發(fā)布時間：2018-01-16 00:03

  本文關鍵詞：RAFT沉淀聚合制備馬兜鈴酸分子印跡聚合物及吸附性能研究　出處：《湘潭大學》2016年碩士論文　論文類型：學位論文

  更多相關文章： 馬兜鈴酸 分子印跡 RAFT聚合 關木通 Material Studio軟件模擬

【摘要】：馬兜鈴酸I(AA I)在體內的還原產物與DNA不可逆結合,引發(fā)了國際上轟動一時的“馬兜鈴酸腎病”。國內外紛紛叫停與AA I相關的各種醫(yī)藥保健產品,這既對我國中藥產業(yè)產生巨大沖擊,也造就了“馬兜鈴酸腎病”這一世界難題。國內外學者對含AA I植物“減毒存效”進行了大量研究,并取得了一定成就。如何高效去除醫(yī)藥產品中AA I,仍然具有重要的現實意義和科學意義,又富有挑戰(zhàn)性。我們采用AA I為模板分子構筑了AA I分子印跡聚合物(MIP)并研究其性能,在此基礎上研究MIP吸附關木通乙醇提取物中AA I的能力。具體內容及結果如下:1、采用MS模擬優(yōu)選出構筑MIP的功能單體和溶劑,分別為丙烯酸(AA)和DMF-水溶液。采用差示紫外光譜法,研究AA I與AA在80%(g/g)DMF-水溶液中的氫鍵結合能力,明確了二者的結合比例:AA I:AA=1:4。2、以AA I為模板分子、AA為功能單體、乙二醇二甲基丙烯酸酯(EGDMA)為交聯劑、偶氮二異丁腈(AIBN)為鏈引發(fā)劑、二硫代苯甲酸(4-氰基戊酸)酯(CTP)為鏈轉移劑、80%(g/g)DMF-水混合溶液為致孔劑,通過RAFT技術制備MIP,收率為63.42%,非印跡分子聚合物(NIP)的收率為79.22%。3、通過紅外光譜、固體紫外、氮氣吸附、激光粒度等方法對MIP和NIP的結構、組成、粒徑等進行了比較。結果表明:二者組成、結構相同,說明已經成功制備MIP。此外,MIP、NIP的比表面積分別為19.524、10.617 m2/g,平均孔徑分別為2.454、2.167nm。4、研究了MIP和NIP的等溫靜態(tài)吸附行為,Langmuir模擬結果表明,AA I濃度在0.002~0.01mg·mL-1范圍之間,MIP和NIP的吸附符合Langmuir模型,其吸附常數分別為232.45、58.02 mL/mg,說明MIP對AA I吸附能力比NIP強;Scatchard模擬結果表明,MIP和NIP都只具一種吸附方式,且MIP和NIP的平衡解離常數分別為8.9、26.2mg/L,即MIP對AA I的親和力顯著強于NIP,進一步證明了MIP對AA I具特異性吸附能力。5、研究了MIP和NIP的等溫動態(tài)吸附行為(25℃),MIP符合一級動力學反應模型(log(Qeq-Qt)=-0.160t+0.181,R2=0.993),NIP符合二級動力學反應模型(t/Qt=2.186t+3.745,R2=0.997),表明MIP中印跡位點具有特異性吸附能力。6、變溫動態(tài)吸附實驗表明,MIP吸附AA I的能力幾乎不受溫度影響;選擇性吸附實驗表明,MIP對AA I具良好的特異性識別能力;可重復利用性實驗表明,MIP可多次重復使用。7、采用高效液相色譜法研究MIP吸附關木通乙醇提取物中AA I的能力,結果表明:用25.0 mg MIP吸附5.0 mL關木通乙醇提取物中的AA I(其中CAA I為0.0018 mg/mL),可使AA I含量減少到液相檢測限以下;AA I的回收率為41.70%綜上所述,RAFT沉淀聚合成功構筑了MIP,并表現了優(yōu)良的性能,且對AA I有選擇性吸附。探索了MIP應用于關木通乙醇提取液中AA I的去除。為中草藥“減毒存效”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.
【學位授予單位】：湘潭大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O631.3
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本文編號：1430635