Copper ion-selective fluorescent sensor based on the inner filter effect using a spiropyran derivative

A highly selective copper(II) ion fluorescent sensor has been designed based on the UV-visible absorption of a spiropyran derivative coupled with the use of a metal porphyrin operative on the fluorescence inner filter effect. Spiropyrans, which combine the characteristics of metal binding and signal transduction, have been widely utilized in cationic ion recognition by UV-visible spectroscopy. In the present work, the viability of converting the absorption signal of the spiropyran molecule into a fluorescence signal was explored. On account of overlap of the absorption band of the spiropyran (λ_abs = 547 nm) in the presence of copper ion with the Q-band of an added fluorophore, zinc meso-tetraphenylporphyrin (λ_abs = 556 nm), the effective light absorbed by the porphyrin and concomitantly the emitted light intensity vary as a result of varying absorption of the spiropyran via fluorescence inner filter effect. The metal binding characteristic of the spiropyran presents an excellent selectivity for copper ion in comparison with several other heavy or transition metal ions. Since the changes in the absorbance of the absorber translate into exponential changes in fluorescence of the fluorophore, the novelty of the present device is that the analytical signal is more sensitive over that of the absorptiometry or that of the fluorometry using one single dye. To realize a practical fluorescent sensor, both the absorber and fluorophore were immobilized in a plasticized poly(vinyl chloride) membrane, and the sensing characteristics of the membrane for copper ion were investigated. The sensor is useful for measuring Cu²⁺ at concentrations ranging from 7.5 × 10^-7 to 3.6 × 10 ^-5 M with a detection limit of 1.5 × 10^-7 M. The sensor is chemically reversible, the fluorescence was switched off by immersing the membrane in copper ion solution and switched on by washing it with EDTA solution.