本文選題：整體柱 + 點(diǎn)擊化學(xué)�。� 參考：《西北大學(xué)》2017年碩士論文

【摘要】：整體柱是一種具有廣闊應(yīng)用前景的新型色譜固定相,也是目前液相色譜領(lǐng)域研究的一個(gè)熱點(diǎn)�；趲�基的綠色點(diǎn)擊化學(xué)反應(yīng),具有反應(yīng)條件溫和、產(chǎn)率高等特點(diǎn),目前已經(jīng)被廣泛應(yīng)用于聚合物的制備以及材料表面修飾等方面。然而,目前鮮有文獻(xiàn)報(bào)道點(diǎn)擊化學(xué)反應(yīng)直接制備整體柱的研究。本論文針對目前有機(jī)整體柱和雜化整體柱中存在的一些問題,本文發(fā)展了三種基于點(diǎn)擊反應(yīng)制備整體柱的新技術(shù):1.針對整體柱制備周期長的問題,采用巰基-丙烯酸酯(thiol-acrylate)點(diǎn)擊聚合反應(yīng)快速制備有機(jī)整體柱。十八硫醇的引入有效地抑制傳統(tǒng)自由基聚合過程中的氧阻聚現(xiàn)象。此反應(yīng)過程中既包含丙烯酸酯間的自聚反應(yīng),又存在丙烯酸酯與巰基間的共聚反應(yīng)。所制備的有機(jī)整體柱對苯系物實(shí)現(xiàn)高效分離,最高柱效達(dá)75,000 N/m。對四種標(biāo)準(zhǔn)混合蛋白酶解液的分離效果與C-18填充柱結(jié)果相當(dāng)。并且結(jié)合液質(zhì)聯(lián)用(cLC-MS)技術(shù)首次將毛細(xì)管整體柱應(yīng)用于長柄扁桃蛋白質(zhì)的分離鑒定。2.針對整體柱表面性質(zhì)較難調(diào)控的問題,采用“兩步”巰基-烯(thiol-ene)點(diǎn)擊聚合反應(yīng)制備了一種多孔親水性雜化整體柱。通過與1-硫代甘油反應(yīng),疏水性單體八乙烯基倍半硅烷在致孔劑中的溶解性得到了顯著提高,然后將其作為前驅(qū)體成功制備了雜化整體柱。所制備的雜化整體柱具有連續(xù)均勻的網(wǎng)狀結(jié)構(gòu),在cLC應(yīng)用中顯示出典型的HILIC保留機(jī)理,最高柱效達(dá)65,000 N/m。此外,本研究將肼功能化后的雜化整體材料成功應(yīng)用于糖肽的富集。3.針對有機(jī)聚合物整體柱分離柱效低的問題,首次使用巰基-馬來酰亞胺(thiol-maleimide)點(diǎn)擊聚合反應(yīng)直接合成兩種高交聯(lián)的有機(jī)聚合物整體柱。所制備的有機(jī)整體柱具有良好的熱穩(wěn)定性和機(jī)械強(qiáng)度。在5分鐘內(nèi)實(shí)現(xiàn)對苯系物的高效分離,最高柱效可達(dá)180,500 N/m。此外,對苯酚類、堿性化合物、EPA 610、HeLa酶解液等樣品均展現(xiàn)出令人滿意的分離效果,為提高有機(jī)整體柱對小分子化合物分離柱效提供了一種新思路。
[Abstract]:Monolithic column is a new chromatographic stationary phase with broad application prospect, and it is also a hot spot in the field of liquid chromatography. The green click chemical reaction based on sulfhydryl group has been widely used in the preparation of polymers and the surface modification of materials because of its mild reaction conditions and high yield. However, there are few reports on the direct preparation of monolithic columns by clicking on chemical reactions. Aiming at some problems existing in organic monolithic column and hybrid monolithic column, this paper develops three new techniques for preparing monolithic column based on click-reaction: 1. In order to solve the problem of long preparation period of monolithic column, the organic monolithic column was rapidly prepared by mercapto-acrylic acid thiol-acrylate click-polymerization reaction. The introduction of octadecyl mercaptan can effectively inhibit the phenomenon of oxygen inhibition in the process of traditional free radical polymerization. The reaction includes both the self-polymerization of acrylate and the copolymerization of acrylic ester and sulfhydryl group. The organic monolithic column was used to separate benzene series with the highest column efficiency of 75000 N / m. The separation effect of four standard mixed proteolytic solutions was similar to that of C-18 packed column. The capillary monolithic column was applied to the separation and identification of almond protein for the first time. A porous hydrophilic hybrid monolithic column was prepared by "two-step" mercapto thiol-ene click-polymerization to solve the problem that it is difficult to control the surface properties of monolithic column. The solubility of hydrophobic monomer octavinyldisilane in pore-forming agent was significantly improved by reaction with 1-thioglycerol, and then the hybrid monolithic column was successfully prepared as a precursor. The hybrid monolithic column has a continuous and uniform reticular structure, which shows typical HILIC retention mechanism in the application of cLC. The maximum column efficiency is 65000 N / m. In addition, the hybrid monolithic material of hydrazine functionalized was successfully applied to the enrichment of glycopeptide. 3. In order to solve the problem of low column separation efficiency, two highly crosslinked organic polymer monolithic columns were synthesized by using mercapto-maleimide one-click polymerization for the first time. The prepared organic monolithic column has good thermal stability and mechanical strength. The highest column efficiency of 180500 N / m was achieved in 5 minutes. In addition, samples such as phenol, alkaline compound EPA 610N HeLa hydrolysate showed satisfactory separation effect, which provided a new way to improve the column efficiency of organic monolithic column for the separation of small molecular compounds.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O652.6

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