Preparation and Application of Partially Substituted Phenylcarbamate-(3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-Appended Silica Particles as Chiral Stationary Phase for Multi-mode HPLC

Abstract

A new type of partially substituted cyclodextrin-bonded silica particles, phenylcarbamate-(3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica (P-CD-HPS), has been successfully prepared and used as chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC) under normal-phase, reversed-phase, and polar organic mobile-phase conditions. The P-CD-HPS was characterized by elemental analysis and Fourier transform infrared spectroscopic (FTIR) analysis. The chromatographic performance of the new-phase P-CD-HPS has been evaluated in HPLC under multi-mode conditions via separating positional isomers of some disubstituted benzenes and enantiomers of some chiral drug compounds. The separation results show that P-CD-HPS exhibited excellent selectivity for separating the positional isomers of nitrophenol and nitraniline and the enantiomers of some chiral drug compounds. The hydroxyl residues of partially substituted β-cyclodextrin and chiral spacer linking to secondary hydroxyl site of the β-cyclodextrin in the P-CD-HPS not only have important contributions to chiral recognitions and separations, but also allow the P-CD-HPS to be used under multi-mode mobile-phase conditions in HPLC.

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Abbreviations

P-CD-HPS:

Phenylcarbamate-(3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica

CSP:

Chiral stationary phase

FTIR:

Fourier transform infrared spectroscopic analysis

References

  1. 1.

    Yang B, Zhou J, Wang Y, Tang J (2017) Enantioseparation of isoxazolines with functionalized perphenylcarbamate cyclodextrin clicked chiral stationary phases in HPLC. Electrophoresis 38:1939–1947

    CAS  Article  Google Scholar 

  2. 2.

    Shen J, Okamoto Y (2016) Efficient separation of enantiomers using stereoregular chiral polymers. Chem Rev 116:1094–1138

    CAS  Article  Google Scholar 

  3. 3.

    Wang Y, Zhang S, Breitbach ZS, Petersen H, Ellegaard P, Armstrong DW (2016) Enantioseparation of citalopram analogues with sulfated β-cyclodextrin by capillary electrophoresis. Electrophoresis 37:841–848

    CAS  Article  Google Scholar 

  4. 4.

    Gumustas M, Ozkan SA, Chankvetadze B (2018) Analytical and preparative scale separation of enantiomers of chiral drugs by chromatography and related methods. Curr Med Chem 25:4152–4188

    CAS  Article  Google Scholar 

  5. 5.

    Xu C, Ng SC, Chan HSO (2008) Self-assembly of perfunctionalized β-cyclodextrins on a quartz crystal microbalance for real-time chiral recognition. Langmuir 24:9118–9124

    CAS  Article  Google Scholar 

  6. 6.

    Lin C, Fan J, Liu W, Chen X, Ruan L, Zhang W (2018) A new single-urea-bound 3,5-dimethylphenylcarbamoylated β-cyclodextrin chiral stationary phase and its enhanced separation performance in normal-phase liquid chromatography. Electrophoresis 39:348–355

    CAS  Article  Google Scholar 

  7. 7.

    Bai W, Ching B, Ng SC (2003) Monochloro-substituted phenyl carbamoylated β-cyclodextrins as π-acid chiral stationary phases for high-performance liquid chromatography. Chromatographia 58:43–46

    CAS  Google Scholar 

  8. 8.

    AhmedK Si, Tazerouti F, Badjah-Hadj-Ahmed AY, Meklati BY (2007) Preparation and chromatographic properties of a multimodal chiral stationary phase based on phenyl-carbamate-propyl-β-CD for HPLC. J Sep Sci 30:2025–2036

    Article  Google Scholar 

  9. 9.

    Zhang Z, Wu M, Wu R, Dong J, Ou J, Zou H (2011) Preparation of perphenylcarbamoylated β-cyclodextrin-silica hybrid monolithic column with “one-pot” approach for enantioseparation by capillary liquid chromatography. Anal Chem 83:3616–3622

    CAS  Article  Google Scholar 

  10. 10.

    Xiao Y, Ng SC, Tan TTY, Wang Y (2012) Recent development of cyclodextrin chiral stationary phases and their applications in chromatography. J Chromatogr A 1269:52–68

    CAS  Article  Google Scholar 

  11. 11.

    Muderawan IW, Ong TT, Ng SC (2006) Urea bonded cyclodextrin derivatives onto silica for chiral HPLC. J Sep Sci 29:1849–1871

    CAS  Article  Google Scholar 

  12. 12.

    Poon YF, Muderawan IW, Ng SC (2006) Synthesis and application of mono-2A-azido-2A-deoxyperphenylcarbamoylated β-cyclodextrin and mono-2A-azido-2A-deoxyperacetylated β-cyclodextrin as chiral stationary phases for high-performance liquid chromatography. J Chromatogr A 1101:185–197

    CAS  Article  Google Scholar 

  13. 13.

    Ma M, Wei Q, Meng M, Yin J, Du L, Zhu X, Min M, Zhou X, Yin X, Gong Y (2017) Application of partially substituted 3,5-dimethylphenylcarbamate-(3-(2-o-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica particles as chiral stationary phase for multi-mode high-performance liquid chromatography. J Chromatogr Sci 55:839–845

    CAS  Article  Google Scholar 

  14. 14.

    Pang L, Zhou J, Tang J, Ng SC, Tang W (2014) Evaluation of perphenylcarbamated cyclodextrin clicked chiral stationary phase for enantioseparations in reversed phase high performance liquid chromatography. J Chromatogr A 1363:119–127

    CAS  Article  Google Scholar 

  15. 15.

    Lin Y, Zhou J, Tang J, Tang W (2015) Cyclodextrin clicked chiral stationary phases with functionalities-tuned enantioseparations in high performance liquid chromatography. J Chromatogr A 1406:342–346

    CAS  Article  Google Scholar 

  16. 16.

    Tang J, Pang L, Zhou J, Zhang S, Tang W (2016) Per(3-chloro-4-methyl) phenylcarbamate cyclodextrin clicked stationary phase for chiral separation in multiple modes high-performance liquid chromatography. Anal Chim Acta 94:96–103

    Article  Google Scholar 

  17. 17.

    Gong Y, Xue G, Bradshaw JS, Lee ML, Lee HK (2001) Synthesis of crown ether-capped 3-(β-cyclodextrin)-2-hydroxypropylsilyl-appended silica particles for use as chiral stationary phases in chromatography. J Heterocyclic Chem 38:1317–1321

    CAS  Article  Google Scholar 

  18. 18.

    Meng M, Ma M, Yi J, Xu L, Yin X, Gu Q, Yin J, Du L, Zhu X, Zhou X et al (2019) Preparation and evaluation of partially-substituted 3-chloro-4-methylphenylcarbamate-β-cyclodextrin bonded silica particles as chiral stationary phase for multi-mode HPLC. Sep Sci Plus 2:4–11

    CAS  Article  Google Scholar 

  19. 19.

    Thamarai CSK, Yong EL, Gong Y (2010) Application of bromoacetate-substituted β-CD-bonded silica particles as chiral stationary phase for HPLC. J Sep Sci 33:74–78

    Article  Google Scholar 

  20. 20.

    Da S, Feng Y, Da Y, Gong Y, Zhang Y (1999) Preparation and characterization of 3-(aza-18-crown-6) propylsilyl bonded phase for reversed-phase liquid chromatography. J Chromatogr Sci 37:137–144

    CAS  Article  Google Scholar 

  21. 21.

    Armstrong DW, DeMond W (1984) Cyclodextrin bonded phases for the liquid chromatographic separation of optical, geometrical, and structural isomers. J Chromatogr Sci 22:411–415

    CAS  Article  Google Scholar 

  22. 22.

    Zhou ZM, Li X, Chen XP, Fang M, Dong X (2010) Separation performance and recognition mechanism of mono(6-deoxy-Imino)-β-cyclodextrins chiral stationary bases in high-performance liquid chromatography. Talanta 82:775–784

    CAS  Article  Google Scholar 

  23. 23.

    Gong Y, Lee HK (2003) Application of naphthylcarbamate-substituted β-cyclodextrin bonded silica particles as stationary phase for high-performance liquid chromatography. J Sep Sci 26:515–520

    CAS  Article  Google Scholar 

  24. 24.

    Hargitai T, Okamoto Y (1993) Evaluation of 3,5-dimethylphenyl carbamoylated α-, β-, and γ-cyclodextrins as chiral stationary phases for HPLC. J Chromatogr 16:843–859

    CAS  Google Scholar 

  25. 25.

    Lai X, Tang W, Ng SC (2011) Novel cyclodextrin chiral stationary phases for high performance liquid chromatography enantioseparation: effect of cyclodextrin type. J Chromatogr A 1218:5597–5601

    CAS  Article  Google Scholar 

  26. 26.

    Lai X, Tang W, Ng SC (2011) Novel β-cyclodextrin chiral stationary phases with different length spacers for normal-phase high performance liquid chromatography enantioseparation. J Chromatogr A 1218:3496–3501

    CAS  Article  Google Scholar 

  27. 27.

    Huang G, Ou J, Zhang X, Ji Y, Peng X, Zou H (2014) Synthesis of novel perphenylcarbamated β-cyclodextrin based chiral stationary phases via thiol-ene click chemistry. Electrophoresis 35:2752–2758

    CAS  Article  Google Scholar 

  28. 28.

    Cirilli R, Simonelli A, Ferretti R, Bolasco A, Chimenti P, Secci D, Maccioni E, La Torre F (2006) Analytical and semipreparative high performance liquid chromatography enantioseparation of new substituted 1-thiocarbamoyl-3,5-diaryl-4,5-dihydro-(1H)-pyrazoles on polysaccharide-based chiral stationary phases in normal-phase, polar organic and reversed-phase conditions. J Chromatogr A 1101:198–203

    CAS  Article  Google Scholar 

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Acknowledgements

The authors thank Xuzhou Medical University for financial support of this work (Grant no. 531150).

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Correspondence to Qunli Wei or Yinhan Gong.

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Yi, J., Xu, L., Wang, H. et al. Preparation and Application of Partially Substituted Phenylcarbamate-(3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-Appended Silica Particles as Chiral Stationary Phase for Multi-mode HPLC. Chromatographia (2020). https://doi.org/10.1007/s10337-020-03908-w

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Keywords

  • Chiral stationary phase
  • Partially substituted
  • β-Cyclodextrin
  • Phenylcarbamate
  • Chiral separation
  • High-performance liquid chromatography