本文選題：催化非專一性 + 脂肪酶��； 參考：《吉林大學(xué)》2017年碩士論文

【摘要】：酶是具有生物催化功能的大分子物質(zhì),具有催化效率高、專一性強(qiáng)、反應(yīng)條件溫和、生物可降解、對(duì)環(huán)境友好等優(yōu)點(diǎn),符合綠色化學(xué)和原子經(jīng)濟(jì)的要求。隨著酶學(xué)研究的不斷發(fā)展,許多酶被報(bào)道能催化多種類型的反應(yīng),這種特性稱為酶催化非專一性。酶催化非專一性的研究,為綠色化學(xué)的發(fā)展提供一條有效的新途徑。脂肪酶是一種商品化程度高、穩(wěn)定性強(qiáng)、底物作用范圍廣的酶制劑,也是酶催化非專一性領(lǐng)域中研究較為深入的一類酶。本文主要研究脂肪酶介導(dǎo)的氧化反應(yīng)及其在有機(jī)合成中的應(yīng)用。主要研究?jī)?nèi)容和結(jié)果如下:研究脂肪酶催化的Knoevenagel-Epoxidation串聯(lián)反應(yīng),為α-氰基環(huán)氧化合物的合成提供一條綠色高效且溫和的合成路線。我們對(duì)該反應(yīng)的條件進(jìn)行優(yōu)化和篩選:包括酶源、酶的用量、溶劑,進(jìn)而確定了該反應(yīng)最適體系。本節(jié)研究結(jié)果表明:在50oC條件下,300 U Novozym 435、1.5 mmol過(guò)氧化脲(UHP)催化1 mmol底物在N,N-二甲基甲酰胺(DMF)/乙酸乙酯(EA)為2/3體系中具有最佳產(chǎn)率。研究脂肪酶介導(dǎo)的氧化偶氮苯類化合物及其衍生物的合成。氧化偶氮苯類化合物具有廣泛的應(yīng)用,可作為染料、化學(xué)穩(wěn)定劑、藥物中間體,是一種非常重要的化合物。經(jīng)研究本反應(yīng)的最適條件為:在室溫條件下,脂肪酶(300U),苯胺(2mmol),過(guò)氧化脲(2.5 mmol),乙酸乙酯(5 m L),反應(yīng)時(shí)間1 h。值得關(guān)注的是底物分子取代基的電子效應(yīng)對(duì)氧化偶氮苯化合物產(chǎn)率的影響并不大,但是其位阻效應(yīng)對(duì)反應(yīng)產(chǎn)率具有明顯的影響。研究雙酶(葡萄糖氧化酶與脂肪酶)體系共催化N-雜環(huán)化合物和三級(jí)胺的N-氧化合物的氧化合成。本反應(yīng)通過(guò)對(duì)葡萄糖氧化酶與脂肪酶的比例以及用量、反應(yīng)體系中磷酸鹽緩沖液與乙酸乙酯的比例、反應(yīng)時(shí)間等因素進(jìn)行優(yōu)化,在較溫和件下即可獲得很高產(chǎn)率。通過(guò)放大實(shí)驗(yàn)以及底物適用性研究,證實(shí)該雙酶體系具有較高的工業(yè)應(yīng)用價(jià)值。
[Abstract]:Enzyme is a macromolecular material with biocatalytic function, which has the advantages of high catalytic efficiency, strong specificity, mild reaction conditions, biodegradable and environment-friendly. It meets the requirements of green chemistry and atomic economy. With the development of enzymology, many enzymes have been reported to catalyze many kinds of reactions, which is called enzymatic non-specificity. The study of enzyme-catalyzed non-specificity provides an effective new way for the development of green chemistry. Lipase is a kind of enzyme preparation with high degree of commercialization, strong stability and wide range of substrate action. It is also a kind of enzyme which has been studied deeply in the field of enzymatic catalysis. This paper focuses on lipase-mediated oxidation and its application in organic synthesis. The main contents and results are as follows: the lipase-catalyzed Knoevenagel-Epoxidation series reaction provides a green efficient and mild synthetic route for the synthesis of 偽 -cyanoepoxy compounds. We optimized and screened the reaction conditions, including enzyme source, amount of enzyme, solvent, and then determined the optimal reaction system. In this section, the results show that 1 mmol substrate catalyzed by 300U Novozym 435N 1.5 mmol UHP) under 50oC conditions has the best yield in the system of N- (N-dimethylformamide) DMFU / ethyl acetate (EAA) = 2 / 3. The synthesis of oxidized azobenzene compounds and their derivatives mediated by lipase was studied. Oxidized azobenzene compounds are widely used as dyes, chemical stabilizers and pharmaceutical intermediates. The optimum reaction conditions were as follows: lipase 300 U, aniline 2 mmol / L, urea peroxide 2.5 mmol / L, ethyl acetate 5 mL / L, reaction time 1 h. It is worthy of attention that the electronic effect of the substituents of the substrates has little effect on the yield of oxidized azobenzene compounds, but its steric resistance effect has a significant effect on the yield of the reaction. The oxidation synthesis of N-heterocyclic compounds and N-oxide compounds with tertiary amine catalyzed by two enzymes (glucose oxidase and lipase) was studied. By optimizing the ratio and dosage of glucose oxidase to lipase, the ratio of phosphate buffer to ethyl acetate, the reaction time and so on, the yield of high yield could be obtained under mild conditions. It is proved that the double enzyme system has high industrial application value through the experiments of magnification and the study of substrate applicability.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.3;Q55

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