Developing a new anti-counterfeiting strategy is of great significance to combating the global counterfeiting problem. Here we report the construction of a dynamic fluorescence response system for anti-counterfeiting by combining the photochromism induced by the ring-opening of spiropyran (SP) to merocyanine (MC) with the fluorescence resonance energy transfer (FRET) between the conjugated polymer and MC. After elucidating the design principle, a new conjugated polymer, PPETE-SP, consisting of a poly[p-(phenylene ethynylene)-alt-(thienylene-ethynylene)] (PPETE) backbone with pendant SP, was synthesized and characterized. With poly(methyl methacrylate) (PMMA) as the matrix, the PPETE-SP/PMMA fibrous membrane was prepared via electrospinning. Under the irradiation of UV light, the fluorescent color of the membrane dynamically changed from green to light green, then light pink, and finally pink, and this process was reversible under visible light. The fluorescence emission switch was examined for 10 cycles and proved to have good repeatability, indicating that the membrane can be directly used as an anti-counterfeiting label for multiple verifications. The FRET efficiency was found to be about 61% based on the FRET study with confocal laser scanning microscopy. The covalent bonding between PPETE backbone and SP, the confinement of PPETE-SP chains in the fibrous membrane, as well as employing PMMA as the matrix were demonstrated to be crucial in realizing the photochromism and the FRET. Different anti-counterfeiting modes were proposed, providing rich selections for operation of verification. Such facile-to-operate and hard-to-imitate dynamic fluorescent responsive materials are very promising for use in practical anti-counterfeiting applications.
Keywords: anti-counterfeiting; conjugated polymer; dynamic fluorescence response; fibrous membrane; fluorescence resonance energy transfer; photochromism; spiropyran.