Abstract
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.
![](http://media.springernature.com/lw685/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Figa_HTML.png)
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.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig2_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig3_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig4_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig6_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-019-3723-z/MediaObjects/604_2019_3723_Fig7_HTML.jpg)
Similar content being viewed by others
References
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. https://doi.org/10.1039/c8nj04912b
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. https://doi.org/10.1002/jssc.201800853
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. https://doi.org/10.1016/j.talanta.2017.10.004
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. https://doi.org/10.1039/C2AN35923E
Kang J, Wistuba D, Schurig V (2002) Recent progress in enantiomeric separation by capillary electrochromatography. Electrophoresis 23(22–23):4005–4021. https://doi.org/10.1002/elps.200290015
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. https://doi.org/10.1002/jssc.201701234
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. https://doi.org/10.1016/j.chroma.2015.09.018
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. https://doi.org/10.1007/s00604-018-3163-1
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. https://doi.org/10.1007/s00604-019-3318-8
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. https://doi.org/10.1007/s00604-016-2014-1
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. https://doi.org/10.1039/c7an01426k
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. https://doi.org/10.1016/j.talanta.2014.06.032
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. https://doi.org/10.1016/j.chroma.2016.03.075
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. https://doi.org/10.1016/j.chroma.2013.01.112
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. https://doi.org/10.1016/j.aca.2016.02.043
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. https://doi.org/10.1016/j.jare.2014.10.004
Wang K, **g R, Song H, Zhang J, Yan W, Guo S (2011) Biocompatibility of graphene oxide. Nanoscale Res Lett 6(1):8. https://doi.org/10.1007/s11671-010-9751-6
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. https://doi.org/10.1038/nchem.907
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. https://doi.org/10.1016/j.talanta.2017.10.014
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. https://doi.org/10.1002/elps.201300046
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. https://doi.org/10.1016/j.trac.2017.11.008
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. https://doi.org/10.1002/elps.201400458
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. https://doi.org/10.1002/elps.201200497
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. https://doi.org/10.1016/j.aca.2012.05.052
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. https://doi.org/10.1007/s00216-014-8137-5
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. https://doi.org/10.1016/j.chroma.2019.03.032
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. https://doi.org/10.1016/j.chroma.2018.10.008
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. https://doi.org/10.1016/j.chroma.2017.01.025
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. https://doi.org/10.1016/j.chroma.2015.04.039
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. https://doi.org/10.1016/j.chroma.2014.10.067
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. https://doi.org/10.1016/j.chroma.2017.11.068
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. https://doi.org/10.1016/j.chroma.2017.06.007
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. https://doi.org/10.1016/j.chroma.2013.10.093
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. https://doi.org/10.1016/j.chroma.2018.01.024
Acknowledgements
This work was supported by the Natural Science Foundation of Jiangsu Province (Program No.: BK20141353).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
The author(s) declare that they have no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 417 kb)
Rights and permissions
About this article
Cite this article
Zhao, S., Yu, T., Du, Y. et al. 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. Microchim Acta 186, 636 (2019). https://doi.org/10.1007/s00604-019-3723-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00604-019-3723-z