Advertisement

Microchimica Acta

, 186:22 | Cite as

A star-shaped molecularly imprinted polymer derived from polyhedral oligomeric silsesquioxanes with improved site accessibility and capacity for enantiomeric separation via capillary electrochromatography

  • Wen-Fang Song
  • Qing-Li Zhao
  • Xiu-Jie Zhou
  • Li-Shun Zhang
  • Yan-Ping HuangEmail author
  • Zhao-Sheng LiuEmail author
Original Paper
  • 109 Downloads

Abstract

A star-shaped molecularly imprinted coating was prepared starting from octavinyl-modified polyhedral oligomeric silsesquioxanes (Ov-POSS). It possesses a relatively open structure and has good site accessibility and a larger capacity even at lower cross-linking. The imprinted coating was prepared from S-amlodipine (S-AML) as the template and analyte, Ov-POSS as the cross-linker, and methacrylic acid as the functional monomer. The preparation and chromatographic parameters were optimized, including ratio of template to functional monomer, apparent cross-linking degree, pH value, ACN content and salt concentration in the mobile phase. The best resolution in enantiomer separation by means of capillary electrochromatography reaches a value of 33. A good recognition ability (α = 2.60) was obtained and the column efficiency for S-AML was 54,000 plates m−1. The use of Ov-POSS as a cross-linker significantly improves the column capacity and thus the detection sensitivity. The results show that Ov-POSS is an effective cross-linker for the preparation of imprinted polymers with good accessibility and large capacity.

Graphical abstract

Schematic presentation of the preparation of star-shaped imprinted polymer using octavinyl-modified polyhedral oligomeric silsesquioxanes (Ov-POSS) and by using methacrylic acid (MAA) as functional monomer. The best enantiometric resolution (33) for amlodipine (AML) can be achieved in capillary chromatography (CEC).

Keywords

Star-shaped polymers Ov-POSS Molecular recognition Low cross-linking Dendrimers S-Amlodipine Chiral separation Capillary coating Imprinting effect 

Notes

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant No. 21775109).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2018_3151_MOESM1_ESM.doc (10.6 mb)
ESM 1 (DOC 10.6 MB)

References

  1. 1.
    Cieplak M, Kutner W (2016) Artificial biosensors: how can molecular imprinting mimic biorecognition? Trends Biotechnol 34:922–941CrossRefGoogle Scholar
  2. 2.
    Chen L, Wang X, Lu W, Wu X, Li J (2016) Molecular imprinting: perspectives and applications. Chem Soc Rev 45(8):2137–2211CrossRefGoogle Scholar
  3. 3.
    Bai LH, Chen XX, Huang YP, Zhang QW, Liu ZS (2013) Chiral separation of racemic mandelic acids by use of an ionic liquid-mediated imprinted monolith with a metal ion as self-assembly pivot. Anal Bioanal Chem 405(27):8935–8943CrossRefGoogle Scholar
  4. 4.
    Li ZY, Liu ZS, Zhang QW, Duan HQ (2007) Chiral separation by (S)-naproxen imprinted monolithic column with mixed functional monomers. Chin Chem Lett 18(3):322–324CrossRefGoogle Scholar
  5. 5.
    Sellergren B, Dauwe C, Schneider T (1997) Pressure-induced binding sites in molecularly imprinted network polymers. Macromolecules 30(8):2454–2459CrossRefGoogle Scholar
  6. 6.
    Sellergren B (1989) Molecular imprinting by noncovalent interactions. Enantioselectivity and binding capacity of polymers prepared under conditions favoring the formation of template complexes. Macromol Chem Phys 190:2703–2711CrossRefGoogle Scholar
  7. 7.
    Ban L, Zhao L, Deng BL, Huang YP, Liu ZS (2013) Preparation and characterization of imprinted monolith by atom transfer radical polymerization assisted with crowding agents. Anal Bioanal Chem 405(7):2245–2253CrossRefGoogle Scholar
  8. 8.
    Mignani S, Rodrigues J, Tomas H, Zablocka M, Shi X, Caminade AM, Majoral JP (2018) Dendrimers in combination with natural products and analogues as anti-cancer agents. Chem Soc Rev 47(2):514–532CrossRefGoogle Scholar
  9. 9.
    Gorain B, Tekade M, Kesharwani P, Iyer AK, Kalia K, Tekade RK (2017) The use of nanoscaffolds and dendrimers in tissue engineering. Drug Discov Today 22(4):652–664CrossRefGoogle Scholar
  10. 10.
    Tang R, Li Z (2017) Second-order nonlinear optical dendrimers and dendronized hyperbranched polymers. Chem Rec 17(1):71–89CrossRefGoogle Scholar
  11. 11.
    Wan J, Alewood PF (2016) Peptide-decorated dendrimers and their bioapplications. Angew Chem Int Ed Engl 55(17):5124–5134CrossRefGoogle Scholar
  12. 12.
    Caminade AM (2016) Inorganic dendrimers: recent advances for catalysis, nanomaterials, and nanomedicine. Chem Soc Rev 45(19):5174–5186CrossRefGoogle Scholar
  13. 13.
    Wang HM, Xu Q, Wang J, Du W, Liu FP, Hu XY (2018) Dendrimer-like amino-functionalized hierarchical porous silica nanoparticle: a host material for 2,4-dichlorophenoxyacetic acid imprinting and sensing. Biosens Bioelectron 100:105–114CrossRefGoogle Scholar
  14. 14.
    Pan MF, Fang GZ, Lu Y, Kong LJ, Yang YK, Wang S (2015) Molecularly imprinted biomimetic QCM sensor involving a poly(amidoamine) dendrimer as a functional monomer for the highly selective and sensitive determination of methimazole. Sens Actuators B Chem 207:588–595CrossRefGoogle Scholar
  15. 15.
    Prasad BB, Fatma S (2017) One monomer doubly imprinted dendrimer nanofilm modified pencil graphite electrode for simultaneouselectrochemical determination of norepinephrine and uric acid. Electrochim Acta 232:474–483CrossRefGoogle Scholar
  16. 16.
    Prasad BB, Madhuri R, Tiwari MP, Sharma PS (2010) Electrochemical sensor for folic acid based on a hyperbranched molecularly imprinted polymer-immobilized sol-gel-modified pencil graphite electrode. Sens Actuators B Chem 146(1):321–330CrossRefGoogle Scholar
  17. 17.
    Zimmerman SC, Wendland MS, Rakow NA, Zharov I, Suslick KS (2002) Synthetic hosts by monomolecular imprinting inside dendrimers. Nature 418(6896):399–403CrossRefGoogle Scholar
  18. 18.
    Ren JM, McKenzie TG, Fu Q, Wong EHH, Xu J, An Z, Shanmugam S, Davis TP, Boyer C, Qiao GG (2016) Star polymers. Chem Rev 116:6743–6836CrossRefGoogle Scholar
  19. 19.
    Ye Q, Zhou H, Xu J (2016) Cubic polyhedral oligomeric silsesquioxane based functional materials: synthesis, assembly, and applications. Chem Asian J 11(9):1322–1337CrossRefGoogle Scholar
  20. 20.
    Ghanbari H, Cousins BG, Seifalian AM (2011) A nanocage for nanomedicine: polyhedral oligomeric silsesquioxane (POSS). Macromol Rapid Commun 32(14):1032–1046CrossRefGoogle Scholar
  21. 21.
    Xu J, Song J (2010) High performance shape memory polymer networks based on rigid nanoparticle cores. PNAS 107:7652–7657CrossRefGoogle Scholar
  22. 22.
    Bagheri H, Soofi G, Javanmardi H, Karimi M (2018) A 3D nanoscale polyhedral oligomeric silsesquioxanes network for microextraction of polycyclic aromatic hydrocarbons. Microchim Acta 185(9):418CrossRefGoogle Scholar
  23. 23.
    Li F, Chen XX, Huang YP, Liu ZS (2015) Preparation of polyhedral oligomeric silsesquioxane based imprinted monolith. J Chromatogr A 1425:180–188CrossRefGoogle Scholar
  24. 24.
    Zhao QL, Zhou J, Zhang LS, Huang YP, Liu ZS (2016) Coatings of molecularly imprinted polymers based on polyhedral oligomeric silsesquioxane for open tubular capillary electrochromatography. Talanta 152:277–282CrossRefGoogle Scholar
  25. 25.
    Liu X, Zhong HY, Huang YP, Liu ZS (2013) Liquid crystal-based molecularly imprinted nanoparticles with low crosslinking for capillary electrochro- matography. J Chromatogr A 1309:84–89CrossRefGoogle Scholar
  26. 26.
    Wei ZH, Mu LN, Huang YP, Liu ZS (2012) Low crosslinking imprinted coatings based on liquid crystal for capillary electrochromatography. J Chromatogr A 1237:115–121CrossRefGoogle Scholar
  27. 27.
    Wei ZH, Wu X, Zhang B, Li R, Huang YP, Liu ZS (2011) Coatings of one monomer molecularly imprinted polymers for open tubular capillary electrochromatography. J Chromatogr A 1218(37):6498–6504CrossRefGoogle Scholar
  28. 28.
    Gong ZS, Duan LP, Tang AN (2015) Amino-functionalized silica nanoparticles for improved enantiomeric separation in capillary electrophoresis using carboxymethyl-β-cyclodextrin (CM-β-CD) as a chiral selector. Microchim Acta 182(7–8):1297–1304CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics (Theranostics), School of PharmacyTianjin Medical UniversityTianjinChina

Personalised recommendations