目的: 利用气相色谱-质谱(gas chromatography-mass spectrometry, GC-MS)联用技术,建立华佗救心丸GC-MS特征图谱,同时测定龙脑、异龙脑和麝香酮3个成分的含量。方法: 采用VF-WAXms毛细管色谱柱(0.25 mm×30 m,0.25 μm),柱温为程序升温(140 ℃,停留2 min,然后以35 ℃·min-1线性升温至230 ℃,停留5 min),进样口温度:210 ℃,检测器温度250 ℃;离子源为电子轰击源(electrospray ion source, EI),离子源温度为230 ℃,MS四极杆温度为150 ℃,发射电流为34.6 μA,发射能量为70.0 eV,质谱监测模式为全扫描(SCAN),溶剂延迟为3 min。应用2012版中药色谱指纹图谱相似度评价软件对12批华佗救心丸进行相似度分析,同时对龙脑、异龙脑和麝香酮3个成分含量进行测定。结果: 建立了华佗救心丸的GC-MS指纹图谱,12批华佗救心丸的色谱图与特征图谱的相似度均在0.999以上,标定共有峰8个,并指认了其中3个共有峰,分别为异龙脑、龙脑和麝香酮。12批样品中龙脑、异龙脑和麝香酮的含量范围分别为每丸0.875 7~1.525 0 g、0.730 4~1.140 5 g、0.097 1~0.112 0 g。结论: 所建立的GC-MS特征图谱结合3个成分的含量测定,能较全面地反映华佗救心丸中挥发性化学成分质量,该方法简便可行,准确稳定,重复性和专属性好,可对华佗救心丸质量控制提供参考。
Objective: To establish a GC-MS characteristic chromatogram of Huatuo Jiuxin pills and to develop simultaneous determination method of borneol, isborneol and muscone in the sample. Methods: GC-MS analysis was performed on a VF-WAXms column (0.25 mm×30 m,0.25 μm). The column temperature was programmed to start at 140 ℃ maintaining for 2 min, and rose to 230 ℃ at a rate of 35 ℃·min-1, maintaining for 5 min. The inlet temperature was 210 ℃ and the detector temperature was 250 ℃. The ion source was electrospray ion source, with the ion source of 300 ℃, MS quadrupole temperature of 150 ℃, the emission current of 34.6 μA, the ionization energy of 70 eV and the solvent delay of 3 min, quantized by the full scan method.Traditional Chinese medicine chromatographic fingerprint similarity evaluation software(2012 version)was used for similarity analysis in 12 batches of Huatuo Jiuxin pills, and the contents of borneol, isoborneol and muscone in 12 batches of samples were determined at the same time. Results: The GC-MS characteristic chromatogram of Huatuo Jiuxin pills was established, and the similarities between the characteristic chromatogram and chromatograms of 12 batches of Huatuo Jiuxin pills were above 0.999. There were altogether 8 common peaks, and 3 of them were identified as isoborneol,borneol andmuscone, respectively. The contents of borneol, isborneol and muscone in 12 batches of samples were in the range of 0.875 7-1.525 0, 0.730 4-1.140 5, 0.097 1-0.112 0 g per pill, respectively. Conclusion: The combination of the GC-MS characteristic chromatogram and content determination of three components can reflect inherent quality of volatile chemical components in Huatuo Jiuxin pills. The method is simple, feasible, accurate, stable, repeatable and specific, and can provide a reference for the quality control of Huatuo Jiuxin pills.
[1] 中华人民共和国卫生部药品标准中药成方制剂.第十九册[S].1998: 178
Drug Specifications for Traditional Chinese Medicine Preparations by the Ministry of Public Health,P R China. Part 19[S].1998: 178
[2] 周文莉, 祝宇龙, 李龙飞, 等.HPLC法同时测定华佗救心丸中8种蟾蜍二烯内酯[J].中成药, 2020, 42(5):1135
ZHOU WL, ZHU YL, LI LF, et al. Simultaneous determination of eight bufadienolides in Huatuo Jiuxin pills by HPLC[J].Chin Tradit Pat Med, 2020, 42(5): 1135
[3] 李霞, 祝宇龙, 叶梦群, 等.高效液相色谱法同时测定蟾酥中8种成分的含量[J].中南药学, 2020, 18(2):250
LI X, ZHU YL, YE MQ, et al. Simultaneous determination of 8 components in Bufonis Venenum by HPLC[J].Cent South Pharm, 2020, 18(2): 250
[4] 中华人民共和国药典2020年版.一部[S].2020:61,152,402,233
ChP 2020. Vol Ⅰ[S].2020:61,152,402,233
[5] BHATIA SP, LETIZIA CS, API AM. Fragrance material review on borneol[J].Food Chem Toxicol, 2008, 46(11): S77
[6] HO TJ, HUNG CC, SHIH TL, et al. Investigation of borneols sold in Taiwan by chiral gas chromatography[J].J Food Drug Anal, 2018, 26(1): 348
[7] 闵祺, 王闯. 气相色谱法同时测定苏合香丸中龙脑、丁香酚及麝香酮的含量[J].药物分析杂志, 2018, 38(2): 359
MIN Q, WANG C. Simultaneous determination of borneol, eugenol and muscone in Suhexiang pills by GC[J].Chin J Pharm Anal, 2018, 38(2): 359
[8] 朱炳辉, 梁艺英, 莫金垣, 等.冰片中右旋龙脑及其异构体的手性毛细管气相色谱法测定[J].分析测试学报, 1999, 18(4):70
ZHU BH, LIANG YY, MO JH, et al. Determination of (+) -borneol and its isomers in Borneolum syntheticum by chiral capillary gas chromatography[J].J Instrum Anal, 1999, 18(4): 70
[9] 于娟. 不同麝香的气相色谱指纹图谱[J].中国实验方剂学杂志, 2019, 25(6): 175
YU J. Gas chromatographic fingerprints of different musk[J].Chin J Exp Tradit Med Form, 2019, 25(6): 175
[10] SONG YF, CHU Y, MA XH, et al. GC-MS/MS method for the determination and pharmacokinetic analysis of borneol and muscone in rat after the intravenous administration of Xingnaojing injection[J].J Sep Sci, 2017, 40(21): 4264
[11] 彭敏, 邓楠, 刘文, 等. GC-MS法同时测定复方麝香注射液中麝香酮、β-细辛醚、百秋李醇、龙脑、薄荷脑[J].药物分析杂志, 2014, 34(5): 855
PENG M, DENG N, LIU W, et al. Simultaneous determination of muscone, β-asarone, patchoulic alcohol, borneol, menthol in compound Shexiang injection by GC-MS[J].Chin J Pharm Anal, 2014, 34(5): 855
[12] 王振, 杜守颖, 陆洋, 等. 复方丹参肠黏附微丸中龙脑含量测定方法的建立及不同剂型龙脑溶出度的研究[J].中国中药杂志, 2015, 40(16): 3194
WANG Z, DU SY, LU Y, et al. Determination of borneol in Fufang Danshen intestinal adhesion pelletsand study its in vitro dissolution in different dosage form[J].China J Chin Mater Med, 2015, 40(16): 3194
[13] 王伟, 刘星雨, 金辉辉, 等. GC同时测定麝香通心滴丸中龙脑、异龙脑和麝香酮的含量[J].中国现代应用药学, 2020, 37(11): 1328
WANG W, LIU XY, JIN HH, et al. Simultaneous determination of borneol, isoborneol and muscone in Shexiang Tongxin dripping pills by GC[J].Chin J Mod Appl Pharm, 2020, 37(11): 1328
[14] 杨晓玲, 郝福, 侯金才. 气相色谱内标法测定五福心脑清软胶囊中冰片含量[J].亚太传统医药, 2019, 15(6): 86
YANG XL, HAO F, HOU JC. Determination of borneol in Wufu Xinnaoqing soft capsules by GC internal standard method[J].Asia Pac Tradit Med, 2019, 15(6): 86
[15] 汪建君, 陈惠玲. 气相色谱法测定紫金散中麝香酮的含量[J].中国药品标准, 2011, 12(1): 37
WANG JJ, CHEN HL. Determination of the content of muscone in Zijin powder by GC[J].Drug Stand China, 2011, 12(1): 37
[16] 石巧娟, 陈琴华, 戴方伟, 等. 复方丹参片中冰片的GC-MS法测定[J].中国医药工业杂志, 2006, 37(10): 706
SHI QJ, CHEN QH, DAI FW, et al. Determination of borneol in compound Salvia tablets by GC-MS[J].Chin J Pharm, 2006, 37(10): 706
