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Surface Modification of Sporopollenin with Calixarene Derivative

Characterization and Application for Metal Removal


In this study, p-tert-butylcalix[4]-aza-crown (CAC) immobilized sporopollenin (Sp) was used as a sorbent for the removal of Cu(II), Pb(II) and Zn(II) from aqueous media. Sporopollenin was firstly functionalized with 3-chloropropyltrimethoxysilane (CPTS) in order to obtain chloro-sporopollenin (Sp-Cl). The Sp-Cl was reacted subsequently with CAC yielding CAC-bonded sporopollenin (Sp-Cl-CAC). The new sorbent was characterized by infrared spectroscopy (FTIR), thermal analysis (TG/DTG) and scanning electron microscopy (SEM). The sorption properties of modified sorbent (Sp-Cl-CAC) are also investigated. The optimum pH values for the separation of metal ions from aqueous solution onto Sp-Cl-CAC were 5.0 for Pb(II) and Cu(II) and 5.5 for Zn(II). The maximum sorption capacities for Cu(II), Pb(II) and Zn(II) were 0.07 (4.44 mg g−1), 0.07 (4.58 mg g−1) and 0.14 (29.00 mg g−1) mmol g−1, respectively. Sorption thermodynamic parameters of such as free energy (∆G o), enthalpy (∆H o), and entropy (∆S o) were evaluated.

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  1. Amini, M., Younesi, H., & Bahramifar, N. (2009). Biosorption of nickel(II) from aqueous solution by Aspergillus niger: Response surface methodology and isotherm study. Chemosphere, 75, 1483–1491.

  2. Anwar, J., Shafique, U., Zaman, W., Salman, M., Dar, A., & Anwar, S. (2010). Removal of Pb(II) and Cd(II) from water by adsorption on peels of banana. Bioresource Technology, 101, 1752–1755.

  3. Asfari, Z., Böhmer, V., Harrowfield, J., & Vicens, J. (2001). Calixarenes. Dordrecht: Kluwer Academic Publishers.

  4. Balazs, B., Toth, G., Horvath, G., Grün, A., Csokai, V., Töke, L., et al. (2001). Studies on Calix(aza) crowns: IV. Synthesis and structure elucidation of chromogenic calix[4]arene indophenols capped by carboxamide bridges. European Journal of Organic Chemistry, 61–71.

  5. Baniamerian, M. J., Moradi, S. E., Noori, A., & Salahi, H. (2009). The effect of surface modification on heavy metal ion removal from water by carbon nanoporous adsorbent. Applied Surface Science, 256, 1347–1354.

  6. Bhattacharyya, K. G., & Gupta, S. S. (2011). Removal of Cu(II) by natural and acid-activated clays: an insight of adsorption isotherm, kinetic and thermodynamics. Desalination, 272, 66–75.

  7. Brooks, J., & Shaw, G. (1968). Identity of sporopollenin with older kerogen and new evidence for the possible biological source of chemicals in sedimentary rocks. Nature, 220, 678–679.

  8. Fernane, F., Mecherri, M. O., Sharrock, P., Hadioui, M., Lounici, H., & Fedoroff, M. (2008). Sorption of cadmium and copper ions on natural and synthetic hydroxylapatite particles. Materials Characterization, 59, 554–559.

  9. Fu, F., Zeng, H., Cai, Q., Qiu, R., Yu, J., & Xiong, Y. (2007). Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant. Chemosphere, 69, 1783–1789.

  10. Garg, B. S., Sharma, R. K., Bist, J. S., Bhojak, N., & Mittal, S. (1999). Separation and preconcentration of metal ions and their estimation in vitamin, steel and milk samples using o-vanilin-immobilized silica gel. Talanta, 48, 49–55.

  11. Gode, F., & Pehlivan, E. (2007). Sorption of Cr(III) onto chelating b-DAEG–sporopollenin and CEP–sporopollenin resins. Bioresource Technology, 98, 904–911.

  12. Gubbuk, I. H., Hatay, I., Coskun, A., & Ersoz, M. (2009). Immobilization of oxime derivative on silica gel for the preparation of new adsorbent. Journal of Hazardous Materials, 172, 1532–1537.

  13. Gubbuk, I. H., Gup, R., Kara, H., & Ersoz, M. (2009). Adsorption of Cu(II) onto silica gel immobilized Schiff base derivative. Desalination, 249, 1243–1248.

  14. Gubbuk, I. H. (2011). Isotherms and thermodynamics for the sorption of heavy metal ions onto functionalized sporopollenin. Journal of Hazardous Materials, 186, 416–422.

  15. Gutsche, C. D. (1998). Calixarenes revisited. Cambridge: The Royal Society of Chemistry.

  16. Horowitz, H. H., & Metzger, G. (1963). A new analysis of thermogravimetric traces. Analytical Chemistry, 35, 1464–1468.

  17. Miretzky, P., & Muñoz, C. (2011). Enhanced metal removal from aqueous solution by Fenton activated macrophyte biomass. Desalination, 271, 20–28.

  18. Monier, M., Ayad, D. M., Wei, Y., & Sahran, A. A. (2010). Preparation and characterization of magnetic chelating resin based on chitosan for adsorption of Cu(II), Co(II), and Ni(II) ions. Reactive and Functional Polymers, 70, 257–266.

  19. Naiya, T. K., Bhattacharya, A. K., & Das, S. K. (2009). Adsorption of Cd(II) and Pb(II) from aqueous solutions on activated alumina. Journal of Colloid and Interface Science, 333, 14–26.

  20. Pan, B. C., Zhang, Q. R., Zhang, W. M., Pan, B. J., Du, W., Lv, L., Zhang, Q. J., Xu, Z. W., & Zhang, Q. X. (2007). Highly effective removal of heavy metals by polymer-based zirconium phosphate: A case study of lead ion. Journal of Colloid and Interface Science, 310, 99–105.

  21. Rao, R. A. K., & Khan, M. A. (2009). Biosorption of bivalent metal ions from aqueous solution by an agricultural waste: Kinetics, thermodynamics and environmental effects. Colloid Surface A, 332, 121–128.

  22. Roundhill, D. M., Solangi, I. B., Memon, S., Bhanger, M. I., & Yilmaz, M. (2009). The liquid–liquid extraction of toxic metals (Cd, Hg and Pb) by calixarenes. Pakistan Journal of Analytical and Environmental Chemistry, 10, 1–13.

  23. Santana, S. A. A., Vieira, A. P., Filho, E. C. S., Melo, J. C. P., & Airoldi, C. (2010). Immobilization of ethylenesulfide on babassu coconut epicarp and mesocarp for divalent cation sorption. Journal of Hazardous Materials, 174, 714–719.

  24. Solangi, I. B., Memon, S., & Bhanger, M. I. (2009). Synthesis and application of a highly efficient tetraestercalix[4]arene based resin for the removal of Pb2+ from aqueous environment. Analytica Chimica Acta, 638, 146–153.

  25. Solangi, I. B., Bhatti, A. A., Kamboh, M. A., Memon, S., & Bhanger, M. I. (2011). Comparative fluoride sorption study of new calix[4]arene-based resins. Desalination, 272, 98–106.

  26. Taakeyama, T., & Quinn, F. X. (1994). Thermal analysis fundamentals and applications to polymer science. Chichester: Wiley.

  27. Tabakcı, M., & Yılmaz, M. (2008). Sorption characteristics of Cu(II) ions onto silica gel-immobilized calix[4]arene polymer in aqueous solutions: batch and column studies. Journal of Hazardous Materials, 151, 331–338.

  28. Tan, I. A. W., Ahmad, A. L., & Hameed, H. (2009). Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon. Journal of Hazardous Materials, 164, 473–482.

  29. Tang, X., Li, Z., & Chen, Y. (2009). Adsorption behavior of Zn(II) on Chinese loess. Journal of Hazardous Materials, 161, 824–834.

  30. Tutar, H., Yılmaz, E., Pehlivan, E., & Yılmaz, M. (2009). Immobilization of Candida rugosa lipase on sporopollenin from Lycopodium clavatum. International Journal of Biological Macromolecules, 45, 315–320.

  31. Wang, J., Zhang, D., Lawson, T. R., & Bartsch, R. A. (2009). Sorption of heavy metal ions by silica gel-immobilized, proton-ionizable calix[4]arenes. Talanta, 78, 477–483.

  32. Yilmaz, M., & Memon, S. (2009). Calixarene based sorbents for the extraction of ions and neutral molecules. In T. P. Willis (Ed.), Sorbents: Properties, materials and applications (pp. 285–333). New York: Nova Sci. Publishing.

  33. Zaman, M. I., Mustafa, S., Khan, S., & Xing, B. (2009). Effect of phosphate complexation on Cd2+ sorption by manganese dioxide (β-MnO2). Journal of Colloid and Interface Science, 330, 9–19.

  34. Zhu, X., Chang, Y., Cui, X., Zou, D., & Yang, Z. (2007). Solid-phase extraction of trace Cu(II) Fe(III) and Zn(II) with silica gel modified with curcumin from biological and natural water samples by ICP-OES. Microchemical Journal, 86, 189–194.

  35. Zhang, X., Hong, H., Li, Z., Guan, J., & Schulz, L. (2009). Removal of azobenzene from water by kaolinite. Journal of Hazardous Materials, 170, 1064–1069.

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We would like to thank Scientific Research Foundation of Selcuk University (SUAF), Konya, Turkey for its financial support for this work.

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Correspondence to Ilkay Hilal Gubbuk.

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Gubbuk, I.H., Gürfidan, L., Erdemir, S. et al. Surface Modification of Sporopollenin with Calixarene Derivative. Water Air Soil Pollut 223, 2623–2632 (2012).

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  • Surface immobilization
  • Thermodynamic
  • Calixarene
  • Sorption