It has been established by combined absorption and fluorescence measurements that the cationic dye Oxazine 1 (OX) and the polyvalent anionic host calixarenesulfonate (SCA8) form two complexes in simultaneous reactions: OX + SCA8 ↔ OX·SCA8 (1), and OX·SCA8 + OX ↔
OX2·SCA8 (2). The equilibrium constants for the two reactions, as functions of the ionic strength (I), and the absorption and fluorescence spectra of the two complex species have been determined by a least-squares fitting method from the experimental data. The variations
of the binding constants with the ionic strength could be described on the basis of Debye–Hückel theory. The equilibrium constants are large; their values extrapolated to I = 0 are K(1) = 5.5 x 106 M-1 and K(2) = 4.4 x 105 M-1.
The fluorescence of OX undergoes a strong static quenching upon complexation. These results indicate that the complexes are held together by strong electrostatic forces. The addition of non-fluorescent tetramethylammonium chloride to OX–SCA8 mixtures results in a dramatic fluorescent
enhancement, which demonstrates the potential applicability of this supramolecular system in fluorescence assays.
Department of Physical Chemistry, Budapest University of Technology and Economics, 1521 Budapest, Hungary
Publication date: January 1, 2005
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