AJAC  Vol.4 No.1 , January 2013
Silica Gel Supported Hydrophobic Ionic Liquid for Selective Extraction and Determination of Coumarin

In this study, a modified silica gel surface with a hydrophobic ionic liquid (SG-1,10-PhenanNTf2) was used as an adsorbent for a selective extraction of coumarin prior to its determination by use of high performance liquid chromatography. Results demonstrated that SG-1,10-PhenanNTf2 phase had a good adsorption capacity up to 85.29 mg?g?1, high selectivity, good site accessibility and fast binding kinetics toward coumarin. The adsorption capacity for coumarin was improved by 62.33% with the SG-1,10-PhenanNTf2 phase as compared to activated silica gel. Adsorption isotherm data displayed that the adsorption process was mainly monolayer on a homogeneous adsorbent surface, confirming the validity of Langmuir adsorption isotherm model. The adsorption of coumarin on the SG-1,10-PhenanNTf2 phase was accomplished after only 60 min contact time. Results of kinetic models showed that the adsorption of coumarin on the SG-1,10-PhenanNTf2 phase obeyed a pseudo second-order kinetic model. Finally, the efficiency of this methodology was confirmed by applying it to real water samples.

Cite this paper: H. Marwani and E. Bakhsh, "Silica Gel Supported Hydrophobic Ionic Liquid for Selective Extraction and Determination of Coumarin," American Journal of Analytical Chemistry, Vol. 4 No. 1, 2013, pp. 8-16. doi: 10.4236/ajac.2013.41002.

[1]   M. Ahnoff and B. Josefsson, “Simple Apparatus for on-Site Continuous Liquid-Liquid Extraction of Organic Compounds from Natural Waters,” Analytical Chemistry, Vol. 46, No. 6, 1974, pp. 658-663. doi:10.1021/ac60342a025

[2]   S. Nishihama, T. Hirai and I. Komasawa, “Review of Advanced Liquid-Liquid Extraction Systems for the Separation of Metal Ions by a Combination of Conversion of the Metal Species with Chemical Reaction,” Industrial & Engineering Chemistry Research, Vol. 40, No. 14, 2001, pp. 3085-3091. doi:10.1021/ie010022+

[3]   M. R. Pourjavid, P. Norouzi and M. R. Ganjali, “Light Lanthanides Determination by Fast Fourier Transform Continuous Cyclic Voltammetry after Separation by Ion-Exchange Chromatography,” International Journal of Electrochemical Science, Vol. 4, No. 7, 2009, pp. 923- 942.

[4]   X. Xue, J. Zhao, L. Chen, J. Zhou, B. Yue, Y. Li, L. Wu and F. Liu, “Analysis of Coenzyme Q10 in Bee Pollen Using Online Cleanup by Accelerated Solvent Extraction and High Performance Liquid Chromatography,” Food Chemistry, Vol. 133, No. 2, 2012, pp. 573-578. doi:10.1016/j.foodchem.2011.12.085

[5]   S. Zhong, S. N. Tan, L. Ge, W. Wang and J. Chen, “Determination of Bisphenol A and Naphthols in River Water Samples by Capillary Zone Electrophoresis after Cloud Point Extraction,” Talanta, Vol. 85, No. 1, 2011, pp. 488- 492. doi:10.1016/j.talanta.2011.04.009

[6]   W.-L. Liu, B.-H. Hwang, Z.-G. Li, J.-F. Jen and M.-R. Lee, “Headspace Solid Phase Microextraction in-Situ Supercritical Fluid Extraction Coupled to Gas Chromatography—Tandem Mass Spectrometry for Simultaneous Determination of Perfluorocarboxylic Acids in Sediments,” Journal of Chromatography A, Vol. 1218, No. 43, 2011, pp. 7857-7863. doi:10.1016/j.chroma.2011.08.062

[7]   I. Li?ka, “Fifty Years of Solid-Phase Extraction in Water Analysis Historical Development and Overview,” Journal of Chromatography A, Vol. 885, No. 1-2, 2000, pp. 3-16. doi:10.1016/S0021-9673(99)01144-9

[8]   L. M. Ravelo-Perez, A. V. Herrera-Herrera, J. Hernandez-Borges and M. A. Rodri-guez-Delgado, “Carbon Nanotubes: Solid-Phase Extraction,” Journal of Chromatography A, Vol. 1217, No. 16, 2010, pp. 2618-2641. doi:10.1016/j.chroma.2009.10.083

[9]   S. Sadeghi and E. Sheikhzadeh, “Solid Phase Extraction Using Silica Gel Modified with Murexide for Preconcentration of Uranium (VI) Ions from Water Samples,” Journal of Hazardous Materials, Vol. 163, No. 2-3, 2009, pp. 861-868. doi:10.1016/j.jhazmat.2008.07.053

[10]   A. Afkhami, T. Ma-drakian, R. Ahmadi, H. Bagheri and M. Tabatabaee, “Chemically Modified Alumina Nanoparticles for Selective Solid Phase Extraction and Preconcentration of Trace Amounts of Cd(II),” Microchimica Acta, Vol. 175, No. 1-2, 2011, pp. 69-77. doi:10.1007/s00604-011-0660-x

[11]   Z. Li, X. Chang, Z. Hu, X. Huang, X. Zou, Q. Wu and R. Nie, “Zincon-Modified Activated Carbon for Solid-Phase Extraction and Preconcentration of Trace Lead and Chromium from Environmental Samples,” Journal of Hazardous Materials, Vol. 166, No. 1, 2009, pp. 133-137. doi:10.1016/j.jhazmat.2008.11.006

[12]   F. M. de Oliveira, B. F. Somera, M. Z. Corazza, M. J. S. Yabe, M. G. Segatelli, E. S. Ribeiro, E. C. Lima, S. L. P. Dias and C. R. T. Tarley, “Cellulose Microfiber Functionalized with N,N’-Bis (2-Aminoethyl)-1,2-Ethanediamine as a Solid Sorbent for the Fast Preconcentration of Cd(II) in Flow System Analysis,” Talanta, Vol. 85, No. 5, 2011, pp. 2417-2424. doi:10.1016/j.talanta.2011.07.088

[13]   Y. Li, X. Xie, M. L. Lee and J. Chen, “Preparation and Evaluation of Hydrophilic C18 Monolithic Sorbents for Enhanced Polar Compound Retention in Liquid Chromatography and Solid Phase Extraction,” Journal of Chromatography A, Vol. 1218, No. 48, 2011, pp. 8608-8616. doi:10.1016/j.chroma.2011.09.070

[14]   Z. Wei, Y. Zu, Y. Fu, W. Wang, C. Zhao, M. Luo and T. Efferth, “Resin Adsorption as a Means to Enrich Rare Stilbenes and Coumarin from Pigeon Pea Leaves Extracts,” Chemical Engineering Journal, Vol. 172, No. 2-3, 2011, pp. 864-871. doi:10.1016/j.cej.2011.06.075

[15]   H. Zeng, Y. Wang, X. Liu, J. Kong and C. Nie, “Preparation of Molecular Imprinted Po-lymers Using Bi-Functional Monomer and Bi-Crosslinker for Solid-Phase Extraction of Rutin,” Talanta, Vol. 93, 2012, pp. 172-181. doi:10.1016/j.talanta.2012.02.008

[16]   R. K. Dey, F. J. V. E. Oliveira and C. Airoldi, “Mesoporous Silica Functionalized with Diethylenetriamine Moieties for Metal Removal and Thermodynamics of Cation-Basic Center Interactions,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 324, No. 1-3, 2008, pp. 41-46. doi:10.1016/j.colsurfa.2008.03.030

[17]   L. Zhang, X. Chang, Y. Zhai, Q. He, X. Huang, Z. Hu and N. Jiang, “Selective Solid Phase Extraction of Trace Sc(III) from Environmental Samples Using Silica Gel Modified with 4-(2-Morinyldiazenyl)-N-(3-(Tri-methyl- silyl)Propyl)Benzamide,” Analytica Chimica Acta, Vol. 629, No. 1-2, 2008, pp. 84-91. doi:10.1016/j.aca.2008.09.039

[18]   Z. Wei, L. Wang, J. Li, X. Liu and S. Jiang, “Cyanobi-phenyl-Mesogened Liquid Crystal-line Polymer Bonded on Silica as the Stationary Phase with Shape and Polarity Recognition for LC,” Chromatographia, Vol. 73, No. 1-2, 2011, pp. 5-16. doi:10.1007/s10337-010-1834-0

[19]   M. Ghaedi and E. Sha-rifpour, “Chemically Modified Nano Silica Gel with 2-((3silylpropylimino) Methyl)-2-Hydroxy-1-Naphthol (SPIMHN) as Good and Efficient Adsorbent for Solid Phase Extraction,” Desalination and Water Treatment, Vol. 41, No. 1-3, 2012, pp. 315-324. doi:10.1080/19443994.2012.664720

[20]   J. Fan, C. Wu, Y. Wei, C. Peng and P. Peng, “Preparation of Xylenol Orange Functionalized Silica Gel as a Selec- tive Solid Phase Extractor and Its Application for Pre- concentration—Separation of Mercury from Waters,” Journal of Hazardous Materials, Vol. 145, No. 1-2, 2007, pp. 323-330. doi:10.1016/j.jhazmat.2006.11.025

[21]   T. Welton, “Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis,” Chemical Reviews, Vol. 99, No. 8, 1999, pp. 2071-2083. doi:10.1021/cr980032t

[22]   G.-T. Wei, Z. Yang and C.-J. Chen, “Room Temperature Ionic Liquid as a Novel Medium for Liquid/Liquid Extraction of Metal Ions,” Analytica Chimica Acta, Vol. 488, No. 2, 2003, pp. 83-192. doi:10.1016/S0003-2670(03)00660-3

[23]   H. Zhao, S. Xia and P. Ma, “Use of Ionic Liquids as ‘Green’ Solvents for Extractions,” Journal of Chemical Technology and Biotechnology, Vol. 80, No. 10, 2005, pp. 1089-1096. doi:10.1002/jctb.1333

[24]   C. F. Poole and S. K. Poole, “Extraction of Organic Compounds with Room Temperature Ionic Liquids,” Journal of Chromatography A, Vol. 1217, No. 16, 2010, pp. 2268-2286. doi:10.1016/j.chroma.2009.09.011

[25]   A. E. Visser, R. P. Swatloski, S. T. Griffin, D. H. Hart- man and R. D. Rogers, “Liquid/Liquid Extraction of Metal Ions in Room Temperature Ionic Liquids,” Separation Science and Technology, Vol. 36, No. 5-6, 2001, pp. 785-804. doi:10.1081/SS-100103620

[26]   F. van Rantwijk, R. Madeira Lau and R. A. Sheldon, “Biocatalytic Transformations in Ionic Liquids,” Trends in Biotechnology, Vol. 21, No. 3, 2003, pp. 131-138. doi:10.1016/S0167-7799(03)00008-8

[27]   W. L. Hough, M. Smiglak, H. Rodriguez, R. P. Swatloski, S. K. Spear, D. T. Daly, J. Pernak, J. E. Grisel, R. D. Carliss, M. D. Soutullo, J. H. J. Davis and R. D. Rogers, “The Third Evolution of Ionic Liquids: Active Pharmaceutical Ingredients,” New Journal of Chemistry, Vol. 31, No. 8, 2007, pp. 1429-1436. doi:10.1039/b706677p

[28]   J.-F. Liu, G.-B. Jiang, J.-F. Liu and J. ?. J?nsson, “Application of Ionic Liquids in Analytical Chemistry,” Trends in Analytical Chemistry, Vol. 24, No. 1, 2005, pp. 20-27. doi:10.1016/j.trac.2004.09.005

[29]   F. Fa-bregat-Santiago, J. Bisquert, E. Palomares, L. Otero, D. Kuang, S. M. Zakeeruddin and M. Gratzel, “Correlation between Photovoltaic Performance and Impedance Spectroscopy of Dye-Sensitized Solar Cells Based on Ionic Liquids,” The Journal of Physical Chemistry C, Vol. 111, 2007, pp. 6550-6560. doi:10.1021/jp066178a

[30]   P. Wang, S. M. Zakeeruddin, P. Comte, I. Exnar and M. Gratzel, “Gelation of Ionic Liquid-Based Electrolytes with Silica Nanoparticles for Quasi-Solid-State Dye-Sensitized Solar Cells,” Journal of the American Chemical Society, Vol. 125, No. 5, 2003, pp. 1166-1167. doi:10.1021/ja029294+

[31]   L. Yu, D. Garcia, R. Ren and X. Zeng, “Ionic Liquid High Temperature Gas Sensors,” Chemical Communica- tions, No. 17, 2005, pp. 2277-2279.

[32]   D. Han, M. Tian, D. W. Park, D. K. Choi and K. H. Row, “Application of Ionic Liquids as Mobile Phase Additives and Surface-Bonded Stationary Phase in Liquid Chromatography,” Korean Journal of Chemical Engineering, Vol. 26, No. 5, 2009, pp. 1353-1358. doi:10.1007/s11814-009-0209-4

[33]   A. Berthod, M. J. Ruiz-Angel and S. Carda-Broch, “Ionic Liquids in Separation Techniques,” Journal of Chromatography A, Vol. 1184, No. 1-2, 2008, pp. 6-18. doi:10.1016/j.chroma.2007.11.109

[34]   M. E. Mahmoud and H. M. Al-Bishri, “Supported Hydrophobic Ionic Liquid on Nano-Silica for Adsorption of Lead,” Chemical Engineering Journal, Vol. 166, No. 1, 2011, pp. 157-167. doi:10.1016/j.cej.2010.10.046

[35]   G. Fang, J. Chen, J. Wang, J. He and S. Wang, “N-Nethylimidazolium Ionic Liquid-Functionalized Sil- ica as a Sorbent for Selective Solid-Phase Extraction of 12 Sulfonylurea Herbicides in Environmental Water and Soil Samples,” Journal of Chromatography A, Vol. 1217, No. 10, 2010, pp. 1567-1574. doi:10.1016/j.chroma.2010.01.010

[36]   L. Vidal, J. Parshintsev, K. Hartonen, A. Canals and M.-L. Riekkola, “Ionic Liquid-Functionalized Silica for Selective Solid-Phase Extraction of Organic Acids, Amines and Aldehydes,” Journal of Chromatography A, Vol. 1226, 2012, pp. 2-10. doi:10.1016/j.chroma.2011.08.075

[37]   H. M. Marwani, “Selective Separation and Determination of Lead Based on Silica Gel Developed by Surface Adsorbed New Hydrophobic Ionic Liquid,” Journal of Dispersion Science and Technology, Vol. 34, No. 1, 2013, pp. 117-124. doi:10.1080/01932691.2011.653925

[38]   H. M. Marwani, “Spectroscopic Evaluation of Chiral and Achiral Fluorescent Ionic Liquids,” Central European Journal of Chemistry, Vol. 8, No. 4, 2010, pp. 946-952. doi:10.2478/s11532-010-0062-7

[39]   D. M. Han, G. Z. Fang and X. P. Yan, “Preparation and Evaluation of a Molecularly Imprinted Sol-Gel Material for on-Line Solid-Phase Extraction Coupled with High Performance Liquid Chromatography for the Determination of Trace Pentachlorophenol in Water Samples,” Journal of Chromatography A, Vol. 1100, No. 2, 2005, pp. 131-136. doi:10.1016/j.chroma.2005.09.035

[40]   H. Freundlich, “üBer Die Adsorption in L?Sungen (Ad- sorption in Solution),” Zeitschrift für Physikalische Chemie, Vol. 57, 1906, pp. 384-470.

[41]   I. Langmuir, “The Constitution and Fundamental Properties of Solids and Liquids,” Journal of the American Chemical Society, Vol. 38, No. 11, 1916, pp. 2221-2295. doi:10.1021/ja02268a002

[42]   G. Mckay, H. S. Blair and J. R. Gardener, “Adsorption of Dyes on Chitin-I: Equilibrium Studies,” Journal of Applied Polymer Science, Vol. 27, No. 8, 1982, pp. 3043-3057. doi:10.1002/app.1982.070270827

[43]   Y. Ho, “Second-order Kinetic Model for the Sorption of Cadmium onto Tree Fern: A Comparison of Linear and Non-Linear Methods,” Water Research, Vol. 40, No. 1, 2006, pp. 119-125. doi:10.1016/j.watres.2005.10.040