Single-layer assembly of pyrene end-capped terthiophene and its sensing performances to nitroaromatic explosives

Abstract

A terthiophene (3T) derivative of 5-(1-pyrenyl)-2,2′:5′,2′′-terthiophene (Py-3T) was synthesized and chemically immobilized onto a glass wafer surface via a flexible spacer by employing a single-layer chemistry technique. Unlike the film fabricated in the same way but with 3T as the fluorophore, the film fabricated in the present study possesses unprecedented photochemical stability at ambient conditions. Fluorescence studies revealed that the emission of the film as fabricated is significantly and selectively quenched by the presence of nitroaromatic compounds (NACs), a group of typical explosives, both in the vapor phase and in aqueous solution. Experimental and theoretical studies demonstrated that the quenching may be a result of electron transfer from the electron-rich Py-3T to the electron-deficient NACs. It was found that for vapor phase sensing, the response time and the quenching efficiency of the systems are dominantly determined by the vapor pressures of the NACs tested. The sensing performances of the film to NACs in aqueous phase were also investigated. In this case, however, the specific binding of the film to picric acid (PA), a typical NAC, makes the compound show a superior quenching efficiency than other NACs. Moreover, the response is fast and reaches equilibrium within 90 s. Furthermore, acids, bases, apple juice, perfume, and commonly found organic solventsetc. show little effect upon the sensing in aqueous phase. Both the vapor phase sensing and the aqueous solution sensing are reversible. Furthermore, the film is stable for at least 6 months provided it is properly preserved. The basic contribution of the present work is not only creating a new fluorescent film of superior sensing properties to NACs in the vapor phase, in particular to PA in the aqueous phase, but also providing a new photochemically stable fluorophore, which may combine the advantages of small molecular fluorophores and those of conjugated polymers/oligomers, for developing new fluorescent sensing films.