金属有机骨架及其复合材料催化鲁米诺化学发光在生物小分子检测中的应用

发布时间：2018-03-10 22:17

本文选题：金属有机骨架　切入点：鲁米诺　出处：《西南大学》2017年硕士论文　论文类型：学位论文

【摘要】：化学发光分析法因其无背景散射光干扰、灵敏度高、线性范围宽、分析速度快及仪器设备简单等优势已成为一种重要的分析检测手段。鲁米诺因水溶性好、发光量子产率较高,是化学发光体系中最常用且应用最广泛的化学发光试剂之一。鲁米诺在水溶液中的发光速率很慢,常需要加入催化剂,而常用的催化剂大多是金纳米颗粒,金属氧化物纳米颗粒等材料。金属有机骨架化合物(Metal-Organic Frameworks,MOFs),是由金属离子和有机配体通过配位键自组装形成的多孔有机-无机杂化材料。MOFs综合了有机和无机的优良性质,具备良好的吸附分离、光学和催化等性质,且拥有规则可调的孔道结构,超高的比表面积,在储氢、催化及分析检测等领域得到广泛应用,但MOFs作为催化剂在化学发光分析中的应用还很少有报道。本文利用两种具有催化性质的MOFs材料,建立了新的化学发光分析体系,在无外加氧化剂的条件下,实现了对半胱氨酸、过氧化氢及葡萄糖的灵敏检测。具体研究内容如下:(1)Co-MOFs-鲁米诺化学发光体系检测半胱氨酸。我们选择了由Co~(2+)介导的从含锌金属有机凝胶(Zn-MOGs)-晶体转换得到的含钴金属有机骨架化合物(Co-MOFs),在无额外添加氧化剂的条件下,直接催化鲁米诺化学发光。研究发现,与水热法合成的Co-MOFs(H)及钴离子相比,由凝胶-结晶转换制备得到的Co-MOFs的催化活性更强。半胱氨酸因能进一步增强鲁米诺-Co-MOFs体系的化学发光强度,且在浓度范围为2μM-10μM内,半胱氨酸浓度与化学发光强度呈良好的线性关系,据此,我们构建一种简单灵敏的化学发光检测方法用于半胱氨酸定量检测,检测限为0.49μM,所建立的方法能用于复方氨基酸注射液中半胱氨酸的含量测定。(2)Fe_3O_4/MIL-101(Fe)-鲁米诺化学发光体系检测过氧化氢和葡萄糖。利用Fe_3O_4/MIL-101(Fe)复合材料的协同催化活性,无需加入氧化剂,Fe_3O_4/MIL-101(Fe)可与溶液中的溶解氧反应产生大量的活性氧自由基,活性氧自由基再氧化鲁米诺化学发光。过氧化氢能增强该Fe_3O_4/MIL-101(Fe)-鲁米诺体系的化学发光强度,并且葡萄糖在葡萄糖氧化酶的氧化作用下能产生过氧化氢,据此,该Fe_3O_4/MIL-101(Fe)-鲁米诺体系被用于定量检测过氧化氢和葡萄糖。在最优的条件下,检测过氧化氢和葡萄糖的的线性范围分别是5nM-150nM和5nM-100nM,检测限分别是3.7nM和4.9nM。将建立的方法用于医用过氧化氢消毒液中过氧化氢及血清中血糖含量的定量分析,获得了较为满意的结果。
[Abstract]:Chemiluminescence analysis has become an important analytical method because of its advantages of no background scattering light interference, high sensitivity, wide linear range, fast analysis speed and simple instrument and equipment. Luminol is one of the most commonly used and widely used chemiluminescence reagents in chemiluminescence systems. Metal oxide nanoparticles. Metal-Organic Framework compounds Metal-Organic frameworks MOFsN, a porous organic-inorganic hybrid material formed by self-assembly of metal ions and organic ligands through coordination bonds, have integrated the excellent properties of organic and inorganic materials. It has good adsorption and separation, optical and catalytic properties, regular and adjustable pore structure, high specific surface area, and has been widely used in hydrogen storage, catalysis and analytical detection, etc. However, the application of MOFs as a catalyst in chemiluminescence analysis is seldom reported. In this paper, a new chemiluminescence analysis system was established by using two kinds of MOFs materials with catalytic properties. Sensitive detection of hydrogen peroxide and glucose-determination of cysteine by the: 1: 1 co-MOFs- luminol chemiluminescence system. We selected cobalt-containing gold from zinc-containing organo-gels Zn-MOGsN-crystal transition mediated by Co~(2. Of the organic skeleton compound Co-MOFsN, without the addition of oxidants, Direct catalysis of luminol chemiluminescence. It was found that compared with Co-MOFsHand cobalt ions synthesized by hydrothermal method, The catalytic activity of Co-MOFs prepared by gel-crystallization conversion is stronger. Cysteine can further enhance the chemiluminescence intensity of Lumino-Co-MOFs system, and in the concentration range of 2 渭 M-10 渭 M, cysteine can further enhance the chemiluminescence intensity of Lumino-Co-MOFs system. There is a good linear relationship between the concentration of cysteine and the intensity of chemiluminescence. Therefore, a simple and sensitive chemiluminescence method is developed for the quantitative detection of cysteine. The detection limit is 0.49 渭 M. the established method can be used for the determination of cysteine in compound amino acid injection, and can be used to determine the synergistic catalytic activity of Fe3O4 / MIL-101FeN-Rumino chemiluminescence system for the determination of hydrogen peroxide and glucose. No need to add oxidant Fe3O-1) can produce a large amount of reactive oxygen radicals, which can be reoxidized by reactive oxygen radicals to luminol chemiluminescence. Hydrogen peroxide can enhance the chemiluminescence intensity of the Fe3O4 / MIL-101FE-Lumino system. And glucose can be oxidized by glucose oxidase to produce hydrogen peroxide, so this Fe3O / MIL-101 Fetio-Rumino system is used to quantitatively detect hydrogen peroxide and glucose. The linear range for the detection of hydrogen peroxide and glucose was 5nM-150nM and 5nM-100nM, respectively, and the detection limits were 3.7nM and 4.9nM. the established method was applied to the quantitative analysis of hydrogen peroxide in medical hydrogen peroxide disinfectant solution and blood sugar content in serum. Satisfactory results have been obtained.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3;R446

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