荧光探针在血清中的高抗干扰能力,我们应用它来测量未稀释的人血清样本p H值,其结果令人满意。(三)过量使用环丙沙星对人类产生负面影响,包括胃肠道疾病,中枢神经系统的紊乱皮肤光敏性反应及肝损伤。因此,我们迫切需要找到高灵敏度的分析方法,准确、有效地确定药物中这些化合物的含量。在这项工作中,我们设计了一个简单而有效的镧系配位聚合物纳米粒子,即Eu/GMP NPs,检测药片中的环丙沙星。Eu/GMP NPs是由鸟苷酸和三价铕离子组成的,是不发光的。然而,加入的环丙沙星,Eu/GMP NPs荧光强度增强。这是由于CIP与Eu3+离子之间有强的相互配位作用,并且改善Eu/GMP NPs内部的疏水性,从而呈现出从CIP到Eu3+的有效能量转移。随着环丙沙星的量不断增加,Eu/GMP在615 nm处荧光强度与CIP的浓度呈现一个比较好的线性关系,其范围为1.0-40μM,检出限为780 n M。作为一种长荧光寿命的镧系传感器,我们认为此种时间分辨荧光分析方法检测生物样品潜力巨大。
[Abstract]:Rare earth coordination polymer fluorescent probe with long fluorescence lifetime, large Stirk shift, sharp emission characteristics such as high sensitivity, based on the development of the time resolved fluorescence analysis in biological monitoring technology has been widely used. Are designed in this paper, and the synthesis and characterization of three novel has specific recognition and sensing function of complexes of rare earth fluorescent probe. The main research contents: (a) water soluble mercury ion (Hg2+) has the properties of biological degradation and poor biological accumulation through the food chain, is one of the most stable form of inorganic mercury. Even at very low concentrations, it will also destroy the human brain, kidney and nervous system. Therefore, sensitive detection of Hg2+ is valuable to research. This paper proposes a Tb-CIP/AMP LCP probe {sensitive (CIP, ciprofloxacin (AMP), adenosine monophosphate)}, by using lanthanide As a metal ion node, CIP as the ligand, AMP as bridging and molecular recognition unit to detect Hg2+. due to the presence of AMP, thus preventing water molecules and the coordination of Tb3+, but also blocked due to quenching effect of O-H vibration Tb3+ fluorescence quenching. After joining Hg2+, the fluorescence between AMP and Hg2+ with specific the role of strong quenching of Tb-CIP/AMP. As a fluorescence sensor for detection of Hg2+ and Hg2+ on the probe showed good selectivity and low detection limit of 0.16 n M. In addition, the probe has a long fluorescence lifetime of milliseconds, and has been applied to the detection of drinking water and urine Hg2+ in the us with satisfactory results. Imagine, LCP based Gao Min perceptual time-resolved luminescence detection will be extended to the design of biological media and biomedical imaging. (two) the normal human serum P H value is between 7.35-7.45, P and H value anomaly Mainly associated with many diseases, such as cancer and Alzheimer's disease. Therefore, P H probe design simple and effective in biological fluids when it is applied to the diagnosis of some diseases is very valuable. In complex biological medium, due to interference and scattering background fluorescence is difficult to eliminate, always there is a great challenge. Rare earth the coordination polymer has good sensitivity and selectivity for these analytes. Rare earth coordination polymers (LCP) due to their unique structure and properties, has become a popular material. In this work, we use water soluble biological molecules of -5'- guanosine monophosphate (GMP) as bridging connections. Lanthanide metal terbium ion (Tb3+) as nodes, and silver ion (Ag+) as sensitizer, synthesis of P H with response coordination polymer of rare earth fluorescent probe, the probe is Tb/GMP/Ag. as the sensitive effect of Ag+ that it has Strong fluorescence. However, in alkaline solution, immediately Tb/GMP/Ag Ag+ combined with OH-, the formation of Ag2O precipitation and lead to obvious fluorescence quenching of Tb/GMP/Ag. The probe of OH- showed high selectivity, and has a wider range of P H detection, the detection range of 7.0-13.0. in addition, based on the Tb/GMP/Ag fluorescence probe in serum the high anti-interference ability, we use it to measure the undiluted human serum samples of P H, with satisfactory results. (three) the excessive use of ciprofloxacin have a negative impact on humans, including gastrointestinal diseases, central nervous system disorder skin photosensitivity reaction and liver injury. Therefore, we urgently need to find analysis method of high sensitivity, accurate determination of drug content of these compounds effectively. In this work, we design a simple and effective lanthanide coordination polymer nanoparticles, namely Eu/GMP NPs. Measuring the tablet of ciprofloxacin.Eu/GMP NPs is composed of guanylic acid and trivalent europium ion, is not luminous. However, addition of ciprofloxacin, Eu/GMP enhanced the fluorescence intensity of NPs. This is due to the interaction with the strong interaction between CIP and Eu3+ ions, and improve the hydrophobicity of Eu/GMP within NPs, thus showing effective energy from CIP to Eu3+ transfer. With the increasing amount of ciprofloxacin, Eu/GMP showed a good linear relationship in the concentration of 615 nm and the fluorescence intensity of CIP, the range of 1.0-40 M, the detection limit was 780 n M. as the lanthanide sensor with a long fluorescence lifetime, we believe that the fluorescence analysis a method of detecting biological samples has great potential to discriminate whether the time.

【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O657.3

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