模拟移动床色谱分离甘草苷和甘草素
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摘要
以十八烷基硅烷键合硅胶(ODS)为固定相,V(乙醇)∶V(水)=30∶70为流动相的模拟移动床色谱(SMBC)体系对甘草黄酮中甘草苷与甘草素进行连续分离。SMBC体系设置洗脱带Ⅰ:1根色谱柱;精制带Ⅱ:2根色谱柱;吸附带Ⅲ:2根色谱柱,Ⅰ带独立,Ⅰ带洗脱液为乙醇。按照理想三角形理论选择SMBC操作参数,操作参数包括流动相流速、进料液流速和切换时间。结果表明:接近三角形底边选择SMBC的操作条件,在萃余液出口得到甘草苷,HPLC纯度高于70.44%,收率高于95.17%,同时在萃取液出口得到甘草素,HPLC纯度高于73.10%,收率高于90.74%,SMBC能有效分离甘草苷和甘草素。甘草苷萃余液和甘草素萃取液分别经浓缩、重结晶后,两种产品HPLC纯度均超过96%。
Liquiritin and liquiritigenin were continuously separated from liquorice flavonoids by simulated moving bed chromatography(SMBC) with ostade-cylsilane(ODS) as stationary phase and a mixture of ethanol and water(30/70,v/v) as mobile phase.The SMBC system contained three zones including the independent eluting zone Ⅰ with one column,the refining zone Ⅱ with two columns and the adsorbing zone Ⅲ with two columns,wherein,the mobile phase of zone Ⅰ was ethanol.The SMBC operating parameters,such as the flow rate of mobile phase,the flow rate of feeding solution and the switching time,were chosen according to ideal triangle theory.When the separation was carried out under the experiment points along the bottom margin of the triangle,the purity(70.44%) of liquiritin from raffinate was checked by HPLC and the recovery of liquiritin was over 95.17%.Meanwhile,the purity and recovery of liquiritigenin from extract were over 73.10% and 90.74%,respectively.The results indicate that it is efficient to separate liquiritin and liquiritigenin in liquorice flavonoids by SMBC.After the raffinate and extract from SMBC were concentrated and recrystallized,eventually over 96% purities of both liquiritin and liquiritigenin were obtained.
Liquiritin and liquiritigenin were continuously separated from liquorice flavonoids by simulated moving bed chromatography(SMBC) with ostade-cylsilane(ODS) as stationary phase and a mixture of ethanol and water(30/70,v/v) as mobile phase.The SMBC system contained three zones including the independent eluting zone Ⅰ with one column,the refining zone Ⅱ with two columns and the adsorbing zone Ⅲ with two columns,wherein,the mobile phase of zone Ⅰ was ethanol.The SMBC operating parameters,such as the flow rate of mobile phase,the flow rate of feeding solution and the switching time,were chosen according to ideal triangle theory.When the separation was carried out under the experiment points along the bottom margin of the triangle,the purity(70.44%) of liquiritin from raffinate was checked by HPLC and the recovery of liquiritin was over 95.17%.Meanwhile,the purity and recovery of liquiritigenin from extract were over 73.10% and 90.74%,respectively.The results indicate that it is efficient to separate liquiritin and liquiritigenin in liquorice flavonoids by SMBC.After the raffinate and extract from SMBC were concentrated and recrystallized,eventually over 96% purities of both liquiritin and liquiritigenin were obtained.
引文
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[17]Lin X J,Gong R,Li J,et al.Enantioseparation of racemic aminoglutethimide using asynchronous simulated moving bed chromatography[J].Journal of Chromatography A,2016,1467:347-355.
[18]Wang S Y,Liang Y,Zheng S W.Separation of epigallocatechin gallate from tea polyphenol by simulated moving bed chromatography[J].Journal of Chromatography A,2012,1265:46-51.
[19]Xu Qingqing(许青青),Kong Liyun(孔利云),LI Min(李敏),et al.Separation and purification of desmosterol by simulated moving bed chromatography[J].Chinese Journal of Analytical Chemistry(分析化学),2013,41(6):851-855.
[20]Cong Jingxiang(丛景香).Separation of active components from Licorice by simulated moving bed and two-dimensional liquid chromatography[D].Dalian:Dalian University of Technology(大连理工大学),2008.
[21]Cong J X,Lin B C.Separation of liquiritin by simulated moving bed chromatography[J].Journal of Chromatography A,2007,1145:190-194.
[22]Mazzotti M.Equilibrium theory based design of simulated moving bed processes for a generalized Langmuir isotherm[J].Journal of Chromatography A,2006,1126:311-322.
[23]Lin Bingchang(林炳昌).Simulated moving bed chromatography technology[M].Beijing:Chemical Industry Press,2008:100-103.
[24]Lee H H,Kim K M,Lee C H.Improved performance of simulated moving bed process using column-modified feed[J].AICh E Journal,2011,57(8):2036-2053.
[2]Zhang Q Y,Ye M.Chemical analysis of the Chinese herbal medicine Gan-Cao(Licorice)[J].Journal of Chromatography A,2009,1216,1954-1969.
[3]Liu Yuchen(刘育辰),Chen Yougen(陈有根),Wang Dan(王丹),et al.Studies on chemical constituents on roots of Glycyrrhiza uralensis[J].Chinese Journal of Pharmaceutical Analysis(药物分析杂志),2011,7:53-57.
[4]Xing Guoxiu(邢国秀),Li Nan(李楠),Wang Tong(王童),et al.Advances in studies on flavonoids of licorice[J].China Journal of Chinese Materia Medica(中国中药杂志),2003,7:10-14.
[5]Li Chaosheng(李超生).Application of liquiritin in medicines:CN101032504[P].2007-09-12.
[6]Guo Hongzhu(郭洪祝),Hu Xinying(胡新颖),Tian Yin(田茵),et al.Application of liquorice glycoside in preparing drugs for preventing and/or treating depression:CN1663578[P].2005-09-07.
[7]Cai Yunqing(蔡云清).Application of glycyrrhizin in the preparation of medicine for preventing and curing tumour:CN101036638[P].2007-09-19.
[8]Thomas H B S,Howaed W Z,Alexis D B.Separation of major components in licorice using high-performance liquid chromatography[J].Journal of Chromatagraphy,1979,175:350-355.
[9]Liang Xinmiao(梁鑫淼),Zhang Hui(张慧),Feng Jiatao(丰加涛),et al.Method for separating and preparing liquiritin:CN101289480[P].2008-10-22.
[10]Shi Renbing(石任兵),Liu bin(刘斌),Li Jun(李军),et al.Glycyrrhiza total flavonoid and total saponin extract and its production:CN101073595[P].2007-11-21.
[11]Fu Boqiang(傅博强),Wang Xiaoru(王小如).Method for extracting multiple liquorice flavone form liquorice:CN1865273[P].2006-11-22.
[12]Rajendran A,Paredes G,Mazzotti M.Simulated moving bed chromatography for the separation of enantiomers[J].Journal of Chromatography A,2009,1216:709-738.
[13]Song J Y,Kim K M,Lee C H.High-performance strategy of a simulated moving bed chromatography by simultaneous control of product and feed streams under maximum allowable pressure drop[J].Journal of Chromatography A,2016,1471:102-117.
[14]Azevedo D C S,Rodrigues A E.Separation of fructose and glucose from cashew apple juice by SMB chromatography[J].Separation Science and Technology,2005,40(9):1761-1780.
[15]Silva Marta S P,Rodrigues Alirio E,Mota Jose P B.Effect of dead volumes on the performance of an industrial-scale simulated moving-bed parex unit for p-xylene purification[J].AICHE Journal,2016,62(1):241-255.
[16]Gomes P S,Zabkova M,Zabka M,et al.Separation of chiral mixtures in real SMB units:the Flex SMB-LSRE[J].AICh E Journal,2010,56:125-142.
[17]Lin X J,Gong R,Li J,et al.Enantioseparation of racemic aminoglutethimide using asynchronous simulated moving bed chromatography[J].Journal of Chromatography A,2016,1467:347-355.
[18]Wang S Y,Liang Y,Zheng S W.Separation of epigallocatechin gallate from tea polyphenol by simulated moving bed chromatography[J].Journal of Chromatography A,2012,1265:46-51.
[19]Xu Qingqing(许青青),Kong Liyun(孔利云),LI Min(李敏),et al.Separation and purification of desmosterol by simulated moving bed chromatography[J].Chinese Journal of Analytical Chemistry(分析化学),2013,41(6):851-855.
[20]Cong Jingxiang(丛景香).Separation of active components from Licorice by simulated moving bed and two-dimensional liquid chromatography[D].Dalian:Dalian University of Technology(大连理工大学),2008.
[21]Cong J X,Lin B C.Separation of liquiritin by simulated moving bed chromatography[J].Journal of Chromatography A,2007,1145:190-194.
[22]Mazzotti M.Equilibrium theory based design of simulated moving bed processes for a generalized Langmuir isotherm[J].Journal of Chromatography A,2006,1126:311-322.
[23]Lin Bingchang(林炳昌).Simulated moving bed chromatography technology[M].Beijing:Chemical Industry Press,2008:100-103.
[24]Lee H H,Kim K M,Lee C H.Improved performance of simulated moving bed process using column-modified feed[J].AICh E Journal,2011,57(8):2036-2053.