Skip to main content
SpringerLink
Log in

Oxidation and lateral diffusion of styryl dyes on the surface of a bilayer lipid membrane

  • Section 2. Physicochemical Mechanics
  • Published:
Russian Journal of Electrochemistry Aims and scope Submit manuscript

Abstract

The mechanism of action of photosensitizers used in the photodynamic tumor therapy is studied by using bilayer lipid membranes (BLM) which adequately simulate the plasma membranes of cells. The formation of singlet oxygen upon photoexcitation of photosensitizer (tetrasulfonated alumophthalocyanine) is revealed by the photosensitizer-induced decomposition of styryl dyes di-4-ANEPPS or RH-421 the adsorption of which on BLM gives rise to changes in the dipole potential at the membrane interface. This potential decreases upon illumination of the membrane covered with adsorbed phthalocyanine and dye molecules as a result of the dye oxidation by singlet oxygen and is recovered upon interruption of illumination as a result of adsorption of new dye molecules from the solution. The changes in the potential are observed both when the dye molecules are adsorbed on the same (cis) membrane side as the photosensitizer molecules and also when they are adsorbed on the opposite (trans) membrane side. When the dye molecules are adsorbed on the trans side, the kinetics of potential variations in the light and its subsequent recovery in the dark depends on the membrane size. This dependence is explained within the framework of a model which assumes that dye molecules can get into the lipid bilayer not only from the aqueous solution but also as a result of lateral diffusion from the bilayer-surrounding circular reservoir containing a lipid solution in decane. The quantitative description of experimental data in terms of this model allows the coefficient of lateral diffusion of di-4- ANEPPS molecules in the lipid bilayer to be assessed as 10–7–10–6 cm2/s. The oxidation rate of dye molecules on the cis side is shown to be lower, which is explained by inhibition of the formation of singlet oxygen by dye molecules.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. O’Connor, A.E., Gallagher, W.M., and Byrne, A.T., Porphyrin and nonporphyrin photosensitizers in oncology: preclinical and clinical advances in photodynamic therapy, Photochem. Photobiol., 2009, vol. 85, p. 1053.

    Article  Google Scholar 

  2. Stozhkova, I.N., Chernyi, V.V., Sokolov, V.S., and Ermakov, Yu.A., Adsorption of hematoporphyrins on a planar biological membrane, Biol. Membr., 1997, vol. 14, p. 310.

    CAS  Google Scholar 

  3. Rokitskaya, T.I., Antonenko, Y.N., and Kotova, E.A., The interaction of phthalocyanine with planar lipid bilayers: photodynamic inactivation of gramicidin channels, FEBS Letters, 1993, vol. 329, p. 332.

    Article  CAS  Google Scholar 

  4. Stozhkova, I.N., Mirskii, V.M., Kayushina, R.L., Erokhin, V.V., and Mironov, A.F., Hematophorphyrin dimethyl ether interaction with artificial membrane systems. Double bonds of lipid hydrocarbon chains–the target of photodynamic damage of lipid membranes, Biol. Membr., 1992, vol. 9, p. 74.

    CAS  Google Scholar 

  5. Pashkovskaya, A.A., Sokolenko, E.A., Sokolov, V.S., Kotova, E.A., and Antonenko, Y.N., Photodynamic activity and binding of sulfonated metallophthalocyanines to phospholipid membranes: contribution of metal-phosphate coordination, Biochim. Biophys. Acta, 2007, vol. 1768, p. 2459.

    Article  CAS  Google Scholar 

  6. Rokitskaya, T.I., Antonenko, Y.N., and Kotova, E.A., Photodynamic inactivation of gramicidin channels: a flash-photolysis study, Biochim. Biophys. Acta, 1996, vol. 1275, p. 221.

    Article  Google Scholar 

  7. Sokolov, V.S., Block, M., Stozhkova, I.N., and Pohl, P., Membrane photopotential generation by interfacial differences in the turnover of a photodynamic reaction, Biophys. J, 2000, vol. 79, p. 2121.

    Article  CAS  Google Scholar 

  8. Kunz, L. and Stark, G., Photodynamic membrane damage at the level of single ion channels, Biochim. Biophys. Acta, 1997, vol. 1327, p. 1.

    Article  CAS  Google Scholar 

  9. Sokolov, V.S. and Pohl, P., Membrane transport of singlet oxygen monitored by dipole potential measurements, Biophys. J., 2009, vol. 96, pp. 77–85.

    Article  CAS  Google Scholar 

  10. Loew, L.M., Scully, S., Simpson, L., and Waggoner, A.S., Evidence for a charge-shift electrochromic mechanism in a probe of membrane potential, Nature, 1979, vol. 281, p. 497.

    Article  CAS  Google Scholar 

  11. Loew, L.M., Bonneville, G.W., and Surow, J., Charge shift optical probes of membrane potential. Theory, Biochemistry, 1978, vol. 17, p. 4065.

    Article  CAS  Google Scholar 

  12. Malkov, D.Y. and Sokolov, V.S., Fluorescent styryl dyes of the RH series affect a potential drop on the membrane/solution boundary, Biochim. Biophys. Acta, 1996, vol. 1278, p. 197.

    Article  Google Scholar 

  13. Sokolov, V.S., Gavrilchik, A.N., Kulagina, A.O., Meshkov, I.N., Pohl, P., and Gorbunova, Y.G., Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane, J. Photochem. Photobiol, 2016, vol. 161, p. 162.

    Article  CAS  Google Scholar 

  14. Sokolov, V.S. and Mirsky, V.M., in Ultrathin Electrochemical Chemo-and Biosensors: Technology and Performance, Mirsky, V.M., Ed., Springer, 2004, p. 255.

  15. Ermakov, Yu.A. and Sokolov, V.S., in Planar Lipid Bilayers (BLMs) and their Applications, Tien, H.T. and Ottova-Leitmannova, A., Eds., Elsevier, 2003, p. 109.

  16. Sokolov, V.S and Kuz’min, V.G., Measuring the potential difference of bilayer membranes by the second harmonics of capacitance current, Biofizika, 1980, vol. 25, p. 170.

    CAS  Google Scholar 

  17. Benz, R., Stark, G., Janko, K., and Lauger, P., Valinomycin-mediated ion transport through neutral lipid membranes: influence of hydrocarbon chain length and temperature, J. Membr. Biol., 1973, vol. 14, p. 339.

    Article  CAS  Google Scholar 

  18. Hladky, S.B., The effect of stirring on the flux of carriers into black lipid membranes, Biochim. Biophys. Acta, 1973, vol. 307, p. 261.

    Article  CAS  Google Scholar 

  19. Benz, R. and Janko, K., Voltage-induced capacitance relaxation of lipid bilayer membranes. Effects of membrane composition, Biochim. Biophys. Acta, 1976, vol. 455, p. 721.

    Article  CAS  Google Scholar 

  20. Gaede, H.C. and Gawrisch, K., Lateral diffusion rates of lipid, water, and a hydrophobic drug in a multilamellar liposome, Biophys. J., 2003, vol. 85, p. 1734.

    Article  CAS  Google Scholar 

  21. Kusba, J., Li, L., Gryczynski, I., Piszczek, G., Johnson, M., and Lakowicz, J.R., Lateral diffusion coefficients in membranes measured by resonance energy transfer and a new algorithm for diffusion in two dimensions, Biophys. J., 2002, vol. 82, p. 1358.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, 119071, Russia

    V. S. Sokolov, A. A. Shcherbakov, V. Yu. Tashkin, A. N. Gavril’chik & Yu. A. Chizmadzhev

  2. Institute of Biophysics of Kepler University, Linz, A-4040, Austria

    P. Pohl

Authors
  1. V. S. Sokolov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. A. Shcherbakov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. Yu. Tashkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. N. Gavril’chik
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yu. A. Chizmadzhev
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. P. Pohl
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. S. Sokolov.

Additional information

Original Russian Text © V.S. Sokolov, A.A. Shcherbakov, V.Yu. Tashkin, A.N. Gavril’chik, Yu.A. Chizmadzhev, P. Pohl, 2017, published in Elektrokhimiya, 2017, Vol. 53, No. 10, pp. 1321–1333.

This paper is the authors’ contribution to the special issue of Russian Journal of Electrochemistry dedicated to the 100th anniversary of the birth of the outstanding Soviet electrochemist Veniamin G. Levich.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sokolov, V.S., Shcherbakov, A.A., Tashkin, V.Y. et al. Oxidation and lateral diffusion of styryl dyes on the surface of a bilayer lipid membrane. Russ J Electrochem 53, 1171–1181 (2017). https://doi.org/10.1134/S1023193517090130

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1023193517090130

Keywords

Search

Navigation