Abstract

Generalized two-dimensional (2D) correlation spectroscopy has been applied to the analysis of fluorescence spectra in two micellar systems: (1) a mixture of pyrene and 1,3,6,8-pyrenetetrasulfonic acid in the cationic micellar solutions of cetyltrimethylammonium chloride (CTAC) and (2) a mixture of pyrene and 9-anthracencepropionic acid in anionic micellar solutions of sodium dodecyl sulfate (SDS). Fluorescence quenching is employed as a perturbation mode for causing intensity changes in fluorescence bands ( quenching perturbation). Iodide ion (I −) is used as a quencher in the former system, and cetyl pridinium chloride (CPC) is used in the latter. Vibronic bands in the complicated fluorescence spectra of the mixture of the analytes were successfully resolved. It is shown that asynchronous maps are especially useful for spectral resolution enhancement when the quenching perturbation is employed in 2D fluorescence correlation spectroscopy. Furthermore, the information about the order of response of the bands to quenching is obtained by comparing the signs of synchronous and asynchronous cross-peaks.

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