限进材料的制备及其在药物分析中的应用
发布时间：2018-07-31 12:17
【摘要】：本论文分别以硅胶和Fe203/Si02为基质,采用原子转移自由基聚合技术(ATRP)制备反相限进材料和磁性反相限进材料。分别考察了两种功能材料对大分子蛋白的排阻能力和对小分子的保留能力。反相限进材料作为吸附剂用于分离富集牛奶中的土霉素;磁性反相限进材料作为固相萃取填料,用于分离富集牛奶和牛血清样品中的磺胺类药物。采用沉淀聚合法制备氯霉素限进分子印迹聚合物,其不仅对目标分子具有特异选择性,而且对牛血清白蛋白具有排阻能力;采用静态、动态、热力学和选择性吸附实验详细考察其性能,固相萃取小柱结合HPLC/UV,用于检测牛血清样品中的氯霉素。论文主要包括以下部分:1.以硅胶为基质,在改性硅胶表面通过两步ATRP反应制备内表面接枝甲基丙烯酸十八烷基酯(C18),外表面接枝甲基丙烯酸环氧丙酯(GMA),酸水解后得到表面具有一层二醇基的反相限进材料。用红外光谱、元素分析和热重分析对反相限进材料进行表征,证明C18和GMA成功接枝到硅胶表面。研究了其对小分子的吸附性能和对牛血清白蛋白(BSA)的排阻能力,其对BSA的排阻能力为90%,对磺胺二甲氧嘧啶和土霉素的最大吸附量分别为18.02 mg/g和4.80 mg/g。反相限进材料用于分离富集牛奶中的土霉素,HPLC检测,土霉素的平均加标回收率为89.19%,相对标准偏差RSD为 3.03%。2.以室温研磨法制备磁性Fe203,溶胶凝胶制备的Fe203/Si02为基质,溴代Fe203/Si02为大分子引发剂,CuBr/Bpy为催化体系,采用ATRP反应在Fe203/Si02内外表面分别接枝甲基丙烯酸十八烷基酯(C18)和甲基丙烯酸缩水甘油酯(GMA),环氧基开环后得到磁性反相限进材料。扫描电镜(SEM)、X射线粉末衍射(XRD)和元素分析对其进行表征;通过亚甲基蓝染料吸附的方法,计算得到磁性反相限进材料的比表面积值为5.235 m2/g;研究了磁性反相限进材料对小分子的吸附性能和对大分子蛋白的排阻能力,开环的磁性反相材料对BSA的排阻能力达到90%,明显优于未开环的磁性反相限进材料。磁性反相限进材料对磺胺二甲氧嘧啶、磺胺异恶唑、磺胺苄啶和磺胺甲氧嘧啶的最大吸附量分别为2.24mg/g、2.76mg/g、1.51mg/g、1.34mg/g。结合固相萃取小柱分离富集牛奶和牛血清中磺胺类药物小分子,高效液相色谱检测,取得较满意的结果。3.沉淀聚合法制备了氯霉素限进分子印迹聚合物(CAP-RAM-MIPs),氯霉素(CAP)为模板分子,乙腈为制孔剂和溶剂,甲基丙烯酸缩水甘油酯(GMA)为外层亲水功能单体。采用傅立叶变换红外光谱、扫描电镜和热重分析对其表征;采用静态、动态、热力学和选择性吸附实验详细考察其性能,CAP-RAM-MIPs对CAP的最大吸附量为178.3mg/g,优于文献报道。选择甲砜霉素和氟苯尼考为竞争分子,研究氯霉素限进分子印迹聚合物的特异性识别能力,结果显示CAP-RAM-MIPs对目标分子具有良好的选择性。Langmuir和Freundlich等温吸附方程均能很好的描述CAP在氯霉素限进分子印迹聚合物上的吸附过程;用准一级和准二级反应动力学方程对实验数据进行拟合,表明CAP-RAM-MIPs对CAP的吸附过程与二级动力学模型相吻合。CAP-RAM-MIPs作为固相萃取小柱填料用于选择性分离富集牛血清中的CAP,HPLC/UV检测,CAP的平均加标回收率为105.22%-120.11%,相对标准偏差为 0.0065%-0.039%。
[Abstract]:In this paper, silica gel and Fe203/Si02 are used as matrix, reverse phase limiting material and magnetic reverse phase limiting material are prepared by atom transfer radical polymerization (ATRP). The resistance ability of two functional materials to large molecular protein and the retention of small molecules are investigated respectively. The reverse phase limiting material is used as adsorbent for the separation and enrichment of milk. The magnetic reverse phase limiting material, as solid phase extraction filler, is used for the separation and enrichment of sulfonamides in milk and bovine serum samples. The preparation of chloramphenicol restricted molecularly imprinted polymers by precipitation polymerization is not only specific to the target molecules, but also has the ability to reject bovine serum albumin; Dynamic, thermodynamic and selective adsorption experiments were used to examine its properties in detail. Solid phase extraction column combined with HPLC/UV was used to detect chloramphenicol in bovine serum samples. The paper mainly included the following parts: 1., silica gel was used as the matrix to prepare the internal surface grafting eighteen alkyl methacrylate (C18) on the surface of the modified silica gel by two step ATRP reaction. Graft copolymer of propylene glycol methacrylate (GMA) was grafted on the surface with a layer of diol based reverse phase limiting material. The reverse phase limiting material was characterized by IR, elemental analysis and thermogravimetric analysis. It was proved that C18 and GMA were successfully grafted onto the surface of silica gel. The adsorption properties for small molecules and bovine serum albumin (BSA) were studied. The rejection capacity of BSA is 90%. The maximum adsorption capacity of sulfadiazine and oxytetracycline and oxytetracycline are 18.02 mg/g and 4.80 mg/g. respectively for oxytetracycline and HPLC detection in the separation and enrichment of milk. The average recovery rate of oxytetracycline is 89.19%, and the standard deviation RSD is 3.03%.2. by room temperature grinding method. Magnetic Fe203, Fe203/Si02 as matrix prepared by sol-gel, brominated Fe203/Si02 as a large molecular initiator and CuBr/Bpy as a catalytic system, eighteen alkyl methacrylate (C18) and glycidyl methacrylate (GMA) were grafted on the internal and external surface of Fe203/Si02 by ATRP reaction. The magnetic reverse phase limiting material was obtained after the epoxide ring opening. Electron microscopy (SEM), X ray powder diffraction (XRD) and elemental analysis are used to characterize it. The specific surface area of the magnetic reverse phase limiting material is 5.235 m2/g by the methylene blue dye adsorption method, and the magnetic reverse material for the magnetic reverse phase limiting material on the small molecules and the resistance to the large molecular protein is studied. The resistance of the material to BSA is 90%, which is obviously superior to the unopen magnetic reverse phase limiting material. The maximum adsorption capacity of magnetic reverse phase limiting materials for sulfadimethoxy, sulfamethoxazole, sulfazidine and sulfadimethoxine is 2.24mg/g, 2.76mg/g, 1.51mg/g, 1.34mg/ g. combined with solid phase extraction column for the separation and enrichment of milk and bovine serum Chloramphenicol limited molecularly imprinted polymer (CAP-RAM-MIPs), chloramphenicol (CAP) as template molecule, acetonitrile as a pore agent and solvent, and glycate methacrylate (GMA) as a outer hydrophilic functional monomer, were prepared by.3. precipitation polymerization. Fu Liye transform was used. Infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis were used to characterize them. The properties of CAP-RAM-MIPs were investigated by static, dynamic, thermodynamic and selective adsorption experiments. The maximum adsorption capacity of CAP was 178.3mg/g, superior to the literature. The results show that CAP-RAM-MIPs has good selectivity to the target molecule.Langmuir and Freundlich isothermal adsorption equation, which can describe the adsorption process of CAP on the molecularly imprinted polymer of chloramphenicol limited. The experimental data are fitted with the pseudo first order and quasi two stage reaction kinetics equation, indicating that CAP-RAM-MIPs to CAP The adsorption process is consistent with the two stage dynamic model.CAP-RAM-MIPs as a solid phase extraction column filler used for selective separation and enrichment of CAP in bovine serum, HPLC/UV detection, the average recovery rate of CAP is 105.22%-120.11%, and the relative standard deviation is 0.0065%-0.039%.
【学位授予单位】：宁夏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB34;O652.6
本文编号：2155559
[Abstract]:In this paper, silica gel and Fe203/Si02 are used as matrix, reverse phase limiting material and magnetic reverse phase limiting material are prepared by atom transfer radical polymerization (ATRP). The resistance ability of two functional materials to large molecular protein and the retention of small molecules are investigated respectively. The reverse phase limiting material is used as adsorbent for the separation and enrichment of milk. The magnetic reverse phase limiting material, as solid phase extraction filler, is used for the separation and enrichment of sulfonamides in milk and bovine serum samples. The preparation of chloramphenicol restricted molecularly imprinted polymers by precipitation polymerization is not only specific to the target molecules, but also has the ability to reject bovine serum albumin; Dynamic, thermodynamic and selective adsorption experiments were used to examine its properties in detail. Solid phase extraction column combined with HPLC/UV was used to detect chloramphenicol in bovine serum samples. The paper mainly included the following parts: 1., silica gel was used as the matrix to prepare the internal surface grafting eighteen alkyl methacrylate (C18) on the surface of the modified silica gel by two step ATRP reaction. Graft copolymer of propylene glycol methacrylate (GMA) was grafted on the surface with a layer of diol based reverse phase limiting material. The reverse phase limiting material was characterized by IR, elemental analysis and thermogravimetric analysis. It was proved that C18 and GMA were successfully grafted onto the surface of silica gel. The adsorption properties for small molecules and bovine serum albumin (BSA) were studied. The rejection capacity of BSA is 90%. The maximum adsorption capacity of sulfadiazine and oxytetracycline and oxytetracycline are 18.02 mg/g and 4.80 mg/g. respectively for oxytetracycline and HPLC detection in the separation and enrichment of milk. The average recovery rate of oxytetracycline is 89.19%, and the standard deviation RSD is 3.03%.2. by room temperature grinding method. Magnetic Fe203, Fe203/Si02 as matrix prepared by sol-gel, brominated Fe203/Si02 as a large molecular initiator and CuBr/Bpy as a catalytic system, eighteen alkyl methacrylate (C18) and glycidyl methacrylate (GMA) were grafted on the internal and external surface of Fe203/Si02 by ATRP reaction. The magnetic reverse phase limiting material was obtained after the epoxide ring opening. Electron microscopy (SEM), X ray powder diffraction (XRD) and elemental analysis are used to characterize it. The specific surface area of the magnetic reverse phase limiting material is 5.235 m2/g by the methylene blue dye adsorption method, and the magnetic reverse material for the magnetic reverse phase limiting material on the small molecules and the resistance to the large molecular protein is studied. The resistance of the material to BSA is 90%, which is obviously superior to the unopen magnetic reverse phase limiting material. The maximum adsorption capacity of magnetic reverse phase limiting materials for sulfadimethoxy, sulfamethoxazole, sulfazidine and sulfadimethoxine is 2.24mg/g, 2.76mg/g, 1.51mg/g, 1.34mg/ g. combined with solid phase extraction column for the separation and enrichment of milk and bovine serum Chloramphenicol limited molecularly imprinted polymer (CAP-RAM-MIPs), chloramphenicol (CAP) as template molecule, acetonitrile as a pore agent and solvent, and glycate methacrylate (GMA) as a outer hydrophilic functional monomer, were prepared by.3. precipitation polymerization. Fu Liye transform was used. Infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis were used to characterize them. The properties of CAP-RAM-MIPs were investigated by static, dynamic, thermodynamic and selective adsorption experiments. The maximum adsorption capacity of CAP was 178.3mg/g, superior to the literature. The results show that CAP-RAM-MIPs has good selectivity to the target molecule.Langmuir and Freundlich isothermal adsorption equation, which can describe the adsorption process of CAP on the molecularly imprinted polymer of chloramphenicol limited. The experimental data are fitted with the pseudo first order and quasi two stage reaction kinetics equation, indicating that CAP-RAM-MIPs to CAP The adsorption process is consistent with the two stage dynamic model.CAP-RAM-MIPs as a solid phase extraction column filler used for selective separation and enrichment of CAP in bovine serum, HPLC/UV detection, the average recovery rate of CAP is 105.22%-120.11%, and the relative standard deviation is 0.0065%-0.039%.
【学位授予单位】：宁夏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB34;O652.6
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