基于β-環(huán)糊精非均相仿酶的構(gòu)筑及其應(yīng)用研究
發(fā)布時間：2019-06-22 12:59
【摘要】：β-環(huán)糊精具有“內(nèi)腔疏水,外壁親水”的特殊結(jié)構(gòu)和性質(zhì),且廉價易得可再生。根據(jù)其豐富的羥基官能團可進一步修飾的特點,可將修飾后的β-環(huán)糊精固載到活性載體上,應(yīng)用于催化苯甲硫醚的不對稱氧化反應(yīng)。首先將FeCl3·6H2O和FeCl2·4H2O在堿性條件下結(jié)合制備Fe3O4納米粒子,再利用3-氯丙基三乙氧基硅烷和正硅酸乙酯與Fe3O4納米粒子結(jié)合制備核-殼結(jié)構(gòu)的活性載體Si@Fe3O4載體。為了考察該載體固載β-環(huán)糊精的活性,實驗采用乙二胺為連接基團將β-環(huán)糊精母體固載到Si@Fe3O4載體上,并利用其吸附水溶液中的p-硝基苯酚的性能來考察其相關(guān)性質(zhì)。通過FT-IR、XPS、XRD、TGA、SEM、TEM、水接觸角,表征分析證明載體的制備與環(huán)糊精的固載已成功。在對p-硝基苯酚的吸附試驗中,考察了溶液pH值、吸附時間和吸附溫度對吸附量的影響。研究表明該吸附劑對p-硝基苯酚的吸附在15 s內(nèi)既能達到吸附平衡,且pH值為7.0時,飽和吸附量達到84.2 mg/g。證明該Si@Fe3O4載體性質(zhì)優(yōu)良。以此為基礎(chǔ),再借助實驗室之前研究過的Cl@Si載體為環(huán)糊精的第二個載體,實現(xiàn)了環(huán)糊精的非均相化。實驗首先采用乙醇胺和丙醇胺為修飾基團合成了6-乙醇胺-β-環(huán)糊精和6-丙醇胺-β-環(huán)糊精,再以1-氯-3-碘-丙烷為連接基團,分別將這兩種β-環(huán)糊精衍生物成功固載到前兩種載體上,再將其與Na2MoO4絡(luò)合,成功構(gòu)筑了β-環(huán)糊精非均相仿生催化劑。通過FT-IR、XPS、XRD、TGA、SEM、TEM、水接觸角,表征分析證明該非均相仿生催化劑配體的制備已成功。并考察了該仿生催化劑對苯甲硫醚不對稱氧化反應(yīng)的調(diào)控性能。研究表明,載體的引入并未影響環(huán)糊精衍生物對苯甲硫醚不對稱氧化反應(yīng)的調(diào)控,底物轉(zhuǎn)化率高達100.0%,產(chǎn)物收率也高達83.4%,ee%值最高達到55.3%。實驗不僅使用了綠色環(huán)保的溶劑代替有機溶劑,而且催化劑可回收再利用,符合“綠色化學(xué)”理念。在篩選催化活性中心的過程中,我們發(fā)現(xiàn)質(zhì)子酸是一類性質(zhì)優(yōu)良的催化劑。為了進一步研究質(zhì)子酸對苯甲硫醚氧化反應(yīng)的催化性能及其原理,我們系統(tǒng)性的探究了一系列質(zhì)子酸催化H2O2氧化硫化物的催化性能,并揭露了其中共性問題。研究表明,對于所有的質(zhì)子酸,其催化活性均與反應(yīng)體系的pH值有關(guān),只要反應(yīng)體系的p H值達到1.30左右,所有的質(zhì)子酸催化劑均可以使反應(yīng)轉(zhuǎn)化率和收率達到98.0%以上。我們首次提出在質(zhì)子酸催化氧化硫化物的體系中,其催化活性是由反應(yīng)體系的pH值所決定。
[Abstract]:尾-cyclodextrin has the special structure and properties of "inner cavity hydrophobic and outer wall hydrophilicity", and it is cheap and easy to regenerate. According to the rich hydroxyl functional groups which can be further modified, the modified 尾-cyclodextrin can be loaded on the active carrier and applied to the asymmetric oxidation of benzothioether. Firstly, FeCl3 路6H2O and FeCl2 路4H2O were combined to prepare Fe3O4 nanoparticles under alkaline conditions, and then the active carrier Si@Fe3O4 carrier with core-shell structure was prepared by the combination of 3-chloropropyl triethoxysilane and tetraethyl orthosilicate with Fe3O4 nanoparticles. In order to investigate the activity of 尾-cyclodextrin supported by the carrier, the matrix of 尾-cyclodextrin was loaded on Si@Fe3O4 carrier with ethylenediamine as the connecting group, and its related properties were investigated by using its adsorption properties of p-nitrophenol in aqueous solution. The preparation of the carrier and the loading of cyclodextrin were proved to be successful by FT-IR,XPS,XRD,TGA,SEM,TEM, water contact angle. In the adsorption test of p-nitrophenol, the effects of pH value, adsorption time and adsorption temperature on the adsorption capacity were investigated. The results show that the adsorption of p-nitrophenol by the adsorbents can reach the adsorption equilibrium in 15 s, and the saturated adsorption capacity reaches 84.2 mg/g. when the pH value is 7.0. It is proved that the Si@Fe3O4 carrier has excellent properties. On this basis, the heterogeneity of cyclodextrin was realized by using the Cl@Si carrier previously studied in the laboratory as the second carrier of cyclodextrin. In this experiment, 6-ethanolamine-尾-cyclodextrin and 6-propanolamine-尾-cyclodextrin were synthesized by using ethanolamine and propanolamine as modified groups, and then the 尾-cyclodextrin derivatives were successfully supported on the first two supports with 1-chloro-3-iodine-propane as the connecting group, and then the 尾-cyclodextrin heterogeneous bionic catalysts were successfully constructed by complexing them with Na2MoO4. The preparation of the heterogeneous bionic catalyst ligand was successfully prepared by FT-IR,XPS,XRD,TGA,SEM,TEM, water contact angle. The regulation performance of the biomimetic catalyst for asymmetric oxidation of benzothioether was investigated. The results showed that the introduction of the carrier did not affect the regulation of cyclodextrin derivatives on the asymmetric oxidation of benzothioether. The conversion of substrate was as high as 100.0%, the yield of the product was 83.4%, and the highest ee% value was 55.3%. The experiment not only uses green environmental protection solvent instead of organic solvent, but also the catalyst can be recycled and reused, which accords with the concept of "green chemistry". In the process of screening catalytic active sites, we found that protonic acid is a kind of catalyst with excellent properties. In order to further study the catalytic performance and principle of proton acid for the oxidation of benzothioether, we systematically investigated the catalytic performance of a series of protonic acids for the oxidation of sulfides by H2O2, and revealed the common problems. The results show that for all proton acids, the catalytic activity is related to the pH value of the reaction system. As long as the pH value of the reaction system is about 1.30, all protonic acid catalysts can make the conversion and yield of the reaction reach more than 98.0%. We propose for the first time that the catalytic activity of sulfides catalyzed by protonic acid is determined by the pH value of the reaction system.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O636.12;O643.36
本文編號：2504604
[Abstract]:尾-cyclodextrin has the special structure and properties of "inner cavity hydrophobic and outer wall hydrophilicity", and it is cheap and easy to regenerate. According to the rich hydroxyl functional groups which can be further modified, the modified 尾-cyclodextrin can be loaded on the active carrier and applied to the asymmetric oxidation of benzothioether. Firstly, FeCl3 路6H2O and FeCl2 路4H2O were combined to prepare Fe3O4 nanoparticles under alkaline conditions, and then the active carrier Si@Fe3O4 carrier with core-shell structure was prepared by the combination of 3-chloropropyl triethoxysilane and tetraethyl orthosilicate with Fe3O4 nanoparticles. In order to investigate the activity of 尾-cyclodextrin supported by the carrier, the matrix of 尾-cyclodextrin was loaded on Si@Fe3O4 carrier with ethylenediamine as the connecting group, and its related properties were investigated by using its adsorption properties of p-nitrophenol in aqueous solution. The preparation of the carrier and the loading of cyclodextrin were proved to be successful by FT-IR,XPS,XRD,TGA,SEM,TEM, water contact angle. In the adsorption test of p-nitrophenol, the effects of pH value, adsorption time and adsorption temperature on the adsorption capacity were investigated. The results show that the adsorption of p-nitrophenol by the adsorbents can reach the adsorption equilibrium in 15 s, and the saturated adsorption capacity reaches 84.2 mg/g. when the pH value is 7.0. It is proved that the Si@Fe3O4 carrier has excellent properties. On this basis, the heterogeneity of cyclodextrin was realized by using the Cl@Si carrier previously studied in the laboratory as the second carrier of cyclodextrin. In this experiment, 6-ethanolamine-尾-cyclodextrin and 6-propanolamine-尾-cyclodextrin were synthesized by using ethanolamine and propanolamine as modified groups, and then the 尾-cyclodextrin derivatives were successfully supported on the first two supports with 1-chloro-3-iodine-propane as the connecting group, and then the 尾-cyclodextrin heterogeneous bionic catalysts were successfully constructed by complexing them with Na2MoO4. The preparation of the heterogeneous bionic catalyst ligand was successfully prepared by FT-IR,XPS,XRD,TGA,SEM,TEM, water contact angle. The regulation performance of the biomimetic catalyst for asymmetric oxidation of benzothioether was investigated. The results showed that the introduction of the carrier did not affect the regulation of cyclodextrin derivatives on the asymmetric oxidation of benzothioether. The conversion of substrate was as high as 100.0%, the yield of the product was 83.4%, and the highest ee% value was 55.3%. The experiment not only uses green environmental protection solvent instead of organic solvent, but also the catalyst can be recycled and reused, which accords with the concept of "green chemistry". In the process of screening catalytic active sites, we found that protonic acid is a kind of catalyst with excellent properties. In order to further study the catalytic performance and principle of proton acid for the oxidation of benzothioether, we systematically investigated the catalytic performance of a series of protonic acids for the oxidation of sulfides by H2O2, and revealed the common problems. The results show that for all proton acids, the catalytic activity is related to the pH value of the reaction system. As long as the pH value of the reaction system is about 1.30, all protonic acid catalysts can make the conversion and yield of the reaction reach more than 98.0%. We propose for the first time that the catalytic activity of sulfides catalyzed by protonic acid is determined by the pH value of the reaction system.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O636.12;O643.36
【參考文獻】
相關(guān)期刊論文 前3條
1 江紅果;楊祖金;周賢太;方巖雄;紀(jì)紅兵;;固定β-環(huán)糊精制備不溶性β-環(huán)糊精聚合物及其催化性能(英文)[J];Chinese Journal of Chemical Engineering;2012年04期
2 李效紅;趙保衛(wèi);朱琨;郝學(xué)奎;;β-環(huán)糊精改性沸石去除水中硝基苯酚(英文)[J];Chinese Journal of Chemical Engineering;2011年06期
3 紀(jì)紅兵;黃麗泉;石東坡;周賢太;;β-環(huán)糊精超分子催化劑用于液相有機合成[J];有機化學(xué);2008年12期
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