以水杨酸为假模板制备印迹聚合物对银杏酸的吸附性能研究
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摘要
目的研究银杏酸吸附分离的新方法。方法采用分子印迹技术,以水杨酸为假模板分子,4-乙烯基吡啶为功能单体,通过分子自组装印迹技术合成对银杏酸具有高吸附性的印迹聚合物,运用核磁共振氢谱、红外光谱分析研究聚合物的印迹机制,扫描电镜考察聚合物的结构表征,HPLC和紫外检测法监测聚合物对总银杏酸的吸附结合特性。结果加入模板分子合成分子印迹聚合物(MIP)具备更好的三维空间结构和吸附性能,其中模板分子与功能单体以非共价键结合。在银杏外种皮提取液中MIP对银杏酸的吸附率达到95.9%;根据Scatchard分析聚合物,存在2种不同的结合位点,其中高亲和力结合位点饱和结合位点数(Q_(max1))=30 mg/g;低亲和力结合位点饱和结合位点数(Q_(max2))=80 mg/g。聚合物的吸附动力学为准二级动力学吸附。结论以水杨酸为模板制备MIP对银杏酸有很强的吸附性能,在银杏酸的分离精制中具有很好的推广应用前景。
objective To develop a new method for the adsorption and separation of ginkgolic acid(GA). Methods Using salicylic acid(SA) as a dummy template and 4-vinylpyridine as the functional monomer, molecularly imprinted polymer(MIP) with high adsorbability to GA was synthesized by molecular self-assembly technique. The imprinting mechanism of the polymers was studied by1 H-NMR and IR spectra, and the structure of the polymers was characterized by SEM. The structure of the polymer was analyzed by FT-IR and the adsorption and binding properties of the polymer to total GA were analyzed by HPLC and UV detection. Results MIP had better three-dimensional space structure and adsorption properties. Template molecules were binded to functional monomers with noncovalent bonds. The adsorption rate of GA by polymer MIP in the extract of Ginkgo biloba was 95.9%. The Scatchard analysis reveals that there were two different recognition sites in MIP in the extract of G. biloba, and the apparent maximal combination amount(Q_(max1)) was 30 mg/g in high affinity recognition sites and with(Q_(max2)) = 80 mg/g in low affinity recognition sites. And the adsorption kinetics can be best described as the pseudo-second-order kinetics model. Conclusion The preparation of MIP with SA as dummy template has strong adsorption properties for GA, which has a good prospect of popularization and application in the separation and purification of GA.
objective To develop a new method for the adsorption and separation of ginkgolic acid(GA). Methods Using salicylic acid(SA) as a dummy template and 4-vinylpyridine as the functional monomer, molecularly imprinted polymer(MIP) with high adsorbability to GA was synthesized by molecular self-assembly technique. The imprinting mechanism of the polymers was studied by1 H-NMR and IR spectra, and the structure of the polymers was characterized by SEM. The structure of the polymer was analyzed by FT-IR and the adsorption and binding properties of the polymer to total GA were analyzed by HPLC and UV detection. Results MIP had better three-dimensional space structure and adsorption properties. Template molecules were binded to functional monomers with noncovalent bonds. The adsorption rate of GA by polymer MIP in the extract of Ginkgo biloba was 95.9%. The Scatchard analysis reveals that there were two different recognition sites in MIP in the extract of G. biloba, and the apparent maximal combination amount(Q_(max1)) was 30 mg/g in high affinity recognition sites and with(Q_(max2)) = 80 mg/g in low affinity recognition sites. And the adsorption kinetics can be best described as the pseudo-second-order kinetics model. Conclusion The preparation of MIP with SA as dummy template has strong adsorption properties for GA, which has a good prospect of popularization and application in the separation and purification of GA.
引文
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[14]李耀,何叶子,陈晓龙,等.替代模板法制备花椒麻味物质分子印迹聚合物及其吸附性能研究[J].食品与发酵工业,2018,44(9):78-83.
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[17]李婷,刘曙,蔡婧,等.双吡啶基功能化Cr(III)印迹介孔二氧化硅材料的制备及其吸附性能研究[J].分析化学,2018,46(11):1836-1844.
[18]邓慧芸,王斌,吴茂,等.没食子酸磁性表面分子印迹聚合物的制备与选择性识别性能[J].应用化学,2018,35(5):600-608.
[19]Yao S J,Guan Y X,Yu L H.Adsorption performance of proteins to CM sepharose FF and DEAE sepharose FFadsorbents[J].Korean J Chem Eng,2003,20(1):93-98.
[2]鞠建明,沈红,钱士辉,等.不同生长季节银杏叶中总银杏酸的动态变化研究[J].中草药,2010,41(2):305-307.
[3]van Beek T A,Montoro P.Chemical analysis and quality control of Ginkgo biloba leaves,extracts,and phytopharmaceuticals[J].J Chromatogr A,2009,1216(11):2002-2032.
[4]Tan J,Chen B,He L,et al.Anacardic acid(6-pentadecylsalicylic acid)induces apoptosis of prostate cancer cells through inhibition of androgen receptor and activation of p53 signaling[J].Chin J Cancer Res,2012,24(4):275-283.
[5]Oh J,Hwang I H,Hong C E,et al.Inhibition of fatty acid synthase by ginkgolic acids from the leaves of Ginkgo biloba and their cytotoxic activity[J].J Enzym Inhib Med Chem 2013,28(3):565-568.
[6]LüJ M,Yan S,Jamaluddin S,et al.Ginkgolic acid inhibits HIV protease activity and HIV infection in vitro[J].Med Sci Monit,2012,18(8):293-298.
[7]Hemshekhar M,Sebastin S M,Kemparaju K,et al.Emerging roles of anacardic acid and its derivatives:Apharmacological overview[J].Basic Clin Pharmacol Toxicol,2012,110(2):122-132.
[8]罗彭,高平,吴俊,等.银杏外种皮杀螨活性物质的分离纯化研究[J].化学研究与应用,2006,18(9):1061-1065.
[9]杨剑婷,吴彩娥.白果致过敏成分及其致敏机理研究进展[J].食品科技,2009(6):282-286.
[10]中国药典[S].一部.2015.
[11]吕俊杰,薛燕斌,乔华,等.硅胶表面高良姜素分子印迹聚合物的制备及其吸附性能[J].中草药,2018,49(21):5093-5099.
[12]王颖,李楠.分子印迹技术及其应用[J].化工进展,2010,29(12):2315-2323.
[13]李博,朱俊访,周伟明,等.硅胶表面延胡索乙素分子印迹聚合物的合成、表征及性能研究[J].中药材,2018,41(2):411-414.
[14]李耀,何叶子,陈晓龙,等.替代模板法制备花椒麻味物质分子印迹聚合物及其吸附性能研究[J].食品与发酵工业,2018,44(9):78-83.
[15]左振宇,张光辉,雷福厚,等.分子印迹聚合物在中药活性成分分离中的应用进展[J].中草药,2017,48(23):5019-5031.
[16]倪学文,吴谋成.银杏酚酸的分离鉴定及其抗菌活性研究[J].食品科学,2004,25(9):59-63.
[17]李婷,刘曙,蔡婧,等.双吡啶基功能化Cr(III)印迹介孔二氧化硅材料的制备及其吸附性能研究[J].分析化学,2018,46(11):1836-1844.
[18]邓慧芸,王斌,吴茂,等.没食子酸磁性表面分子印迹聚合物的制备与选择性识别性能[J].应用化学,2018,35(5):600-608.
[19]Yao S J,Guan Y X,Yu L H.Adsorption performance of proteins to CM sepharose FF and DEAE sepharose FFadsorbents[J].Korean J Chem Eng,2003,20(1):93-98.