本文選題：超分子化學 + 柱芳烴�。� 參考：《浙江大學》2017年博士論文

【摘要】：大環(huán)主體化合物是推動超分子化學迅猛發(fā)展的重要力量。繼冠醚、環(huán)糊精、杯芳烴和葫蘆脲之后,作為新一代大環(huán)主體的柱芳烴自2008年被報道以來,一直受到超分子化學家們的持續(xù)關注,經(jīng)過近十年的發(fā)展,柱芳烴已經(jīng)在超分子化學的舞臺上展現(xiàn)了無限的風采和魅力。作為柱芳烴的重要組成部分,高階柱芳烴具有不同于傳統(tǒng)柱[5]芳烴和柱[6]芳烴的拓撲學結構和主客體性質,然而對于高階柱芳烴的研究尚處不夠深入。本論文首先概述了高階柱芳烴的發(fā)展現(xiàn)狀,然后重點闡述了水溶性柱[7]芳烴和柱[9]芳烴的合成,主客體化學性質及其在超分子自組裝方面的相關研究工作。本論文的正文部分包括以下四個部分:在第一部分工作中,我們第一次制備出了陰離子型水溶柱[7]芳烴,并研究了其與紫精客體的主客體絡合性質。1HNMR、ESI-MS、NOESY、UV-Vis以及熒光實驗證明主體和客體在水中形成1:1[2]準輪烷,并且由于多重靜電相互作用,其絡合常數(shù)高達(2.96±0.31)×109 M-1。由于羧酸根陰離子的特性,該主客體絡合物具有酸堿響應性,通過加酸加堿,可以簡單地控制該絡合物的解絡合與再絡合。這一新的主客體識別體系被進一步用于構筑超分子兩親體系,通過主客體作用,可以實現(xiàn)組裝體從膠束向囊泡的轉變。在第二部分工作中,我們第一次制備出了陰離子型水溶柱[9]芳烴,并且也研究了它與紫精客體的酸堿響應性主客體性質。通過實驗證明主客體在水溶液中自組裝成1:1包結絡合物,其絡合常數(shù)有(2.27±0.24)× 106 M-1。相比較于前一部分的水溶性柱[7]芳烴,絡合常數(shù)的減小是因為柱[9]芳烴的內(nèi)部空腔尺寸比柱[7]芳烴的大,與紫精客體的尺寸匹配性沒有柱[7]芳烴好。在第三部分工作中,我們基于水溶性柱[9]芳烴與2,7-氮雜芘衍生物建立了一種新型的具有雙向酸堿響應性的主客體識別機理。因為水溶性柱[9]芳烴對鹽酸和氫氧化鈉具有可逆響應性,而2,7-氮雜芘衍生物對正己胺和三氟乙酸具有可逆響應性,所以我們不僅利用鹽酸/氫氧化鈉這一酸堿對,而且可以利用正己胺/三氟乙酸這一堿酸對來實現(xiàn)對主客體絡合物的解絡合與再絡合的控制,使該絡合物成為具備雙向酸堿響應性的分子開關。在第四部分工作中,我們研究了陰離子型水溶性柱[7]芳烴與2,7-氮雜芘衍生物之間的酸堿響應性主客體絡合性質�；谶@一主客體識別機理,我們構筑了一個新的超分子兩親體系。通過主客體絡合作用,我們可以方便地調控組裝體在水中的形貌。另外,由于水溶性柱[7]芳烴具有酸堿響應性,我們可以通過簡單地加酸加堿操作來可逆地控制主體客體絡合與解絡合的狀態(tài),從而達到可逆控制超分子兩親自組裝體形貌的目的。
[Abstract]:Macrocyclic host compounds are important forces to promote the rapid development of supramolecular chemistry. After crown ethers, cyclodextrins, calixarenes and cucurbiturides, column aromatics, as the new generation of macrocyclic aromatic hydrocarbons, have been continuously concerned by supramolecular chemists since they were reported in 2008. Column aromatics have shown infinite charm and charm on the stage of supramolecular chemistry. As an important component of column aromatics, high-order aromatics have different topological structures and host and guest properties from traditional [5] aromatics and column [6] aromatics. In this paper, the development of high order column aromatics is reviewed, and the synthesis, host and guest chemical properties of water-soluble [7] aromatics and column [9] aromatics and their research work in supramolecular self-assembly are discussed. The main body of this thesis includes four parts as follows: in the first part, we prepared anion water soluble column [7] aromatics for the first time. The host and guest complexation properties of the host and guest with purple spermatine were studied. 1HNMRESI-MSI NOESYVis and fluorescence experiments showed that the host and guest formed 1:1 [2] quasi rotorane in water, and its complexation constant was as high as 2.96 鹵0.31 脳 109M-1 due to the multiplex electrostatic interaction. Because of the characteristic of carboxylate anion, the host and guest complex is acid-base responsive. By adding acid and alkali, the uncomplexation and recomplexation of the complex can be controlled simply. This new host and guest recognition system is further used to construct a supramolecular amphiphilic system, through which the assembly can be transformed from micelle to vesicle. In the second part, we prepared anion soluble column [9] aromatics for the first time, and also studied the acid-base responsive host and guest properties of the anion column [9] aromatics. It is proved by experiments that the host and guest self-assemble into 1:1 inclusion complex in aqueous solution, and its complexation constant is 2.27 鹵0.24) 脳 106M-1. Compared with the water-soluble column [7] aromatics in the former part, the complexation constant decreases because the inner cavity size of [9] aromatics is larger than that of column [7] aromatics, and the size matching with the column [7] aromatics is not as good as that of column [7] aromatics. In the third part, based on the water-soluble column [9] aromatics and 2O7-azapyrene derivatives, a novel host-guest recognition mechanism with bidirectional acid-base response was established. Because the water-soluble column [9] arene has reversible response to hydrochloric acid and sodium hydroxide, while the derivative of 2O7-azapyrene has reversible response to n-hexylamine and trifluoroacetic acid, we not only use hydrochloric acid / sodium hydroxide as acid-base pair, The alkali-acid pair of n-hexylamine / trifluoroacetic acid can be used to control the uncomplexation and recomplexation of the host and guest complex, which makes the complex become a molecular switch with bidirectional acid-base response. In the fourth part, we have studied the acid-base responsive host and guest complexing properties between [7] aromatics and 2O7-azapyrene derivatives. Based on the host and guest recognition mechanism, a new supramolecular amphiphilic system is constructed. Through the host and guest complexation, we can easily control the morphology of the assembly in water. In addition, due to the acid-base response of water-soluble column [7] aromatics, we can control the complexation and desorption state of the host and guest by simply adding acid and alkali. In order to achieve the purpose of reversible control of supramolecular self-assembly morphology.
【學位授予單位】：浙江大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O641.3

【參考文獻】

相關期刊論文 前1條

1 Herbert Meier;;Synthesis of pillar[7]arene[J];Chinese Chemical Letters;2012年05期

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本文編號：1978919