Development of copper(I) fluorescent sensors based on photoinduced electron transfer mechanism and their application to optical imaging of cells

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We have developed copper(I)-selective fluorescent probes as a chemical tool for monitoring behavior of copper ions in living cells. We initially synthesized various tioether-containing ligands and prepared the corresponding copper(I) complexes. Spectroscopic measurements and X-ray crystal structure analysis of these copper(I) complexes indicate that the linker chain length of the thioether ligand strongly affect the affinity toward copper(I) ion, binding fashion, and redox potential of copper. We next developed novel copper(I) fluorescent probes based on the oxidative cleavage mechanism. These probes contain a reduced form of fluorescein and TPA tetradentate ligand, those are linked through a benzyl ether group. We found that strong fluorescence is observed when copper(I) is added to the probe solution containing sub mM of gluthatione in water. The same reaction undergoes even in cells. Therefore, this will be useful chemical tool to probe intracellular copper(I) ion behavior.