Tunable color hydrogel enables multistage encryption

(Nanowerk Spotlight) Self-assembly, the spontaneous organization of molecules into ordered structures, has long captivated scientists with its elegance and potential. By harnessing the same principles that shape cellular membranes and crystalline materials, researchers aspire to craft advanced functional materials from the bottom up. Among the most sought-after are "smart" materials that can sense and respond to their environment, opening up applications from drug delivery to information security.
In pursuit of these responsive self-assembled materials, one intriguing approach takes inspiration from nature's dazzling structural colors. From butterfly wings to beetle shells, many living things derive their hues not from pigments but from microscopic patterns that selectively reflect light.
Emulating these photonic structures in synthetic materials could enable "tunable" colors controlled by external triggers. Such dynamic optical properties are highly desirable for anti-counterfeiting, where materials must be difficult to replicate yet easy to authenticate.
However, relying on structural color alone comes with limitations. These colors may be vivid in bright light but lose their luster in dimmer conditions. They can also be challenging to "pattern" with specific designs. Fluorescent materials solve some of these issues by emitting light independently, but their colors are often less dynamic and more easily mimicked. An ideal anti-counterfeiting material would marry the strengths of both.
Recognizing this, a team of researchers in China set out to create a "dual-mode" hydrogel – a water-swollen polymer network – that incorporates independently tunable structural color and fluorescence. Their goal was a material that could display different information under various viewing conditions, enabling multilayered encryption. By spatially controlling each optical mode, the gel could conceal messages that are only revealed with the right "key," like a special viewing angle or light source.
They reported their findings in Advanced Materials ("Dual-Mode Hydrogels with Structural and Fluorescent Colors toward Multistage Secure Information Encryption").
Dual-mode hydrogel for multistage information encryption
Dual-mode hydrogel for multistage information encryption. A) Structure diagram of dual-mode hydrogel. B) The preparation of pDGI/p(AAm-DMA-6APA) hydrogel, including the processes of self-assembly and photopolymerization. C) The coordination process of Ln3+ and pDGI/p(AAm-DMA-6APA) hydrogel leads to various fluorescence emissions. D) Schematic of dual-mode hydrogel for multistage information encryption. (Reprinted with permission by Wiley-VCH Verlag) (click on image to enlarge)
The core of their strategy lies in combining self-assembled polymer layers with a fluorescent coordination network. The team synthesized the hydrogel by copolymerizing dodecylglyceryl itaconate (DGI), an amphiphilic monomer that spontaneously forms ordered bilayers, with acrylamide derivatives. Under shear flow, these lamellae align in a specific direction. Once "locked in" by crosslinking, the periodic layers give rise to angle-dependent structural colors.
Critically, the structural color can be tuned independently from the fluorescence by adjusting the spacing between lamellae, either through crosslink density or solvent composition. A densely crosslinked gel remains compact even when hydrated, yielding shorter wavelengths like blue. Conversely, a lightly crosslinked gel swells dramatically, its layers separating to yield reds and yellows.
The fluorescence arises from a coordination network formed between lanthanide ions (terbium or europium) and picolinamide ligands on the hydrogel backbone. These complexes absorb UV light and emit sharp peaks in the visible spectrum. The team demonstrated green (Tb3+), red (Eu3+), and intermediate colors by mixing the ions in various ratios.
A key highlight of this dual-mode system is the non-interference between its structural and fluorescent components. The two optical modes operate independently, their overlap dictated by the "programming" of each component. As a proof of concept, the researchers constructed a grid from hydrogel segments, each bearing a different combination of structural and fluorescent colors.
Under daylight, the assembled grid displayed a fragmented message, its full meaning obscured. But under UV light, a hidden pattern emerged, with some segments glowing green against the dark background. By inducing fluorescence selectively, the team spelled out a secret word decipherable only with the correct filter.
This multistage programmability allows for numerous combinations of public and private information. The structural colors, embedded in the hydrogel's architecture, provide a tamper-proof foundation that is challenging to replicate.
Meanwhile, the fluorescent network operates on a molecular level, its nanoscale structure undetectable to the eye. Integrating these distinct mechanisms yields exponentially more unique "lock and key" pairs for authentication.
The team also showcased the material's reversible responsiveness, toggling its appearance by cycling between solvents. This raises the prospect of "self-erasing" messages that vanish once read, or time-sensitive authenticators that expire after a certain number of uses. Such features could propel information security to new heights.
The implications extend beyond anti-counterfeiting. The same principles could be applied to create smart labels and sensors that relay different information based on their environment, from color-changing packaging that warns of spoilage to weather-adaptive fabrics. With its versatile palette and multi-modal signaling, this dual-mode hydrogel provides a powerful platform for next-generation responsive materials.
As with many advanced materials, challenges remain in scaling up manufacturing. However, this work embodies the spirit of bioinspired engineering – leveraging nature's strategies to solve human problems. By bridging self-assembly, photonics, and coordination chemistry, the authors have achieved a compelling demonstration of multidimensional encryption. As the field progresses, such materials may weave their way into our daily lives, from the currency in our wallets to the clothes on our backs.
Michael Berger By – Michael is author of three books by the Royal Society of Chemistry:
Nano-Society: Pushing the Boundaries of Technology,
Nanotechnology: The Future is Tiny, and
Nanoengineering: The Skills and Tools Making Technology Invisible
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