Skip to main content
Log in

Alternative synthesis of poly(hydroxymethylsiloxane) for lipase immobilization and use of the adsorbates as esterification biocatalysts

  • Published:
Journal of Sol-Gel Science and Technology Aims and scope Submit manuscript

Abstract

A medium molar mass poly(hydrogenomethyl- siloxane), Me3Si(O-SiHMe)nOSiMe3, (PHMS), has been used for preparing poly(hydroxymethylsiloxane) supports (PHOMS) for lipase immobilization. The procedure involved the conversion of PHMS to the corresponding poly(alkoxymethylsiloxanes). Me3Si(OSi(OR) Me/nOSiMe3 (PHMS), their alkaline hydrolysis to form poly(siloxanolates) which were then converted to PHOMS by neutralization. The effect of different catalysts and alcohols (methanol, ethanol, 2-propanol) on the course of poly(alkoxymethylsiloxanes) formation is reported. PHOMS supports were characterized by BET and Hg porosimetry, and the degree of their crosslinking was determined by solid-phase NMR. Fluorescence spectroscopy was used to assess surface polarity and determine lipase loading. The efficiency of lipase adsorbed on these supports was tested in the esterification of stearic acid with propanol in hexane. It was found that the activity of the adsorbates is controlled by their porosity. The addition of an inert addend (e.g. hydrotalcite) in the step of alkaline hydrolysis of poly(alkoxymethylsiloxanes) increases the adsorption efficiency of the supports as compared to PHOMS. The potential application of the biocatalysts, lipase-PHOMS adsorbates, was extended by their encapsulation into a RTV silicone rubber containing Si-substituted poly(imide) as a swelling modifier.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. M.T. Reetz, Curr. Opin. Chern. Biol. 6, 145 (2002).

    Article  CAS  Google Scholar 

  2. U.T. Bornscheuer and R.J. Kazlauskas, Hydrolases in Organic Synthesis. Regio and Stereoselective Biotransformations. (Wiley VCH, Weinheim, 1999).

    Google Scholar 

  3. K. Mori, SYNLETT 1995, 1097.

  4. W. Jin and J.D. Brennan, Anal. Chim. Acta 461, 1 (2002).

    Article  CAS  Google Scholar 

  5. J.D. Brennan, J.S. Hartman, E.I. Ilnicki, and M. Rakic, Chem. Mater. 11, 1853 (1999).

    Article  CAS  Google Scholar 

  6. G. Kuncova, Y. Maleterova, and P. Lovecka, Biotechnol. Tech. 8, 533 (1994).

    Google Scholar 

  7. G. Kuncova, M. Gugliemi, P. Dubina, and B. Safar, Collect. Czech. Chem. Commun. 60, 73 (1995).

    Google Scholar 

  8. G. Kuncova and M. Sivel, J. Sol-Gel Sci. Tech. 8, 667 (1997).

    Article  CAS  Google Scholar 

  9. R. Fernandez-Lafuente, P. Armisen, P. Sabuquillo, G. Fernandez-Lafuente, and J.M. Guisan, Chem Phys. Lipids 93, 185 (1998).

    Article  CAS  Google Scholar 

  10. S.S. Betigeri and S.H. Neau, Biomaterials 23, 3627 (2002).

    Article  CAS  Google Scholar 

  11. S. Maury, P. Buisson, A. Perrard, and A.C. Pierre, J. Molecular Catal. B: Enzymatic 32, 193 (2005).

    Article  CAS  Google Scholar 

  12. M.T. Reetz, A. Zonta, J. Simpelkamp, A. Rufinska, and B. Tesche, J. Sol-Gel Sci. Tech. 7, 35 (1996).

    Article  CAS  Google Scholar 

  13. P. Buisson, H.E.L. Rassy, S. Maury, and A.C. Pierre, J. Sol-Gel Sci. Tech. 27, 373 (2003).

    Article  CAS  Google Scholar 

  14. M.T. Reetz, P. Tielmann, W. Wiesenhoefer, W. Koenen, and A. Zonta, Adv. Synth. Catal. 345, 717 (2003).

    Article  CAS  Google Scholar 

  15. G. Kuncova, J. Hetflejs, J. Szilva, and S. Sabata, Landbauforschung Volkenrode, Sonderheft 241, 41 (2002).

    CAS  Google Scholar 

  16. G. Kuncova, J. Szilva, J. Hetflejs, and S. Sabata, J. Sol-Gel Sci. Technol. 26, 1183, (2003).

    Article  CAS  Google Scholar 

  17. I. Gill, E. Pastor, and A. Ballesteros, J. Am. Chem. Soc. 121, 9487 (1999).

    Article  CAS  Google Scholar 

  18. H. Mimoun, J. Org. Chem. 64, 2581 (1999).

    Google Scholar 

  19. J. Hetflejs, F. Mares, and V. Chvalovsky, Collect. Czech. Chem. Commun. 30, 1643 (1965).

    CAS  Google Scholar 

  20. S. Lu, M.M. Melo, J. Zhao, E.M. Pearce, and T.K. Kwei, Macromolecules 28, 4908 (1995).

    Article  CAS  Google Scholar 

  21. N.J. Lawrence and M.D. Bushell, J. Chem. Soc. Perkin Trans. 1, 3381 (1999).

    Google Scholar 

  22. S. Chandrasekar, Y.R. Reddy, and C. Ramao, Synt. Commun. 27, 2551 (1997).

    Google Scholar 

  23. V. Bazant, V. Chvalovsky and J. Rathousky, Organosilicon Compounds, (Academia, Prague 1977), Vol. 1.

  24. J. Brus and J. Dybal, Macromolecules 35, 10038 (2002).

    Article  CAS  Google Scholar 

  25. J.F. Deye and T.A. Berger, Anal. Chem. 62, 615 (1990).

    Article  CAS  Google Scholar 

  26. P. Greenspan and S.D. Fowler, J. Lipid Research 26, 781 (1985).

    CAS  Google Scholar 

  27. G. Hungerford and J.A. Ferreira, J. Luminiscence 93, 155 (2001).

    Article  CAS  Google Scholar 

  28. A. Lobnik and O.S. Wolbeis, J. Sol-Gel Sci. Tech. 20, 301 (2001).

    Article  Google Scholar 

  29. E.M. Moreno and D. Levy, Chem. Mater. 12, 2334 (2000).

    Article  CAS  Google Scholar 

  30. M.M. Bradford, Anal. Biochem. 72, 248 (1976).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to G. Kuncova.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hetflejs, J., Kuncova, G., Sabata, S. et al. Alternative synthesis of poly(hydroxymethylsiloxane) for lipase immobilization and use of the adsorbates as esterification biocatalysts. J Sol-Gel Sci Technol 38, 121–131 (2006). https://doi.org/10.1007/s10971-006-7115-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10971-006-7115-6

Keywords

Navigation