Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Phospholipid membranes as substrates for polymer adsorption

Abstract

A largely unsolved problem in soft materials is how surface reconstruction competes with the rate of adsorption. Here, supported phospholipid bilayers of DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) were employed as substrates for the adsorption of a weak polyelectrolyte, polymethacrylic acid, whose time-dependent ratio of charged to uncharged functional groups served to probe the local dielectric environment. Chains that encountered sparsely covered surfaces spread to maximize the number of segment–surface contacts at rates independent of the molar mass (which was varied by a factor of 30), but dependent on the phase of the lipid bilayer, gel or liquid crystal. Surface reconstruction rather than molar mass of the adsorbing molecules seemed to determine the rate of spreading. The significance of these findings is the stark contrast with well-known views of polymer adsorption onto surfaces having structures that are 'frozen' and unresponsive, and is relevant not just from biological and biophysical standpoints, but also in the formulation of many cosmetics and pharmaceutical products.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Schematic diagram of the adsorption and subsequent conformational equilibration of flexible polymers at a supported phospholipid membrane.
Figure 2: Mass of polymethacrylic acid (PMA) adsorbed on to the supported lipid bilayer surfaces versus time.
Figure 3: Ionization of the carbonyl group plotted against elapsed time for a surface starved of PMA.
Figure 4: Ionization of the carbonyl group plotted against elapsed time for varying molecular weights of PMA spread on to starved bilayer surfaces.
Figure 5: Dichroic ratio of the −N(CH3)3+ asymmetric stretch vibration at 970 cm−1 of DMPC coated with adsorbed PMA chains in the LC phase (circles) and gel phase (squares), plotted against the fractional ionization of adsorbed PMA during spreading onto starved surfaces after the same adsorption procedure described in Fig. 3.

Similar content being viewed by others

References

  1. de Gennes, P.-G. in New Trends In Physics And Physical Chemistry Of Polymers (ed. Lee, L.-H.) 9–18 (Plenum, New York, 1990).

    Google Scholar 

  2. Fleer, G.J., Cohen Stuart, M.A., Scheutjens, J.M.H.M., Cosgrove, T. & Vincent, B. in Polymers at Interfaces 121–122 (Chapman & Hall, London, 1993).

  3. Mayer, L.D., Krishna, R., Webb, M. & Bally, M. Designing liposomal anticancer drug formulations for specific therapeutic applications. J. Lipid Res. 10, 99–115 (2000).

    CAS  Google Scholar 

  4. Nair, R.R., Rodgers, J.R. & Schwarz, L.A. Enhancement of transgene expression by combining glucocorticoids and anti-mitotic agents during transient transfection using DNA-cationic liposomes. Mol. Ther. 5, 455–462 (2002).

    Article  CAS  Google Scholar 

  5. Vogt, T.C.B. & Bechinger, B. The interactions of histidine-containing amphipathic helical peptide antibiotics with lipid bilayers: The effects of charges and pH. J. Biol. Chem. 274, 29115–29121 (1999).

    Article  CAS  Google Scholar 

  6. Rider, K.B., Hwang, K.S., Salmeron, M. & Somorjai, G.A. Structure and dynamics of dense monolayers of NO adsorbed on Rh(111) in equilibrium with the gas phase in the Torr pressure range. Phys. Rev. Lett. 86, 4330–4333 (2001).

    Article  CAS  Google Scholar 

  7. Douglas, J.F., Johnson, H.E. & Granick, S. A simple kinetic-model of polymer adsorption and desorption. Science 262, 2010–2012 (1993).

    Article  CAS  Google Scholar 

  8. Frantz, P. & Granick, S. Exchange kinetics of adsorbed polymer and the achievement of conformational equilibrium. Macromolecules 27, 2553–2558 (1994).

    Article  CAS  Google Scholar 

  9. Liu, H. & Chakrabarti, A. Molecular dynamics study of adsorption and spreading of a polymer chain onto a flat surface. Polymer 40, 7285–7293 (1999).

    Article  CAS  Google Scholar 

  10. Sackmann, E. Supported membranes: Scientific and practical applications. Science 271, 43–48 (1996).

    Article  CAS  Google Scholar 

  11. Boxer, S.G. Molecular transport and organization in supported lipid membranes. Curr. Opin. Chem. Biol. 4, 704–709 (2000).

    Article  CAS  Google Scholar 

  12. Eum, K.M., Langley, K.H. & Tirrell, D.A. Quasi-elastic and electrophoretic light-scattering studies of the reorganization of dioleoylphosphatidylcholine vesicle membranes by poly (2-ethylacrylic acid). Macromolecules 22, 2755–2760 (1989).

    Article  CAS  Google Scholar 

  13. Cates, M.E. Playing a molecular accordion. Nature 351, 102 (1991).

  14. Jakobs, B. et al. Amphiphilic block copolymers as efficiency boosters for microemulsions. Langmuir 15, 6707–6711 (1999).

    Article  CAS  Google Scholar 

  15. Hiergeist, C., Indrani, V.A. & Lipowsky, R. Membranes with anchored polymer at the adsorption transition. Europhys. Lett. 36, 491–496 (1996).

    Article  CAS  Google Scholar 

  16. Fournier, J-B. Microscopic membrane elasticity and interactions among membrane inclusions. Eur. Phys. J. B 11, 261–262 (1999).

    Article  CAS  Google Scholar 

  17. Breidenich, M., Netz, R.R. & Lipowsky, R. The shape of polymer-decorated membranes. Europhys. Lett. 49, 431–437 (2000).

    Article  CAS  Google Scholar 

  18. Bickel, T., Jeppesen, C. & Marques, C.M. Local entropic effects of polymers grafted to soft interfaces. Eur. Phys. J. E 4, 33–43 (2001).

    Article  CAS  Google Scholar 

  19. Breidenich, M., Netz, R.R. & Lipowsky, R. Adsorption of polymers anchored to membranes. Eur. Phys. J. E 5, 403–414 (2001).

    Article  CAS  Google Scholar 

  20. Brooks, J.T., Marques, C.M. & Cates, M.E. The effect of adsorbed polymer on the elastic-moduli of surfactant bilayers. J. Phys. II 1, 673–690 (1991).

    CAS  Google Scholar 

  21. Kim, Y.W. & Sung, W. Vesicular budding induced by a long and flexible polymer. Europhys. Lett. 47, 292–297 (1999).

    Article  CAS  Google Scholar 

  22. Xie, A.F. & Granick, S. Local electrostatics within a polyelectrolyte multilayer with embedded weak polyelectrolyte. Macromolecules 35, 1805–1813 (2002).

    Article  CAS  Google Scholar 

  23. Xie, A.F. & Granick, S. Weak versus strong: A weak polyacid embedded within a multilayer of strong polyelectrolytes. J. Am. Chem. Soc. 123, 3175–3176 (2001).

    Article  CAS  Google Scholar 

  24. Vaz, W.L.C., Derzko, I. & Jacobson, K.A. Photobleaching measurements of the lateral diffusion of lipids and proteins in artificial phospholipid bilayer membranes. Cell Surf. Rev. 8, 83–135 (1982).

    CAS  Google Scholar 

  25. Devaux, P.F. in Biological Magnetic Resonance (eds Berliner, L.J. & Reuben, J.) 188–190 (Plenum, New York, 1983).

    Google Scholar 

  26. Carré, A. & Shanahan, M.E.R. Direct evidence for viscosity-independent sp reading on a soft solid. Langmuir 11, 24–36 (1995).

    Article  Google Scholar 

  27. Carré, A., Gastel, J.-C. & Shanahan, M.E.R. Viscoelastic effects in the spreading of liquids. Nature 379, 432–434 (1996).

    Article  Google Scholar 

  28. Gennis, R.B. in Biomembranes: Molecular Structure and Function (ed. Cantor, C.R.) 166–198 (Springer, New York, 1989).

    Google Scholar 

  29. van de Pas, J.C., Olsthoorn, Th.M., Schepers, F.J., de Vries, C.H.E. & Buytenhek, C.J. Colloidal effects of anchored polymers in lamellar liquid-crystalline dispensions. Colloids Surf. A 85, 221–236 (1994).

    Article  CAS  Google Scholar 

  30. Hope, M.J., Bally, M.B., Webb, G. & Cullis, P.R. Production of large unilamellar vesicles by a rapid extrusion procedure? characterization of size distribution, trapped volume and ability to maintain a membrane-potential. Biochim. Biophys. Acta 812, 55–65 (1985).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank S. Safran for a discussion. This work was supported by the US Department of Energy, Division of Materials Science, under Award No. DEFG02-91ER45439 through the Frederick Seitz Materials Research Laboratory at the University of Illinois at Urbana-Champaign.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Steve Granick.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Xie, A., Granick, S. Phospholipid membranes as substrates for polymer adsorption. Nature Mater 1, 129–133 (2002). https://doi.org/10.1038/nmat738

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat738

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing