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Analytical and Bioanalytical Chemistry

, Volume 411, Issue 17, pp 3857–3870 | Cite as

A novel two-dimensional liquid chromatography system for the simultaneous determination of three monoterpene indole alkaloids in biological matrices

  • Sha-Sha Liu
  • Kun Yang
  • Zhi-Liang Sun
  • Xiaofeng Zheng
  • Xia Bai
  • Zhao-Ying LiuEmail author
Research Paper

Abstract

The present paper describes a novel two-dimensional liquid chromatography (2D-LC) system, which is comprised of a first-dimensional ion exchange chromatography (IEX1) column, trap column, and second-dimensional reversed-phase chromatography (RP2) column system. The biological sample is separated by the first-dimensional LC using an IEX column to remove interferences. The analytes are transferred to the trap column after heart-cutting. Then, the analytes are transferred to the second-dimensional LC using an RP2 column for further separation and ultraviolet detection. This 2D-LC system can offer a large injection volume to provide sufficient sensitivity and exhibits a strong capacity for removing interferences. Here, the determination of three monoterpene indole alkaloids (MIAs; gelsemine, koumine, and humantenmine) from Gelsemium in biological matrices (plasma, tissue, and urine) was used this 2D-LC system. After a rapid and easy sample preparation method based on protein precipitation, the sample was injected into the 2D-LC. The method was developed and validated in terms of the selectivity, LOD, LOQ, linearity, precision, accuracy, and stability. The sample preparation time for the three MIAs was 15 min. The LOD for these compounds was 10 ng/mL, which was lower than the developed HPLC methods. The results showed that this method had good quantitation performance and allowed the determination of gelsemine, koumine, and humantenmine in biological matrices. The method is rapid, exhibits high selectivity, has good sensitivity, and is low-cost, thus making it well-suited for application in the pharmaceutical and toxicological analysis of Gelsemium.

Graphical abstract

Keywords

Two-dimensional liquid chromatography Gelsemium Indole alkaloid Gelsemine Koumine Humantenmine 

Notes

Acknowledgments

We thank the American Journal Expert for the language help.

Funding

This study was funded by Hunan Provincial Natural Science Foundation of China (Grant Number 2017JJ1017) and Scientific Research Fund of Hunan Provincial Education Department (Grant Number 18A088).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Zhao QC, Hua W, Zhang L, Guo T, Zhao MH, Yan M, et al. Antitumor activity of two gelsemine metabolites in rat liver microsomes. J Asian Nat Prod Res. 2010;12:731–9.  https://doi.org/10.1080/10286020.2010.492951.CrossRefPubMedGoogle Scholar
  2. 2.
    Zhang JY, Wang YX. Gelsemium analgesia and the spinal glycine receptor/allopregnanolone pathway. Fitoterapia. 2015;100:35–43.  https://doi.org/10.1016/j.fitote.2014.11.002.CrossRefPubMedGoogle Scholar
  3. 3.
    Wei X, Yang J, Ma HX, Ding CF, Yu HF, Zhao YL, et al. Antimicrobial indole alkaloids with adductive C 9 aromatic unit from Gelsemium elegans. Tetrahedron Lett. 2018;59:2066–70.  https://doi.org/10.1016/j.tetlet.2018.04.041.CrossRefGoogle Scholar
  4. 4.
    Dutt V, Dhar VJ, Sharma A. Antianxiety activity of Gelsemium sempervirens. Pharm Biol. 2010;48:1091–6.  https://doi.org/10.3109/13880200903490521.CrossRefPubMedGoogle Scholar
  5. 5.
    Zhang JY, Gong N, Huang JL, Guo LC, Wang YX. Gelsemine, a principal alkaloid from Gelsemium sempervirens Ait., exhibits potent and specific antinociception in chronic pain by acting at spinal alpha3 glycine receptors. Pain. 2013;154:2452–62.  https://doi.org/10.1080/10286020.2010.492951.CrossRefPubMedGoogle Scholar
  6. 6.
    Lu JM, Liu GL, Qi ZR. Effect of Gelsemium elegans Benth injection on proliferation of tumor cells. Chin J Cancer. 1990.Google Scholar
  7. 7.
    Su YP, Shen J, Xu Y, Zheng M, Yu CX. Preparative separation of alkaloids from Gelsemium elegans Benth. using pH-zone-refining counter-current chromatography. J Chromatogr A. 2011;1218:3695–8.  https://doi.org/10.1016/j.chroma.2011.04.025.CrossRefPubMedGoogle Scholar
  8. 8.
    Xu Y, Qiu HQ, Liu H, Liu M, Huang ZY, Yang J, et al. Effects of koumine, an alkaloid of Gelsemium elegans Benth, on inflammatory and neuropathic pain models and possible mechanism with allopregnanolone. Pharmacol Biochem Behav. 2012;101:504–14.  https://doi.org/10.1016/j.pbb.2012.02.009.CrossRefPubMedGoogle Scholar
  9. 9.
    Hu Y, Chen M, Wang Z, Lan Y, Tang L, Liu M, Zhao J, Hu M, Zhang L, Ye L. Development of a validated UPLC-MS/MS method for determination of humantenmine in rat plasma and its application in pharmacokinetics and bioavailability studies. Biomed Chromatogr. 2017;31.  https://doi.org/10.1002/bmc.4017.
  10. 10.
    Qiu HQ, Cheng Y, Liu MB. Determination of gelsemine and koumine in human plasma by HPLC-UV. Chin Tradit Herb Drugs. 2016.  https://doi.org/10.7501/j.issn.0253-2670.2016.13.020.
  11. 11.
    Yin R, Chen J, Zhao Y, Jia X, Zhang Z, Feng L, et al. Simultaneous determination of six alkaloid components in rat plasma and its application to pharmacokinetic study of Danmu preparations by an ultra fast liquid chromatography-electrospray ionization-tandem mass spectrometry. J Chromatogr B. 2015;984:10–7.  https://doi.org/10.1016/j.jchromb.2014.12.026.CrossRefGoogle Scholar
  12. 12.
    Zhang S, Hu S, Yang X, Shen J, Zheng X, Huang K, et al. Development of a liquid chromatography with mass spectrometry method for the determination of gelsemine in rat plasma and tissue: application to a pharmacokinetic and tissue distribution study. J Sep Sci. 2015;38:936–42.  https://doi.org/10.1002/jssc.201401168.CrossRefPubMedGoogle Scholar
  13. 13.
    Chen JZ, Li Y, Xiao JP, Wu SS, Song HW. Development of a sensitive and rapid UPLC-MS/MS method for the determination of koumine in rat plasma: application to a pharmacokinetic study. Biomed Chromatogr. 2013;27:736–40.  https://doi.org/10.1002/bmc.2852.CrossRefPubMedGoogle Scholar
  14. 14.
    Wang L, Sun Q, Zhao N, Wen YQ, Song Y, Meng FH. Ultra-liquid chromatography tandem mass spectrometry (UPLC-MS/MS)-based pharmacokinetics and tissue distribution study of koumine and the detoxification mechanism of Glycyrrhiza uralensis Fisch on Gelsemium elegans Benth. Molecules. 2018;23.  https://doi.org/10.3390/molecules23071693.
  15. 15.
    Yang K, Long XM, Liu YC, Chen FH, Liu XF, Sun ZL, et al. Development and in-house validation of a sensitive LC-MS/MS method for simultaneous quantification of gelsemine, koumine and humantenmine in porcine plasma. J Chromatogr B. 2018;1076:54–60.  https://doi.org/10.1016/j.jchromb.2018.01.019.CrossRefGoogle Scholar
  16. 16.
    Sadílek P, Šatínský D, Solich P. Using restricted-access materials and column switching in high-performance liquid chromatography for direct analysis of biologically-active compounds in complex matrices. TrAC Trends Anal Chem. 2007;26:375–84.  https://doi.org/10.1016/j.trac.2007.02.002.CrossRefGoogle Scholar
  17. 17.
    Venkatramani CJ, Patel A. Towards a comprehensive 2-D-LC-MS separation. J Sep Sci. 2015;29:510–8.  https://doi.org/10.1002/jssc.200500341.CrossRefGoogle Scholar
  18. 18.
    Iguiniz M, Heinisch S. Two-dimensional liquid chromatography in pharmaceutical analysis. Instrumental aspects, trends and applications. J Pharm Biomed Anal. 2017;145:482–503.  https://doi.org/10.1016/j.jpba.2017.07.009.CrossRefPubMedGoogle Scholar
  19. 19.
    Gilar M, Fridrich J, Schure MR, Jaworski A. Comparison of orthogonality estimation methods for the two-dimensional separations of peptides. Anal Chem. 2012;84:8722–32.  https://doi.org/10.1021/ac3020214.CrossRefPubMedGoogle Scholar
  20. 20.
    Kilz P, Radke W. Application of two-dimensional chromatography to the characterization of macromolecules and biomacromolecules. Anal Bioanal Chem. 2015;407:193–215.  https://doi.org/10.1007/s00216-014-8266-x.CrossRefPubMedGoogle Scholar
  21. 21.
    Mani-Varnosfaderani A, Ghaemmaghami M. Assessment of the orthogonality in two-dimensional separation systems using criteria defined by the maximal information coefficient. J Chromatogr A. 2015;1415:108–14.  https://doi.org/10.1016/j.chroma.2015.08.049.CrossRefPubMedGoogle Scholar
  22. 22.
    Fujimoto H, Nishino I, Ueno K, Umeda T. Determination of theenantiomers of a new 1,4=dihydropyridine calcium antagonist in dogplasma byachira/chiral coupled high-performance liquid chromatographywith electrochemical detection. J Pharm Sci. 1993;82:319–22.  https://doi.org/10.1002/jps.2600820320.CrossRefGoogle Scholar
  23. 23.
    Yamashita K, Motohashi M, Yashiki T. Column-switching techniques for high-performance liquid chromatography of ibuprofen and mefenamic acid in human serum with short-wavelength ultraviolet detection. J Chromatogr B. 1991;570:329–38.  https://doi.org/10.1016/0378-4347(91)80536-l.CrossRefGoogle Scholar
  24. 24.
    Yang Y, Rosales-Conrado N, Guillén-Casla V, León-González ME, Pérez-Arribas LV, Polo-Díez LM. Chiral determination of salbutamol, salmeterol and atenolol by two-dimensional LC-LC: application to urinesamples. Chromatographia. 2012;75:1365–75.  https://doi.org/10.1007/s10337-012-2353-y.CrossRefGoogle Scholar
  25. 25.
    Lamprecht G, Stoschitzky K. Enantioselective analysis of R- and S-propafenone in plasma by HPLC applying column switching and liquid-liquid extraction. J Chromatogr B Biomed Sci Appl. 2009;877:3489–94.  https://doi.org/10.1016/j.jchromb.2009.08.024.CrossRefGoogle Scholar
  26. 26.
    Barhate CL, Regalado EL, Contrella ND, Lee J, Jo J, Makarov AA, et al. Ultrafast chiral chromatography as the second dimension in two-dimensional liquid chromatography experiments. Anal Chem. 2017;89:3545–53.  https://doi.org/10.1021/acs.analchem.6b04834.CrossRefPubMedGoogle Scholar
  27. 27.
    D’Attoma A, Heinisch S. On-line comprehensive two dimensional separations of charged compounds using reversed-phase high performance liquid chromatography and hydrophilic interaction chromatography. Part II: application to the separation of peptides. J Chromatogr A. 2013;1306:27–36.  https://doi.org/10.1016/j.chroma.2013.07.048.CrossRefPubMedGoogle Scholar
  28. 28.
    Sagirli O, Ertürk Toker S, Kepekci Tekkeli SE. Two-dimensional liquid chromatographic analysis of ramelteon in human serum. Arab JChem. 2015.  https://doi.org/10.1016/j.arabjc.2015.06.021.
  29. 29.
    Lia X, Wang F, Xu B, Yu XW, Yang Y, Zhang L, et al. Determination of the free and total concentrations of vancomycin by two-dimensional liquid chromatography and its application in elderly patients. J Chromatogr B. 2014;969:181–9.  https://doi.org/10.1016/j.jchromb.2014.08.002.CrossRefGoogle Scholar
  30. 30.
    Sheng Y, Zhou B. High-throughput determination of vancomycin in human plasma by a cost-effective system of two-dimensional liquid chromatography. J Chromatogr A. 2017;1499:48–56.  https://doi.org/10.1016/j.chroma.2017.02.061.CrossRefPubMedGoogle Scholar
  31. 31.
    Agency EM. Guideline on bioanalytical method validation. Drug Eval Res. 2012;5:54–60.Google Scholar
  32. 32.
    Timmerman P, Lowes S, Fast DM. Request for global harmonization of the guidance for bioanalytical method validation and sample analysis. Bioanalysis. 2010;2:683.  https://doi.org/10.4155/bio.10.34.CrossRefPubMedGoogle Scholar
  33. 33.
    Qu L, Fan Y, Wang W, Ma K, Yin Z. Development, validation and clinical application of an online-SPE-LC-HRMS/MS for simultaneous quantification of phenobarbital, phenytoin, carbamazepine, and its active metabolite carbamazepine 10,11-epoxide. Talanta. 2016;158:77–88.  https://doi.org/10.1016/j.talanta.2016.05.036.CrossRefPubMedGoogle Scholar
  34. 34.
    Pedersen-Bjergaard S, Rasmussen KE. Electrical potential can drive liquid-liquid extraction for sample preparation in chromatography. Trends Anal Chem. 2008;27:934–41.  https://doi.org/10.1016/j.trac.2008.08.005.CrossRefGoogle Scholar
  35. 35.
    Novakova L, Vlckova H. A review of current trends and advances in modern bio-analytical methods: chromatography and sample preparation. Anal Chim Acta. 2009;656:8–35.  https://doi.org/10.1016/j.aca.2009.10.004.CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Sha-Sha Liu
    • 1
    • 2
  • Kun Yang
    • 1
    • 2
  • Zhi-Liang Sun
    • 1
    • 2
  • Xiaofeng Zheng
    • 1
    • 2
  • Xia Bai
    • 1
    • 2
  • Zhao-Ying Liu
    • 1
    • 2
    Email author
  1. 1.Hunan Engineering Technology Research Center of Veterinary DrugsHunan Agricultural UniversityChangshaChina
  2. 2.College of Veterinary MedicineHunan Agricultural UniversityChangshaChina

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