Investigation of developed photoactive security inks and anticounterfeiting technologies in recent years indicates significant challenges for future of this research area, such as increase of security, fast responsivity, and facile authentication. Here, amine-functionalized latex nanoparticles were synthesized by emulsion copolymerization of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). Size of the latex nanoparticles was increased as a function of poly(dimethylaminoethyl acrylate) (PDMAEMA) contents, and also a decrease of particle size was obtained in response to an increase of temperature from 25 to 70 °C, above the lower critical solution temperature (LCST) of PDMAEMA. Surface physical modification of the functional latex nanoparticle with spiropyran photoswitches led to the development of anticounterfeiting nanoinks that have multilevel security and photochromic/fluorescence properties with a higher intensity and also brightness. The photoluminescent nanoinks were made of spiropyran latex nanoparticles and used for printing of the encoded optical security tags on cellulosic papers and banknotes. The results displayed that an increase of the particle size above 100 nm and an increase of the PDMAEMA contents led to a remarkable decrease of printability, fluorescent emission, brightness, intensity of photochromism, and also resolution of the printed security tags. As a significant advantage of the developed security inks, the printed security tags could be authenticated easily and fast upon sunlight irradiation by means of photochromism. The responsivity of encoded tags from the invisible to visible state is immediate upon sunlight irradiation for some seconds, whose intensity of coloration is appropriate and detectable clearly by naked eyes. The security anticounterfeiting inks based on spiropyran with multilevel security have been reported for the first time for applying in printing of encoded security tags on cellulosic papers, banknotes, and other documents, where the printed marks are detectable on sunlight exposure.

Photoluminescent Nanoinks with Multilevel Security for Quick Authentication of Encoded Optical Tags by Sunlight: Effective Physicochemical Parameters on Responsivity, Printability, and Brightness

• Synthesis of colloidal nanoparticles with different polarity and particle size, • Preparation of spiropyran-containing photochromic colloidal nanoparticles, • Effect of polarity on the fluorescence emision and photochromism of colloidal nanoparticles, • Development of the photochromic colloidal nanoparticles as anticounterfeiting nanoinks, • Application of the smart nanoinks for encrypting security documents. Dual photochromic and photoluminescent latex nanoparticles were synthesized to develop innovative anticounterfeiting nanoinks with applications in encryption technology. The colloidal nanoparticles bearing hydroxyl groups were resulted from semi-continuous miniemulsion copolymerization of 2-hydroxyethyl methacrylate and methyl methacrylate. Investigation of the particle size determination and microscopic analysis results demonstrated spherical morphologies for the latex nanoparticles with a mean size of about 80 nm and narrow size distribution. Modification of the polymer nanoparticles with hydroxyl functional groups led to the formation of a high level of hydrogen bonding between the hydroxyl groups and spiropyran chromophore, which is an advantage in the preparation of security anticounterfeiting nanoinks. In addition, optical analysis of the photochromic latex samples showed various UV-vis spectra, fluorescence emission, kinetics of isomerization, and photo-fatigue resistance depending on different amounts of the polar monomers. Further investigations on optical properties exhibited that reducing the size of the colloidal samples can affect their photoluminescence characteristics. This is an efficient way to provide remarkable photoreversible anticounterfeiting inks for different applications, such as printed photo-marking, rewritable handwriting patterns, security encoded tags, and labeling. 

Photochromic polymer nanoparticles as highly efficient anticounterfeiting nanoinks for development of photo-switchable encoded tags

Colloidal materials have widely been used to develop innovative anticounterfeiting nanoinks for information encryption. Latex nanoparticles based on methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) bearing hydroxyl functional groups were synthesized via semicontinuous miniemulsion polymerization. The size determination of the nanoparticles and microscopic results showed mostly spherical nanoparticles with a narrow size distribution and a mean size of about 80 nm. Two oxazolidine derivatives were physically doped at the surface of the nanoparticles to prepare photoluminescent polymer nanoparticles. Hydroxyl functional groups at the surface of the nanoparticles led to their hydrogen bonding interactions with the doped luminescent compounds. Optical analysis of the photoluminescent nanoparticles displayed different fluorescence emission and UV-vis absorbance intensities based on the amount of polar groups located at the surface of colloidal nanoparticles. Reducing the particle size to below 100 nm along with increasing the surface area can assist the decrease of the light reflectance and improvement of the latex nanoparticles' efficiency in the anticounterfeiting industry. This preparation methodology can efficiently provide remarkable photoreversible anticounterfeiting nanoinks used in different applications, such as print marking, security encoded tags, labeling, probing, and handwriting.

Photoluminescent Polymer Nanoparticles Based on Oxazolidine Derivatives for Authentication and Security Marking of Confidential Notes.

The conventional nanoscale anti-counterfeiting scheme, exhibiting limited encoding capacity, faces growing challenges of being falsified with the advent of advanced high-resolution equipment. In this study, we propose a multilevel anti-counterfeiting device based on a femtosecond laser (fs-laser) treated plasmonic gold nanocluster/graphene (AuNC/Gr) hybrid structure integrated with a resonant cavity. The covert structural features encoded in random colored patterns, optical reflection spectra, and Raman spectra constitute three classes of anti-counterfeiting signatures, which originate from the AuNC-covered Gr, which initiates plasmonic and thermal couplings. The attendant inverted thermal distribution is presumed to confine the structural features to the AuNC-Gr interface while leaving no detectable traces on the surface of AuNC/Gr even under advanced high-resolution equipment. Therefore, the proposed approach achieves multilevel anti-counterfeiting accomplishing physically unclonable functions in the form of random colored patterns, reflection spectra, and Raman spectra. As the first report for realizing remarkable optical modulation (i.e., random colored patterns) without any surface trace or damage via fs-laser-AuNC/Gr interaction, our study also discloses the outstanding performance of Gr in fs-laser-induced optothermoplasmonic lithography on near-percolation metal films. Simultaneously, the demonstrated fs-laser-processed plasmonic hybrid structure in conjunction with a resonant cavity is anticipated to expand the encoding capabilities for nanoscale anti-counterfeiting while avoiding the risk of being imitated because of the covert structural features.

Multilevel Anti-Counterfeiting Based on Covert Structural Features Embedded in Femtosecond-Laser-Treated Gold Nanocluster/Graphene Hybrid Layer.

Real-time characterization of gelatin doped with potassium dichromate as a photosensitive material

Direct texturing of nanostructures on consumable substrates and products is a challenge because of incompatible ingredients and materials' properties. Here, we developed a direct laser-based method to print nanostructured holograms on dried films of consumable corn syrup solutions. A holographic laser (λ = 1050 nm) interference system was used to construct the nanostructures of the holograms on food for rainbow effects. The relationship between wavelength and periodicity contributed to the changing diffraction angle through the change of the refractive index (1.642). Increasing the sugar concentration (25-175 mg) in the syrup increased the diffraction efficiency of these holograms. The added amount of sugar in the composition increased the refractive index (7%) and decreased the light absorption (12.9%), which influenced the change of diffraction angle by 4.4°. The surface holograms displayed wideband visual diffraction of light extending from violet to red wavelengths. These holograms on edible materials can be imprinted onto commercial food products for adding aesthetic value and controlling perception.

Joelle Doocey

Papers

Direct Printing of Nanostructured Holograms on Consumable Substrates.