王可兴,王宏,韩静,赵宇明,郭永学
WANG Ke-xing,WANG Hong,HAN Jing,ZHAO Yu-ming,GUO Yong-xue

• 1:沈阳药科大学制药工程学院

摘要(Abstract)：

目的研究紫杉醇分子印迹聚合物在固相萃取中的应用。方法采用分子印迹沉淀合成技术,以紫杉醇为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸为交联剂、偶氮二异丁腈为引发剂,在氯仿与甲苯混合液中合成紫杉醇分子印迹聚合物,并以此为填料进行固相萃取,分离纯化紫杉醇。印迹聚合物对紫杉醇的吸附选择性优化聚合反应条件,通过平衡结合法和Scatchard模型评价聚合物吸附特点,再用固相萃取技术对清洗洗脱方法进行优化,采用实际提取浸膏考察固相萃取柱的可用性。结果甲基丙烯酸和紫杉醇的摩尔比为4∶1,聚合温度为60℃时,分子印迹聚合物(molecularly imprinted polymers,MIPs)对紫杉醇呈现高特异性吸附;印迹吸附符合Scatchard模型,计算MIPs对紫杉醇的最大表观结合点数为3.66 mg·g~(-1),K_d为6.627。结论分子印迹聚合物可以为紫杉醇的分离纯化提供新型选择性富集材料。
Objective To investigate the application of solid phase extraction in paclitaxel molecularly imprinted polymer.Methods Molecularly imprinted polymer was prepared through molecular imprinting technique by using paclitaxel as the template molecule,methacrylic acid as the functional monomer,ethylene glycol dimethacrylate as the cross-linker and 2,2'-azobisisobutyronitrile as the initiator in the porogen of the mixture for chloroform and methylbenzene.The polymer was loaded into the self-made solidphase extraction cartridge.Results The results showed that when the ratio of functional monomer and template molecules is 4∶1,polymerization temperature was 60 ℃,the adsorption effect was well.MIPs in acetonitrile solvent adsorption quantity was moderate,MIPs was 2.68 mg·g~(-1),NMIPs was 1.21 mg·g~(-1),however the selectivity was well,MIPs adsorption quantity was significantly higher than NMIPs.Scatchard analysis model of the molecularly imprinted polymer,r~2=0.977 9,showed that imprinting adsorption conformed to Scatchard model,the calculated MIPs of paclitaxel Q_(max) was 3.66 mg·g~(-1),K_d was 6.627.Conclusions Molecularly imprinted polymer can provide new materials with selectivity and enrichment for the separation and purification of paclitaxel.

关键词(KeyWords)： 紫杉醇;固相萃取;分子印迹技术;萃取柱;分离富集
paclitaxel;solid phase extraction;molecular imprinting technique;extraction column;separation enrichment

Abstract:

Keywords:

基金项目(Foundation): 国家基础科学人才培养基金本科生“能力提高(科研训练)项目”(J1103606)

作者(Author): 王可兴,王宏,韩静,赵宇明,郭永学
WANG Ke-xing,WANG Hong,HAN Jing,ZHAO Yu-ming,GUO Yong-xue

DOI: 10.14066/j.cnki.cn21-1349/r.2017.04.008

参考文献(References)：

• [1]江苏红豆杉药业有限公司.一种从紫杉醇浸膏分离纯化紫杉醇的方法:103275039 A[P].2013-09-04.
• [2]江苏斯威森生物医药工程研究中心.一种紫杉醇的提取分离纯化方法:103232417 A[P].2013-08-07.
• [3]祝顺琴,谈锋,唐克轩.紫杉醇提取纯化技术研究进展[J].中国生化药物杂志,2004,25(1):59-62.
• [4]赖家平,何锡文,郭洪声,等.分子印迹技术的回顾、现状与展望[J].分析化学,2001,29(7):836-844.
• [5]胡树国,李礼,何锡文.一种高选择性固相萃取吸附剂-分子印迹聚合物[J].化学进展,2005,17(3):531-543.
• [6]ELMETS C A,SINGH D,TUBESING K,et a1.Cutaneous photoprotection from ultraviolet injury by green tea polyphenols[J].Journal of the American Academy of Dermatology,2001,44:425-432.
• [7]贺敏强,宋承成,陈永强,等.芹菜素分子印迹聚合物的分子识别性能及机理[J].江苏大学学报:自然科学版,2010,31(5):596-600.
• [8]CARBONI D,FLAVIN K,SERVANT A,et a1.The first example of molecularly imprinted nanogels with aldolase type I activity[J].Chemistry-A European Journal,2008,14(23):7059-7065.
• [9]吕晖,梁坚,丁学全,等.SAW-CA传感器印迹敏感膜吸附机理的研究[J].分析仪器,2008,13(2):8-11.
• [10]吴洪,赵艳艳,俞应霞,等.分子印迹壳聚糖膜分离手性苯丙氨酸[J].功能高分子学报,2007,9(3):262-266.
• [11]张海霞,朱彭龄.固相萃取[J].分析化学,2000,28(9):1172-1180.
• [12]张海晖,段玉清,秦宇,等.分子印迹-固相萃取分离/富集EGCG试验[J].江苏大学学报:自然科学版,2013,34(6):658-674.
• [13]胡树国,李礼,何锡文.一种高选择性固相萃取吸附剂-分子印迹聚合物[J].化学进展,2005,17(3):531-542.
• [14]QI J Y,LI X,BIAN J.Preparation and property of microspheric Fe(Ⅲ)imprinted polymer[J].Materals Science and Technology,2007,6:765-773.
• [15]LAI J P,LU X Y,LU C Y,et al.Preparation and evaluation of molecularly imprinted polymeric microspheres by aqueous suspension polymerization for use as a highperformance liquid chromatography stationary phase[J].Anal Chim Acta,2001,442:105-111.
• [16]CHEONG W J,ALI F,CHOI J H,et al.Recent applications of molecular imprinted polymers for enantio-selective recognition[J].Talanta,2013,11:2195-2199.
• [17]HAGINAKA J,ASNBE H.Uniformly sized molecularly imprinted polymer for(S)-naproxen-retention and molecular recognition properties in aqueous mobile phase[J].J Chromatogr A,2001,913:141-146.
• [18]JOSLLI V P,KULKAMI M C,MASHCLKAR R A.Molecularly imprinted adsorbrents for positional isomer separation[J].J Chromatogr A,1999,849:319-330.
• [19]郭洪声,何锡文,邓昌辉,等.药物扑热息痛分子末班聚合物的选择性富集与识别特性研究[J].高等化学学报,2000,3(21):363-367.
• [20]佘永新,王淼,史晓梅,等.类特异性分子印迹聚合物微球的识别机理及其光谱学研究[J].光谱学与光谱分析,2010,30(11):3052-3055.
• [21]洪美花,陈元涛,王倩,等.白藜芦醇分子印迹聚合物微球的制备及特性评价[J].天然产物研究与开发,2010,22(4):559-563.