Quantification of the 25 Components in Onkyung-Tang by Ultra Performance Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry

UPLC-ESI-MS/MS를 이용한 온경탕 중 25종 성분의 함량분석

  • 서창섭 (한국한의학연구원 K-herb연구단) ;
  • 신현규 (한국한의학연구원 K-herb연구단)
  • Received : 2015.12.24
  • Accepted : 2016.02.02
  • Published : 2016.03.31

Abstract

In this study, an ultra-performance liquid chromatography-electrospray ionization-mass spectrometry (UPLC-ESI-MS/MS) method was established for simultaneous determination of the 25 marker components, including chlorogenic acid, gallic acid, oxypaeoniflorin, homogentisic acid, methyl gallate, caffeic acid, 3,4-dihydroxybenzaldehyde, paeoniflorin, albiflorin, liquiritin, nodakenin, ferulic acid, ginsenoside Rg1, liquiritigenin, coumarin, cinnamic acid, benzoylpaeoniflorin, ginsenoside Rb1, cinnamaldehyde, paeonol, glycyrrhizin, 6-gingerol, evodiamine, rutecarpine, and spicatoside A in traditional Korean formula, Onkyung-tang. All analytes were separated on a Waters Acquity UPLC BEH $C_{18}$ analytical column ($2.1{\times}100mm$, $1.7{\mu}m$) at $45^{\circ}C$ using a mobile phase of 0.1% (v/v) formic acid in water and acetonitrile with gradient elution. The MS analysis was carried out using a Waters ACQUITY TQD LC-MS/MS coupled with an electrospray ionization (ESI) source in the positive and negative modes. The flow rate and injection volume were 0.3 mL/min and $2.0{\mu}L$, respectively. The correlation coefficient of all analytes in the test ranges was greater than 0.98. The limits of detection and quantification values of the 25 marker compounds were in the ranges 0.03-19.43 and 0.09-58.29 ng/mL, respectively. As a result, methyl gallate, 3,4-dihydroxybenzaldehyde, evodiamine, and rutecarpine were not detected in this sample and the concentrations of the 21 compounds except for the above 4 compounds were $33.09-3,496.32{\mu}g/g$ in Onkyung-tang decoction. Among these compounds, paeonol was detected at the highest amount as a $3,496.32{\mu}g/g$.

Keywords

References

  1. 곽동렬. (2002) 금궤요락역해, 512. 성보사, 성남.
  2. 한의과대학방제학 교수 공편저. (1999) 방제학, 419-420. 영림사, 서울.
  3. Heo, J. (2004) Donguibogam, 605. Namsandang, Seoul.
  4. Chen, H., Emura, S., Isono, H. and Shoumura, S. (2005) Effects of traditional Chinese medicine on bone loss in SAMP6: A murine model for senile osteoporosis. Biol. Pharm. Bull. 28: 865-869. https://doi.org/10.1248/bpb.28.865
  5. Kno, S. T. and Kim, I. R. (2000) Preventive effects of Onkyungtang against ovarioectomized rat's osteoporosis. Kor. J. Herbology. 15: 129-136.
  6. Okamoto, Y., Hidaka, S., Yamada, Y., Ouchi, K., Miyazaki, K. and Liu, SY. (1998) Thermal analysis of bones from ovariectomized rats. J. Biomed. Mater. Res. 41: 221-226. https://doi.org/10.1002/(SICI)1097-4636(199808)41:2<221::AID-JBM6>3.0.CO;2-K
  7. Chen, H. Y., Lin, Y. H., Su, I. H., Chen, Y. C., Yang, S. H. and Chen, J. L. (2014) Inverstigation on Chinese herbal medicine for primary dysmenorrhea: Implication from a nationwide prescription database in Taiwan. Complement. Ther. Med. 22: 116-125. https://doi.org/10.1016/j.ctim.2013.11.012
  8. Hsu, C. S., Yang, J. K. and Yang, L. L. (2003) Effect of a dysmenorrhea Chinese medicinal prescription on uterus contractility in vitro. Phytother. Res. 17: 778-783. https://doi.org/10.1002/ptr.1235
  9. Kim, H. I., Lim, E. M. and Kwon, K. R. (2006) Effects of Onkyung-tang on surgically induced endometriosis in rats. J. Orient. Obstetrics Gynecol. 19: 18-33.
  10. Kwon, C. N. and Lee, I. S. (2001) The effect of Onkyungtang on uterine changes of ovariectomized rats. J. Orient. Gynecol. 14: 56-68.
  11. Choi, K. H., Kim, C. W. and Yu, S. K. (1996) The influence of Onkyungtang for soothing of pain, spasmolutic, removal of uterus muscle by animal experiment. J. Orient. Gynecol. 9: 27-39.
  12. Kim, C. W. (1994) Studies on the effects of Onkyungtang. J. Korean Med. 12: 269-280.
  13. Kim, S. h., Kim, H. K., Yang, E. S., Lee, K. Y., Kim, S. D., Kim, Y. C. and Sung, S. H. (2010) Optimization of pressurized liquid extraction for spicatoside A in Liriope platyphylla. Sep. Purif. Technol. 71: 168-172. https://doi.org/10.1016/j.seppur.2009.11.016
  14. Ahn, M. J., Lee, M. K., Kim, Y. C. and Sung, S. H. (2008) The simultaneous determination of coumarins in Angelica gigas root by high performance liquid chromatography-diode array detector coupled with electrospray ionization/mass spectrometry. J. Pharm. Biomed. Anal. 46: 258-266. https://doi.org/10.1016/j.jpba.2007.09.020
  15. Shan, S. M., Luo, J. G., Huang, F. and Kong, L. Y. (2014) Chemical characteristics combined with bioactivity for comprehensive evaluation of Panax ginseng C.A.Meyer in different ages and seasons based on HPLC-DAD and chemometric methods. J. Pharm. Biomed. Anal. 89: 76-82. https://doi.org/10.1016/j.jpba.2013.10.030
  16. Han, J. H., Jo, S. G., Lee, M. J., Baek, S. H. and Park, S. H. (2004) Contents of homogentisic acid and 3,4-dihydrobenzaldehyde in the Pinellia ternate by various processing method and its safety estimate. Korean J. Orient. Physiol. Pathol. 18: 846-853.
  17. Li, P., Zhang, Z. M., Li, T., Zhang, Y. B., Sze, S. C. W., Wang, G. C., Li, Y. L. and Ye, W. C. (2014) Monoterpene derivatives from the roots of Paeonia lactiflora and their antiproliferative activity. Fitoterapia. 98: 124-129. https://doi.org/10.1016/j.fitote.2014.07.017
  18. Lu, G. H., Chan, K., Liang, Y. Z., Leung, K., Chan, C. L., Jiang, Z. H. and Zhao, Z. Z. (2005) Development of high-performance liquid chromatography fingerprints for distinguishing Chinase Angelica form related umbelliferae herbs. J. Chromatogr. A. 1073: 383-392. https://doi.org/10.1016/j.chroma.2004.11.080
  19. Li, G., Seo, C. S., Lee, K. S., Kim, H. J., Chang, H. W., Jung, J. S., Song, D. K. and Son, J. K. (2004) Protective constituents against sepsis in mice from the root cortex of Paeonia suffruticosa. Arch. Pharm. Res. 27: 1123-1126. https://doi.org/10.1007/BF02975116
  20. Zhang, Q. and Ye, M. (2009) Chemical analysis of the Chinese herbal medicine Gan-Cao (licorice). J. Chromatogr. A. 1216: 1954-1969. https://doi.org/10.1016/j.chroma.2008.07.072
  21. Xu, M. L., Li, G., Moon, D. C., Lee, C. S., Woo, M. H., Lee, E. S., Jahang, Y., Chang, H. W., Lee, S. H. and Son, J. K. (2006) Cytotoxicity and DNA topoisomerase inhibitory activity of constituents isolated from the fruits of Evodia officinalis. Arch. Pharm. Res. 29: 541-547. https://doi.org/10.1007/BF02969262
  22. Lv, G. P., Huang, W. H., Yang, F. Q., Li, J. and Li, S. P. (2010) Pressurized liquid extraction and GC-MS analysis for simultaneous determination of seven components in Cinnamomum cassia and the effect of sample preparation. J. Sep. Sci. 33: 2341-2348. https://doi.org/10.1002/jssc.201000208
  23. Zick, S. M., Ruffin, M. T., Djuric, Z., Normolle, D. and Brenner, D. E. (2010) Quantitation of 6-, 8- and 10-gingerols and 6-shogaol in human plasma by high-performance liquid chromatography with electrochemical detection. Int. J. Biomed. Sci. 6: 233-240.
  24. Jaiswal, R., Muller, H., Muller, A., Karar, M. G. E. and Kuhnert, N. (2014) Identification and characterization of chlorogenic acid, chlorogenic acid glycosides and flavonoids from Lonicera henryi L. (Caprifoliaceae) leaves by LC-MSn. Phytochemistry. 108: 252-263. https://doi.org/10.1016/j.phytochem.2014.08.023
  25. Huang, H., Ji, L., Song, S., Wang, J., Wei, N., Jiang, M., Bai, G. and Luo, G. (2011). Identification of the major constituents in Xuebijing injection by HPLC-ESI-MS. Phytochem. Anal. 22: 330-338. https://doi.org/10.1002/pca.1284
  26. Elgstoen, K. B., Zhao, J. Y., Anacleto, J. F. and Jellum, E. (2001) Potential of capillary electrophoresis, tandem mass spectrometry and coupled capillary electrophoresis-tandem mass spectrometry as diagnostic tools. J. Chroamtogr. A. 914: 265-275. https://doi.org/10.1016/S0021-9673(00)01117-1
  27. Wang, X., Ma, X., Li, W., Chu, Y., Guo, J., Li, S., Wang, J., Zhang, H., Zhou, S. and Zhu, Y. (2013) Simultaneous determination of five phenolic components and paeoniflorin in rat plasma by liquid chromatography-tandem mass spectrometry and pharmacokinetic study after oral administration of Cerebralcare $granule^{(R)}$. J. Pharm. Biomed. Anal. 86: 82-91. https://doi.org/10.1016/j.jpba.2013.07.042
  28. He, Q., Hu, X. J. and Cheng, Y. Y. (2006) Analysis of 'SHUANGDAN' granules by high-performance liquid chromatography- diode array detection-electrospray ionization tandem mass spectrometry. J. Pharm. Biomed. Anal. 41: 485-492. https://doi.org/10.1016/j.jpba.2006.01.010
  29. Sudjaroen, Y., Hull, W. E., Erben, G., Wurtele, G., Changbumrung, S., Ulrich, C. M. and Owen, R. W. (2012) Isolation and characterization of ellagitannins as the major polyphenolic components of Longan (Dimocarpus longan Lour) seeds. Phytochemistry. 77: 226-237. https://doi.org/10.1016/j.phytochem.2011.12.008
  30. Li, Y., Qu, H. and Cheng, Y. (2008) Identification of major constituents in the traditional Chinese medicine "QI-SHENYI-QI" dropping pill by high-performance liquid chromatography coupled with diode array detection-electrospray ionization tandem mass spectrometry. J. Pharm. Biomed. Anal. 47: 407-412. https://doi.org/10.1016/j.jpba.2007.12.037
  31. Cao, W., Wang, X., Li, H., Shi, X., Fan, W., Zhao, S., Liu, M. and Niu, L. (2015) Studies on metabolism of total glucosides of paeony from Paeoniae Radix Alba in rats by UPLC-QTOF-MS/MS. Biomed. Chromagogr. 29: 1769-1779. https://doi.org/10.1002/bmc.3493
  32. Tan, G., Zhu, Z., Jing, J., Lv, L., Lou, Z., Zhang, G. and Chai, Y. (2011) Characterization of constituents in Sini decoction and rat plasma by high-performance liquid chromatography with diode array detection coupled to time-of-flight mass spectrometry. Biomed. Chromagogr. 25: 913-924. https://doi.org/10.1002/bmc.1544
  33. Kim, M. K., Yang, D. H., Jung, M., Jung, E. H., Eom, H. Y., Suh, J. H., Min, J. W., Kim, U., Min, H., Kim, J. and Han, S. B. (2011) Simultaneous determination of chromones and coumarins in Radix Saposhnikoviae by high performance liquid chromatography with diode array and tandem mass detectors. J. Chromatogr. A. 1218: 6319-6330. https://doi.org/10.1016/j.chroma.2011.06.103
  34. Zhao, J., Su, C., Yang, C., Liu, M., Tang, L., Su, W. and Liu, Z. (2012) Determination of ginsenosides Rb1, Rb2, and Rb3 in rat plasma by a rapid and sensitive liquid chromatography tandem mass spectrometry method: Application in a pharmacokinetic study. J. Pharm. Biomed. Anal. 64-65: 94-97. https://doi.org/10.1016/j.jpba.2012.02.017
  35. Gardana, C., Scaglianti, M., Pietta, P. and Simonetti, P. (2007) Analysis of the polyphenolic fraction of propolis from different sources by liquid chromatography-tandem mass spectrometry. J. Pharm. Biomed. Anal. 45: 390-399. https://doi.org/10.1016/j.jpba.2007.06.022
  36. Flamini, R., Vedova, A. D., Cancian, D., Panifhel, A. and Rosso, M. D. (2007) GC/MS-positive ion chemical ionization and MS/MS study of volatile benzene compounds in five different woods used in barrel making. J. Mass Spectrom. 42: 641-646. https://doi.org/10.1002/jms.1193
  37. Concannon, S., Ramachandran, V. N. and Smyth, W. F. (2000) A study of the electrospray ionization of selected coumarin derivatives and their subsequent fragmentation using an ion trap mass spectrometer. Rapid Commun. Mass Spectrom. 14: 1157-1166. https://doi.org/10.1002/1097-0231(20000730)14:14<1157::AID-RCM4>3.0.CO;2-V
  38. Zhao, J., Su, C., Yang, C., Liu, M., Tang, L., Su, W. and Liu, Z. (2012) Determination of ginsenosides Rb1, Rb2, and Rb3 in rat plasma by a rapid and sensitive liquid chromatography tandem mass spectrometry method: Application in a pharmacokinetic study. J. Pharm. Biomed. Anal. 64-65: 94-97. https://doi.org/10.1016/j.jpba.2012.02.017
  39. He, Q., Ge, Z. W., Song, Y. and Cheng, Y. Y. (2006) Quality evaluation of Cortex Moutan by high performance liquid chromatography coupled with diode array detector and electrospray ionization tandem mass spectrometry. Chem. Pharm. Bull. 54: 1271-1275. https://doi.org/10.1248/cpb.54.1271
  40. Zhao, Y., Zhao, Y., Zhou, X. and Gong, X. (2014) Development and validation of an UPLC-ESI-MS/MS method for determination of dehydroevodiamine, limonin, evodiamine, and rutaecarpine in Eovidae Fructus. Pharmacogn. Mag. 10: 374-383. https://doi.org/10.4103/0973-1296.137381
  41. Choi, S. J., Choi, J., Jeon, H., Bae, S. K., Ko, J., Kim, J. and Yoon, K. E. (2015) Application of high-performance countercurrent chromatography for the isolation of steroidal saponins from Liriope plathyphylla. J. Sep. Sci. 38: 18-24. https://doi.org/10.1002/jssc.201401007