Skip to main content
Log in

The aqueous environment in AOT and Triton X-100 (w/o) microemulsions probed by fluorescence

  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

The confined aqueous medium of Triton X-100/cyclohexane-hexanol/water microemulsions was studied and compared with that of AOT/isooctane/water. The microenvironment generated was assessed by following the photophysical behaviour of the cationic dye, acridine orange (AO). This dye presents an acid-base equilibrium in free bulk water (pKa ≈ 10.2) which is clearly affected in Triton X-100 microemulsions where the neutral species is stabilised at low ω0. The addition of water contributes to the appearance of the protonated species. This, however, presents spectral features that show a less polar and/or protic character of the encapsulated water even at high contents. The “anomalous” microviscosity dependence on the amount of solubilised water (ω0 = [H2O]/[Surf]) in Triton X-100 microemulsions obtained from steady-state anisotropy data was used to discuss the existence of bulk free water within these confined media, where at ω0= 8, properties seem to change. In AOT, a complex AO-AOT is detected in equilibrium with the protonated AO, at pH = 7. The two-state excited-state formalism was applied to describe the transient data which in the case of AOT introduces a rate constant that accounts for the water quenching (kq = 0.51 ± 0.03 × 108 M1 cm1).

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. K. Kalyanasundaram, Photochemistry in Microheterogeneous Systems, Academic Press, N. Y, 1987.

    Google Scholar 

  2. A. Kabalnov, B. Lindman, B. Olsson, L. Piculell, K. Thuresson and H. Wennerstrom, Microemulsions in amphiphilic and polymer-surfactant systems, Colloid Polym. Sci., 1996, 247, 297–308.

    Article  Google Scholar 

  3. N.E. Levinger, Ultrafast dynamics in reverse micelles, micro-emulsions, and vesicles, Curr. Opin. Colloid Interface Sci., 2000, 5, 118–124.

    Article  CAS  Google Scholar 

  4. K. Bhattacharyya and B. Bagchi, Slow dynamics of constrained water in complex geometries, J. Phys. Chem. A, 2000, 104, 10603–10613.

    Article  CAS  Google Scholar 

  5. M. Hasegawa, T. Sugimura, Y. Suzaki and Y. Shindo, Microviscosity in water pool of aeorosol-OT reversed micelle determined with viscosity-sensitive fluorescence probe, auramine O, and fluorescence depolarization of xanthene dyes, J. Phys. Chem., 1994, 98, 2120–2124.

    Article  CAS  Google Scholar 

  6. M. Hasegawa, Buffer-like action in water-pool of aerosol OT reverse micelles, Langmuir, 2001, 17, 1426–1431.

    Article  CAS  Google Scholar 

  7. H. Christenson, S.E. Friberg and D.W. Larsen, NMR investigations of aggregation of nonionic surfactants in a hydrocarbon medium, J. Phys. Chem., 1980, 84, 3633–3638.

    Article  CAS  Google Scholar 

  8. D. Christopher, J. Yarwood, P. S. Belton and B. P. Hills, A Fourier Transform Infrared Study of Water-Head Group Interactions in Reversed Micelles Containing Sodium (2-Ethylhexyl) Sulfosuccinate (AOT), J. Colloid Interface Sci., 1992, 152, 465–471.

    Article  CAS  Google Scholar 

  9. J. Faeder and B.M. Ladanyi, Molecular simulations of the interior of aqueous reverse micelles, J. Phys. Chem. B, 2000, 104, 1033–1046.

    Article  CAS  Google Scholar 

  10. T. K. Jain, M. Varshney and A. Maitra, Structural studies of aerosol OT reverse micellar aggregates by FT-IR spectroscopy, J. Phys. Chem., 1989, 93, 7409–7414.

    Article  CAS  Google Scholar 

  11. M. Zulauf and H.-F. Eicke, Inverted micelles and microemulsions in the ternary system H2O/aerosol-OT/isoocatane as studied by photon correlation spectroscopy, J. Phys. Chem., 1979, 83, 480–486.

    Article  CAS  Google Scholar 

  12. M. Almgren, R. Jóhannsson and J. C. Eriksson, Polydispersity of AOT droplets measured by time-resolved fluorescence quenching, J. Phys. Chem., 1993, 97, 8590–8594.

    Article  CAS  Google Scholar 

  13. S. M. Andrade, S. M. B. Costa and R. Pansu, The influence of water on the photophysical and photochemical properties of piroxicam in AOT/isooctane/water reversed micelles, Photochem. Photobiol., 2000, 71, 405–412.

    Article  CAS  Google Scholar 

  14. S. M. Andrade, S. M. B. Costa and R. Pansu, Structural changes in w/o Triton X-100//cyclohexane-hexanol/water microemulsions probed by a fluorescent drug piroxicam, J. Colloid Interface Sci., 2000, 226, 260–268.

    Article  CAS  Google Scholar 

  15. A. Kellmann and Y. Lion, Acid–base equilibria of the excited singlet and triplet states and the semi-reduced form of acridine orange, Photochem. Photobiol., 1979, 29, 217–222.

    Article  CAS  Google Scholar 

  16. M. S. Chan and J. R. Bolton, Mechanism of the photosensitized redox reactions of acridine orange in aqueous solutions–A system of interest in the photochemical storage of solar energy, Photochem. Photobiol., 1981, 34, 537–547.

    Article  CAS  Google Scholar 

  17. H. Schmidt, A. Al-Ibrahim, U. Dietzel and L. Bieker, On the acridine and thiazine dye sensitized photodynamic inactivation of lysozyme-singlet oxygen self-quenching by the sensitizers, Photochem. Photobiol., 1981, 33, 127–130.

    Article  CAS  Google Scholar 

  18. M. Belletete and G. Durocher, Interfacial micropolarity in the micellar region of the sodium (2-ethylhexyl) sulfosuccinate (AOT) inverted micelles, J. Colloid Interface Sci., 1990, 134, 289–293.

    Article  Google Scholar 

  19. C. A. T. Laia and S. M. B. Costa, Probing the interface polarity of AOT reversed micelles using centro-symmetrical squaraine molecules, Phys. Chem. Chem. Phys., 1999, 1, 4409–4416.

    Article  CAS  Google Scholar 

  20. P. López-Cornejo and S. M. B. Costa, Luminescence of zinc tetraphenylporphyrin in ethylene glycol-in-oil microemulsions, Langmuir, 1998, 14, 2042–2049.

    Article  Google Scholar 

  21. D. M. Togashi and S. M. B. Costa, Absorption, fluorescence and transient triplet-triplet absorption spectra of zinc tetramethyl-pyridylporphyrin in reverse micelles and microemulsions of aerosol OT-(AOT), Phys. Chem. Chem. Phys., 2000, 2, 5437–5444.

    Article  CAS  Google Scholar 

  22. C. Kumar and D. Balasubramanian, Studies on the triton X-100:alcohol:water reverse micelles in cyclohexane, J. Colloid Interface Sci, 1979, 69, 271–279.

    Article  CAS  Google Scholar 

  23. J. Olmsted III, Calorimetric determination of absolute quantum yields, J. Phys. Chem., 1979, 83, 2581–2584.

    Article  CAS  Google Scholar 

  24. E. Keh and B. Valeur, Investigation of water-containing inverted micelles by fluorescence polarization. Determination of size and internal fluidity, J. Colloid Interface Sci, 1981, 79, 465–478.

    Article  CAS  Google Scholar 

  25. D. V. O’Connor and D. Phillips, Time-correlated Single Photon Counting, Academic Press, London, 1984.

    Google Scholar 

  26. N. Mataga and T. Kubota, Molecular Interactions and Electronic Spectra, Marcel Dekker Inc., NY, 1970.

    Google Scholar 

  27. S. M. Andrade and S. M. B. Costa, Hydrogen bonding effects in the photophysics of a drug, piroxicam, in homogeneous media and dioxane-water mixtures, Phys. Chem. Chem. Phys, 1999, 1, 4213–4218.

    Article  CAS  Google Scholar 

  28. R. Andriessen, N. Boens, M. Ameloot and F. C. Schryver, Non a priori analysis of fluorescence decay surfaces of excited-state processes. 1. Theory, J. Phys. Chem., 1991, 95, 2041–2047.

    Article  Google Scholar 

  29. J. S. Melo and A. L. Maçanita, Three interconverting excited species: experimental study and solution of the general photokinetic triangle by time-resolved fluorescence, Chem. Phys. Lett., 1993, 204, 556–562.

    Article  Google Scholar 

  30. G. B. Dutt, N. Boens, A. Kowalczyk, F. C. Schryver and M. Ameloot, Experimental design in global compartimental analysis of reversible intramolecular two-state excited-state processes with added quencher, J. Phys. Chem. A, 1997, 101, 1993–2002.

    Article  CAS  Google Scholar 

  31. C. A. T. Laia and S. M. B. Costa, Fluorescence quenching of a squarine dye by water in AOT reversed micelles, J. Chem. Soc, Faraday Trans., 1998, 94, 2367–2373.

    Article  CAS  Google Scholar 

  32. J. Ferguson and A. W. H. Mau, Absorption studies of acid-base equilibria of dye solutions, Chem. Phys. Lett., 1972, 17, 543–546.

    Article  CAS  Google Scholar 

  33. S.-H. Chou and M. J. Wirth, Rotational diffusion of acridine orange attached to SDS micelles, J. Phys. Chem., 1989, 93, 7694–7698.

    Article  CAS  Google Scholar 

  34. O. A. El Seoud, L. T. Okano, L. P. Novaki and G. K. Barlow, Proton NMR studies on the structure of water in ionic and nonionic water-in-oil microemulsions, Ber. Bunsen-Ges Phys. Chem., 1996, 100, 1147–1152.

    Article  Google Scholar 

  35. C. Oldfield, B. H. Robinson and R. B. Freedman, Acid-base behaviour of 4-nitrophenol and 4-nitrophenyl-2-sulphonate in water-in-oil microemulsions stabilized by aerosol-OT, J. Chem. Soc, Faraday Trans., 1990, 86, 833–841.

    Article  CAS  Google Scholar 

  36. O. Ortona, V. Vitagliano, R. Sartorio and L. Constantino, Spectrophotometric study of the interaction of poly(styrenesulfonic acid) with a metachromatic dye in methanol, J. Phys. Chem., 1984, 88, 3244–3248.

    Article  CAS  Google Scholar 

  37. R. Allen, S. Bandyopadhyay and M.L. Klein, C12E2 reverse micelle: A molecular dynamics study, Langmuir, 2000, 16, 10547–10552.

    Article  CAS  Google Scholar 

  38. D.-M. Zhu, X. Wu and Z. A. Schelly, Investigation of the micropolarity in reverse micelles of triton X-100 in mixed solvents of benzene and hexane, J. Phys. Chem., 1992, 96, 7121–7126.

    Article  CAS  Google Scholar 

  39. R. J. Robson and E. A. Dennis, The size, shape and hydration of nonionic surfactant micelles. Triton X-100, J. Phys. Chem., 1977, 81, 1075–1077.

    Article  CAS  Google Scholar 

  40. D. Pant and N. E. Levinger, Polar solvation dynamics in nonionic reverse micelles and model polymer solutions, Langmuir, 2000, 16, 10123–10130.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Andrade, S.M., Costa, S.M.B. The aqueous environment in AOT and Triton X-100 (w/o) microemulsions probed by fluorescence. Photochem Photobiol Sci 1, 500–506 (2002). https://doi.org/10.1039/b201477g

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b201477g

Navigation