RAFT沉淀聚合制备马兜铃酸分子印迹聚合物及吸附性能研究

发布时间：2018-01-16 00:03

  本文关键词：RAFT沉淀聚合制备马兜铃酸分子印迹聚合物及吸附性能研究　出处：《湘潭大学》2016年硕士论文　论文类型：学位论文

  更多相关文章： 马兜铃酸 分子印迹 RAFT聚合 关木通 Material Studio软件模拟

【摘要】：马兜铃酸I(AA I)在体内的还原产物与DNA不可逆结合,引发了国际上轰动一时的“马兜铃酸肾病”。国内外纷纷叫停与AA I相关的各种医药保健产品,这既对我国中药产业产生巨大冲击,也造就了“马兜铃酸肾病”这一世界难题。国内外学者对含AA I植物“减毒存效”进行了大量研究,并取得了一定成就。如何高效去除医药产品中AA I,仍然具有重要的现实意义和科学意义,又富有挑战性。我们采用AA I为模板分子构筑了AA I分子印迹聚合物(MIP)并研究其性能,在此基础上研究MIP吸附关木通乙醇提取物中AA I的能力。具体内容及结果如下:1、采用MS模拟优选出构筑MIP的功能单体和溶剂,分别为丙烯酸(AA)和DMF-水溶液。采用差示紫外光谱法,研究AA I与AA在80%(g/g)DMF-水溶液中的氢键结合能力,明确了二者的结合比例:AA I:AA=1:4。2、以AA I为模板分子、AA为功能单体、乙二醇二甲基丙烯酸酯(EGDMA)为交联剂、偶氮二异丁腈(AIBN)为链引发剂、二硫代苯甲酸(4-氰基戊酸)酯(CTP)为链转移剂、80%(g/g)DMF-水混合溶液为致孔剂,通过RAFT技术制备MIP,收率为63.42%,非印迹分子聚合物(NIP)的收率为79.22%。3、通过红外光谱、固体紫外、氮气吸附、激光粒度等方法对MIP和NIP的结构、组成、粒径等进行了比较。结果表明:二者组成、结构相同,说明已经成功制备MIP。此外,MIP、NIP的比表面积分别为19.524、10.617 m2/g,平均孔径分别为2.454、2.167nm。4、研究了MIP和NIP的等温静态吸附行为,Langmuir模拟结果表明,AA I浓度在0.002~0.01mg·mL-1范围之间,MIP和NIP的吸附符合Langmuir模型,其吸附常数分别为232.45、58.02 mL/mg,说明MIP对AA I吸附能力比NIP强;Scatchard模拟结果表明,MIP和NIP都只具一种吸附方式,且MIP和NIP的平衡解离常数分别为8.9、26.2mg/L,即MIP对AA I的亲和力显著强于NIP,进一步证明了MIP对AA I具特异性吸附能力。5、研究了MIP和NIP的等温动态吸附行为(25℃),MIP符合一级动力学反应模型(log(Qeq-Qt)=-0.160t+0.181,R2=0.993),NIP符合二级动力学反应模型(t/Qt=2.186t+3.745,R2=0.997),表明MIP中印迹位点具有特异性吸附能力。6、变温动态吸附实验表明,MIP吸附AA I的能力几乎不受温度影响;选择性吸附实验表明,MIP对AA I具良好的特异性识别能力;可重复利用性实验表明,MIP可多次重复使用。7、采用高效液相色谱法研究MIP吸附关木通乙醇提取物中AA I的能力,结果表明:用25.0 mg MIP吸附5.0 mL关木通乙醇提取物中的AA I(其中CAA I为0.0018 mg/mL),可使AA I含量减少到液相检测限以下;AA I的回收率为41.70%综上所述,RAFT沉淀聚合成功构筑了MIP,并表现了优良的性能,且对AA I有选择性吸附。探索了MIP应用于关木通乙醇提取液中AA I的去除。为中草药“减毒存效”提供了新方法和新思路。
[Abstract]:The reductive product of aristolochic acid IbAA-I was irreversibly bound to DNA in vivo. Aristolochic acid nephropathy caused by the international sensation. At home and abroad to stop all kinds of medical and health products associated with AA I, which has a huge impact on the Chinese traditional medicine industry. Aristolochic acid nephropathy is also a worldwide problem. Scholars at home and abroad have done a lot of research on the "detoxification effect" of AA-I plants. Some achievements have been made. How to effectively remove AA I from pharmaceutical products is still of great practical and scientific significance. AA-I molecular imprinted polymer (MIP) was constructed using AA I as template molecule and its properties were studied. On the basis of this, the ability of MIP to adsorb AA I in ethanol extract of Akebia japonica was studied. The specific contents and results were as follows: 1. The functional monomers and solvents for constructing MIP were selected by MS simulation. The hydrogen bonding ability of AA and AA in 80 g / g DMF- aqueous solution was studied by differential ultraviolet spectroscopy (DUV). The ratio of AA: I: AA1: 4.2, AA I as template molecule AA as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent were determined. Azodiisobutyronitrile (AIBN) as chain initiator and dithiobenzoate 4-cyanopentanoate (CTP) as chain transfer agent. The yield of MIP was 63.42, and the yield of non-imprinted molecular polymer was 79.22.3.The yield of MIP was 79.22.3.The yield of MIP was determined by IR, solid UV and nitrogen adsorption. The structure, composition and particle size of MIP and NIP were compared by laser particle size method. The results showed that the structure of MIP and NIP were the same, which indicated that MIP had been prepared successfully. The specific surface area of NIP is 19.524% 10.617 m2 / g, and the average pore size is 2.454nm.4 and 2.167nm.4, respectively. The isothermal static adsorption behavior of MIP and NIP was studied. The results showed that the concentration of AA-I was in the range of 0.002 ~ 0.01mg 路mL-1. The adsorption constants of MIP and NIP were 232.45% 58.02 mL / mg, respectively, which indicated that the adsorption ability of MIP to AA I was stronger than that of NIP. The results of Scatchard simulation show that both MIP and NIP have only one adsorption mode, and the equilibrium dissociation constants of MIP and NIP are 8.9 ~ 26.2mg / L. That is, the affinity of MIP to AA I is significantly stronger than that of nip, which further proves that MIP has a specific adsorption ability of AA I. 5. The isothermal dynamic adsorption behavior of MIP and NIP was studied. R _ 2N _ (0.993) NIP accords with the second-order kinetic reaction model (t / Q ~ (t) 2.186t 3.745N ~ (2) N ~ (2) O ~ (0.997)). The results showed that the imprinting sites in MIP had specific adsorption ability. 6. The dynamic adsorption experiments showed that the adsorption ability of AA-I was almost unaffected by temperature. The selective adsorption experiment showed that MIP had good recognition ability to AA I. The reusability experiment showed that MIP could be reused for several times. The ability of MIP to adsorb AA I in ethanol extract was studied by high performance liquid chromatography (HPLC). The results showed that AA I (CAA I = 0.0018 mg / mL) was adsorbed by 25.0 mg MIP. The content of AA I can be reduced to below the detection limit of liquid phase. The recovery rate of AA I was 41.70%. In summary, MIP was successfully constructed by precipitation polymerization of raft and showed excellent properties. The application of MIP to the removal of AA I from the ethanol extract of Allium mandshurica was explored, which provided a new method and new idea for the "detoxification and storage effect" of Chinese herbal medicine.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.3
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本文编号：1430635