Fabrication of Robust Spatially Resolved Photochromic Patterns on Cellulose Papers by Covalent Printing for Anticounterfeiting Applications

Abstract

Despite its millennial age, cellulose paper remains the preferred material for domestic and professional printings, covering applications from simple office paperwork to fiducial solutions such as bills, passports, and head letters. The creation of robust photochromic patterns on cellulose papers for anti-counterfeiting applications is an important and still partially unaddressed challenge. In this contribution, we report the covalent printing of dibenzothienylethenes as photochromic compounds through a spatially-controlled light mediated thiol-X ligations. Photophysical and theoretical studies provide evidences for a reversible photochromism behavior, not affected significantly by the polar environment of the cellulose matrix, and demonstrates a high fatigue resistance over 18 successive write-erase cycles. The strong coloration-discoloration switch can be easily followed by a direct nakedeye readout.

Photoluminescent and Chromic Nanomaterials for Anticounterfeiting Technologies: Recent Advances and Future Challenges

“…They reported chemical incorporation of a diarylethene derivative to cellulosic papers via covalent printing of dibenzothienylethenes as the photochromophore through spatially controlled light-mediated thiol-X ligations. 105 The results obtained from the photophysical and theoretical studies confirmed reversible photochromism of diarylethene without any negative photochromism with higher photostability and photofatigue resistance, where polarity of the cellulosic substrate could not affect the optical properties and reversible photochromism. Therefore, diarylethene derivatives show maximum photostability and resistance toward environmental degradation because of the lower polar nature of both of the diarylethene isomers under UV and visible light compared to the other photochromic compounds.…”

“…As discussed in the case of a spiropyran photoswitch, its incorporation into polar environments without a carrier results in negative photochromism and irreversible coloration, which is a significant weak point for the photochromic systems. , Felpin and co-workers investigated the probability of such a behavior for the other photochromic compounds such as diarylethene. They reported chemical incorporation of a diarylethene derivative to cellulosic papers via covalent printing of dibenzothienylethenes as the photochromophore through spatially controlled light-mediated thiol-X ligations . The results obtained from the photophysical and theoretical studies confirmed reversible photochromism of diarylethene without any negative photochromism with higher photostability and photofatigue resistance, where polarity of the cellulosic substrate could not affect the optical properties and reversible photochromism.…”

The gorgeous transformation of paper: from cellulose paper to inorganic paper to 2D paper materials with multifunctional properties

“…Nawaz et al 148 reviewed the methods for the chemical modification of cellulose-based materials such as 2D cellulose paper into smart fluorescent materials and their multifunctional applications, including anticounterfeiting, 146,149,150 chemical sensing, 151–153 and gas detection. 154 For example, Wang et al 146 constructed a superhydrophobic and photoluminescent cellulose-based paper for anticounterfeiting application by doping lanthanide-based nanocrystal/nanotitania in cellulose fibers.…”

Organic photoresponsive materials for information storage: a review

“…S1 in the Supplemental Materials) and the cellulose paper to create robust photochromic patterns. 63 First, dithiodiglycolic acid was grafted onto cellulose paper (Cell-DiS). Second, Cell- DiS was inserted into the sample holder composed of two aluminum plates, in which the top plate was processed into the letter "U."…”