限進(jìn)材料的制備及其在藥物分析中的應(yīng)用
發(fā)布時(shí)間：2018-07-31 12:17
【摘要】：本論文分別以硅膠和Fe203/Si02為基質(zhì),采用原子轉(zhuǎn)移自由基聚合技術(shù)(ATRP)制備反相限進(jìn)材料和磁性反相限進(jìn)材料。分別考察了兩種功能材料對大分子蛋白的排阻能力和對小分子的保留能力。反相限進(jìn)材料作為吸附劑用于分離富集牛奶中的土霉素;磁性反相限進(jìn)材料作為固相萃取填料,用于分離富集牛奶和牛血清樣品中的磺胺類藥物。采用沉淀聚合法制備氯霉素限進(jìn)分子印跡聚合物,其不僅對目標(biāo)分子具有特異選擇性,而且對牛血清白蛋白具有排阻能力;采用靜態(tài)、動(dòng)態(tài)、熱力學(xué)和選擇性吸附實(shí)驗(yàn)詳細(xì)考察其性能,固相萃取小柱結(jié)合HPLC/UV,用于檢測牛血清樣品中的氯霉素。論文主要包括以下部分:1.以硅膠為基質(zhì),在改性硅膠表面通過兩步ATRP反應(yīng)制備內(nèi)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環(huán)氧丙酯(GMA),酸水解后得到表面具有一層二醇基的反相限進(jìn)材料。用紅外光譜、元素分析和熱重分析對反相限進(jìn)材料進(jìn)行表征,證明C18和GMA成功接枝到硅膠表面。研究了其對小分子的吸附性能和對牛血清白蛋白(BSA)的排阻能力,其對BSA的排阻能力為90%,對磺胺二甲氧嘧啶和土霉素的最大吸附量分別為18.02 mg/g和4.80 mg/g。反相限進(jìn)材料用于分離富集牛奶中的土霉素,HPLC檢測,土霉素的平均加標(biāo)回收率為89.19%,相對標(biāo)準(zhǔn)偏差RSD為 3.03%。2.以室溫研磨法制備磁性Fe203,溶膠凝膠制備的Fe203/Si02為基質(zhì),溴代Fe203/Si02為大分子引發(fā)劑,CuBr/Bpy為催化體系,采用ATRP反應(yīng)在Fe203/Si02內(nèi)外表面分別接枝甲基丙烯酸十八烷基酯(C18)和甲基丙烯酸縮水甘油酯(GMA),環(huán)氧基開環(huán)后得到磁性反相限進(jìn)材料。掃描電鏡(SEM)、X射線粉末衍射(XRD)和元素分析對其進(jìn)行表征;通過亞甲基藍(lán)染料吸附的方法,計(jì)算得到磁性反相限進(jìn)材料的比表面積值為5.235 m2/g;研究了磁性反相限進(jìn)材料對小分子的吸附性能和對大分子蛋白的排阻能力,開環(huán)的磁性反相材料對BSA的排阻能力達(dá)到90%,明顯優(yōu)于未開環(huán)的磁性反相限進(jìn)材料。磁性反相限進(jìn)材料對磺胺二甲氧嘧啶、磺胺異惡唑、磺胺芐啶和磺胺甲氧嘧啶的最大吸附量分別為2.24mg/g、2.76mg/g、1.51mg/g、1.34mg/g。結(jié)合固相萃取小柱分離富集牛奶和牛血清中磺胺類藥物小分子,高效液相色譜檢測,取得較滿意的結(jié)果。3.沉淀聚合法制備了氯霉素限進(jìn)分子印跡聚合物(CAP-RAM-MIPs),氯霉素(CAP)為模板分子,乙腈為制孔劑和溶劑,甲基丙烯酸縮水甘油酯(GMA)為外層親水功能單體。采用傅立葉變換紅外光譜、掃描電鏡和熱重分析對其表征;采用靜態(tài)、動(dòng)態(tài)、熱力學(xué)和選擇性吸附實(shí)驗(yàn)詳細(xì)考察其性能,CAP-RAM-MIPs對CAP的最大吸附量為178.3mg/g,優(yōu)于文獻(xiàn)報(bào)道。選擇甲砜霉素和氟苯尼考為競爭分子,研究氯霉素限進(jìn)分子印跡聚合物的特異性識(shí)別能力,結(jié)果顯示CAP-RAM-MIPs對目標(biāo)分子具有良好的選擇性。Langmuir和Freundlich等溫吸附方程均能很好的描述CAP在氯霉素限進(jìn)分子印跡聚合物上的吸附過程;用準(zhǔn)一級(jí)和準(zhǔn)二級(jí)反應(yīng)動(dòng)力學(xué)方程對實(shí)驗(yàn)數(shù)據(jù)進(jìn)行擬合,表明CAP-RAM-MIPs對CAP的吸附過程與二級(jí)動(dòng)力學(xué)模型相吻合。CAP-RAM-MIPs作為固相萃取小柱填料用于選擇性分離富集牛血清中的CAP,HPLC/UV檢測,CAP的平均加標(biāo)回收率為105.22%-120.11%,相對標(biāo)準(zhǔn)偏差為 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%.
【學(xué)位授予單位】：寧夏大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB34;O652.6
本文編號(hào)：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%.
【學(xué)位授予單位】：寧夏大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB34;O652.6
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