4-(8-Quinolyl)amino-7-nitro-2,1,3-benzoxadiazole as a new selective and sensitive fluorescent and colorimetric pH probe with dual-responsive ranges in aqueous solutions

•A new fluorescent and colorimetric pH probe (1) was synthesized.•The probe could be applied as a colorimetric probe to pH change from 8.5 to 13.3.•The probe could be used as a fluorescent “turn-on” pH probe with a pH range from 2.2 to 0.2.

Fluorescent and colorimetric pH probe possess many advantages including rapid response time, nondestructive testing, and excellent pH sensitivity. However, they usually cannot be utilized simultaneously in both acidic and basic pH ranges. In this study, a new selective and sensitive fluorescent and colorimetric pH probe, 4-(8- quinolyl)amino-7-nitro-2,1,3-benzoxadiazole (1), was designated and synthesized. The optical probe exhibited dual-responsive pH ranges to both acidic and basic aqueous solutions. When the solution pH was gradually increased from 8.5 to 13.3, the absorption spectra of 1 showed an obvious hyperchromicity, accompanied with a red shift of the absorption band at 340 nm, a blue shift of the absorption band at 482 nm, and a distinct color change from orange to violet pink to yellow. Within the pH range from 2.2 to 0.2, the fluorescent spectra of 1 showed a “turn-on” response signal to solution pH. In order to understand the response mechanism of the probe to solution pH, the probe molecule was split into two parts, 8-aminoquinoline (2) and 4-amino-7- nitro-benzofurazan (3). UV–vis absorption and fluorescent experiments of 2 and 3 indicated that both are sensitive optical pH probes. Furthermore, the NMR experiment of 1 was explored in basic and acidic conditions. The results indicated that the colorimetric responses of 1 to pH under basic condition should be attributed to the deprotonation of the imino group on the quinolyl ring, and the fluorescent recognition of 1 to pH under acidic condition was probably due to the protonation of the nitrogen atoms from the benzofurazan and quinolyl rings.

Graphical abstractA fluorescent and colorimetric pH probe, 4-(8-quinolyl)amino-7-nitro-2,1,3-benzoxadiazole (1), was synthesized. Under alkaline condition, 1 with a pKa value 10.5 could be applied as a colorimetric probe to pH change from 8.5 to 13.3. And 1 with a pKa value 1.4 could be used as a fluorescent “turn-on” pH probe under strong acidic condition (pH value is from 2.2 to 0.2).Figure optionsDownload full-size imageDownload as PowerPoint slide