Thermodynamic and Kinetic Study of the Interaction between Alkylpyridinium Ions and Pyrene Derivatives in Aqueous Solution

Photochemistry and Photobiology - Tập 66 Số 6 - Trang 802-809 - 1997
Helen Rosenbluth1, Boris Weiss‐López1, Andrés F. Olea1
1Departamento de Química, Facultad de Ciencias, Universidad de Chile , Casilla 653, Santiago, Chile.

Tóm tắt

Abstract— The kinetics of fluorescence quenching of pyrene and three of its derivatives by a series of n ‐alkylpyridinium ions has been studied. The quenching process is diffusion controlled for all the systems studied, independent of the charge in the aromatic molecule and the size of the alkyl chain in the pyridinium ions. Pyrensulfonate, PS, and pyranine form ground‐state complexes with these quenchers. The association constants were determined by using a kinetic scheme where both dynamic and static quenching were included. A linear relationship between the free energy change and number of carbon atoms was found for PS, and a methylene contribution equal to ‐1.1 kJ/mol was determined from the slope. A similar correlation was established for pyranine, but a slope change was observed when the alkyl chain has more than 10 carbon atoms. From the initial slope, an incremental free energy of ‐0.35 kJ/mol was obtained. The ground‐state complex formation is determined mainly by an electrostatic interaction, but there is a hydrophobic effect on the value of the measured association constants.

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Photochemistry and Photobiology

Tập 66 Số 6

802-809

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