Fluorene-naphthalene Schiff base as a smart pigment in invisible ink with multiple security features for advanced anticounterfeiting and forensic applications

J Colloid Interface Sci. 2024 Jan;653(Pt A):209-219. doi: 10.1016/j.jcis.2023.09.033. Epub 2023 Sep 7.

Abstract

Smart functional materials with captivating optical properties are of immense importance due to their versatile applicability in anticounterfeiting and forensic science. A fluorene-naphthalene Schiff base (FNH) that displays aggregation induced emission, mechanofluorochromism and excitation wavelength dependent fluorescence inherent to the pristine and ground samples is synthesized. Water/solvent-based invisible security inks for flexo/screen printing were formulated using FNH as a smart pigment to check the originality of documents/branded products etc. The prints with good photostability, adherence to substrate and rub resistance are invisible in daylight showcasing multiple non-destructive and destructive techniques to authenticate the document. The inked area on UV dull paper substrate exhibits a weak emission, which is observed by the forger under UVA light. However, the user can validate the authenticity of the document by rubbing the print with hard objects, especially using a metal coin or glass rod to perceive a human eye detectable intensification in the orange fluorescence under the same illumination source. The intensity of the orange fluorescence reverts to the original, which enables the reuse of the security document after originality check. Yet another nondestructive authentication method is to observe a cyan fluorescence from the print and orangish yellow fluorescence from the rubbed printed region when shined with a 270-400 nm light source, whereas a cyanish green fluorescence both from the unrubbed and rubbed regions of the print when illuminated with a visible light source ranging from 420 to 480 nm. An additional verification through a destructive technique is to perceive red and yellow fluorescence of the ink film upon contact with THF and NaOH/KOH, respectively and a penetrating red fluorescence from the rear side of the THF-exposed printed area of the paper. The multi-level security features that cannot be easily replicated by the forger but allows a simple and easy validation process by the user are unique to FNH, used as a single pigment in the inks. Further, the applicability of the ground FNH in forensic science is established to distinctly observe Level I to II details of latent fingerprints.

Keywords: Aggregation induced emission; Fluorene-naphthalene Schiff base; Invisible security ink for anticounterfeiting, Latent fingerprint detection; Rub-induced excitation wavelength dependent fluorescence.