高效液相色谱—质谱法同时测定辛夷提取物中4种木脂素成分
赵鑫等
摘 要 建立了高效液相色谱质谱电雾式检测器（HPLCMSCAD）联用技术同时测定辛夷中4种木脂素类成分的定量分析方法。采用YMCPack ODSA（250 mm×4.6 mm， 5 μm）色谱柱，甲醇水梯度洗脱，柱温25 ℃， 流速1 mL/min，检测波长278 nm，紫外检测器后3∶7分流，分别进入质谱和电雾式检测器进行检测。以木兰脂素为内参物，建立松脂素二甲醚、里立脂素B二甲醚和表木兰脂素A与内参物的相对校正因子，并进行含量计算，实现一测多评。同时采用外标法测定辛夷提取物中4种木脂素成分的含量，比较计算值与实测值的差异，验证所建立方法的准确定。
Reference
1 Chinese Pharmacopoeia. The First Volume. 2010： 169-170
中国药典. 一部. 2010： 169-170
2 YU PeiMing， TIAN ZhiYong， XU QiTai， DONG ChengMin， LI Heng. Lishizhen Medicine and Materia Medica Research， 2005， 16（7）： 652-653
于培明， 田智勇， 许启泰， 董诚明， 李 恒. 时珍国医国药， 2005， 16（7）： 652-653
3 ZHANG YongZhong， LI XiaoLi， GUO Qun. Hubei Journal of Traditional Chinese Medicine， 2001， 23（10）： 7
张永忠， 李小莉， 郭 群. 湖北中医杂志， 2001， 23（10）： 7
4 CAO WeiGuo， TAO YanDuo， YAN XueWei， ZHANG Dan， WANG Gang. Lishizhen Medicine and Materia Medica Research， 2014， 25（7）： 1598-1599
曹玮国， 陶燕铎， 颜学伟， 张 丹， 王 刚. 时珍国医国药， 2014， 25（7）： 1598-1599
5 WANG YanHan， GAO JianPing， CHEN DaoFeng. China Journal of Chinese Materia Medic， 2003， 28（12）： 1154-1158
王彦涵， 高建平， 陈道峰. 中国中药杂志， 2003， 28（12）： 1154-1158
6 WANG ZhiMin， GAO HuiMin， FU XueTao， WANG WeiHao. China Journal of Chinese Materia Medic， 2006， 31（23）： 1925-1929
王智民， 高慧敏， 付雪涛， 王维皓. 中国中药杂志， 2006， 31（23）： 1925-1929
7 WANG YiBo， WANG ChunYu， QU FanNa， ZHANG LiYing， LIANG LiNa， YU YanHai， PAN YuanYuan. Chinese J. Anal. Chem. ， 2014， 42（1）： 109-112
王一博， 王春雨， 曲范娜， 张丽英， 梁丽娜， 余彦海， 潘媛媛. 分析化学， 2014， 42（1）： 109-112
8 BAI ChangCai， CHAI XingYun， WANG HaiLong， CUI XiuMing， LI Ping， TU PengFei. Journal of China Pharmaceutical University， 2009， 40（1）： 54-58
白长财， 柴兴云， 王海龙， 崔秀明， 李 萍， 屠鹏飞. 中国药科大学学报， 2009， 40（1）： 54-58
9 GUO Qun， FANG Hong， SU Wei. Chinese Traditional and Herbal Drugs， 2004， 35（8）： 849-852
郭 群， 方 红， 苏 玮. 中草药， 2004， 35（8）： 849-852
10 Zhao W， Zhou T， Fan G， Chai Y， Wu Y. Journal of Separation Science， 2007， 30（15）：2370-2381
11 WANG ZhiMin， QIAN ZhongZhi， ZHANG QiWei， ZHU JingJing， GAO HuiMin， WANG ZhengTao. China Journal of Chinese Materia Medic， 2011， 36（6）： 657-658
王智民， 钱忠直， 张启伟， 朱晶晶， 高慧敏， 王峥涛. 中国中药杂志， 2011， 36（6）： 657-658
Simultaneous Determination of Four Lignans in Magnoliae Flos
Extract by High Performance Liquid Chromatography
Electrospray Ionization Mass Spectrometry
ZHAO Xin1， YANG Guang2，3， ZHENG GuoShuai2，3， HANG TaiJun*1， FAN GuoRong*2，3
1（School of Pharmacy， China Pharmaceutical University， Nanjin 210009， China）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
摘 要 建立了高效液相色谱质谱电雾式检测器（HPLCMSCAD）联用技术同时测定辛夷中4种木脂素类成分的定量分析方法。采用YMCPack ODSA（250 mm×4.6 mm， 5 μm）色谱柱，甲醇水梯度洗脱，柱温25 ℃， 流速1 mL/min，检测波长278 nm，紫外检测器后3∶7分流，分别进入质谱和电雾式检测器进行检测。以木兰脂素为内参物，建立松脂素二甲醚、里立脂素B二甲醚和表木兰脂素A与内参物的相对校正因子，并进行含量计算，实现一测多评。同时采用外标法测定辛夷提取物中4种木脂素成分的含量，比较计算值与实测值的差异，验证所建立方法的准确定。
Reference
1 Chinese Pharmacopoeia. The First Volume. 2010： 169-170
中国药典. 一部. 2010： 169-170
2 YU PeiMing， TIAN ZhiYong， XU QiTai， DONG ChengMin， LI Heng. Lishizhen Medicine and Materia Medica Research， 2005， 16（7）： 652-653
于培明， 田智勇， 许启泰， 董诚明， 李 恒. 时珍国医国药， 2005， 16（7）： 652-653
3 ZHANG YongZhong， LI XiaoLi， GUO Qun. Hubei Journal of Traditional Chinese Medicine， 2001， 23（10）： 7
张永忠， 李小莉， 郭 群. 湖北中医杂志， 2001， 23（10）： 7
4 CAO WeiGuo， TAO YanDuo， YAN XueWei， ZHANG Dan， WANG Gang. Lishizhen Medicine and Materia Medica Research， 2014， 25（7）： 1598-1599
曹玮国， 陶燕铎， 颜学伟， 张 丹， 王 刚. 时珍国医国药， 2014， 25（7）： 1598-1599
5 WANG YanHan， GAO JianPing， CHEN DaoFeng. China Journal of Chinese Materia Medic， 2003， 28（12）： 1154-1158
王彦涵， 高建平， 陈道峰. 中国中药杂志， 2003， 28（12）： 1154-1158
6 WANG ZhiMin， GAO HuiMin， FU XueTao， WANG WeiHao. China Journal of Chinese Materia Medic， 2006， 31（23）： 1925-1929
王智民， 高慧敏， 付雪涛， 王维皓. 中国中药杂志， 2006， 31（23）： 1925-1929
7 WANG YiBo， WANG ChunYu， QU FanNa， ZHANG LiYing， LIANG LiNa， YU YanHai， PAN YuanYuan. Chinese J. Anal. Chem. ， 2014， 42（1）： 109-112
王一博， 王春雨， 曲范娜， 张丽英， 梁丽娜， 余彦海， 潘媛媛. 分析化学， 2014， 42（1）： 109-112
8 BAI ChangCai， CHAI XingYun， WANG HaiLong， CUI XiuMing， LI Ping， TU PengFei. Journal of China Pharmaceutical University， 2009， 40（1）： 54-58
白长财， 柴兴云， 王海龙， 崔秀明， 李 萍， 屠鹏飞. 中国药科大学学报， 2009， 40（1）： 54-58
9 GUO Qun， FANG Hong， SU Wei. Chinese Traditional and Herbal Drugs， 2004， 35（8）： 849-852
郭 群， 方 红， 苏 玮. 中草药， 2004， 35（8）： 849-852
10 Zhao W， Zhou T， Fan G， Chai Y， Wu Y. Journal of Separation Science， 2007， 30（15）：2370-2381
11 WANG ZhiMin， QIAN ZhongZhi， ZHANG QiWei， ZHU JingJing， GAO HuiMin， WANG ZhengTao. China Journal of Chinese Materia Medic， 2011， 36（6）： 657-658
王智民， 钱忠直， 张启伟， 朱晶晶， 高慧敏， 王峥涛. 中国中药杂志， 2011， 36（6）： 657-658
Simultaneous Determination of Four Lignans in Magnoliae Flos
Extract by High Performance Liquid Chromatography
Electrospray Ionization Mass Spectrometry
ZHAO Xin1， YANG Guang2，3， ZHENG GuoShuai2，3， HANG TaiJun*1， FAN GuoRong*2，3
1（School of Pharmacy， China Pharmaceutical University， Nanjin 210009， China）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
2（School of Pharmacy， Second Military Medical University， Shanghai 200433， China）
3（Shanghai Key Laboratory for Pharmaceutical （Chinese Materia Medica） Metabolite Research， Shanghai 200433， China）
Abstract A high performance liquid chromatographyelectrospray ionization mass spectrometry charged aerosol detection （HPLCMSCAD） method was established for the simultaneous quantitative analysis of four Lignans in Magnoliae Flos extract. The components were separated on a YMCPack ODSA column （250 mm× 4.6 mm， 5 μm） by gradient elution with methanol and water as the mobile phase at aflow rate of 1.0 mL/min. Then the elution solution was routed into MS equipment at a flow rate of 0.3 mL/min and CAD detector at a flow rate of 0.7 mL/min by a split ratio of 3∶7 for the further detection. The column temperature was 25 ℃ and the detection wavelength was 278 nm. A method was developed for the quantitative analysis of muticomponents by single maker （QAMS） to determine pinoresinol dimethylether， magnoli， 1irioresinol B dimethylethe and epi magnoli A . Magnoli was selected as internal standard and the relative correction factors （RCF） of the four Lignans were calculated. The contents of the four Lignans in Magnoliae Flos extract were determined by both external standard method and QAMS. The QAMS method was evaluated by comparison of its assay result and that of external standard method. Under the selected chromatographic condition， the limits of detection of pinoresinol dimethylether， magnoli， lirioresinol B dimethylethe and epimagnoli A were 0.34， 0.55， 0.50 and 0.58 mg/L， respectively， while the linear range were within 6.8-270 mg/L， 11-546 mg/L， 2.0-101 mg/L and 2.3-116 mg/L. The recoveries （n=9） were 98.2%-99.5%， and the correlation coefficient were 0.9995-0.9998. No significant differences were found between the quantitative results of external standard method and QAMS method. The developed method is accurate， feasible， and can be used for quality evaluation of Magnoliae Flos .
Keywords Magnoliae Flos ； High performance liquid chromatography； Mass spectrometry； Charged aerosol detector； Lignans
（Received 1 September 2014； accepted 11 October 2014）
This work was supported by the National Natural Science Foundation of China （No.81173019）
