Preparation and dynamic color-changing study of fluorescent polymer nanoparticles for individualized and customized anti-counterfeiting application

Abstract

Preparing new fluorescent materials for individualized and customized anti-counterfeiting applications to meet needs from the rapid development of e-commerce is of great significance. This paper reports the preparation of dynamic color-changing fluorescent polymer nanoparticles (PNPs) by constructing a fluorescence resonance energy transfer (FRET) pair between aggregation-induced emission (AIE) structures and photochromic structures. At first, methyl methacrylate (MMA) was used as the main monomer and tetraphenylethylene (TPE, a typical AIE structure) modified methacrylate (TPE-MA) and photochromic spiropyran (SP) modified methacrylate (SP-MA) as minor monomers were copolymerized to obtain the ternary copolymer PMMA-TPE-SP. Then, two types of PNPs based on this terpolymer was prepared via the reprecipitation method, with and without the addition of an amphiphilic polymer as the surfactant. The photophysical study shows that the fluorescence color of PNPs dynamically changes from blue to light violet and finally to red under UV light irradiation, a process that can be reversed under visible light. The PNPs were alternately irradiated with UV light and visible light for 10 cycles, which proved their good photoswitching reproducibility. The PNPs prepared with addition of surfactant were found to have stronger fluorescence and better stability. Finally, the photochromic fluorescent inks were prepared based on these PNPs. Several anti-counterfeiting scenarios and modes were designed, exhibiting excellent photochromic behavior on cellulose paper, even after 120 days of long-term storage. With simple equipment, desirable anti-counterfeiting effects with dynamic fluorescence color changing was achieved. This study demonstrated a promising hard-to-imitate anti-counterfeiting encryption strategy, which can achieve multiple outputs with simple operation and can be personalized and customized as needed.