Inner Filter Effect and Resonance Energy Transfer Based Attogram Level Detection of Nitroexplosive Picric Acid Using Dual Emitting Cationic Conjugated Polyfluorene

Abstract

A novel conjugated cationic polyfluorene (polyelectrolyte) derivative, PFBT, was developed by means of simple and cost-effective oxidative coupling polymerization method. PFBT displayed dual state emission in dimethyl sulfoxide (DMSO) as well as in water, a characteristic phenomenon of polyfluorene homopolymers, and tested for nitroexplosive analytes detection to observe a remarkable fluorescence quenching response for picric acid (PA) in the both solvents. The polymer PFBT demonstrated substantial selectivity and ultrasensitivity toward nitroexplosive PA in both the solvents (DMSO and H₂O) with exceptional quenching constant values of 2.69 × 10⁴ and 2.18 × 10⁵ M^-1 and a ultralow limit of detection of 92.7 nM (21.23 ppb) and 0.19 nM (43.53 ppt) in respective solvents. Furthermore, economical portable test strip devices were prepared for easy and fast on-site PA sensing, which can detect up to 0.22 ag level of PA. PA sensing in vapor phase was also established, that could detect up to 42.6 ppb level of PA vapors. Interestingly, the mechanism of sensing in DMSO solvent was attributed to substantial inner filter effect and photoinduced electron transfer, while in H₂O the sensing occurs via possible resonance energy transfer and photoinduced electron transfer, which is exceptional and not reported earlier for a single probe.