發(fā)布時(shí)間：2018-06-22 22:26

  本文選題：柱芳烴 + 氣體響應(yīng)　； 參考：《浙江大學(xué)》2017年博士論文

【摘要】：超分子化學(xué)是研究分子之間非共價(jià)相互作用的一門學(xué)科。其中,主客體化學(xué)又是超分子化學(xué)領(lǐng)域中極為重要的一個(gè)分支。大環(huán)主體分子的合成與性質(zhì)研究便成為了主客體分子識(shí)別研究的重中之重。自從主客體化學(xué)這個(gè)概念被提出以來(lái),每一類大環(huán)的發(fā)現(xiàn)和研究都極大地豐富了主客體化學(xué)以及整個(gè)超分子化學(xué)領(lǐng)域。從第一代大環(huán)分子冠醚被發(fā)現(xiàn)之后,越來(lái)越多的化學(xué)家和材料學(xué)家都投身于超分子化學(xué)的研究中去。到目前為止,被廣泛認(rèn)可的四代大環(huán)主體分子主要包括冠醚、杯芳烴、環(huán)糊精和葫蘆脲,并且這四代大環(huán)主體分子在分子識(shí)別、分子自組裝、納米技術(shù)、分子分離與純化、超分子聚合物和超分子兩親等領(lǐng)域都得到了深入的研究與應(yīng)用。柱芳烴是2008年報(bào)道的一種新型大環(huán)分子,因?yàn)槠渚哂刑厥獾姆肿咏Y(jié)構(gòu)和良好的主客體化學(xué)等性質(zhì)所以被廣泛地認(rèn)為是第五代大環(huán)主體分子�；谇叭说墓ぷ�,本人博士期間的工作主要圍繞柱芳烴功能化來(lái)進(jìn)行研究,主要包括溶液相部分和固體部分。本論文將通過(guò)以下五個(gè)方面闡述柱芳烴在溶液中的組裝與應(yīng)用和固體分離材料等方面的性質(zhì)。在第一部分工作中,我們?cè)O(shè)計(jì)并合成了第一種二氧化碳響應(yīng)性的兩親性柱[5]芳烴2.1。它可以在鹽酸的作用下在水里自組裝形成膠束,而在二氧化碳的作用下自組裝形成大環(huán)形圈。跟鹽酸作為刺激響應(yīng)相比,二氧化碳具有諸如無(wú)污染,生物相容性等等優(yōu)點(diǎn)。這些規(guī)則的可控自組裝在控制釋放,藥物傳遞和生物材料方面具有潛在應(yīng)用價(jià)值。在第二部分工作中,我們利用柱[5]芳烴3.2和SDS成功構(gòu)筑了一個(gè)具有二氧化碳響應(yīng)性的主客體分子識(shí)別體系,并且將其應(yīng)用于超分子囊泡的制備和氣體控制釋放。與之前報(bào)道的基于環(huán)糊精的二氧化碳響應(yīng)性分子識(shí)別相比,我們這個(gè)體系有所不同�；谥紵N的二氧化碳響應(yīng)性主客體絡(luò)合物是在鼓入二氧化碳的情況下形成而在鼓入氮?dú)庵蟊黄茐?正好與環(huán)糊精的例子相反。而且,基于柱芳烴的二氧化碳響應(yīng)性主客體分子識(shí)別由于透光率的原因可以直接用肉眼來(lái)觀察到。這個(gè)新的二氧化碳響應(yīng)性主客體分子識(shí)別和自組裝體系也許在藥物傳遞和傳感器方面具有潛在應(yīng)用,而且有助于我們了解某些氣體相關(guān)的生命過(guò)程。在第三部分工作中,我們成功利用含有三聯(lián)吡啶基團(tuán)的配體4.2制成了一種金屬水凝膠,這種水凝膠只有在二價(jià)銅離子的存在下才會(huì)形成凝膠,其他二價(jià)金屬離子并不能誘導(dǎo)其凝膠化。通過(guò)電鏡實(shí)驗(yàn)我們證實(shí)凝膠的微觀結(jié)構(gòu)實(shí)際上是很多直徑在10 nm左右的納米線交織而成的網(wǎng)絡(luò)結(jié)構(gòu)。這種金屬水凝膠還展示了很多響應(yīng)性包括觸變性,溫度響應(yīng)性和化學(xué)響應(yīng)性(堿和抗壞血酸鈉)。除此之外,因?yàn)樗苄灾鵞5]芳烴WP5可以和4.2絡(luò)合,從而也可以引發(fā)凝膠到溶膠的轉(zhuǎn)變,并且在微觀上表現(xiàn)為從納米線轉(zhuǎn)變成了囊泡。這些發(fā)現(xiàn)為許多生物相關(guān)領(lǐng)域提供了潛在的應(yīng)用也為自組裝的發(fā)展歷程提供了很好的參考價(jià)值。在第四部分工作中,我們研究了乙基化柱芳烴(EtP5和EtP6)對(duì)于乙苯和苯乙烯的吸附性質(zhì)。我們發(fā)現(xiàn)EtP6在吸附乙苯和苯乙烯方面具有比EtP5更好的性質(zhì)。而且,無(wú)論晶態(tài)的還是無(wú)定形態(tài)的EtP6都具有選擇性吸附苯乙烯的能力。這個(gè)選擇性主要是由于客體誘導(dǎo)的EtP6選擇性結(jié)構(gòu)變化而不是EtP6空腔大小和客體的匹配性。跟其他小分子有機(jī)分離材料比如多孔籠狀分子相比,EtP6的分離過(guò)程更像是一個(gè)結(jié)晶分離而不是吸附分離。盡管目前利用多孔框架來(lái)分離苯乙烯已經(jīng)有過(guò)報(bào)道,但是我們所提供的方法有些潛在的優(yōu)勢(shì)。比如,EtP6是可溶的,容易合成,而且和MOF5、COFs相比具有更好的化學(xué)穩(wěn)定性。雖然EtP6中的苯乙烯吸附量相對(duì)較低,但是我們可以通過(guò)一次吸附得到高純度的苯乙烯。未來(lái)我們將要試著通過(guò)幾種不同柱芳烴結(jié)晶來(lái)提高吸附量和吸附速率,同時(shí)不降低其選擇性。在第五部分工作中,我們研究了乙基化柱芳烴(EtP5和EtP6)對(duì)于二甲苯異構(gòu)體的吸附性質(zhì)。我們發(fā)現(xiàn)EtP6在溶液相中和固態(tài)相都可以選擇性地吸附對(duì)二甲苯。這個(gè)選擇性不僅是由于EtP6的空腔大小和對(duì)二甲苯非常匹配,還跟EtP6的選擇性結(jié)構(gòu)變化有關(guān)。這跟利用flexible MOFs作分離材料的情況非常類似,但是跟上一章苯乙烯的分離具有較大的不同,因?yàn)楸揭蚁┓蛛x中EtP6的空腔并沒(méi)有起到多大的作用。這個(gè)發(fā)現(xiàn)證明EtP6可以分離除了苯乙烯之外別的碳?xì)浠衔?說(shuō)明它本身可能在含苯碳?xì)浠衔锓蛛x方面是一個(gè)多功能的材料,值得進(jìn)一步研究下去。盡管EtP5在這兩個(gè)分離工作中表現(xiàn)不佳,但是它很可能具有分離別的碳?xì)浠衔锏哪芰?相關(guān)工作正在進(jìn)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.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.3

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