|关键词||分子印迹 三氯生 三氯卡班 双氯芬酸 醋氯芬酸|
随着经济社会的快速发展，全球生态环境面临着前所未有的压力，也出现了许多新型环境污染物，它们进入自然环境后会严重破坏生态系统并危害人类健康，已经成为全球面临的重大环境问题。药物及个人护理品（PPCPs）就属于这一类重要的新型环境污染物。随着具有毒副作用和持久性污染特征的PPCPs的大量使用，使水体、土壤等自然环境受到了越来越严重的污染，备受国内外广泛关注。因此，设计和制备对新型污染物具有特异性识别和吸附的功能材料，在环境监测、污染物去除、生态环境安全等领域具有重要的意义。本研究的目标物质是三氯生、三氯卡班、双氯芬酸和醋氯芬酸，这四种新型环境污染物都属于PPCPs。分子印迹技术是一种特异性识别与吸附技术，研究目标是合成与模板分子在空间结构和结合位点上相匹配的聚合物，制备的分子印迹聚合物作为一种具有特异性识别能力的新型高分子材料，具有选择性好、机械性能高、化学性质稳定等优异特性，能在复杂体系中识别目标分子，且对目标分子具有较强的富集作用，因此成为了一种检测、识别和去除环境污染物的高效材料。采用本体热引发聚合，应用DMAEMA、DEAM、AMA、4-VP和MAA五种功能单体，EDGMA和DVB为交联剂，AIBN为引发剂，乙腈为溶剂，设计合成了TCS的MIPs，筛选出了最佳功能单体DEAM。对于60 mg/L的TCS-乙腈溶液，DEAM-MIPs对TCS的吸附率达到了78.5%，印迹因子为1.7；DEAM-MIPs吸附容量明显高于其结构类似物3,4-二氯二苯醚，表现出优异的选择性；对DEAM-MIPs进行了重复再利用实验，吸附容量仅降低5.1 %，表明可多次重复使用。采用本体热引发聚合，应用本课题组合成的FM1、FM2、FM3三种含脲基功能单体，DVB为交联剂，AIBN为引发剂，四氢呋喃为溶剂，设计合成了TCC的MIPs，筛选出最佳功能单体FM3。对于6.0 mg/L的TCC-THF溶液，FM3-MIPs的吸附率达到了93.9%，印迹因子为2.0，显示出良好的吸附效果；FM3-MIPs对TCC的吸附容量明显高于其结构类似物TCS，说明具有较高的吸附选择性；FM3-MIPs经过5次吸附-解吸附循环后吸附容量仅降低7.3%，显示出较好的应用前景。 采用溶胶凝胶法， APTES为功能单体，TEOS为交联剂，甲醇为溶剂，设计合成了针对双氯芬酸和醋氯芬酸的MIPs。MIPs对60 mg/L的双氯芬酸和醋氯芬酸甲醇溶液的吸附率分别达到了87.9%和 81.2%，印迹因子分别为1.8和1.7；MIPs对双氯芬酸和醋氯芬酸的选择性实验显示，它们的吸附容量明显高于其结构类似物TCS，表现出优异的吸附选择性；对MIPs进行了5个吸附-解吸附循环回收后再利用的考察，双氯芬酸和醋氯芬酸MIPs的吸附容量分别仅降低了7.7%和8.3%，表明设计制备的MIPs可多次重复使用，具有较好的实用性。
With the rapid development of the economy and society, the global ecological environment is facing unprecedented pressure, and many new environmental pollutants have appeared. After they enter the natural environment, they will seriously destroy the ecosystem and harm human health, which has become a major environmental problem in the world. Drugs and personal care products (PPCPs) belong to this kind of important new environmental pollutants. With the extensive use of PPCPs, which has the characteristics of toxic and side effects and persistent pollution, the natural environment, such as water and soil, has been seriously polluted. This issue has attracted much attention at home and abroad. Therefore, the design and preparation of functional materials with specific recognition and adsorption for new pollutants are of great significance in the fields of environmental monitoring, pollutant removal, ecological environment safety. The goals of this study are to design functional materials for the recognition and adsorption of four new environmental pollutants triclosan, triclosan, diclofenac and aceclofenac.Molecular imprinting is a specific recognition and adsorption technology. The goal is to synthesize polymers (molecularly imprinted polymers, MIPs) that have pre- designed binding sites which are complimentary to its target template molecules in terms of three dimensional structure and functionality. MIPs feature good selectivity, high mechanical properties and chemical properties. It is a highly efficient material for detection, identification and removal of environmental pollutants, which can identify, detect and enrich the target molecules in complex systems.MIPs of TCS were designed and synthesized via bulk thermal polymerization, using DMAEMA, DEAM, AMA, 4-VP and MAA as functional monomers, EDGMA and DVB as cross-linkers, AIBN as initiator and acetonitrile as solvent, DEAM was selected as the best functional monomer among them. Adsorption percentage of DEAM-MIPs for TCS reached to 78.5%, imprinting factor of 1.7; The adsorption capacity of DEAM-MIPs is significantly higher than that of its structurally similar analogue; DEAM-MIPs were used for repeated reuse, and the adsorption capacity only was reduced by 5.1 %, indicated that it could be reused for many times and had a good practical application prospect. MIPs of TCC was designed and synthesized via bulk thermal polymerization, using homemade FM1, FM2, FM3 contains urea based as functional monomers, DVB as cross-linker, AIBN as initiator and tetrahydrofuran as solvent, FM3 was selected as the best functional monomer. Adsorption percentage of FM3-MIPs for TCC reached to 93.9%, imprinting factor of 2.0, showed good adsorption effect; The adsorption capacity of FM3-MIPs was significantly higher than that of its structurally similar analogues; The adsorption capacity of FM3-MIPs only was reduced by 7.3% after 5 adsorption - desorption recycles, which had a good application prospect.MIPs of diclofenac and aceclofenac were designed and synthesized by sol-gel method, APTES as functional monomer, TEOS as cross-linker and methanol as solvent. Adsorption percentage of MIPs reached to 87.9% and 81.2% respectively, imprinting factors of of 1.8 and 1.7 respectively; The selective experiments of MIPs for diclofenac and aceclofenac showed that their adsorption capacity were significantly higher than that of its structurally similar analogues. The adsorption capacity of MIPs only was reduced by 7.7% and 8.3% respectively after 5 adsorption-desorption recycles, showed a good application prospect.
|范维刚. 新型环境污染物特异性识别与吸附功能材料的设计与应用[D]. 北京. 中国科学院大学,2018.|
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