| 题名 | 磁性吸附剂的合成和表征及吸附甘草黄酮的应用研究 |
| 作者 | 张波 |
| 学位类别 | 博士 |
| 答辩日期 | 2009-06-05 |
| 授予单位 | 中国科学院过程工程研究所 |
| 授予地点 | 过程工程研究所 |
| 导师 | 刘会洲 |
| 关键词 | 磁性吸附剂 合成 甘草黄酮 芦丁 吸附分离 |
| 其他题名 | Preparation of magnetic adsorbents and application for adsorption of licorice flavonoids |
| 学位专业 | 化学工艺 |
| 中文摘要 | 本论文将磁性分离技术应用于中草药活性成分的分离纯化中，探索磁性分离技术在中草药分离纯化研究中的可行性。选择甘草黄酮为分离纯化的对象，根据甘草黄酮化合物多羟基的结构特点，采用改进的悬浮聚合法和硅烷化法制备了用于分离纯化甘草黄酮的磁性吸附剂，并将它们用于吸附纯黄酮类物质芦丁和实际体系甘草提取液的研究中，对吸附的机理和吸附工艺进行了研究。 采用硅酸钠水解法和正硅酸乙酯法合成出了磁性二氧化硅纳米颗粒。在此基础上采用硅烷偶联剂γ-氨丙基三乙氧基硅烷对磁性颗粒表面进行了功能化修饰，在颗粒表面引入氨基功能基团，得到表面具有氨基的磁性SiO2-NH2吸附剂。 通过改进悬浮聚合法原料配方和聚合工艺，降低Fe3O4的阻聚作用，制备出了分散性较好的氢键型高分子吸附剂磁性脲醛吸附剂和磁性丙烯腈吸附剂。合成工艺简单，适合规模化制备。磁性脲醛吸附剂的比饱和磁化强度为15.1emu/g，磁性丙烯腈吸附剂的比饱和磁化强度为17.9emu/g，因此用常规磁铁可实现快速分离。Fe3O4纳米颗粒的直径为14.4nm，表现出超顺磁性。因此这两种磁性吸附剂在外加磁场下不会被永久磁化，当去掉外加磁场后能够很容易重新分散。 采用甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯共聚合成了磁性甲基丙烯酸缩水甘油酯（PGMA）载体，并利用PGMA微球表面丰富的环氧基团，使用间氨基苯硼酸在室温下与之发生偶联反应进行表面功能化修饰，得到表面含有硼酸基团的磁性PGMA吸附剂。 选择纯黄酮类化合物芦丁作为模拟体系，研究了吸附影响因素和解吸附条件。制备的磁性PGMA吸附剂、磁性脲醛吸附剂和磁性γ-Al2O3吸附剂能快速达到吸附平衡，比大孔吸附树脂所需时间更短。磁性吸附剂对芦丁都有一定的吸附能力，磁性PGMA吸附剂吸附芦丁的最大吸附量为8.4mg/g；磁性γ-Al2O3吸附剂的最大吸附量为18.7mg/g；磁性脲醛吸附剂的最大吸附量为22.1mg/g，高于磁性PGMA吸附剂和磁性γ-Al2O3吸附剂对芦丁的吸附量。机理研究表明，磁性PGMA吸附剂和磁性γ-Al2O3吸附剂吸附芦丁，主要是通过配位作用进行吸附。 在模拟吸附的基础上，将制备的磁性吸附剂用于甘草提取液实际体系中。pH值对吸附影响表明，磁性脲醛吸附剂、磁性丙烯腈吸附剂和磁性SiO2-NH2吸附剂受pH影响较大，说明这三种吸附剂主要通过氢键作用吸附甘草黄酮。本论文制备的磁性吸附剂对甘草黄酮均有一定的吸附能力，其中磁性脲醛吸附剂和磁性丙烯腈吸附剂吸附甘草黄酮的最大吸附量分别是16.3mg/g和20.6mg/g，高于磁性PGMA吸附剂、磁性γ-Al2O3吸附剂和磁性SiO2-NH2吸附剂对甘草黄酮的吸附量。对于磁性脲醛吸附剂和磁性丙烯腈吸附剂，可以使用无毒低沸点的乙醇作为解吸附剂。用75%乙醇洗脱磁性脲醛吸附剂上的黄酮时，纯度达到25.1%，远远高于甘草提取液中3.7%的黄酮纯度，也高于报道的XDA-1大孔吸附树脂浓缩后的黄酮纯度21.9%，说明该磁性吸附剂对甘草黄酮具有较好的选择性；HPLC分析还表明，75%乙醇洗脱部位中甘草酸含量很低，因此可以用这种吸附剂有效地分离甘草黄酮和甘草酸。 |
| 英文摘要 | This thesis applied the magnetic separation technology into the separation and purification of active compounds of Chinese medicine. The licorice flavonoids were selected as the target of separation study. Magnetic adsorbents were synthesized by improved suspension polymerization and silanization based on the polyhydroxy structure of licorice flavonoids. Moreover, these magnetic adsorbents were used to the adsorption study of rutin (one kind of flavonoids) and licorice extract; furthermore, the adsorption mechanism and adsorption processing were studied. Magnetic silica nanoparticles were synthesized through hydrolyzation of sodium silicate and ethyl orthosilicate. Functional modification was made on the surface of the magnetic nanoparticles adopting silane coupling agent γ-aminopropyl triethoxy silane, and amino functional groups were introduced onto the surface of silica nanoparticles. Magnetic SiO2-NH2 adsorbents with amino groups on the surface were obtained. Magnetic poly (acrylonitrile-divinylbenzene) (PAN-DVB) adsorbents and poly (urea-formaldehyde) (PUF) adsorbents were synthesized through improved suspension polymerization. The polymerization inhibitive influence of ferroferric oxide was minimized through changing the polymerization technology and material ingredients. The preparation processing is simple and suitable for large-scale preparation. The saturation magnetizations of magnetic poly (acrylonitrile-divinylbenzene) adsorbents and poly (urea-formaldehyde) adsorbents were 17.9emu/g and 15.1emu/g respectively. As a result, the separate operation can be practiced by using regular magnet. The diameter of ferroferric oxide is about 14.4 nanometers, and so these magnetic particles show superparamagnetic property. These kinds of magnetic adsorbents can not be permanently magnetized in the external magnetic field; the adsorbents would be easily dispersed again when the external magnetic field was removed. Magnetic poly (glycidyl ester of methyl acrylic acid) (PGMA) microspheres were synthesized through the copolymerization of glycidyl ester of methyl acrylic acid and ethylene glycol dimethacrylate. There are abundant epoxy groups on the surface of PGMA microspheres. Metanilic acid can easily react with epoxy group at mild conditions. The boric acid can be introduced onto the surface of PGMA microspheres. Rutin (one kind of pure flavonoids) was selected as the model system. The factors influencing adsorption and desorption conditions were studied. The prepared magnetic adsorbents of PGMA, PUF andγ-Al2O3 can quickly reach the adsorption equilibrium, which is faster than that of macroporous resins. All the prepared magnetic adsorbents in the thesis have certain adsorption capacities for rutin. The maximum adsorption capacity of magnetic PUF adsorbents is 22.1mg/g, which is higher than that of magnetic PGMA adsorbents and magnetic γ-Al2O3 adsorbents. Mechanism study shows that magnetic PGMA absorbents and magneticγ-Al2O3 adsorbents adsorb rutin primarily through the formation of complex compounds. Based on the study of model adsorption, these magnetic adsorbents were used to absorb the flavonoids of licorice extract. The influence of pH value demonstrates that the pH value play an important role on the adsorption for the magnetic PUF adsorbents, magnetic PAN adsorbents and magntic SiO2-NH2 adsorbents. With the increase of pH value, the adsorption capacity decrease greatly. The reason is that these three kinds of adsorbents adsorb flavonoids through H bonding, and H bonding is easy to be affected by pH value. The magnetic adsorbents synthesized in the thesis can absorb certain flavonoids. The maximum adsorption capacities of magnetic PUF and magnetic PAN adsorbents were 16.3mg/g and 20.6mg/g, which are higher than that of magnetic PGMA adsorbents, magnetic γ-Al2O3 adsorbents and magntic SiO2-NH2 adsorbents. Ethanol is ideal eluent for magnetic PUF adsorbents and magnetic PAN adsorbents. When 75% ethanol was used as the eluent, the purity of flavonoids attains 25.1%, higher than the purity of 3.7% of licorice extract and 21.9% of macroporous resins XDA-1 reported, which shows that magnetic adsorbents have an excellent selection for flavonoids. HPLC analysis shows that the contents of glycyrrihizic acid is very low in the 75% ethanol parts, so glycyrrihizic acid can be effectively removed from the desorption fraction by these prepared adsorbents in the thesis. |
| 语种 | 中文 |
| 公开日期 | 2013-09-13 |
| 页码 | 132 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1114]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 张波. 磁性吸附剂的合成和表征及吸附甘草黄酮的应用研究[D]. 过程工程研究所. 中国科学院过程工程研究所. 2009. |
| 个性服务 |
| 查看访问统计 |
| 相关权益政策 |
| 暂无数据 |
| 收藏/分享 |
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。
修改评论