Ebru Birlik ÖZKÜTÜK, Elif ÖZALP, Ayça Atılır ÖZCAN, Sibel Emir DİLTEMİZ

Selective Separation of Thiocyanate Ion by Ion-Imprinted Polymer

Molecular imprinting is a emerging technology to create recognition sites in a polymeric matrix using a molecular template. The molecularly imprinted polymers MIPs are easy to prepare, stable, inexpensive and capable of molecular recognition. This manuscript describes a method for the selective binding behavior of SCN- ions on surface imprinted polymers which were prepared using chitosan succinate-Zn II complex. This polymer was prepared in the presence of epichlorohydrin and was imprinted with SCN- ions. After that, the template SCN- ions was removed using 1 M KOH solution. Selective cavities for the SCN- ions was obtained in the SCN- -imprinted chitosan-succinate beads. The effect of initial concentration of SCN- ions, adsorption time and imprinting efficiency on adsorption selectivity for SCN- -imprinted polymer were investigated. The adsorption process was fast and equilibrium was reached at around 30 min. Maximum adsorption capacity was found to be 95 mg g-1. The number of accessible binding sites Qmax , relative selectivity coefficient k’ and binding ability were also evaluated. The observed adsorption order under competitive conditions was SCN- >F- > Cl- > PO4 3- in mass basis.

Keywords:

Ion-imprinted polymer Thiocyanate separation, chitosan, solid phase extraction, Removal,

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1. Denson, P.M., Davodow, B., Bass, M.E., Jones, E.W. Determination of trace thiocyanate with nano-silver coated multi-walled carbon nanotubes modified glassy carbon electrode, Arch. Environ. Health, 14, 865, 1967.
2. Glatz, Z., Novakova, S., Sterbova, H. Analysis of thiocyanate in biological fluids by capillary zone electrophoresis, J. Chromatogr. A, 916, 273, 2001.
3. Bendtsen, A. B., Hansen, E.H. Spectrophotometric flow injection determination of trace amounts of thiocyanate based on its reaction with 2-(5-bromo-2-pyridylazo)-5- diethylaminophenol and dichromate: assay of the thiocyanate level in saliva from smokers and nonsmokers, Analyst, 116, 647, 1991.
4. Pinillos, S.C., Vincente, I.S., Bernal, J.G., Asensio, J.S. Highly selective thiocyanate membrane electrode based on butane-2,3-dione bis(salicylhydrazonato)zinc(II) complex, Anal. Chim. Acta, 318, 377, 1996.
5. van Staden, J.F., Botha, A. A simple flow injection system with bead injection for trace iron determination, Anal. Chim. Acta, 403, 279, 2000.
6. Ghasemi, J., Amini, R., Afkhami, A. Kinetic spectrophotometric determination of thiocyanate based on ıts ınhibitory effect on the oxidation of methyl red by bromate, Anal. Sci., 17, 435, 2001.
7. Tanaka, A., Deguchi, K., Deguchi, T. Determination of thiocyanate by carbonyl sulphide (OCS) generation and gas-phase molecular absorption spectrometry, Anal. Chim. Acta, 261, 281, 1992.
8. Gong, B., Gong, G. Fluorimetric method for the determination of thiocyanate with 2′,7′-dichlorofluorescein and iodine, Anal. Chim. Acta, 394, 171, 1999.
9. Cox, J.A., Gray, T., Kulkarni, K.R. Controlled-potential electrolysis of bulk solutions at a modified electrode: application of oxdations of cysteine, cystine, methionine, and thiocyanate, Anal. Chem., 60, 1710, 1988.
10. Li, L., Wang, A., He, P., Fang, Y. Determination of inorganic anions in saliva by capillary isotachophoresis, Fresenius J. Anal. Chem., 367, 649, 2000.
11. Wang, G.F., Li, M.G., Gao, Y.C., Fang, B. Amperometric sensor used for determination of thiocyanate with a silver nanoparticles modified electrode, Sensors, 4, 147, 2004.
12. Ozoemena, K.I., Nyokong, T. Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode: Applications to electrocatalytic oxidation and detection of thiocyanate, J. Electroanal. Chem., 579, 283, 2005.
13. Cai, X., Zhao, Z. Determination of trace thiocyanate by linear sweep polarography, Anal. Chim. Acta, 212, 43, 1988.
14. Tanabe, S., Kitahara, M., Nawata, N., Kawanabe, K. Simultaneous determination of cyanide and thiocyanate in blood by ion chromatography with fluorescence and ultraviolet detection, J. Chromatogr. B, 424, 29, 1988.
15. Michigami, Y., Fujii, K., Ueda, K., Yamamoto, Y. Determination of thiocyanate in human saliva and urine by ion chromatography, Analyst, 117, 1855, 1992.
16. Connolly, D., Barron, L., Paull, B. Determination of urinary thiocyanate and nitrate using fast ion-interaction chromatography, J. Chromatogr. B, 767, 175, 2002.
17. Bakker, E., Buhlmann, P., Pretsch, E. Carrier-Based IonSelective Electrodes and Bulk Optodes. 1. General characteristics, Chem. Rev., American Chemical Society, 1997.
18. Brown, D.V., Chaniotakis, N.A., Lee, I.H., Ma, S.C., Park, S.B., Meyerhoff, M.E., Nick, R.J., Groves, J.T. Response Characteristics of anion-selective polymer membrane electrodes based on gallium(III), indium(III) and thallium(III) porphyrins, Electroanal. 1, 477, 1989.
19. Florido, A., Bachas, L.G., Valiente, M., Villaescusa, I. Anion-selective electrodes based on a gold(III)- triisobutylphosphine sulfide complex, Analyst, 119, 2421, 1994.
20. Gao, D., Gu, J., Yu, R.Q., Zheng, G.D. Substituted metalloporphyrin derivatives as anion carrier for PVC membrane electrodes, Anal. Chim. Acta, 302, 263, 1995.
21. Ganjali, M.R., Poursaberi, T., Basiripour, F., SalavatiNiassari, M., Yousefi, M., Shamsipur, M. Highly selective thiocyanate poly(vinyl chloride) membrane electrode based on a cadmium-Schiff's base complex, Fresenius J. Anal. Chem., 370, 1091, 2001.
22. Shamsipur, M., Khayatian, G., Tangestaninejad, S., Thiocyanate-selective membrane electrode based on (octabromo tetraphenyl porphyrinato) manganese(III) chloride, Electroanal., 11, 1340, 1999.
23. Amini, M.K., Shahrokhian, S., Tangestaninejad, S. Selective thiocyanate poly(vinyl chloride) membrane based on a 1,8-dibenzyl- 1,3,6,8,10,13 hexaazacyclo tetradecane- Ni(II) perchlorate, Anal. Lett., 32, 2737, 1999.
24. Amini, M.K., Shahrokhian, S., Tangestaninejad, S., Thiocyanate-selective electrodes based on nickel and iron phthalocyanines, Anal. Chim. Acta, 402, 137, 1999.
25. Hea, J., Zhub, Q., Deng, Q. Investigation of imprinting parameters and their recognition nature for quininemolecularly imprinted polymers, Spectrochim. Acta Part A: Mol. Biomol. Spect., 67, 1297, 2007.
26. Tamayo, T.G., Titirici, M.M., Esteban, A.M., Sellergren, B. Synthesis and evaluation of new propazine-imprinted polymer formats for use as stationary phases in liquid chromatography, Anal. Chim. Acta, 542, 38, 2005.
27. Fairhurst, R.E., Chassaing, C., Mayes, A.G. et al., Nonlinear adsorption isotherm as a tool for understanding and characterizing molecularly imprinted polymers, Biosens. Bioelectron. 20, 1098, 2004.
28. Kriz, D., Ramstrom, O., Mosbach, K. Flow injection chemiluminescence determination of epinephrine using epinephrine-imprinted polymer as recognition material, Anal. Chem., 69, 345A, 1997.
29. Motherwell, W.B., Bingham, M.J., Pothier, J. Highly efficient Meinwald rearrangement reactions of epoxides catalyzed by copper tetrafluoroborate, Tetrahedron, 60, 3231, 2004.
30. Haupt, K. Molecularly imprinted polymers: the next generation, Anal. Chem., 75, 376A, 2003.
31. Widstrand, C., Larsson, F., Fiori, M. et al., Evaluation of MISPE for the multi-residue extraction of β-agonists from calves urine, J. Chromatogr. B, 804, 85, 2004
32. Caro, E., Marce, R.M., Borrull, F. et al., Application of molecularly imprinted polymers to solid-phase extraction of compounds from environmental and biological samples, Trends Anal. Chem., 25, 143, 2006.
33. Aiedeh, K., Taha, M.O. Synthesis of iron-crosslinked chitosan succinate and iron-crosslinked hydroxamated chitosan succinate and their in vitro evaluation as potential matrix materials for oral theophylline sustainedrelease beads, Arch. Pharm., 332, 103, 1999.
34. Eaton, A.D., Clesceri, L.S., Greenberg, A.E. Standard methods for the examination of waters and wastewater, 19th ed., American Public Health Association, Washigton DC.USA, 1995.
35. Inukai, Y., Chinen, T., Matsuda, T., Kaida, Y., Yasuda, S. Selective separation of germanium(IV) by 2,3- dihydroxypropyl chitosan resin, Anal. Chim. Acta, 371, 187, 1998.
36. Guo, T.Y., Xia, Y.Q., Hao, G.J., Song, M.D., Zhang, B.H. Chitosan beads as molecularly imprinted polymer matrix for selective separation of proteins, Biomaterials, 26(28) 5737, 2005.
37. Namasivayam, C., Sangeetha, D. Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste, Chemosphere, 60, 1616, 2005.
38. Ho, Y.S., McKay, G. Pseudo-second order model for sorption processes, Proc. Biochem., 34, 451, 1999.
39. Kuchen, W., Schram, J. Metal-ion-selective exchange resins by matrix ımprint with methacrylates, Angew. Chem. Int. Ed. Engl., 27(12) 1695, 1988.
40. Dai, S., Burleig, M.C., Shin, Y., Morrow, C.C., Barnes, C.E., Xue, Z. Imprint coating: a novel synthesis of selective functionalized ordered mesoporous sorbents, Angew. Chem. Int. Ed., 38(9) 1235, 1999.