Skip to main content
Log in

Superhydrophilic molecularly imprinted polymers based on a single cross-linking monomer for the recognition of iridoid glycosides in Di-huang pills

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

An efficient analytical method based on molecularly imprinted solid-phase extraction (MISPE) coupled with high-performance liquid chromatography-diode array detection (HPLC-DAD) was established for the determination of iridoid glycosides (IGs) in Di-huang pills. As the solid-phase extraction medium, superhydrophilic molecularly imprinted polymers (MIPs) with high affinity and selectivity to IGs in water media were fabricated using divinyl galactose as a single cross-linking monomer. The structure, porosity, and hydrophilicity of MIPs were characterized. The properties involving dynamic adsorption, kinetic adsorption, and selectivity were evaluated. Under optimal conditions the MISPE-HPLC-DAD based method was applied for loganin, morroniside, cornin, and sweroside determination in three kinds of Di-huang pills. The limits of detection of four IGs were 0.002–0.003 mg g−1. Furthermore, the proposed method exhibited some merits including good linearity, excellent precision, and desirable accuracy. The established MISPE-HPLC-DAD method has great potential for the selective determination of IGs in Chinese patent drugs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Chen L, Xu S, Li J. Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev. 2011;40:2922–42.

    Article  CAS  PubMed  Google Scholar 

  2. Chen L, Wang X, Lu W, Wu X, Li J. Molecular imprinting: perspectives and applications. Chem Soc Rev. 2016;45:2137–211.

    Article  CAS  PubMed  Google Scholar 

  3. Liang S, Yan H, Cao J, Han Y, Shen S, Bai L. Molecularly imprinted phloroglucinol-formaldehyde-melamine resin prepared in a deep eutectic solvent for selective recognition of clorprenaline and bambuterol in urine. Anal Chim Acta. 2017;951:68–77.

    Article  CAS  PubMed  Google Scholar 

  4. Díaz-Álvarez M, Martín-Esteban A. Hollow fiber membrane-protected molecularly imprinted microspheres for micro solid-phase extraction and clean-up of thiabendazole in citrus samples. J Chromatogr A. 2018;1531:39–45.

    Article  CAS  PubMed  Google Scholar 

  5. Rossetti C, Ore OG, Sellergren B, Halvorsen TG, Reubsaet L. Exploring the peptide retention mechanism in molecularly imprinted polymers. Anal Bioanal Chem. 2017;409:5631–43.

    Article  CAS  PubMed  Google Scholar 

  6. Jia M, Yang J, Sun Y, Bai X, Wu T, Liu Z, et al. Improvement of imprinting effect of ionic liquid molecularly imprinted polymers by use of a molecular crowding agent. Anal Bioanal Chem. 2018;410:595–604.

    Article  CAS  PubMed  Google Scholar 

  7. Sun Y, Pang Y, Zhang J, Li Z, Liu J, Wang B. Application of molecularly imprinted polymers for the analysis of polycyclic aromatic hydrocarbons in lipid matrix-based biological samples. Anal Bioanal Chem. 2017;409:6851–60.

    Article  CAS  PubMed  Google Scholar 

  8. Sun Y, Zhong S. Molecularly imprinted polymers fabricated via Pickering emulsions stabilized solely by food-grade casein colloidal nanoparticles for selective protein recognition. Anal Bioanal Chem. 2018; https://doi.org/10.1007/s00216-018-1006-x.

    Article  CAS  PubMed  Google Scholar 

  9. Ye L. Molecularly imprinted polymers with multi-functionality. Anal Bioanal Chem. 2016;408:1727–33.

    Article  CAS  PubMed  Google Scholar 

  10. Guo P, Yuan X, Zhang J, Wang B, Sun X, Chen X, et al. Dummy-surface molecularly imprinted polymers as a sorbent of micro-solid-phase extraction combined with dispersive liquid–liquid microextraction for determination of five 2-phenylpropionic acid NSAIDs in aquatic environmental samples. Anal Bioanal Chem. 2018;410:373–89.

    Article  CAS  PubMed  Google Scholar 

  11. Sibrian-Vazquez M, Spivak DA. Molecular imprinting made easy. J Am Chem Soc. 2004;126:7827–33.

    Article  CAS  PubMed  Google Scholar 

  12. Sibrian-Vazquez M, Spivak DA. Enhanced enantioselectivity of imprinted polymers formulated with novel crosslinking monomers. Macromolecules. 2003;36:5105–13.

    Article  CAS  Google Scholar 

  13. Wei Z, Wu X, Zhang B, Li R, Huang Y, Liu Z. Coatings of one monomer molecularly imprinted polymers for open tubular capillary electrochromatography. J Chromatogr A. 2011;1218:6498–504.

    Article  CAS  PubMed  Google Scholar 

  14. Sibrian-Vazquez M, Spivak DA. Improving the strategy and performance of molecularly imprinted polymers using cross-linking functional monomers. J Organomet Chem. 2003;68:9604–11.

    Article  CAS  Google Scholar 

  15. Yoshimatsu K, LeJeune J, Spivak DA, Ye L. Peptide-imprinted polymer microspheres prepared by precipitation polymerization using a single bi-functional monomer. Analyst. 2009;134:719–24.

    Article  CAS  PubMed  Google Scholar 

  16. Boros CA, Stemrmitz FR. Iridoids. An updated review. Part I. J Nat Prod. 1990;53:1055–147.

    Article  CAS  Google Scholar 

  17. Boros CA, Stemrmitz FR. Iridoids. An updated review. Part II. J Nat Prod. 1991;54:1173–246.

    Article  CAS  Google Scholar 

  18. Chinese Pharmacopoeia Commission. Chinese pharmacopoeia, vol. I. Beijing: People’s Medical Publishing House; 2015. p. 704–−705.

    Google Scholar 

  19. Chinese Pharmacopoeia Commission. Chinese pharmacopoeia, vol. I. Beijing: People’s Medical Publishing House; 2015. p. 775–−777.

    Google Scholar 

  20. Chinese Pharmacopoeia Commission. Chinese pharmacopoeia, vol. I. Beijing: People’s Medical Publishing House; 2015. p. 935–−936.

    Google Scholar 

  21. Song Y, Li SL, Wu MH, Li HJ, Li P. Qualitative and quantitative analysis of iridoid glycosides in the flower buds of Lonicera species by capillary high performance liquid chromatography coupled with mass spectrometric detector. Anal Chim Acta. 2006;564:211–8.

    Article  CAS  Google Scholar 

  22. Cao XY, Wang ZZ. Simultaneous determination of four iridoid and secoiridoid glycosides and comparative analysis of Radix Gentianae macrophyllae and their related substitutes by HPLC. Phytochem Anal. 2010;21:348–54.

    Article  CAS  PubMed  Google Scholar 

  23. Yang L, Wang Y, Wang L, Xiao H, Wang Z, Hu Z. Rapid quantification of iridoid glycosides analogues in the formulated Chinese medicine Longdan Xiegan decoction using high-performance liquid chromatography coupled with mass spectromentry. J Chromatogr A. 2009;1216:2098–103.

    Article  CAS  PubMed  Google Scholar 

  24. He ML, Cheng XW, Chen JK, Zhou TS. Simultaneous determination of five major biologically active ingredients in different parts of Gardenia jasminoides fruits by HPLC with diode-array detection. Chromatographia. 2006;64:713–7.

    Article  CAS  Google Scholar 

  25. Zhao M, Tao J, Qian D, Liu P, Shang E, Jiang S, et al. Simultaneous determination of loganin, morroniside, catalpol and acteoside in normal and chronic kidney disease rat plasma by UPLC–MS for investigating the pharmacokinetics of Rehmannia glutinosa and Cornus officinalis Sieb drug pair extract. J Chromatogr B. 2016;1009–1010:122–9.

    Article  CAS  Google Scholar 

  26. Li H, Li P, Ye W. Determination of five major iridoid glucosides in Flos Lonicerae by high-performance liquid chromatography coupled with evaporative light scattering detection. J Chromatogr A. 2003;1008:167–72.

    Article  CAS  PubMed  Google Scholar 

  27. Du W, Cai H, Wang M, Ding X, Yang H, Cai B. Simultaneous determination of six active components in crude and processed Fructus Corni by high performance liquid chromatography. J Pharm Biomed Anal. 2008;48:194–7.

    Article  CAS  PubMed  Google Scholar 

  28. Si W, Yang W, Guo D, Wu J, Zhang J, Qiu S, et al. Selective ion monitoring of quinochalcone C-glycoside markers for the simultaneous identification of Carthamus tinctorius L. in eleven Chinese patent medicines by UHPLC/QTOF MS. J Pharm Biomed Anal. 2016;117:510–21.

    Article  CAS  PubMed  Google Scholar 

  29. Yao C, Yang W, Wu W, Da J, Hou J, Zhang J, et al. Simultaneous quantitation of five Panax notoginseng saponins by multi heart-cutting two-dimensional liquid chromatography: method development and application to the quality control of eight Notoginseng containing Chinese patent medicines. J Chromatogr A. 2015;1402:71–81.

    Article  CAS  PubMed  Google Scholar 

  30. Zhao J, Ma S, Li S. Advanced strategies for quality control of Chinese medicines. J Pharm Biomed Anal. 2018;147:473–8.

    Article  CAS  PubMed  Google Scholar 

  31. Ji W, Zhang M, Wang D, Wang X, Liu J, Huang L. Superhydrophilic molecularly imprinted polymers based on a water-soluble functional monomer for the recognition of gastrodin in water media. J Chromatogr A. 2015;1425:88–96.

    Article  CAS  PubMed  Google Scholar 

  32. Kong XJ, Zheng C, Lan YH, Chi SS, Dong Q, Liu HL, et al. Synthesis of multirecognition magnetic molecularly imprinted polymer by atom transfer radical polymerization and its application in magnetic solid-phase extraction. Anal Bioanal Chem. 2018;410:247–57.

    Article  CAS  PubMed  Google Scholar 

  33. Gao SP, Zhang X, Zhang LS, Huang YP, Liu ZS. Molecularly imprinted polymer prepared with polyhedral oligomeric silsesquioxane through reversible addition–fragmentation chain transfer polymerization. Anal Bioanal Chem. 2017;409:3741–8.

    Article  CAS  PubMed  Google Scholar 

  34. Ji W, Sun R, Geng Y, Liu W, Wang X. Rapid, low temperature synthesis of molecularly imprinted covalent organic frameworks for the highly selective extraction of cyano pyrethroids from plant samples. Anal Chim Acta. 2018;1001:179–88.

    Article  CAS  PubMed  Google Scholar 

  35. Wang N, Wang YF, Omer AM, Ouyang X. Fabrication of novel surface-imprinted magnetic graphene oxide-grafted cellulose nanocrystals for selective extraction and fast adsorption of fluoroquinolones from water. Anal Bioanal Chem. 2017;409:6643–53.

    Article  CAS  PubMed  Google Scholar 

  36. Dima ŞO. Equilibrium and kinetic isotherms and parameters for molecularly imprinted with sclareol poly(acrylonitrile-co-acrylic acid) matrix. Polym Eng Sci. 2015;55:1152–62.

    Article  CAS  Google Scholar 

  37. Umpleby RJ, Baxter SC, Chen Y, Shah RN, Shimizu KD. Characterization of molecularly imprinted polymers with the Langmuir-Freundlich isotherm. Anal Chem. 2001;73:4548–91.

    Article  CAS  Google Scholar 

  38. Ji W, Wang T, Liu W, Liu F, Guo L, Geng Y, et al. Water-compatible micron-sized monodisperse molecularly imprinted beads for selective extraction of five iridoid glycosides from Cornus officinalis fructus. J Chromatogr A. 2017;1504:1–8.

    Article  CAS  PubMed  Google Scholar 

  39. Ji W, Zhang M, Liu W, Wang X, Duan W, Xie H, et al. Development of hydrophilic magnetic molecularly imprinted polymers by directly coating onto Fe3O4 with a water-miscible functional monomer and application in a solid-phase extraction procedure for iridoid glycosides. RSC Adv. 2016;6:50487–96.

    Article  CAS  Google Scholar 

  40. Ji W, Zhang M, Gao Q, Cui L, Chen L, Wang X. Preparation of hydrophilic molecularly imprinted polymers via bulk polymerization combined with hydrolysis of ester groups for selective recognition of iridoid glycosides. Anal Bioanal Chem. 2016;408:5319–28.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

Financial support from the National Natural Science Foundation of China (No. 81603286), the Key Science and Technology Program of Shandong (No. 2016GSF202033), the Natural Science Foundation of Shandong (ZR2016YL006), the Priority Research Program of the Shandong Academy of Sciences (Lanping Guo), and the Shandong Province Taishan Scholar Program (Lanping Guo) are acknowledged.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Wenhua Ji.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

ESM 1

(PDF 955 kb)

ESM 2

(AVI 247 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ji, W., Wang, R., Mu, Y. et al. Superhydrophilic molecularly imprinted polymers based on a single cross-linking monomer for the recognition of iridoid glycosides in Di-huang pills. Anal Bioanal Chem 410, 6539–6548 (2018). https://doi.org/10.1007/s00216-018-1257-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1257-6

Keywords

Navigation