Microchimica Acta

, 186:636 | Cite as

An organic polymer monolith modified with an amino acid ionic liquid and graphene oxide for use in capillary electrochromatography: application to the separation of amino acids, β-blockers, and nucleotides

  • Shiyuan Zhao
  • Tao YuEmail author
  • Yingxiang DuEmail author
  • Xiaodong Sun
  • Zijie Feng
  • Xiaofei Ma
  • Wen Ding
  • Cheng Chen
Original Paper


The preparation of an organic polymer monolithic column modified with an amino acid ionic liquid and graphene oxide (AAIL-GO) and its application to capillary electrochromatography (CEC) was described. The AAIL tetramethylammonium-L-arginine was bonded to a monolithic column that was previously modified with graphene oxide by using an hydrochloride/N-hydroxysuccinimide coupling reaction. The morphology of a poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith was examined by scanning electron microscopy. The incorporation of AAIL and graphene oxide was detected by infrared spectroscopy and elemental analysis. The resulting monolithic column produced a strong and stable electroosmotic flow from the anode to the cathode in the pH range from 3 to 9. Compared with a column modified with AAIL or graphene oxide only, the AAIL-GO-modified column has a better separation ability for amino acids, β-blockers, and nucleotides (the resolution of three amino acids: 2.231 and 2.036, β-blockers: 2.779 and 2.470 and nucleotides: 8.345 and 3.321). Molecular modeling was applied to demonstrate the separation mechanism of small molecules which showed a good support for experimental results.

Graphical abstract

Schematic representation of capillary electrochromatography (CEC) systems with an amino acid ionic liquid-graphene oxide modified organic polymer monolithic column as stationary phases for separation of amino acids, β-blockers, and nucleotides.


Molecular modeling Splitting mechanism Tetramethylammonium-L-arginine Ionic liquid Small molecule Glycidyl methacrylate Monolithic column Nanoparticles 



This work was supported by the Natural Science Foundation of Jiangsu Province (Program No.: BK20141353).

Compliance with ethical standards

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

Supplementary material

604_2019_3723_MOESM1_ESM.docx (418 kb)
ESM 1 (DOCX 417 kb)


  1. 1.
    Tang Y, Cui X, Zhang Y, Ji Y (2019) Preparation and evaluation of a polydopamine-modified capillary silica monolith for capillary electrochromatography. New J Chem 43(2):1009–1016. CrossRefGoogle Scholar
  2. 2.
    Stege PW, Forlin GL, Gásquez JA, Sombra LL (2019) Open-tubular capillary electrochromatography for the simultaneous determination of cadmium and copper in plants. J Sep Sci 42(7):1459–1467. CrossRefPubMedGoogle Scholar
  3. 3.
    Tang P, Chen Z (2018) Capillary electrochromatography using knitted aromatic polymer as the stationary phase for the separation of small biomolecules and drugs. Talanta 178:650–655. CrossRefPubMedGoogle Scholar
  4. 4.
    Lu J, Ye F, Zhang A, Chen X, Wei Y, Zhao S (2012) Preparation and evaluation of ionic liquid-gold nanoparticles functionalized silica monolithic column for capillary electrochromatography. Analyst 137(24):5860. CrossRefPubMedGoogle Scholar
  5. 5.
    Kang J, Wistuba D, Schurig V (2002) Recent progress in enantiomeric separation by capillary electrochromatography. Electrophoresis 23(22–23):4005–4021. CrossRefPubMedGoogle Scholar
  6. 6.
    Noel Echevarria R, Carrasco-Correa EJ, Keunchkarian S, Reta M, Herrero-Martinez JM (2018) Photografted methacrylate-based monolithic columns coated with cellulose tris (3, 5-dimethylphenylcarbamate) for chiral separation in CEC. J Sep Sci 41(6):1424–1432. CrossRefPubMedGoogle Scholar
  7. 7.
    Dixit S, Park JH (2015) Enantioseparation of basic chiral drugs on a carbamoylated erythromycin-zirconia hybrid monolith using capillary electrochromatography. J Chromatogr A 1416:129–136. CrossRefPubMedGoogle Scholar
  8. 8.
    Sun X, Du Y, Zhao S, Huang Z, Feng Z (2019) Enantioseparation of propranolol, amlodipine and metoprolol by electrochromatography using an open tubular capillary modified with β-cyclodextrin and poly (glycidyl methacrylate) nanoparticles. Microchim Acta 186(2):128. CrossRefGoogle Scholar
  9. 9.
    Yang X, Sun X, Feng Z, Du Y, Chen J, Ma X, Li X (2019) Open-tubular capillary electrochromatography with β-cyclodextrin-functionalized magnetic nanoparticles as stationary phase for enantioseparation of dansylated amino acids. Microchim Acta 186(4):244. CrossRefGoogle Scholar
  10. 10.
    Liu Z, Du Y, Feng Z (2016) Enantioseparation of drugs by capillary electrochromatography using a stationary phase covalently modified with graphene oxide. Microchim Acta 184(2):583–593. CrossRefGoogle Scholar
  11. 11.
    Ganewatta N, Rassi ZE (2017) Monolithic capillary columns consisting of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) and their diol derivatives with incorporated hydroxyl functionalized multiwalled carbon nanotubes for reversed-phase capillary electrochromatography. Analyst 143(1):270–279. CrossRefPubMedGoogle Scholar
  12. 12.
    Mayadunne E, El Rassi Z (2014) Facile preparation of octadecyl monoliths with incorporated carbon nanotubes and neutral monoliths with coated carbon nanotubes stationary phases for HPLC of small and large molecules by hydrophobic and π–π interactions. Talanta 129:565–574. CrossRefPubMedGoogle Scholar
  13. 13.
    AydoğanC ERZ (2016) Monolithic stationary phases with incorporated fumed silica nanoparticles. Part I. Polymethacrylate-based monolithic column with incorporated bare fumed silica nanoparticles for hydrophilic interaction liquid chromatography. J Chromatogr A 1445:55–61. CrossRefGoogle Scholar
  14. 14.
    Liu YX, Chen YZ, Yang HH, Nie LH, Yao SZ (2013) Cage-like silica nanoparticles-functionalized silica hybrid monolith for high performance capillary electrochromatography via “one-pot” process. J Chromatogr A 1283:132–139. CrossRefPubMedGoogle Scholar
  15. 15.
    Vergara-Barberán M, Lerma-García MJ, Simó-Alfonso EF, Herrero-Martínez JM (2016) Solid-phase extraction based on ground methacrylate monolith modified with gold nanoparticles for isolation of proteins. Anal Chim Acta 917:37–43. CrossRefPubMedGoogle Scholar
  16. 16.
    Terborg L, Masini JC, Lin M, Lipponen K, Riekolla ML, Svec F (2015) Porous polymer monolithic columns with gold nanoparticles as an intermediate ligand for the separation of proteins in reverse phase-ion exchange mixed mode. J Adv Res 6(3):441–448. CrossRefPubMedGoogle Scholar
  17. 17.
    Wang K, Jing R, Song H, Zhang J, Yan W, Guo S (2011) Biocompatibility of graphene oxide. Nanoscale Res Lett 6(1):8. CrossRefPubMedGoogle Scholar
  18. 18.
    Loh KP, Bao Q, Eda G, Chhowalla M (2010) Graphene oxide as a chemically tunable platform for optical applications. Nat Chem 2(12):1015–1024. CrossRefPubMedGoogle Scholar
  19. 19.
    Li X, Zhang L, Wang C, Huang Y, Liu Z (2018) Green synthesis of monolithic column incorporated with graphene oxide using room temperature ionic liquid and eutectic solvents for capillary electrochromatography. Talanta 178:763–771. CrossRefPubMedGoogle Scholar
  20. 20.
    Liu XL, Liu X, Liu X, Guo LP, Yang L, Wang ST (2013) Graphene oxide and reduced graphene oxide as novel stationary phases via electrostatic assembly for open-tubular capillary electrochromatography. Electrophoresis 34(13):1869–1876. CrossRefPubMedGoogle Scholar
  21. 21.
    Liang X, Hou X, Chan JHM, Guo Y, Hilder EF (2018) The application of graphene-based materials as chromatographic stationary phases. Trac-trend Anal Chem 98:149–160. CrossRefGoogle Scholar
  22. 22.
    Lin Z, Wang J, Yu R, Yin X, He Y (2015) Incorporation of graphene oxide nanosheets into boronate-functionalized polymeric monolith to enhance the electrochromatographic separation of small molecules. Electrophoresis 36(4):596–606. CrossRefPubMedGoogle Scholar
  23. 23.
    Wang C, de Rooy S, Lu CF, Fernand V, Moore L Jr, Berton P, Warner IM (2013) An immobilized graphene oxide stationary phase for open-tubular capillary electrochromatography. Electrophoresis 34(8):1197–1202. CrossRefPubMedGoogle Scholar
  24. 24.
    Arrua RD, Talebi M, Causon TJ, Hilder EF (2012) Review of recent advances in the preparation of organic polymer monoliths for liquid chromatography of large molecules. Anal Chim Acta 738:1–12. CrossRefPubMedGoogle Scholar
  25. 25.
    Liu C, Deng Q, Fang G, Feng X, Qian H, Wang S (2014) Facile preparation of organic-inorganic hybrid polymeric ionic liquid monolithic column with a one-pot process for protein separation in capillary electrochromatography. Anal Bioanal Chem 406(28):7175–7183. CrossRefPubMedGoogle Scholar
  26. 26.
    Li M, Lei X, Huang Y, Guo Y, Zhang B, Tang F, Wu X (2019) Ternary thiol-ene photopolymerization for facile preparation of ionic liquid-functionalized hybrid monolithic columns based on polyhedral oligomeric silsesquioxanes. J Chromatogr A 1597:167–178. CrossRefPubMedGoogle Scholar
  27. 27.
    Mao Z, Bao T, Li Z, Chen Z (2018) Ionic liquid-copolymerized monolith incorporated with zeolitic imidazolate framework-8 as stationary phases for enhancing reversed phase selectivity in capillary electrochromatography. J Chromatogr A 1578:99–105. CrossRefPubMedGoogle Scholar
  28. 28.
    Miao C, Bai R, Xu S, Hong T, Ji Y (2017) Carboxylated single-walled carbon nanotube-functionalized chiral polymer monoliths for affinity capillary electrochromatography. J Chromatogr A 1487:227–234. CrossRefPubMedGoogle Scholar
  29. 29.
    Gao X, Mo R, Ji Y (2015) Preparation and characterization of tentacle-type polymer stationary phase modified with graphene oxide for open-tubular capillary electrochromatography. J Chromatogr A 1400:19–26. CrossRefPubMedGoogle Scholar
  30. 30.
    Yuan H, Zhang L, Zhang Y (2014) Preparation of high efficiency and low carry-over immobilized enzymatic reactor with methacrylic acid–silica hybrid monolith as matrix for on-line protein digestion. J Chromatogr A 1371:48–57. CrossRefPubMedGoogle Scholar
  31. 31.
    Li J, Yu T, Xu G, Du Y, Liu Z, Feng Z, Yang X, Liu J (2017) Synthesis and application of ionic liquid functionalized β-cyclodextrin, mono-6-deoxy-6-(4-amino-1,2,4-triazolium)-β-cyclodextrin chloride, as chiral selector in capillary electrophoresis. J Chromatogr A 1559:178–185. CrossRefPubMedGoogle Scholar
  32. 32.
    Yang X, Du Y, Feng Z, Liu Z, Li J (2018) Establishment and molecular modeling study of maltodextrin-based synergistic enantioseparation systems with two new hydroxy acid chiral ionic liquids as additives in capillary electrophoresis. J Chromatogr A 1559:170–177. CrossRefPubMedGoogle Scholar
  33. 33.
    Xu L, Cui P, Wang D, Tang C, Dong L, Zhang C, Duan HQ, Yang VC (2014) Preparation and characterization of lysine-immobilized poly (glycidyl methacrylate) nanoparticle-coated capillary for the separation of amino acids by open tubular capillary electrochromatography. J Chromatogr A 1323:179–183. CrossRefPubMedGoogle Scholar
  34. 34.
    Liu X, Sun S, Nie R, Ma J, Qu Q, Yang L (2018) Highly uniform porous silica layer open-tubular capillary columns produced via in-situ biphasic sol–gel processing for open-tubular capillary electrochromatography. J Chromatogr A 1538:86–93. CrossRefPubMedGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Shiyuan Zhao
    • 1
    • 2
  • Tao Yu
    • 1
    • 2
    Email author
  • Yingxiang Du
    • 1
    • 2
    Email author
  • Xiaodong Sun
    • 1
    • 2
  • Zijie Feng
    • 1
    • 2
  • Xiaofei Ma
    • 1
    • 2
  • Wen Ding
    • 1
    • 2
  • Cheng Chen
    • 1
    • 2
  1. 1.Key Laboratory of Drug Quality Control and Pharmacovigilance (Ministry of Education)China Pharmaceutical UniversityNanjingPeople’s Republic of China
  2. 2.State Key Laboratory of Natural MedicinesChina Pharmaceutical UniversityNanjingPeople’s Republic of China

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