Abstract
Programmable dual-mode (two- or three- dimension, 2D/3D)-coupling responsive coating constitutes one of the most promising strategies to ensure the security of anti-counterfeiting and information encryption, but it is still lack of effective approaches to integrate stimuli-responsive 2D and 3D information. Herein, we develop a self-growing method to achieve this purpose based on photoswitchable fluorescence and supramolecular interaction (dipole-dipole interaction) toward advanced multi-dimensional anti-counterfeiting and encryption. In our method, trifluoromethyl-rich monomers (2,2,2-trifluoroethyl methacrylate (TFEMA) and 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA)), polymerizable green fluorescent dye (2-(6-(dimethylamino)−1,3-dioxo- 1H-benzodeisoquinolin-2...
Abstract
Programmable dual-mode (two- or three- dimension, 2D/3D)-coupling responsive coating constitutes one of the most promising strategies to ensure the security of anti-counterfeiting and information encryption, but it is still lack of effective approaches to integrate stimuli-responsive 2D and 3D information. Herein, we develop a self-growing method to achieve this purpose based on photoswitchable fluorescence and supramolecular interaction (dipole-dipole interaction) toward advanced multi-dimensional anti-counterfeiting and encryption. In our method, trifluoromethyl-rich monomers (2,2,2-trifluoroethyl methacrylate (TFEMA) and 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA)), polymerizable green fluorescent dye (2-(6-(dimethylamino)−1,3-dioxo- 1H-benzodeisoquinolin-2(3H)-yl) ethyl acrylate, MNEA) and photochromic diarylethene derivative (4-(acryloyloxy) butyl-4-(2-methyl-3-(2-(2-methylbenzo thiophen-3-yl)−4-oxo-5,6-dihydro-4H-thieno 2,3- thiopyran-3-yl) benzo thiophen-6-yl)−4-oxobutanoate, BTBA) are introduced into specific 3D structure via a self-growing method. The coating is capable of reversible fluorescence switching from green to red through photo-induced fluorescence resonance energy transfer (FRET) process between MNEA and BTBA, and reversible switch of 3D structure based on force- and thermo-induced shape memory caused by dipole-dipole interaction and covalent bond. Interestingly, when the 2D information is stimulated, the 3D information remains unchanged. Several examples demonstrate that the great application potential of the programmable responsive coating in high-security of multilevel anti-counterfeiting and information encryption. We thus envision the great potential of our method in developing advanced anti-counterfeiting, multilevel information encryption and high-density data storage.
Data availability
The authors declare that the main data supporting the findings of this study are available within the article and its Supplementary Information files. Data are available from the corresponding author upon request.
References
Purohit, K., Abdul-Baki, S. & Purohit, H. Mind the inclusion gap: a critical review of accessibility in anti-counterfeiting technologies. In Proc. 2024 IEEE 6th International Conference on Trust, Privacy and Security in Intelligent Systems, and Applications (TPS-ISA), 455–460 (IEEE, 2024). 1.
Shen, Y., Le, X., Wu, Y. & Chen, T. Stimulus-responsive polymer materials toward multi-mode and multi-level information anti-counterfeiting: recent advances and future challenges. Chem. Soc. Rev. 53, 606–623 (2024).
Wang, X. et al. Manipulating electroluminochromism behavior of viologen-substituted iridium (III) complexes through ligand engineering for information display and encryption. Adv. Mater. 34, 2107013 (2022).
Yang, Y. et al. Multi-stimulus room temperature phosphorescent polymers sensitive to light and acid cyclically with energy transfer. Angew. Chem. Int. Ed. 62, e202308848 (2023).
Zuo, M. et al. A spatiotemporal cascade platform for multidimensional information encryption and anti-counterfeiting mechanisms. Adv. Optical Mater. 12, 2302146 (2024).
Yang, J. et al. Bionic micro-texture duplication and RE3+ space-selective doping of unclonable silica nanocomposites for multilevel encryption and intelligent authentication. Adv. Mater. 35, 2306003 (2023).
Quan, Z., Zhang, Q., Li, H., Sun, S. & Xu, Y. Fluorescent cellulose-based materials for information encryption and anti-counterfeiting. Coordin. Chem. Rev. 493, 215287 (2023).
Hu, W. et al. Realizing multicolor and stepwise photochromism for on-demand information encryption. ACS Energy Lett. 9, 2145–2152 (2024).
Guo, J. M. & Seshathiri, S. Visually encrypted watermarking for ordered-dithered clustered-dot halftones. IEEE Trans. Circuits Syst. Video 33, 4375–4387 (2023). 1.
Qin, Y. & Gong, Q. Optical information encryption based on incoherent superposition with the help of the QR code. Opt. Commun. 310, 69–74 (2014).
Xie, Y. et al. 2D hierarchical microbarcodes with expanded storage capacity for optical multiplex and information encryption. Adv. Mater. 36, 2308154 (2024).
Huang, Y. et al. Stimuli-fluorochromic smart organic materials. Chem. Soc. Rev. 53, 1090–1166 (2024).
Yang, Y. et al. Photo-response with radical afterglow by regulation of spin populations and hole-electron distributions. Angew. Chem. Int. Ed. 62, e202218994 (2023).
Xu, W.-C. et al. Designing rewritable dual-mode patterns using a stretchable photoresponsive polymer via orthogonal photopatterning. Adv. Mater. 34, 2202150 (2022).
Xu, F. & Feringa, B. L. Photoresponsive supramolecular polymers: from light-controlled small molecules to smart materials. Adv. Mater. 35, 2204413 (2023).
Li, Z. & Yin, Y. Stimuli-responsive optical nanomaterials. Adv. Mater. 31, 1807061 (2019).
Li, C. et al. Photoswitchable and reversible fluorescent eutectogels for conformal information encryption. Angew. Chem. Int. Ed. 62, e202313971 (2023).
Tong, X. et al. Oxygen-doped carbon nitrides with visible room-temperature phosphorescence and invisible thermal-stimuli-responsive ultraviolet delayed fluorescence for security applications. Angew. Chem. Int. Ed. 64, e202415312 (2025).
Lou, D. et al. Double lock label based on thermosensitive polymer hydrogels for information camouflage and multilevel encryption. Angew. Chem. Int. Ed. 61, e202117066 (2022).
Chen, J. et al. Hydrochromic perovskite system with reversible blue-green color for advanced anti-counterfeiting. Small 19, 2301010 (2023).
Yang, Y. et al. High-throughput printing of customized structural-color graphics with circularly polarized reflection and mechanochromic response. Matter 7, 2091–2107 (2024).
Sagara, Y. et al. Rotaxanes as mechanochromic fluorescent force transducers in polymers. J. Am. Chem. Soc. 140, 1584–1587 (2018).
Meng, K. et al. A reversibly responsive fluorochromic hydrogel based on lanthanide–mannose complex. Adv. Sci. 6, 1802112 (2019).
Lan, R. et al. Humidity-responsive liquid crystalline network actuator showing synergistic fluorescence color change enabled by aggregation-induced emission luminogen. Adv. Funct. Mater. 31, 2010578 (2021).
Jiang, Y. et al. Solid-state intramolecular motions in continuous fibers driven by ambient humidity for fluorescent sensors. Nat. Sci. Rev. 8, nwaa135 (2020).
Zhao, J.-L. et al. Photochromic crystalline hybrid materials with switchable properties: recent advances and potential applications. Coord. Chem. Rev. 475, 214918 (2023).
Yang, H. et al. Erasable, rewritable, and reprogrammable dual information encryption based on photoluminescent supramolecular host–guest recognition and hydrogel shape memory. Adv. Mater. 35, 2301300 (2023).
Xie, Y. et al. Hydrogen bond-associated photofluorochromism for time-resolved information encryption and anti-counterfeiting. Angew. Chem. Int. Ed. 64, e202414846 (2025).
Chen, X., Hou, X.-F., Chen, X.-M. & Li, Q. An ultrawide-range photochromic molecular fluorescence emitter. Nat. Commun. 15, 5401 (2024).
Zhao, Y., Xie, Z., Gu, H., Zhu, C. & Gu, Z. Bio-inspired variable structural color materials. Chem. Soc. Rev. 41, 3297–3317 (2012).
Yang, M. et al. Stimuli-responsive mechanically interlocked polymer wrinkles. Nat. Commun. 15, 5760 (2024).
Sun, Y. et al. Dual-mode hydrogels with structural and fluorescent colors toward multistage secure information encryption. Adv. Mater. 36, 2401589 (2024).
Liu, N. et al. Wrinkled interfaces: Taking advantage of anisotropic wrinkling to periodically pattern polymer surfaces. Adv. Sci. 10, 2207210 (2023).
Lin, E.-L., Hsu, W.-L. & Chiang, Y.-W. Trapping structural coloration by a bioinspired gyroid microstructure in solid state. ACS Nano 12, 485–493 (2018).
Li, Y. et al. Structural coloration: shear-induced assembly of liquid colloidal crystals for large-scale structural coloration of textiles. Adv. Funct. Mater. 31, 2170133 (2021).
He, Y. et al. Dynamically tunable chiroptical activities of flexible chiral plasmonic film via surface buckling. Small 21, 2407635 (2025).
Chen, D. et al. Orthogonal photochemistry toward direct encryption of a 3D-printed hydrogel. Adv. Mater. 35, 2209956 (2023).
Lou, K., Hu, Z., Zhang, H., Li, Q. & Ji, X. Information storage based on stimuli-responsive fluorescent 3D code materials. Adv. Funct. Mater. 32, 2113274 (2022).
Li, T. et al. Micropatterns fabricated by photodimerization-induced diffusion. Adv. Mater. 33, 2007699 (2021).
Lyu, B., Ouyang, Y., Gao, D., Wan, X. & Bao, X. Multilevel and flexible physical unclonable functions for high-end leather products or packaging. Small 21, 2408574 (2025).
Kanika, Kedawat, G., Srivastava, S. & Gupta, B. K. A strategic approach to design multi-functional RGB luminescent security pigment-based golden ink with myriad security features to curb counterfeiting of passports. Small 19, 2206397 (2023).
Tomar, A., Gupta, R. R., Mehta, S. K. & Sharma, S. An overview of security materials in banknotes and analytical techniques in detecting counterfeits. Crit. Rev. Anal. Chem. 54, 2865–2878 (2024).
Szydłowski, P., Madej, J. P. & Mazurkiewicz-Kania, M. Histology and ultrastructure of the integumental chromatophores in tokay gecko (Gekko gecko) (Linnaeus, 1758) skin. Zoomorphology 136, 233–240 (2017).
Wen, T. et al. Phase-transition-induced dynamic surface wrinkle pattern on gradient photo-crosslinking liquid crystal elastomer. Nat. Commun. 15, 10821 (2024).
Tang, J., Xing, T., Chen, S. & Feng, J. A shape memory hydrogel with excellent mechanical properties, water retention capacity, and tunable fluorescence for dual encryption. Small 20, 2305928 (2024).
Huang, J., Jiang, Y., Chen, Q., Xie, H. & Zhou, S. Bioinspired thermadapt shape-memory polymer with light-induced reversible fluorescence for rewritable 2D/3D-encoding information carriers. Nat. Commun. 14, 7131 (2023).
Feng, D. et al. Viscoelasticity-controlled relaxation in wrinkling surface for multistage time-resolved optical information encryption. Adv. Mater. 36, 2314201 (2024).
Matsuda, T., Kawakami, R., Namba, R., Nakajima, T. & Gong, J. P. Mechanoresponsive self-growing hydrogels inspired by muscle training. Science 363, 504–508 (2019).
Wu, B. et al. Interfacial reinitiation of free radicals enables the regeneration of broken polymeric hydrogel actuators. CCS Chem. 5, 704–717 (2023).
Xiong, X., Wang, H., Xue, L. & Cui, J. Self-growing organic materials. Angew. Chem. Int. Ed. 62, e202306565 (2023).
Xiong, X. et al. Controlled macroscopic shape evolution of self-growing polymeric materials. Nat. Commun. 16, 2131 (2025).
Szabó, Á, Szöllősi, J. & Nagy, P. Principles of resonance energy transfer. Curr. Protoc. 2, e625 (2022).
Jiang, J. et al. Dual photochromics-contained photoswitchable multistate fluorescent polymers for advanced optical data storage, encryption, and photowritable pattern. Chem. Eng. J. 425, 131557 (2021).
Deng, H. et al. Highly stretchable and self-healing photoswitchable supramolecular fluorescent polymers for underwater anti-counterfeiting. Mater. Horiz. 10, 5256–5262 (2023).
Wang, S. & Urban, M. W. Self-healing polymers. Nat. Rev. Mater. 5, 562–583 (2020).
Yang, Y., Ding, X. & Urban, M. W. Chemical and physical aspects of self-healing materials. Prog. Polym. Sci. 49-50, 34–59 (2015).
Wang, H. et al. Alternating growth for insitu post-programing hydrogels’ sizes and performance. Adv. Funct. Mater. 33, 2212402 (2023).
Fang, Y. et al. Damage restoration in rigid materials via a keloid-inspired growth process. J. Mater. Chem. A 10, 174–179 (2022).
Acknowledgements
H.W. acknowledges support from the National Natural Science Foundation of China (52403266) and China Postdoctoral Science Foundation (2024M760887). J.C. (Jian Chen) acknowledges support from the National Natural Science Foundation of China (52273206), the National Key R&D Program of China (2023YFB3812400, 2023YFB3812403), Huxiang High-level Talent Gathering Project (2022RC4039). The authors appreciate Dr. Tingchuan Zhou from Analysis and Testing Center, University of Electronic Science and Technology of China, for technical support.
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Author notes
These authors contributed equally: Hong Wang, Haitao Deng.
Authors and Affiliations
Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan, China
Hong Wang, Haitao Deng, Junyi Chen, Yong Tian, Yi Zhao, Zhihua Zhou & Jian Chen 1.
Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan, China
Hong Wang, Haitao Deng, Junyi Chen, Yong Tian, Yi Zhao, Zhihua Zhou & Jian Chen 1.
School of Resource & Environment and Safety Engineering, Hunan University of Science and Technology, Xiangtan, Hunan, China
Hong Wang & Jian Chen 1.
Hunan Provincial Key Laboratory of Environmental Catalysis & Waste Recycling, College of Materials and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, China
Fuhua Huang 1.
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, Sichuan, China
Jiaxi Cui 1.
Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory, Jieyang, China
Xudong Chen 1.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, China
Xudong Chen
Authors
- Hong Wang
- Haitao Deng
- Junyi Chen
- Yong Tian
- Fuhua Huang
- Yi Zhao
- Zhihua Zhou
- Jiaxi Cui
- Jian Chen
- Xudong Chen
Contributions
H.W. and H.D. equally contributed to this work. J.C. (Jian Chen), J.C. (Jiaxi Cui), X.C., H.W., and H.D. conceived the concepts of the research. H.W. and H.D. designed the experiments and prepared samples. H.W., H.D., J.C. (Junyi Chen), Y.T., F.H., and Y.Z. performed the sample characterization. H.W., H.D., J.C. (Junyi Chen), F.H., J.C. (Jiaxi Cui), and J.C. (Jian Chen) analyzed the experimental data. J.C. (Jian Chen), J.C. (Jiaxi Cui), H.W., H.D., and Z.Z. wrote the manuscript. All the authors discussed the results and commented on the manuscript.
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Correspondence to Jiaxi Cui or Jian Chen.
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Wang, H., Deng, H., Chen, J. et al. Self-growth of programmable 2D- and 3D-coupling responsive coating for anti-counterfeiting. Nat Commun (2025). https://doi.org/10.1038/s41467-025-67742-0
Received: 14 July 2025
Accepted: 08 December 2025
Published: 23 December 2025
DOI: https://doi.org/10.1038/s41467-025-67742-0