Abstract
This work shows that the metal organic framework (MOF) HKUST-1 of type Cu3(BTC)2 (also referred to as MOF-199; a face-centered-cubic MOF containing nanochannels) is a most viable coating for use in enantioseparation in capillary electrochromatography (CEC). A HKUST-1 modified capillary was prepared and characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, elemental analysis and thermogravimetric analysis. CEC-based enantioseparation of the basic drugs propranolol (PRO), esmolol (ESM), metoprolol (MET), amlodipine (AML) and sotalol (SOT) was performed by using carboxymethyl-β-cyclodextrin as the chiral selector. Compared with a fused-silica capillary, the resolutions are improved (ESM: 1.79; MET: 1.80; PRO: 4.35; SOT: 1.91; AML: 2.65). The concentration of chiral selector, buffer pH value, applied voltage and buffer concentration were optimized, and the reproducibilities of the migration times and Rs values were evaluated.
Similar content being viewed by others
Change history
15 August 2019
The published version of this article, unfortunately, contains error. The author found out that the given name interchanged with the family name. The second author’s family name should be “Yu” and the first name should be “Tao”. Given in this article is the correct author name.
References
Guihen E, Glennon JD (2004) Recent highlights in stationary phase design for open-tubular capillary electrochromatography. J Chromatogr A 1044:67–81
Liu Z, Otsuka K, Terabe S (2002) Evaluation of extended light path capillary and etched capillary for use in open tubular capillary electrochromatography. J Chromatogr A 961:285–291
Yang L, Guihen E, Holmes JD, Loughran M, O'Sulliva GP, Glennon JD (2005) Gold nanoparticle-modified etched capillaries for open-tubular capillary electrochromatography. Anal Chem 77:1840–1846
Gong Z, Duan L, Tang A (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 182:1297–1304
Liu Z, Du Y, Feng Z (2018) Enantioseparation of drugs by capillary electrochromatography using a stationary phase covalently modified with graphene oxide. Microchim Acta 184:583–593
Zhang Q, Du Y, Du S (2014) Evaluation of ionic liquids-coated carbon nanotubes modified chiral separation system with chondroitin sulfate E as chiral selector in capillary electrophoresis. J Chromatogr A 1339:185–191
Li L, Yang F, Wang H, Yan X (2013) Metal-organic framework poly methylmethacrylate composites for open-tubular capillary electrochromatography. J Chromatogr A 1316:97–103
Furukawa H, Cordova KE, O'Keeffe M, Yaghi OM (2013) The chemistry and applications of metal-organic frameworks. Science 341:1230444
Zhou H, Long J, Yaghi OM (2012) Introduction to metal-organic frameworks. Chem Rev 112:673–674
Huang H, Lin C, Wu C, Cheng Y, Lin C (2013) Metal organicframework-organic polymer monolith stationary phases for capillary electrochromatography and nano-liquid chromatography. Anal Chim Acta 779:96–103
Li J, Sculley J (2011) Zhou H metal-organic frameworks for separations. Chem Rev 112:869–932
Yu Y, Ren Y, Shen W, Deng H, Gao Z (2013) Applications of metal-organicframeworks as stationary phases in chromatography. TrAC Trends Anal Chem 50:33–41
Yang C, Yan X (2011) Metal-organic framework MIL-101 (Cr) for high-performance liquid chromatographic separation of substitutedaromatics. Anal Chem 83:7144–7150
Liu S, Yang C, Wang S, Yan X (2012) Metal-organic frameworks for reverse-phase high-performance liquid chromatography. Analyst 137:816–818
Yu Y, Ren Y, Shen W, Deng H, Gao Z (2013) Applications of metal-organic frame-works as stationary phases in chromatography. TrAC Trends Anal Chem 50:33–41
Zhang K, Cai S, Yan Y, He Z, Lin H, Huang X, Zheng R, Fan J, Zhang W (2017) Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography. J Chromatogr A 1519:100–109
Chen B, Liang C, Yang J, Contreras DS, Clancy YL, Lobkovsky EB, Yaghi OM, Dai S (2006) A microporous metal-organic framework forgas-chromatographic separation of alkanes. Angew Chem 118:1418–1421
Ye N, Ma J, An J, Li J, Cai Z, Zong H (2016) Separation of amino acid enantiomers by a capillary modified with a metal-organic framework. RSC Adv 6:41587–41593
Ma J, Ye N, Li J (2016) Covalent bonding of homochiral metal-organic framework in capillaries for stereoisomer separation by capillary electrochromatography. Electrophoresis 37:601–608
Yu L, Yang C, Yan X (2014) Room temperature fabrication of post-modified zeolitic imidazolate framework-90 as stationary phase for open-tubular capillary electrochromatography. J Chromatogr A 1343:188–194
Tang P, Bao T, Chen Z (2016) Novel Zn-based MOFs stationary phase with large pores for capillary electrochromatography. Electrophoresis 37:2181–2189
Yang S, Ye F, Lv Q, Zhang C, Shen S, Zhao S (2014) Incorporation of metal-organic framework HKUST-1 into porous polymer monolithic capillary columns to enhance the chromatographic separation of small molecules. J Chromatogr A 1360:143–149
El-Hankari S, Huo J, Ahmed A, Zhang H, Bradshaw D (2014) Surface etching of HKUST-1 promoted via supramolecular interactions for chromatography. J Mater Chem A 2:13479–13485
Münch AS, Mertens FO (2012) HKUST-1 as an open metal site gas chromatographic stationary phase-capillary preparation, separation of small hydrocarbons and electron donating compounds, determination of thermodynamic data. J Mater Chem 22:10228–10234
Ahmed A, Forster M, Clowes R, Bradshaw D, Myers P, Zhang H (2013) Silica SOS@HKUST-1 composite microspheres as easily packed stationary phases for fast separation. J Mater Chem A 1:3276–3286
Bao T, Zhang J, Zhang W, Chen Z (2015) Growth of metal-organic framework HKUST-1 in capillary using liquid-phase epitaxy for open-tubular capillary electrochromatography and capillary liquid chromatography. J Chromatogr A 1381:239–246
Prestipino C, Regli L, Vitillo J, Bonino F, Damin A, Lamberti C, Zecchina A, Solari P, Kongshaug K, Bordiga S (2006) Local structure of framework cu(II) in HKUST-1metallorganic framework: spectroscopic characterization upon activation and interaction with adsorbates. Chem Mater 18:1337–1346
Biemmi E, Scherb C, Bein T (2007) Oriented growth of the metal organic framework Cu3(BTC)2(H2O)3·xH2O tunable with functionalized self-assembled mono-layers. J Am Chem Soc 129:8054–8055
Shekhah O, Wang H, Kowarik S, Schreiber F, Paulus M, Tolan M, Sterne-mann C, Evers F, Zacher D, Fischer RA (2007) Step-by-step route for the synthesis ofmetal-organic frameworks. J Am Chem Soc 129:15118–15119
Xu Y, Lv W, Ren C, Niu X, Chen H, Chen X (2017) In situ preparation of multilayer coated capillary column with HKUST-1 for separation of neutral small organic molecules by open tubular capillary electrochromatography. J Chromatogr A 1532:223–231
Qu Q, Si Y, Xuan H, Zhang K, Chen X, Ding Y, Feng S, Xu H (2017) A nanocrystalline metal organic framework confined in the fibrous pores of core-shell silica particles for improved HPLC separation. Microchem Acta 6149:1–8
Rowsell JLC, Yaghi OM (2006) Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks. J Am Chem Soc 128:1304–1315
Buschmann HJ, Knittel D, Schollmeyer E (2001) New textile applications of cyclodextrins. J Incl Phenom Macro 40:169–172
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 329 kb)
Rights and permissions
About this article
Cite this article
Sun, X., Tao, Y., Du, Y. et al. Metal organic framework HKUST-1 modified with carboxymethyl-β-cyclodextrin for use in improved open tubular capillary electrochromatographic enantioseparation of five basic drugs. Microchim Acta 186, 462 (2019). https://doi.org/10.1007/s00604-019-3584-5
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00604-019-3584-5