基于柱芳烃的功能材料研究

发布时间：2018-06-22 22:26

本文选题：柱芳烃 + 气体响应　；参考：《浙江大学》2017年博士论文

【摘要】：超分子化学是研究分子之间非共价相互作用的一门学科。其中,主客体化学又是超分子化学领域中极为重要的一个分支。大环主体分子的合成与性质研究便成为了主客体分子识别研究的重中之重。自从主客体化学这个概念被提出以来,每一类大环的发现和研究都极大地丰富了主客体化学以及整个超分子化学领域。从第一代大环分子冠醚被发现之后,越来越多的化学家和材料学家都投身于超分子化学的研究中去。到目前为止,被广泛认可的四代大环主体分子主要包括冠醚、杯芳烃、环糊精和葫芦脲,并且这四代大环主体分子在分子识别、分子自组装、纳米技术、分子分离与纯化、超分子聚合物和超分子两亲等领域都得到了深入的研究与应用。柱芳烃是2008年报道的一种新型大环分子,因为其具有特殊的分子结构和良好的主客体化学等性质所以被广泛地认为是第五代大环主体分子。基于前人的工作,本人博士期间的工作主要围绕柱芳烃功能化来进行研究,主要包括溶液相部分和固体部分。本论文将通过以下五个方面阐述柱芳烃在溶液中的组装与应用和固体分离材料等方面的性质。在第一部分工作中,我们设计并合成了第一种二氧化碳响应性的两亲性柱[5]芳烃2.1。它可以在盐酸的作用下在水里自组装形成胶束,而在二氧化碳的作用下自组装形成大环形圈。跟盐酸作为刺激响应相比,二氧化碳具有诸如无污染,生物相容性等等优点。这些规则的可控自组装在控制释放,药物传递和生物材料方面具有潜在应用价值。在第二部分工作中,我们利用柱[5]芳烃3.2和SDS成功构筑了一个具有二氧化碳响应性的主客体分子识别体系,并且将其应用于超分子囊泡的制备和气体控制释放。与之前报道的基于环糊精的二氧化碳响应性分子识别相比,我们这个体系有所不同。基于柱芳烃的二氧化碳响应性主客体络合物是在鼓入二氧化碳的情况下形成而在鼓入氮气之后被破坏,正好与环糊精的例子相反。而且,基于柱芳烃的二氧化碳响应性主客体分子识别由于透光率的原因可以直接用肉眼来观察到。这个新的二氧化碳响应性主客体分子识别和自组装体系也许在药物传递和传感器方面具有潜在应用,而且有助于我们了解某些气体相关的生命过程。在第三部分工作中,我们成功利用含有三联吡啶基团的配体4.2制成了一种金属水凝胶,这种水凝胶只有在二价铜离子的存在下才会形成凝胶,其他二价金属离子并不能诱导其凝胶化。通过电镜实验我们证实凝胶的微观结构实际上是很多直径在10 nm左右的纳米线交织而成的网络结构。这种金属水凝胶还展示了很多响应性包括触变性,温度响应性和化学响应性(碱和抗坏血酸钠)。除此之外,因为水溶性柱[5]芳烃WP5可以和4.2络合,从而也可以引发凝胶到溶胶的转变,并且在微观上表现为从纳米线转变成了囊泡。这些发现为许多生物相关领域提供了潜在的应用也为自组装的发展历程提供了很好的参考价值。在第四部分工作中,我们研究了乙基化柱芳烃(EtP5和EtP6)对于乙苯和苯乙烯的吸附性质。我们发现EtP6在吸附乙苯和苯乙烯方面具有比EtP5更好的性质。而且,无论晶态的还是无定形态的EtP6都具有选择性吸附苯乙烯的能力。这个选择性主要是由于客体诱导的EtP6选择性结构变化而不是EtP6空腔大小和客体的匹配性。跟其他小分子有机分离材料比如多孔笼状分子相比,EtP6的分离过程更像是一个结晶分离而不是吸附分离。尽管目前利用多孔框架来分离苯乙烯已经有过报道,但是我们所提供的方法有些潜在的优势。比如,EtP6是可溶的,容易合成,而且和MOF5、COFs相比具有更好的化学稳定性。虽然EtP6中的苯乙烯吸附量相对较低,但是我们可以通过一次吸附得到高纯度的苯乙烯。未来我们将要试着通过几种不同柱芳烃结晶来提高吸附量和吸附速率,同时不降低其选择性。在第五部分工作中,我们研究了乙基化柱芳烃(EtP5和EtP6)对于二甲苯异构体的吸附性质。我们发现EtP6在溶液相中和固态相都可以选择性地吸附对二甲苯。这个选择性不仅是由于EtP6的空腔大小和对二甲苯非常匹配,还跟EtP6的选择性结构变化有关。这跟利用flexible MOFs作分离材料的情况非常类似,但是跟上一章苯乙烯的分离具有较大的不同,因为苯乙烯分离中EtP6的空腔并没有起到多大的作用。这个发现证明EtP6可以分离除了苯乙烯之外别的碳氢化合物,说明它本身可能在含苯碳氢化合物分离方面是一个多功能的材料,值得进一步研究下去。尽管EtP5在这两个分离工作中表现不佳,但是它很可能具有分离别的碳氢化合物的能力,相关工作正在进一步研究中。
[Abstract]:Supramolecular chemistry is a subject to study the non covalent interaction between molecules. Among them, the object chemistry is a very important branch in the field of supramolecular chemistry. The study of the synthesis and properties of the main molecules of large rings has become the most important part of the study of the recognition of the host and guest molecules. Since the concept of host and guest chemistry has been put forward, The discovery and research of each kind of large rings have greatly enriched the host and guest chemistry and the whole field of supramolecular chemistry. After the discovery of the first large ring molecular crown ethers, more and more chemists and materials scientists have been involved in the study of supramolecular chemistry. Up to now, the four generation macrocyclic main body molecules have been widely recognized as the main package. Including crown ethers, calixarene, cyclodextrin and cucurbit urea, and the four generation macrocyclic main molecules have been studied and applied in the fields of molecular recognition, molecular self-assembly, nanotechnology, molecular separation and purification, supramolecular polymers and supramolecular two parents. Column aromatics are a new type of macrocyclic molecule reported in 2008 because of its special characteristics. The molecular structure and good host and guest chemistry are widely regarded as the fifth generation macrocyclic molecules. Based on the previous work, the work of the PhD is mainly focused on the functionalization of column aromatics, mainly including the solution phase and the solid part. This article will explain the column aromatics in the following five aspects. In the first part of the work, we designed and synthesized the first carbon dioxide responsive column of two amphiphilic column [5] arene 2.1., which can be self assembled into a micelle in water under the action of hydrochloric acid, and a large ring ring is formed by self assembly under the action of two carbon dioxide. Compared with acid as a stimulus response, carbon dioxide has such advantages as non pollution and biocompatibility. The controlled self-assembly of these rules has potential application value in controlling release, drug delivery and biomaterials. In the second part, we successfully constructed a carbon dioxide response with [5] aromatics 3.2 and SDS The molecular recognition system of the host and guest molecules is applied to the preparation of supramolecular vesicles and gas control release. Compared with the previously reported carbon dioxide responsive molecular recognition based on cyclodextrin, the carbon dioxide responsive host guest complex based on the column aromatics is in the case of carbon dioxide. It is formed and destroyed after the drum enters nitrogen, just contrary to the example of cyclodextrin. Moreover, the carbon dioxide responsive host molecule recognition based on the column aromatics can be observed directly by the naked eye because of the transmittance. This new carbon dioxide responsive host molecule recognition and self-assembly system may be in drug delivery and The sensor has potential applications and helps us to understand some gas related life processes. In the third part, we successfully used a ligand 4.2 containing the tripline group to make a metal hydrogel that only formed gels in the presence of two valence copper ions and other two valence metal ions. The microstructures of the gel are actually a network structure of a number of nanowires around 10 nm in diameter. This metal hydrogel also shows a lot of responsiveness, temperature responsiveness and chemical responsiveness (alkali and sodium ascorbate). The water-soluble column [5] arene WP5 can be complexed with 4.2, which can also lead to the gel to the sol transformation, and at the microcosmic level, it is transformed from nanowires to vesicles. These findings provide potential applications for many biological related fields and provide a good reference for the development of self-assembly. In the fourth part, I work. We studied the adsorption properties of ethylbenzene (EtP5 and EtP6) for ethylbenzene and styrene. We found that EtP6 has better properties than EtP5 in the adsorption of ethylbenzene and styrene. Moreover, both crystalline and amorphous EtP6 have the energy of selective adsorption of styrene. This selectivity is mainly due to the EtP induced by the object. 6 the selective structural change is not the size of the EtP6 cavity and the compatibility of the object. Compared with other small molecular organic separation materials such as porous cage molecules, the separation process of EtP6 is more like a crystalline separation rather than a adsorption separation. Although the current porous frame has been reported to separate styrene, we have provided a recipe. There are some potential advantages. For example, EtP6 is soluble, easy to synthesize, and has a better chemical stability compared with MOF5, COFs. Although the adsorption amount of styrene in EtP6 is relatively low, we can get high purity styrene by one adsorption. In the future we will try to increase the absorption through several different column aromatic crystals. In the fifth part, we studied the adsorption properties of ethylene column aromatics (EtP5 and EtP6) for xylene isomers. We found that EtP6 can selectively adsorb p-xylene in both solution and solid phase. This selectivity is not only due to the cavity size and the pair of EtP6. Dimethylbenzene is very matched and is related to the selective structural change of EtP6. This is very similar to the use of flexible MOFs as a separation material, but the separation of the previous chapter of styrene is quite different because the cavity of the EtP6 is not much used in the separation of styrene. This discovery shows that EtP6 can be separated from B B. Other hydrocarbons other than alkenes indicate that it itself may be a multifunctional material in the separation of benzene containing hydrocarbons. It is worth further study. Although EtP5 is poor in the two separation work, it is likely to have the ability to separate other hydrocarbons, and the related work is being further studied.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.3

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