基于MOF—磁性石墨烯功能材料的制备及其分离和制备手性药物中间体的研究

发布时间：2018-05-30 20:50

本文选题：金属有机骨架(MOF) + 手性分离　；参考：《郑州大学》2017年硕士论文

【摘要】：金属有机骨架化合物(MOF)作为一种新型的多孔功能材料,因其具有较高的比表面积、丰富的拓扑结构、稳定的孔结构以及孔道表面可修饰等特点,使得它在气体储存、催化剂、吸附分离等诸多领域都具有非常广泛的应用前景。手性金属有机骨架材料是MOFs发展的重要组成部分,由于手性MOFs多孔的功能位点和手性的特点,因而在不对称合成和手性选择分离方面受到了广泛的推崇。氧化石墨烯(GO)作为制备石墨烯(G)的重要前驱体,除了具有层状结构和比表面积大的特点外,还含有大量含氧基团,例如羟基、环氧基团和羧基等。这些含氧基团的存在不仅可以提高氧化石墨烯的亲水性能,也为制备功能化氧化石墨烯材料提供了反应位点。氧化石墨烯与手性MOFs材料结合而制备的复合功能材料,能集各种材料的优点于一体,并利用它们的协同效应提高整体复合功能材料的性能。然而通过文献调研,尚未见到有关手性MOF-磁性石墨烯功能材料用于磁性固相萃取(MSPE)的研究,也尚未见到将此类功能化磁性粒子应用于手性分析的研究报道。本论文合成了磁性氧化石墨烯功能化的手性MOFs材料,并将其应用于磁性固相萃取来实现对手性药物中间体的选择性吸附分离。这些功能材料既具有氧化石墨烯大的比表面积和良好的分散性,又兼具手性MOFs的多孔性及手性,还能结合磁性材料的磁性,因而具有广泛的应用前景。主要内容如下:第一,首先利用水热法制备磁性四氧化三铁,然后通过溶胶-凝胶法在磁性Fe_3O_4纳米粒子表面包覆一层二氧化硅,再利用3-氨丙基三乙氧基硅烷(APTES)对Fe_3O_4@SiO_2进一步功能化,最后通过化学键合法将氨基化的磁性材料键合到石墨烯表面,制得Fe_3O_4@SiO_2-NH_2-GO(简称MGO)磁性材料,并通过扫描电镜(SEM)、透射电镜(TEM)、红外(IR)、X射线粉末衍射(XRD)进行表征。第二,常压下制备了纯手性MOF1,[Zn2(bdc)(L-lac)(dmf)](bdc=对苯二甲酸;L-lac=L-乳酸),并将制得的MGO按照不同的掺杂量分散在手性MOF1中得到了磁性石墨烯功能化的MOF,Fe_3O_4@SiO_2-NH_2-GO@MOF1(简称MGO-ZnBLD),并通过扫描电镜(SEM)、透射电镜(TEM)、红外(IR)、热重(TGA)、磁滞回线(VSM)、X射线粉末衍射(XRD)、氮气吸附等进行表征。用磁性固相萃取(MSPE)对甲基苯基亚砜进行选择性吸附与分离,在磁性石墨烯掺杂量为5%时对映体过量值(ee值)可达90.9%,整个吸附过程仅用了2分钟,且重复7次后ee值未见明显降低。第三,常压下制备了另一种纯手性MOF2,[Zn2(D-Cam)2(4,4'-bpy)]n(D-Cam=D樟脑酸;4,4'-bpy=4,4'-联吡啶),同样通过不同掺杂量的MGO制得Fe_3O_4@SiO_2-NH_2-GO@MOF2(简称MGO-ZnCB),并通过扫描电镜、透射电镜、红外、热重、磁滞回线、X射线粉末衍射、氮气吸附、EDS能谱等进行表征。用磁性固相萃取对联萘酚进行选择性吸附与分离,在磁性石墨烯掺杂量为10%时对映体过量值(ee值)可达74.8%,整个吸附过程可以在3分钟内完成,且重复7次后ee值仍未见明显降低。第四,利用制得Fe_3O_4@SiO_2-NH_2-GO@MOF2(简称MGO-ZnCB)对另一种手性药物中间体联糠醛进行选择性吸附分离,在磁性石墨烯掺杂量为8%时对映体过量值(ee值)为57.4%,整个吸附过程仅需要2分钟,同样重复7次后ee值未见明显降低。
[Abstract]:As a new type of porous functional material, metal organic framework compound (MOF) has the characteristics of high specific surface area, rich topological structure, stable pore structure and surface modifier, which make it widely used in many fields such as gas storage, catalyst, adsorption separation and so on. Chiral metals have a wide range of applications. The framework material is an important part of the development of MOFs. Due to the functional sites and chiral features of the chiral MOFs, it has been widely respected in the asymmetric synthesis and chiral separation. GO is an important precursor for the preparation of Shi Moxi (G), except for the characteristics of large layer structure and specific surface area. The presence of oxygen groups, such as hydroxyl groups, epoxy groups and carboxyl groups, can not only improve the hydrophilic properties of graphene oxide, but also provide a reaction site for the preparation of functionalized graphene oxide materials. The composite functional materials, which are prepared by the combination of graphene oxide and chiral MOFs materials, can be used to collect various materials. The properties of the composite functional materials are improved by their synergistic effects. However, the study of chiral MOF- magnetic graphene functional materials for magnetic solid phase extraction (MSPE) has not yet been seen through literature research, and the research reports on the application of such functionalized magnetic particles to chiral analysis have not yet been seen. The functionalized chiral MOFs materials of magnetic graphene oxide are synthesized and used in magnetic solid phase extraction to achieve selective adsorption and separation of chiral drug intermediates. These functional materials have both the specific surface area and good dispersion of graphene oxide, also the porosity and chirality of chiral MOFs, and the combination of magnetic materials. The magnetic properties of the material are widely used. The main contents are as follows: first, the magnetic Fe_3O_4 is prepared by the hydrothermal method. Then a layer of silica is coated on the surface of the magnetic Fe_3O_4 nanoparticles by the sol-gel method, and then the Fe_3O_4@SiO_2 is further functionalized with 3- amipropyl triethoxane (APTES). Fe_3O_4@SiO_2-NH_2-GO (SEM), transmission electron microscope (TEM), infrared (IR), X ray powder diffraction (XRD) were characterized by bonding the amino - magnetic materials to the surface of graphene. Second, pure chiral MOF1, [Zn2 (BDC) (L-lac) (DMF)] were prepared under atmospheric pressure. Ac=L- lactic acid), and the synthesized MGO was dispersed in the chiral MOF1 by different doping amount in the chiral MOF, Fe_3O_4@SiO_2-NH_2-GO@MOF1 (MGO-ZnBLD), and was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared (IR), thermogravimetric (TGA), hysteresis loop (VSM), X ray powder diffraction, nitrogen adsorption, etc. The selective adsorption and separation of methyl phenyl sulfoxide by magnetic solid phase extraction (MSPE), the overdose of enantiomers (EE value) can reach 90.9% when the doping amount of magnetic graphene is 5%, the whole adsorption process is only 2 minutes, and the EE value is not obviously reduced after 7 times. Third, another kind of pure chiral MOF2, [Zn2 (D-Cam) 2 (4,4'-bpy)]n is prepared under constant pressure. (D-Cam=D camphor acid; 4,4'-bpy=4,4'- bipyridine), Fe_3O_4@SiO_2-NH_2-GO@MOF2 (abbreviated as MGO-ZnCB) was obtained by different doping amounts of MGO, and was characterized by scanning electron microscopy, transmission electron microscopy, infrared, thermogravimetry, hysteresis loop, X ray powder diffraction, nitrogen adsorption, EDS spectrum and so on. The selective adsorption of naphthol by magnetic solid phase extraction was carried out. With the separation, the overdose of enantiomers (EE value) can reach 74.8% when the amount of magnetic graphene is 10%, and the whole adsorption process can be completed in 3 minutes, and the EE value is still not obviously reduced after 7 times. Fourth, Fe_3O_4@SiO_2-NH_2-GO@MOF2 (MGO-ZnCB) is used to selectively adsorb the other kind of intermediate fural furfural. The overdose of enantiomers (EE value) is 57.4% when the amount of magnetic graphene is 8%, and the whole adsorption process takes only 2 minutes, and the EE value is not significantly reduced after the same repetition of 7 times.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB34;TQ460.1

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