Dual-Color Photoluminescent Functionalized Nanoparticles for Static-Dynamic Anticounterfeiting and Encryption: First Collaboration of Spiropyran and Coumarin

Increasing the security of anticounterfeiting materials has been the most important challenge in recent years, and the development of dual-color photoluminescent inks with multi-level security, static/dynamic emission, and dynamic color change is an important solution to overcome this problem. In this study, the multi-functionalized copolymer nanoparticles containing different functional groups (with a concentration of 20 wt %), including ester, carboxylic acid, hydroxyl, epoxide, amide, and amine groups were synthesized successfully by the emulsion polymerization method. The results showed that the particle size and morphology of nanoparticles are affected by the polarity of functional groups. The prepared multi-functionalized copolymer nanoparticles were modified physically with spiropyran (photochromic and red fluorescence emission) and coumarin (cyan emission) derivatives to develop dual-color photoluminescent polymer nanoparticles with application in static-dynamic photoluminescent anticounterfeiting inks, which have multi-level security. The investigation of optical properties indicates that the kinetics of photochromism and photoluminescence properties of samples containing spiropyran is dependent on the local polarity on the surface of polymer nanoparticles. Hence, an increase in the polarity (functionalization with amide, carboxylic acid, and hydroxyl groups) has resulted in fast photochromism, high-intensity photoluminescence emission and increased the efficiency of the photoswitchable color change of emission from cyan to pink. Dual-color photoluminescent anticounterfeiting inks were prepared by mixing polymer nanoparticles containing spiropyran with polymer nanoparticles containing coumarin, in different ratios (1:1, 1:3, 1:5, 1:8, and 1:10). Obtained results showed that prepared samples have cyan emission under UV light of 254 nm (static mode), and a dynamic photoswitching of fluorescence emission from cyan to pink (as a function of irradiation time) was also observed under UV-light irradiation of 365 nm, which is well known as a dynamic mode of emission. The responsivity and intensity of dynamic photoluminescence emission are dependent on the local polarity of the surface functional groups, in which the samples based on amide functionalized copolymer nanoparticles displayed high-intensity emission in the static mode and high-intensity photoswitchable dual-color emission in the dynamic mode, in the case of all ratios of colloid solution mixtures. Printing security tags on cellulose paper by dual-color photoluminescent inks indicates advantages such as maximum printability, resolution, brightness, and static-dynamic photoluminescence emission with high intensity for inks based on amide functionalized nanoparticles. The static-dynamic dual-color photoluminescent anticounterfeiting ink with unique properties and multi-level security was reported for the first time by the collaboration of spiropyran and coumarin. This study can open a new approach and window to the future of advanced and high-security anticounterfeiting technologies.