Journal of Colloid and Interface Science, Vol.213, No.1, 29-35, 1999
Self-assembled supramolecular micellar structures based on non-ionic surfactants and cyclodextrins
The complexation between non-ionic polyethylene oxide (PEO)-based surfactants (Triton X-45, Triton X-100, polyethylene glycol 1000-monostearate, and Brij 35) and cyclodextrins is studied. It is shown that the addition of surfactant solutions to the aqueous solution of alpha, beta-, and gamma-cyclodextrins affords poorly soluble crystalline precipitates. Parameters of crystalline structure and the composition of complexes are analogues to those obtained on the basis of polyethylene oxide. Using a method of surface tension it is shown that cyclodextrins favor the increase of the value of critical micelle concentration (CMC) of surfactants. The dependence of CMC from the molar ratio cyclodextrin/surfactant permits us to determine the composition of inclusion complexes in solution. For Triton X-100 and polyethylene glycol-1000-monostearate values of stoichiometric composition of complexes in solution and in condensed phase agree well. It is shown that in the presence of beta-cyclodextrin the destruction of micelles based on Triton X-100 occurs. UV-spectroscopy is used for the investigation of the microenvironment of a phenyl group in inclusion complexes based on alpha- and beta-cyclodextrins. The interaction of gamma-cyclodextrin with PEO surfactants results in the formation of novel double-tailed surfactants. The values of CMC registered in solutions of these complexes is lower than the corresponding value of Triton X-100 and polyethylene glycol-1000-monostearate. The stoichiometric composition of complexes in solution is established from the dependence of CMC versus the gamma-cyclodextrin/surfactant ratio. The composition of the complexes in solution and condensed phase agree well. The interaction of alpha- and gamma-cyclodextrins with Brij 35 results in the formation of nonstoichiometric complexes. The investigation of the dependences of CMC of modified surfactants from temperature shows that these supramolecular structures exist at high temperatures.
Keywords:cyclodextrin;nonionic surfactants;inclusion complexes;crystalline structure;surface tension;molecular necklaces;self-assembly