Skip to main content
SpringerLink
Log in

Chromatographic and Spectroscopic Studies on β-Cyclodextrin Functionalized Ionic Liquid as Chiral Stationary Phase: Enantioseparation of Flavonoids

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

In this study, β-cyclodextrin functionalized ionic liquid was prepared by adding 1-benzylimidazole onto 6-monotosyl-6-deoxy-β-cyclodextrin (β-CDOTs) to obtain β-CD-BIMOTs. β-CD-BIMOTs were then bonded onto the modified silica to produce chiral stationary phases (β-CD-BIMOTs-CSP). The performance of β-CD-BIMOTs-CSP was evaluated by observing the enantioseparation of flavonoids. The performance of β-CD-BIMOTs stationary phase was also compared with native β-CD stationary phase. For the selected flavonoids, flavanone and hesperetin obtained a high resolution factor in reverse phase mode. Meanwhile, naringenin and eriodictyol attained partial enantioseparation in polar organic mode. In order to understand the mechanism of separation, the interaction of selected flavonoids and β-CD-BIMOTs was studied using spectroscopic methods (1H NMR, NOESY and UV–Vis spectrophotometry). The enantioseparated flavanone and hesperetin were found to form an inclusion complex with β-CD-BIMOTs. However, naringenin and eriodictyol were not enantioseparated due to the formation of hydrogen bonding at exterior torus of β-CD-BIMOTs.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Di Carlo G, Mascolo N, Izzo A, Papasso F (1999) Flavonoids: old and new aspects of a class of natural therapeutic drugs. Life Sci 65:337–353

    Article  Google Scholar 

  2. El-Mahdy MA, Zhu Q, Wang QE, Wani G, Patnaik S, Zhao Q, Arafa E, Barakat B, Mir S, Wani AA (2008) Naringenin protects HaCaT human keratinocytes against UVB-induced apoptosis and enhances the removal of cyclobutane pyrimidine dimers from the genomet. J Photochem Photobio 84:307–316

    Article  CAS  Google Scholar 

  3. Pietta P (1998) In: Rice-Evans CA, Packer L (eds) Flavonoids in health and disease. Marcel Dekker Inc., New York

    Google Scholar 

  4. Cao G, Sofic E, Prior RL (1997) Antioxidant and pro-oxidant behavior of flavonoids: structure-activity relationships. Free Radic Biol Med 22:749–760

    Article  CAS  Google Scholar 

  5. Lees P, Taylor PM, Landoni FM, Arifah AK, Waters C (2003) Ketoprofen in the cat: pharmacodynamics and chiral pharmacokinetics. Vet J 1:21–35

    Article  Google Scholar 

  6. Wolf C (2008) Dynamic stereochemistry of chiral compounds: principles and applications. Royal Society of Chemistry, UK

    Google Scholar 

  7. Schurig V (2002) Chiral separations using gas chromatography. Trends Anal Chem 21:647–661

    Article  CAS  Google Scholar 

  8. Juvancz Z, Szejtli J (2002) The role of cyclodextrins in chiral selective chromatography. Trends Anal Chem 21:379–388

    Article  CAS  Google Scholar 

  9. Scriba GK, Altria K (2009) Using cyclodextrins to achieve chiral and non-chiral separations in capillary electrophoresis. LC GC Eur 22:420

    CAS  Google Scholar 

  10. Stalcup AM, Chang SC, Armstrong DW, Pitha J (1990) (S)-2-hydroxyprophyl-β-cyclodextrin, a new chiral stationary phase for reversed-phase liquid chromatography. J Chromatogr A 513:181–194

    Article  CAS  Google Scholar 

  11. Wang Y, Young DJ, Tan TTY, Ng SC (2010) “Click” immobilized perphenylcarbamated and permethylated cyclodextrin stationary phases for chiral high-performance liquid chromatography application. J Chromatogr A 1217:5103–5108

    Article  CAS  Google Scholar 

  12. Li X, Zhou Z (2014) Enantioseparation performance of novel benzimido-β-cyclodextrins derivatized by ionic liquids as chiral stationary phases. Anal Chim Acta 819:122–129

    Article  CAS  Google Scholar 

  13. Li X, Zhou Z, Zhou W, Dai L, Li Z (2011) Preparation of a novel cyclodextrin derivative of benzimido-β-cyclodextrin and its enantioseparation performance in HPLC. Analyst 136:5017–5024

    Article  CAS  Google Scholar 

  14. Wasserscheid P, Keim W (2000) Ionic liquids-new “solutions” for transition metal catalysis. Angew Chem 39:3772–3789

    Article  CAS  Google Scholar 

  15. Pandey S (2006) Analytical applications of room-temperature ionic liquids: a review of recent efforts. Anal Chim Acta 556:38–45

    Article  CAS  Google Scholar 

  16. Canongia Lopes JN, Pádua AA (2006) Nanostructural organization in ionic liquids. J Phys Chem B 110:3330–3335

    Article  CAS  Google Scholar 

  17. Anderson JL, Armstrong DW (2003) High-stability ionic liquids. A new class of stationary phases for gas chromatography. Anal Chem 75:4851–4858

    Article  CAS  Google Scholar 

  18. Rahim NY, Tay KS, Mohamad S (2016) β-Cyclodextrin functionalized ionic liquid as chiral stationary phase of high performance liquid chromatography for enantioseparation of β-blockers. J Incl Phenom Macrocycl Chem 85:303–315

    Article  CAS  Google Scholar 

  19. Raoov M, Mohamad S, Abas MR (2013) Removal of 2, 4-dichlorophenol using cyclodextrin-ionic liquid polymer as a macroporous material: characterization, adsorption isotherm, kinetic study, thermodynamics. J Hazard Mater 263:501–516

    Article  CAS  Google Scholar 

  20. Yatabe J, Kageyama T (1994) Preparation of hydrophobic silica with isocyanate. J Ceram Soc Jpn 102:595–598

    Article  Google Scholar 

  21. Manske RHF (1965) The alkaloids: chemistry and physiology, vol 5. Academic Press Inc, New York

    Google Scholar 

  22. Cwiertnia B, Hladon T, Stobiecki M (1999) Stability of diclofenac sodium in the inclusion complex with β-cyclodextrin in the solid state. J Pharm Pharmacol 51:1213–1218

    Article  CAS  Google Scholar 

  23. Zhang W, Lee HR (2010) Grafting of polyethylene glycols onto nanometer silica surface by 1,4-phenylene diisocyanate. Surf Interface Anal 42:1495–1498

    Article  CAS  Google Scholar 

  24. Ng SC, Ong TT, Fu P, Ching CB (2002) Enantiomer separation of flavour and fragrance compounds by liquid chromatography using novel urea-covalent bonded methylated β-cyclodextrins on silica. J Chromatogr A 968:31–40

    Article  CAS  Google Scholar 

  25. Lin C, Liu W, Fan J, Wang Y, Zheng S, Lin R, Zhang W (2013) Synthesis of a novel cyclodextrin-derived chiral stationary phase with multiple urea linkages and enantioseparation toward chiral osmabenzene complex. J Chromatogr A 1283:68–74

    Article  CAS  Google Scholar 

  26. Hunter CA, Lawson KR, Perkins J, Urch CJ (2001) Aromatic interactions. J Chem Soc Perkin Trans 2(5):651–669

    Article  Google Scholar 

  27. Kafková B, Bosáková Z, Tesařová E, Coufal P (2005) Chiral separation of beta-adrenergic antagonists, profen non-steroidal anti-inflammatory drugs and chlorophenoxypropionic acid herbicides using teicoplanin as the chiral selector in capillary liquid chromatography. J Chromatogr A 1088:82–93

    Article  Google Scholar 

  28. Chang SC, Reid GL, Chen S, Chang CD, Armstrong DW (1993) Evaluation of a new polar-organic high-performance liquid chromatographic mobile phase for cyclodextrin-bonded chiral stationary phases. TrAC Trends Anal Chem 12:144–153

    Article  CAS  Google Scholar 

  29. Van Dijk C, Driessen AJ, Recourt K (2000) The uncoupling efficiency and affinity of flavonoids for vesicles. Biochem Pharm 60:1593–1600

    Article  Google Scholar 

  30. Ventura CA, Giannone I, Musumeci T, Pignatello R, Ragni L, Landolfi C, Milanese C, Paolino D, Puglisi G (2006) Physico-chemical characterization of disoxaril–dimethyl-β-cyclodextrin inclusion complex and in vitro permeation studies. Eur J Med Chem 41:233–240

    Article  CAS  Google Scholar 

  31. Hu Y, Wang X, Pan H, Ding L (2012) Interaction mode between methylene blue-Sm(III) complex and herring sperm DNA. Bull Chem Soc Ethiop 3:395–405

    Google Scholar 

  32. Frieden E (1975) Non-covalent interactions: key to biological flexibility and specificity. J Chem Educ 12:754–761

    Article  Google Scholar 

Download references

Acknowledgments

Authors would like to seize this opportunity to express their gratitude to the University Malaya for the IPPP Grant (PG027/2013A) and UMRG Grant (RP006A–13SUS, RP020A–16SUS and RP011B–14SUS). The authors also acknowledge Ministry of Higher Education (MOHE) for providing fellowship to one of the authors-cum-researchers, Ms. NurulYani Rahim.

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, University of Malaya, 50603, Kuala Lumpur, Malaysia

    Nurul Yani Rahim, Kheng Soo Tay & Sharifah Mohamad

  2. University of Malaya Centre for Ionic Liquids (UMCiL), University of Malaya, 50603, Kuala Lumpur, Malaysia

    Sharifah Mohamad

Authors
  1. Nurul Yani Rahim
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kheng Soo Tay
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sharifah Mohamad
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sharifah Mohamad.

Ethics declarations

Conflict of Interest

All authors declare that they have no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 552 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rahim, N.Y., Tay, K.S. & Mohamad, S. Chromatographic and Spectroscopic Studies on β-Cyclodextrin Functionalized Ionic Liquid as Chiral Stationary Phase: Enantioseparation of Flavonoids. Chromatographia 79, 1445–1455 (2016). https://doi.org/10.1007/s10337-016-3169-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-016-3169-y

Keywords

Search

Navigation