Dual-Mode Photonic Sensor Array for Detecting and Discriminating Hydrazine and Aliphatic Amines

Colorimetric chemosensors have attracted tremendous interest for sensing hazardous substances in an uncomplicated and economical manner. Herein, a series of push–pull dicyanovinyl-substituted oligothiophene derivatives were designed, and the impacts of different end-cappers on their photophysical properties were comprehensively investigated. Interestingly, combined with a zinc porphyrin derivative (Zn-TPP), one dicyanovinyl-substituted oligothiophene derivative (NA-3T-CN) can be further developed into colorimetric and fluorescent sensor array for dual-mode detection of aliphatic amines and hydrazine. The obtained sensors showed satisfactory results between optical response and analyte’s concentration both in selective single-sensor type and in enhanced multisensory mode. Based on the fluorescence change of the NA-3T-CN system, the detection limit for N₂H₄ was calculated to be around 1.22 × 10^–5 mol/L in THF. The stained TLC-supported sensor array offers obvious optical changes for down to 0.5 wt % hydrazine solution for naked-eye sensing. An aromatic amine like aniline has no obvious effect on the dicyanovinyl-substituted oligothiophene derivatives. We also found that a zinc porphyrin derivative has an obvious colorimetric response to the presence of hydrazine, ethanolamine, and aniline. Furthermore, smartphone-enabled readout system and data treatment based on RGB changes of the sensor array were performed, and the discrimination capability among hydrazine, aliphatic amines, and aromatic amine was satisfactory. In this regard, related push–pull oligothiophene derivatives not only can be regarded as models for a fundamental understanding of the relationship between molecular structure and photophysical properties but also present potential applications in the field of real-time and visual detection of hazardous chemicals.