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中文题名:

 葡萄糖氧化酶和氯高铁血红素级联催化体系的构建及其应用研究    

姓名:

 王若馨    

保密级别:

 公开    

论文语种:

 chi    

学科代码:

 070302    

学科专业:

 分析化学    

学生类型:

 硕士    

学位:

 理学硕士    

学位类型:

 学术学位    

学位年度:

 2023    

校区:

 北京校区培养    

学院:

 化学学院    

研究方向:

 污染物的降解    

第一导师姓名:

 谢孟峡    

第一导师单位:

  化学学院    

提交日期:

 2023-06-06    

答辩日期:

 2023-06-02    

外文题名:

 Construction and application of a cascade catalytic system for glucose oxidase and heme chloride    

中文关键词:

 级联 ; 模拟酶 ; 生物酶 ; ZIF-8 ; 降解    

外文关键词:

 Cascade ; mimic enzyme ; biological enzyme ; ZIF-8 ; degradation.    

中文摘要:

生物酶是人体生命活动中一类重要的蛋白质,具有催化效率高、特异性强的特点。近些年来,生物酶在合成化学、生物传感器的构建、环境污染物催化降解等诸多领域具有广泛的应用。但是,生物酶存在对环境条件敏感、稳定性不强等弱点,在一定程度上限制了其应用前景。因此,对生物酶的固定化、开发模拟纳米酶等研究工作备受人们关注,这些策略可以有效提高酶的稳定性和催化活性。

本文将葡萄糖氧化酶(GOx)和过氧化物模拟酶氯高铁血红素(Hemin)同时封装在金属有机框架材料(ZIF-8)中,制备了Hemin@GOx@ZIF-8 纳米多孔复合材料,对它们在葡萄糖存在下的级联催化活性进行了研究。同时,把该级联催化体系应用于染料等环境污染物的降解,并对其稳定性、可重复利用性、以及降解机理进行了探讨。该复合材料对染料等环境污染物具有高效的级联催化活性,且具有较高的稳定性和可重复使用性。具体研究内容如下:

采用原位沉淀法把Hemin和GOx同时封装到ZIF-8金属有机框架材料中,制备了多孔级联复合材料,对复合材料制备的投料比例进行了优化,结果表明当GOx和Hemin质量比为1:1时,复合材料的级联催化活性最好。

采用扫描电镜、X-衍射、光电子能谱、红外光谱、紫外光谱、热重等对制备的Hemin@GOx@ZIF-8复合材料的结构和性能进行了表征,结果显示Hemin和GOx 被成功的包封进了ZIF-8骨架中,且保持了ZIF-8的晶体结构。

研究了Hemin@GOx@ZIF-8复合材料对刚果红(CR)染料的降解性能,发现CR染料的最高催化降解率可达89.0%。考察了降解体系中催化剂用量、底物浓度等多种因素对级联降解反应的影响。同时,该级联催化降解体系可对染料、酚类以及抗生素类环境污染物等均具有良好的降解性能。

研究了级联复合材料在极端条件下的稳定性,发现在高温,有机体系处理后,复合材料仍能保持其催化活性,且具有比较宽的pH值使用范围。同时,根据材料级联催化反应的过程,探究了级联反应中起作用的活性物种主要为羟基自由基。

综上所述,本文制备了基于葡糖氧化酶和氯高铁血红素模拟酶的级联多孔复合催化材料,构建了可应用于环境污染物降解的级联催化体系,为提高生物酶的稳定性和催化活性、以及其对环境污染物的去除提供了一个新的思路和方法。

外文摘要:

Biological enzymes are a kind of important proteins in human life activities, which have the characteristics of high catalytic efficiency and strong specificity. In recent years, biological enzymes have been widely used in many fields such as synthetic chemistry, the construction of biosensors, and the catalytic degradation of environmental pollutants. However, biological enzymes have some weaknesses such as sensitivity to environmental conditions and weak stability, which limits their application prospects to a certain extent. Therefore, the immobilization of biological enzymes and the development of simulated nano-enzymes have attracted much attention. These strategies can effectively improve the stability and catalytic activity of enzymes.

In this paper, the Hemin@GOx@ZIF-8 nanoporous composites were prepared by encapsulating glucose oxidase (GOx) and peroxide mimetic enzyme Hemin in metal organic framework (ZIF-8) simultaneously, and their cascading catalytic activities in the presence of glucose were studied. At the same time, the cascade catalytic system was applied to the degradation of dyes and other environmental pollutants, and its stability, reusability and degradation mechanism were discussed. The composite has high cascading catalytic activity against dyes and other environmental pollutants, and has high stability and reusability. The specific research content is as follows:

(1) In situ precipitation method was used to package Hemin and GOx into the ZIF-8 metal organic framework material at the same time, and the porous cascade composite material was prepared. The feeding ratio of the composite material was optimized. The results showed that when the mass ratio of GOx and Hemin was 1:1, the cascade catalytic activity of the composite material was the best.

(2) The structure and properties of the prepared Hemin@GOx@ZIF-8 composite were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), photoelectron spectroscopy (XPS), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), and thermogravity. The results showed that Hemin and GOx were successfully encapsulated into the ZIF-8 skeleton, and the crystal structure of ZIF-8 was maintained.

(3) The degradation performance of Hemin@GOx@ZIF-8 composite for Congo Red (CR) dye was studied, and the highest catalytic degradation rate of CR dye was found to be 89.0%. The effects of catalyst dosage, substrate concentration and other factors on the cascade degradation reaction were investigated. At the same time, the cascade catalytic degradation system has good degradation performance for dyes, phenols and antibiotics.

(4) The stability of the cascade composite under extreme conditions was studied, and it was found that the composite can still maintain its catalytic activity after the treatment of high temperature and organic system, and has a relatively wide pH value application range. At the same time, according to the process of material cascade catalytic reaction, the active species in the cascade reaction is mainly hydroxyl radical.

In summary, this paper prepared a cascade porous composite catalytic material based on glucose oxidase and chlormethemoglobin mimic enzyme, and constructed a cascade catalytic system that can be applied to the degradation of environmental pollutants, which provides a new idea and method for improving the stability and catalytic activity of biological enzymes and the removal of environmental pollutants.

参考文献总数:

 162    

馆藏号:

 硕070302/23006    

开放日期:

 2024-06-05    

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