Immobilization of pyrene on quartz plate surface via a flexible long spacer and its sensing properties to dicarboxylic acids

Abstract

A novel photo-induced luminescence film has been prepared by immobilizing pyrene on quartz plate surface via a flexible long spacer, 1,3-diaminopropane and 3-glycidoxypropyl trimethoxysilane. The film shows combined monomer and excimer emission of pyrene in both wet and dry states. Steady-state and time-resolved fluorescence emission measurements demonstrated that the excimer emission mainly came from direct excitation of ground state dimers, and/or monomers in aggregated state. Classical Birks’ scheme plays little role in the formation of the excimers. The structures of the excimers formed during the excitation are complex. Both “standard excimer” of sandwich-like fully overlapped structure and ‘distorted excimer” of partially overlapped structure exist in the excited state of the fluorophore. The emission of the film is sensitive to the presence of dicarboxylic acids, including ethanedioic acid, malonic acid, succinic acid, etc. The emission in the monomer and excimer region increases along with increasing the concentration of the dicarboxylic acids. The time needed for the emission to reach equilibrium depends on the nature of the acids. It has been shown that the longer the chain length of the acids, the more the time needed. This observation is explained by considering the conformational reorganization of the immobilized pyrene due to insertion of the dicarboxylic acids into the space between neighboring spacers. Experimental results from similar studies using formic acid and acetic acid are in support of this explanation. Furthermore, the response of the film to dicarboxylic acids is reversible.