Sarin, used as chemical warfare agents (CWAs) for terrorist attacks, can induce a number of virulent effects. Therefore, countermeasures which could realize robust and convenient detection of sarin are in exigent need. A concise charge-transfer colorimetric and fluorescent probe (4-(6-(tert-butyl)pyridine-2-yl)-N,N-diphenylaniline, TBPY-TPA) that could be capable of real-time and on-site monitoring of DCP vapor was reported in this contribution. Upon contact with DCP, the emission band red-shifted from 410 to 522 nm upon exposure to DCP vapor. And the quenching rate of TBPY-TPA reached up to 98% within 25 s. Chemical substances such as acetic acid (HAc), dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PAMP), and triethyl phosphate (TEP) do not interfere with the detection. A detection limit for DCP down to 2.6 ppb level is remarkably achieved which is below the Immediately Dangerous to Life or Health concentration. NMR data suggested that a transformation of the pyridine group into pyridinium salt via a cascade reaction is responsible for the sensing process which induced the dramatic fluorescent red shift. All of these data suggest TBPY-TPA is a promising fluorescent sensor for a rapid, simple, and low-cost method for DCP detection, which could be easy to prepare as a portable chemosensor kit for its practical application in real-time and on-site monitoring.

A series of benzothiadiazole-pyridine branched triphenylamine derivatives TPA1BP, TPA2BP and TPA3BP have been designed and synthesized to sense aniline vapor with distinguished sensitivity, selectivity and repeatability via photoinduced electron transfer (PET). Suitable energy levels ensure the high selectivity to aniline for all three sensory materials. However, the aggregations of the three materials in the film state on a quartz substrate increase along with the branches, which highly deteriorate the sensing performance for less efficient fluorescence, lower contact area and inferior vapor penetration. The oriented ZnO nanorod array is introduced as the substrate to eliminate the aggregation and enhance the sensing performance, because of its high surface-to-volume ratio and 3D structure. Therefore, the cooperative effect that the sensing performance of TPAnBP increases with the number of branches could be observed; fluorescence intensities of the films on the nano-substrate are 34%, 45% and 54% quenched for TPA1BP, TPA2BP and TPA3BP, respectively, after exposure to 300 ppm aniline vapor for less than 5 s. Moreover, the fluorescences of all three sensory materials are almost 100% recovered by eluting with fresh air for 20 s and could be reused immediately. The detection limits are predicted to be 1 ppm for TPA1BP, 100 ppb for TPA2BP and 1 ppb for TPA3BP according to the fitted plot, demonstrating a significant cooperative effect of the molecular branches.