【作者】 王顺；

【导师】 徐如人；

【作者基本信息】 吉林大学 ， 无机化学， 2021， 博士

【摘要】 作为多孔有机聚合物的典型代表,共轭微孔聚合物（CMPs）不仅将优异的孔隙特性与扩展的共轭体系完美地结合,而且具有较高的稳定性和多样化的合成策略,已被广泛的应用于光催化、吸附、储能、传感等诸多领域。以功能为导向,通过变换构筑基元可以设计合成具有特定目标性能的CMPs,同时也可以通过后合成修饰（PSM）策略向已建立的CMP框架内引入多种官能团来对其进行功能化修饰。氮原子的引入不仅丰富了CMPs的骨架结构,而且赋予其优异的性能。本文通过对结构与性能关系的研究,采用不同的含氮构筑基元,含氮小分子为功能构筑块,通过“自下而上”和PSM策略合成出一系列含氮CMPs材料,探索了其在光响应仿酶、碘捕获、染料与气体吸附分离等方面的应用。主要结果如下:1.首先,我们利用Suzuki偶联反应合成了一例基于吡嗪并喹喔啉的CMP,该材料在可见光照射下展现较好的仿氧化酶催化活性。我们首次采用CMPs作为光响应仿氧化酶用于构建生物酶荧光传感器。在可见光驱动下CMP催化水中的溶解氧产生超氧自由基,氧化硫胺素生成具有蓝色荧光的脱氢硫胺素,且此催化过程具有高度的pH（4.6-8.6）依赖性。脲酶可以水解其相应的底物以触发pH值变化。因此,构建了一个对脲酶有较高灵敏度和选择性的pH荧光传感器。该方法的检测限为0.42 U L^-1,且可以用于实际唾液样品中的脲酶分析。在此基础上,我们设计合成了一例基于吡嗪并喹喔啉的D-π-A型CMP作为光驱动的仿氧化酶用于谷胱甘肽（GSH）的比色传感。可见光下CMP能有效的氧化无色的TMB变为蓝色的ox-TMB,而GSH可以有效地抑制催化反应的进行,实现对还原型谷胱甘肽的比色传感。GSH的定量检测范围为0.2-20μM,检出限为0.06μM。该方法还被用于人血清样品中的GSH分析,证明了其在实际检测中的应用前景。这两项研究不仅丰富了光响应CMPs的结构类型,也拉开了CMPs材料作为光响应模拟酶用于生物医学传感领域的序幕。2.为制备具有高效碘吸附能力的吸附剂,我们通过Pd催化的Sonogashira和Suzuki偶联反应合成了三种基于三苯胺衍生物的CMPs。所得聚合物具有较高的BET比表面积(最大为1185 m² g^-1),由于出色的孔隙性能,富电子的π共轭网络结构,以及骨架中N原子与I₂分子的相互作用,该系列材料展现出较高的碘蒸气捕获性能,并且在乙醇洗涤后可以实现对碘的循环吸附。接着,我们通过Suzuki偶联反应合成了两种基于吡啶的CMPs,最高BET比表面积达到2028 m² g^-1,其表现出的挥发性碘蒸气吸附量为5.29 g g^-1,这与以往所报道材料的吸附能力相比是较突出的,并且具有良好的循环吸附效果。高吸附量应归因于聚合物优异的多孔性、有效的吸附位点和扩展的π共轭网络骨架的综合效应。此外,该材料将四环素的传感和吸附功能合二为一,既可以作为四环素的新型荧光探针,同时还显示出较高的四环素吸附能力。3.我们通过一种后合成修饰策略构建了一例阳离子型CMP。首先采用均三溴苯与对苯二硼酸合成苯基CMP材料（CMP-O）,第一步经Blanc氯甲基化反应引入氯甲基,第二步经N-甲基咪唑后修饰合成含有咪唑鎓的阳离子骨架（CMP-Im）。它的多孔、共轭和阳离子骨架有利于其与阴离子染料的相互作用。CMP-Im表现出甲基橙（MO）和刚果红（CR）阴离子染料的高效吸附,吸附容量分别为588和2500 mg g^-1,并且对MO与亚甲基蓝（MB）混合液、CR与MB混合液具有选择性吸附的能力。此外,我们以CMP-O为前驱体,在AlCl₃催化下采用二氯甲烷和三氯甲烷为溶剂和交联剂进行Friedel-Crafts反应,增加孔径的同时引入氯甲基,然后在此基础上引入对CO₂具有亲和能力的二乙烯三胺。以第一步修饰三氯甲烷为例,BET比表面积由起初的1182 m²g^-1增加到1828 m²g^-1,CO₂吸附量从2.58增至4.92 mmol g^-1（273 K,1 bar）。此外,将多胺基团修饰到孔壁上后,CO₂的吸附热从19.50增至37.07 k J mol^-1,CO₂/N₂选择性分离系数从16.68提升至48.70（273K,1 bar）。这两项工作通过简单的后修饰策略制备了含氮CMPs,提高了其在染料与气体吸附方面的性能,为CMPs的功能化提供了研究思路。更多还原

【Abstract】 As a typical representative of porous organic polymers,conjugated microporous polymers（CMPs）not only perfectly combine porosity with extended conjugated networks,but also possess high stability and various synthetic strategies,which have been widely used in many fields.Function-oriented,CMPs with specific target properties can be successfully synthesized by transforming the building units.Besides,a variety of functional groups can be introduced into the established CMPs framework through post-synthetic modification（PSM）strategy.The introduction of nitrogen atoms can enrich the structure of CMPs,and then endow them excellent properties and applications.By analyzing the relationship between structure and performance,a series of CMPs materials were designed and synthesized using different nitrogen-containing building blocks through direct polymerization or PSM strategies.And the applications of these CMPs in light-responsive oxidase mimic,iodine capture,dyes and gas adsorption/separation were systematically explored.The main results were summarized as follows:1.A pyrazinoquinoxaline-based CMP was designed and synthesized through Suzuki coupling,and exhibited excellent oxidase mimic catalytic activity under visible light irradiation.It is the first work to use CMP as light-responsive oxidase mimic for biological enzyme fluorescence sensors.Under the visible-light irradiation,CMP employed dissolved oxygen as electron acceptor to generate superoxide radicals for easily oxidizing thiamine to generate dehydrothiamine with blue fluorescence,and this catalytic process was highly pH dependent in the range of 4.6-8.6.Urease can hydrolyze its corresponding substrate to trigger a change of pH.Hence,a sensing platform of urease was constructed.The detection limit of this method is 0.42 U L^-1,and this method was also used for the analysis of urease in actual saliva samples.Based on the above work,a pyrazinoquinoxaline-containing D-π-A CMP was synthesized as a light-driven oxidase mimic for the colorimetric sensing of glutathione（GSH）.CMP can effectively oxidize the colorless TMB to blue ox-TMB under visible light,while glutathione can effectively inhibit the progress of the catalytic reaction.Therefore,the CMP/TMB system can realize the colorimetric sensing of reduced glutathione.The quantitative detection range of GSH is 0.2-20μM,and the detection limit is 0.06μM.This method was also used in the application of GSH analysis in human serum samples,which exhibited its prospect in actual detection.These two works not only enriched the structural types of light-responsive CMPs,but also opened the prelude to the use of CMPs materials as light-responsive mimic enzymes in the field of biomedical sensing.2.In order to prepare adsorbents with high-efficiency iodine adsorption capacity,we synthesized three CMPs based on triphenylamine derivatives through Pd-catalyzed Sonogashira and Suzuki coupling reactions.The resulting polymers possessed high BET surface areas(up to 1185 m² g^-1).Due to their excellent pore properties,electron-richπ-conjugated network structure,and the interaction of N atoms and I₂ molecules in the framework,CMPs exhibited high iodine vapor capture performance and good recyclability after ethanol washing.Then,two CMPs containing pyridine were synthesized using the Suzuki coupling reaction.The highest BET surface area was 2028 m² g^-1,and the capture capacity of iodine vapor was 5.29 g g^-1,which is more prominent compared with the previously reported literatures.These CMPs also exhibited good recyclability.The high adsorption capacity can be attributed to the combined effect of the excellent porosity,the effective adsorption sites,and the extendedπ-conjugated network framework.In addition,these materials combined the sensing and adsorption functions of tetracycline,which can be used as new fluorescent probe for detection of tetracycline,and at the same time,it also showed high tetracycline adsorption capacity.3.We provided a post-synthetic modification（PSM）strategy to construct cationic conjugated microporous polymers.First,the phenyl conjugated microporous polymer（CMP-O）was synthesized by using 1,3,5-tribromobenzene and terephthalic acid.In the first PSM step,chloromethyl was introduced through Blanc chloromethylation,and in the second step,N-methylimidazole reacted with chloromethyl to construct an imidazolium-containing cationic skeleton（CMP-Im）.The porous,conjugated and cationic skeleton of CMP-Im facilitated its interaction with anionic dyes.Hence,CMP-Im exhibited effective adsorption of such as methyl orange（MO）and congo red（CR）,and the adsorption capacities were 588 and 2500 mg g^-1 for MO and CR,respectively.Besides,it possessed the ability to selectively adsorb the mixed liquid of MO and methylene blue（MB）,and the mixed liquid of CR and MB.In addition,we use CMP-O as the precursor,dichloromethane and chloroform as cross-linking agents.The intermediates were obtained by AlCl₃-catalyzed Friedel-Crafts alkylation reaction,which not only increased the BET surface areas,but also introduced the functional group of chloromethyl.Then the next step was to introduce CO₂-philic diethylenetriamine.Taking the first modification of chloroform as an example,the BET surface area increased from the initial 1182 m² g^-1 to 1828 m² g^-1,and the CO₂ adsorption capacity improved from 2.58 to 4.92 mmol g^-1（1 bar,273 K）.Besides,after modifying the polyamine group on the pore wall,the adsorption of CO₂increased from 19.50 to 37.07 k J mol^-1,and the selectivity of CO₂/N₂ increased from16.68 to 48.70（1 bar,273 K,）.These two works constructed N-containing CMPs through easily available post-synthetic modification strategies,which improved their performance in dyes and gas adsorption,and provided meaningful guidance for the functionalization of CMPs.更多还原