Separation of Inorganic Anions Using Methacrylate-Based Monolithic Column Modified with Trimethylamine in Ion Chromatography Capillary System

Abstract

Methacrylate-based monolithic column was prepared in fused-silica capillary (80 0.32 mm i.d.) by in situ polymerizetion reaction using glycidyl methacrylate as monomer; ethylene dimethacrylate as crosslinker; 1-propanol, 1,4-butanediol, and water as porogenic solvents. The monolith matrix was modified with trimethylamine to create strong anion exchanger via ring opening reaction of epoxy groups. The morphology of the monolithic column was studied by using Scanning Electron Microscope (SEM). This column had good mechanical stability and permeability. The effects of various mobile phases for separation of inorganic anions were investigated. Iodate, bromate, nitrite, bromide, and nitrate were separated within 11 min using100 mMpotassium chloride as mobile phase and detected at 210 nm. This method showed good precision of retention time, acceptable linearity and good sensitivity. Under the optimum condition, the RSD of the retention time was in the range of 1.09%-1.75% (n = 6). The calibration curve showed linear relationships between the peak area and the concentration. The limits of detection (LOD) and the limits of quantitation (LOQ) were between 0.08-0.18 mM and 0.26-0.61 mM, respectively. This method was applied to the determination of inorganic anions in tap water and ground water samples.

Share and Cite:

F. Mairizki, A. Rahmah,  . Hilma, R. Putri, R. Zein, L. Lim, T. Takeuchi and E. Munaf, "Separation of Inorganic Anions Using Methacrylate-Based Monolithic Column Modified with Trimethylamine in Ion Chromatography Capillary System," American Journal of Analytical Chemistry, Vol. 4 No. 9, 2013, pp. 451-456. doi: 10.4236/ajac.2013.49057.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] A. Sedyohutomo, H. Suzuki and C. Fujimoto, “Determination of Inorganic Anions by Capillary Ion-Exchange Chromatography Using Polyethylenimine-coated Octadecyl-Bonded Phases,” Analytical Sciences, Vol. 28, No. 6, 2012, pp. 625-629. doi:10.2116/analsci.28.625
[2] R. Zein, E. Munaf, T. Takeuchi and T. Miwa, “Microcolumn Ion Chromatography of Inorganic UV-Absorbing Anions Using Bovine Serum Albumin as Stationary Phases,” Analytica Chimica Acta, Vol. 335, No. 3, 1996, pp. 261-266. doi:10.1016/S0003-2670(96)00383-2
[3] E. Munaf, R. Zein, T. Takeuchi and T. Miwa, “Microcolumn Ion Chromatography of Inorganic Anions Using Bovine Serum Albumin Stationary Phase with Indirect Photometric Detection,” Chromatographia, Vol. 43, No. 5-6, 1996, pp. 304-308. doi:10.1007/BF02271000
[4] T. Takeuchi, Safni, T. Miwa, Y. Hashimoto and H. Moriyama, “Ion Chromatography Using Anion Exchangers Modified with Heparin,” Analusis, Vol. 26, No. 2, 1998, pp. 61-64. doi:10.1051/analusis:1998111
[5] M. G. Kiseleva, P. A. Kebets and P. N. Nesterenko, “Simultaneous Ion Chromatographic Separation of Anions and Cations on Poly(aspartic acid) Functionalized Silica,” Analyst, Vol. 126, No. 12, 2001, pp. 2119-2123. doi:10.1039/b106283m
[6] M. Amin, L. W. Lim and T. Takeuchi, “Peak Parking Technique for The Simultaneous Determination of Anions and Cations,” Analytical and Bioanalytical Chemistry, Vol. 381, No. 7, 2005, pp. 1426-1431. doi:10.1007/s00216-005-3073-z
[7] Z. A. AlOthman, A. Aqel, H. A. Al Abdelmoneim, A.Y. Badjah-Hadj-Ahmed and A. A. Al-Warthan, “Preparation and Evaluation of Long Chain Alkyl Methacrylate Monoliths for Capillary Chromatography,” Chromatographia, Vol. 74, No. 1, 2011, pp. 1-8.
[8] A. Sabarudin, J. Huang, S. Shu, S. Sakagawa and T. Umemura, “Preparation of Methacrylate-based AnionExchange Monolithic Microbore Column for Chromatographic Separation of DNA Fragments and Oligonucleotides,” Analytica Chimica Acta, Vol. 736, 2012, pp. 108-114. doi:10.1016/j.aca.2012.05.039
[9] N. Wang, S. He and Y. Zhu, “Low-Level Bromate Analysis by Ion Chromatography on a Polymethacrylate-based Monolithic Column Followed by a Post-Column Reaction,” European Food Research and Technology, Vol. 235, No. 4, 2012, pp. 685-692. doi:10.1007/s00217-012-1800-1
[10] T. A. E. Jakschitz, C.W. Huck, S. Lubbad and G. K. Bonn, “Monolithic Poly[(trimethylsilyl-4-methylstyrene)-co-bis (4-vinylbenzyl) dimethylsilane] Stationary Phases for the Fast Separation of Proteins and Oligonucleotides,” Journal of Chromatography A, Vol. 1147, No. 1, 2007, pp. 53-58. doi:10.1016/j.chroma.2007.02.078
[11] P. Pruim, M. Ohman, Y. Huo, P. J. Schoenmakers and W.Th. Kok, “Methacrylate Monolithic Capillary Columns for Gradient Peptide Separations,” Journal of Chromatography A, Vol. 1208, No. 1-2, 2008, pp. 109-115. doi:10.1016/j.chroma.2008.08.069
[12] B. Gu, J. M. Armenta and M. L. Lee, “Preparation and Evaluation of Poly(polyethylene glycol methylether acrylate-co-polyethylene glycol diacrylate) Monolith for Protein Analysis,” Journal of Chromatography A, Vol. 1079, No. 1-2, 2005, pp. 382-391. doi:10.1016/j.chroma.2005.02.088
[13] Y. Li, B. Gu, H. D. Tolley and M. L. Lee, “Preparation of Polymeric Monoliths by Copolymerization of Acrylate Monomers with Amine Functionalities for Anion-exchange Capillary Liquid Chromatography of Proteins,” Journal of Chromatography A, Vol. 1216, No. 29, 2009, pp. 5525-5532. doi:10.1016/j.chroma.2009.05.037
[14] J. Krenkova, A. Gargano, N. A. Lacher, J. M. Schneiderheinze and F. Svec, “High Binding Capacity Surface Grafted Monolithic Columns for Cation Exchange Chromatography of Proteins and Peptides,” Journal of Chromatography A, Vol. 1216, No. 40, 2009, pp. 6824-6830. doi:10.1016/j.chroma.2009.08.031
[15] X. Chen, H. D. Tolley and M. L. Lee, “Monolithic Capillary Columns Synthesized from a Single Phosphate-containing Dimethacrylate Monomer for Cation-exchange Chromatography of Peptides and Proteins,” Journal of Chromatography A, Vol. 1218, No. 28, 2011, pp. 4322-4331. doi:10.1016/j.chroma.2011.04.074
[16] C. Gu, L. Lin, X. Chen, J. Jia, J. Ren and N. Fang, “Fabrication of a Poly(styrene-octadecene-divinylbenzene) Monolithic Column and Its Comparison with a Poly(styrene-divinylbenzene) Monolithic Column for The Separation of Proteins,” Journal of Separation Science, Vol. 30, No. 7, 2007, pp. 1005-1012. doi:10.1002/jssc.200600397
[17] T. Hirano, S. Kitagawa and H. Ohtani, “Methacrylate-Ester-Based Reversed Phase Monolithic Columns for High Speed Separation Prepared by Low Temperature UV Photo-polymerization,” Analytical Sciences, Vol. 25, No. 9, 2009, pp. 1107-1113. doi:10.2116/analsci.25.1107
[18] I. Nischang and O. Bruggemann, “On the Separation of Small Molecules by Means of Nano-Liquid Chromatography with Methacrylate-Based Macroporous Polymer Monoliths,” Journal of Chromatography A, Vol. 1217, No. 33, 2010, pp. 5389-5397. doi:10.1016/j.chroma.2010.06.021
[19] A. Svobodova, T. Krizek, J. Sirc, P. Salek, E. Tesarova, P. Coufal and K. Stulik, “Monolithic Columns Based on a Poly(styrene-divinylbenzene-methacrylic acid) Copolymer for Capillary Liquid Chromatography of Small Organic Molecules,” Journal of Chromatography A. Vol. 1218, No. 11, 2011, pp. 1544-1547. doi:10.1016/j.chroma.2011.01.042
[20] A. Suzuki, L. W. Lim and T. Takeuchi, “Rapid Separation of Inorganic Anions by Capillary Ion Chromatography Using Monolithic Silica Columns Modified with Dilauryldimethylammonium Ion,” Analytical Sciences, Vo. 23, No. 9, 2007, pp. 1081-1084. doi:10.2116/analsci.23.1081
[21] M. Takahashi, T. Hirano, S. Kitagawa and H. Ohtani, “Separation of Small Inorganic Anions Using Methacrylate-based anion-exchange Monolithic Column Prepared by Low Temperature UV Photo-polymerization,” Journal of Chromatography A, Vol. 1232, 2012, pp. 123-127. doi:10.1016/j.chroma.2011.10.070
[22] M. Motokawa, H. Kobayashi, N. Ishizuka, H. Minakuchi, K. Nakanishi, H. Jinnai, K. Hosoya, T. Ikegami and N. Tanaka, “Monolithic Silica Columns with Various Skeleton Sizes and Through-pore Sizes for Capillary Liquid Chromatography,” Journal of Chromatography A, Vol. 961, No. 1, 2002, pp. 53-63. doi:10.1016/S0021-9673(02)00133-4
[23] K. M. Glenn, C. A. Lucy and P. R. Haddad, “Ion Chromatography on a Latex-coated Silica Monolith Column, Journal of Chromatography A, Vol. 1155, No. 1, 2007, pp. 8-14. doi:10.1016/j.chroma.2007.01.098
[24] M. Rogeberg, S. R. Wilson, H. Malerod, E. Lundanes, N. Tanaka and T. Greibrokk, “High Efficiency, High Temperature Separations on Silica Based Monolithic Columns,” Journal of Chromatography A, Vol. 1218, No. 41, 2011, pp. 7281-7288. doi:10.1016/j.chroma.2011.08.049
[25] R. Shediac, S. M. Ngola, D. J. Throckmorton, D. S. Anex, T. J. Shepodd and A. K. Singh, “Reversed-phase Electrochromatography of Amino Acids and Peptides Using Porous Polymer Monoliths,” Journal of Chromatography A, Vol. 925, No. 1-2, 2001, pp. 251-263. doi:10.1016/S0021-9673(01)01036-6
[26] C. J. Evenhuis, W. Buchberger, E. F. Hilder, K. J. Flook, C. A. Pohl, P. N. Nesterenko and P. R. Haddad, “Separation of Inorganic Anions on a High Capacity Porous Polymeric Monolithic Column and Application to Direct Determination of Anions in Seawater,” Journal of Separation Science, Vol. 31, No. 14, 2008, pp. 2598-2604. doi:10.1002/jssc.200800205
[27] D. Moravcova, P. Jandera, J. Urban and J. Planeta, “Comparison of Monolithic Silica and Polymethacrylate Capillary Columns for LC,” Journal of Separation Science, Vol. 27, No. 10-11, 2004, pp. 789-800. doi:10.1002/jssc.200401778
[28] T. Nakaza, A. Kobayashi, T. Hirano, S. Kitagawa and H. Ohtani, “Determination of Monomer Conversion in Methacrylate-based Polymer Monoliths Fixed in a Capillary Column by Pyrolysis-Gas Chromatography,” Analytical Sciences, Vol. 28, No. 9, 2012, pp. 917-920. doi:10.2116/analsci.28.917
[29] Y. Zhong, W. Zhou, P. Zhang and Y. Zhu, “Preparation, Characterization, and Analytical Applications of a Novel Polymer Stationary Phase with Embedded or Grafted Carbon Fibers,” Talanta, Vol. 82, No. 4, 2010, pp. 1439-1447. doi:10.1016/j.talanta.2010.07.019
[30] Y. Huo, P. J. Schoenmakers and W. Th. Kok, “Efficiency of Methacrylate Monolithic Columns in Reversed-phase Liquid Chromatographic Separations,” Journal of Chromatography A, Vol. 1175, No. 1, 2007, pp. 81-88. doi:10.1016/j.chroma.2007.10.048
[31] D. Moravcova, P. Jandera, J. Urban and J. Planeta, “Characterization of Polymer Monolithic Stationary Phases for Capillary HPLC,” Journal of Separation Science, Vol. 26, No. 11, 2003, pp. 1005-1016. doi:10.1002/jssc.200301498
[32] X. Shu, L. Chen, B. Yang and Y. Guan, “Preparation and Characterization of Long Methacrylate Monolithic Column for Capillary Liquid Chromatography,” Journal of Chromatography A, Vol. 1052, No. 1-2, 2004, pp. 205-209. doi:10.1016/j.chroma.2004.08.099
[33] A. Bruchet, V. Dugas, C. Mariet, F. Goutelard and J. Randon, “Improved Chromatographic Performances of Glycidyl Methacrylate Anion-exchange Monolith for Fast Nano-ion Exchange Chromatography,” Journal of Separation Science, Vol. 34, No. 16-17, 2011, pp. 2079-2087.
[34] Y. Fan, Y. Q. Feng, S. L. Da and Z. G. Shi, “Poly (methacrylic acid-ethylene glycol dimethacrylate) Monolithic Capillary for In-tube Solid Phase Microextraction Coupled to High Performance Liquid Chromatography and Its Application to Determination of Basic Drugs in Human Serum,” Analytica Chimica Acta, Vol. 523, No. 2, 2004, pp. 251-258. doi:10.1016/j.aca.2004.07.052
[35] M. Wu, R. Wu, R. Li, H. Qin, J. Dong, Z. Zhang and H. Zou, “Polyhedral Oligomeric Silsesquioxane as a Cross-Linker for Preparation of Inorganic-Organic Hybrid Monolithic Columns,” Analytical Chemistry, Vol. 82, No. 13, 2010, pp. 5447-5454. doi:10.1021/ac1003147

Copyright © 2021 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.