Stimulus-responsive polymer materials toward multi-mode and multi-level information anti-counterfeiting: recent advances and future challenges.

Information storage and security is one of the perennial hot issues in society, while the further advancements of related chemical anti-counterfeiting systems remain a formidable challenge. As emerging anti-counterfeiting materials, stimulus-responsive polymers (SRPs) have attracted extensive attention due to their unique stimulus-responsiveness and charming discoloration performance. At the same time, single-channel decryption technology with low-security levels has been unable to effectively prevent information from being stolen or mimicked. As a result, it would be of great significance to develop SRPs with multi-mode and multi-level anti-counterfeiting characteristics. This study summarizes the latest achievements in advance anti-counterfeiting strategies based on SRPs, including multi-mode anti-counterfeiting (static information) and multi-level anti-counterfeiting (dynamic information). In addition, the promising applications of such materials in anti-counterfeiting labels, identification platforms, intelligent displays, and others are briefly reviewed. Finally, the challenges and opportunities in this emerging field are discussed. This review serves as a useful resource for manipulating SRP-based anti-counterfeiting materials and creating cutting-edge information security and encryption systems.

Mimicking Color-Changing Organisms to Enable the Multicolors and Multifunctions of Smart Fluorescent Polymeric Hydrogels.

Fluorescent polymer hydrogels (FPHs) are of significant interest for diverse emerging applications such as visualized sensing, smart display, camouflaging skins, soft actuators/robots, because they can synergize the features of classic fluorescent polymers and hydrogels. With great efforts in the past decades, the major challenge in this field has been believed to be not whether a given FPH of interest can be prepared but how to fabricate robust FPHs with multicolor tunability and multifunctional synergy. Such materials will conceptually minimize the contribution of passive materials to the mass and size of the final system, holding great potential to facilitate multiple applications. To this end, one promising way is to learn from the Nature that has superb capability to forge delicate or sometimes beyond-imagination materials. Chameleons and cephalopods serve as typical examples, which are famous for not only diverse skin color adaptability under changing environmental demands, but also synergistic skin color and body gesture changes to communicate, warn, camouflage, etc. Biological studies revealed their structural color-changing capacity derives from different types of skin chromatophores and their rational multilayer arrangement in under-skin tissues. Besides, their superb ability to heterogeneously integrate soft tissues with disparate functions into topology-optimized architectures has led to various multifunctional performances. Such natural strategies, if replicated and implemented in artificial systems, would significantly benefit and advance the development of robust FPHs for various applications.In this Account, we summarizes the key advances of smart FPHs mainly achieved by our groups. We start by introducing the unique hierarchical multilayer structures of skin chromatophores in structural color-changing reptiles, followed by an in-depth discussion on how a rational integration of bioinspiration and man-made design makes it possible to largely expand the fluorescence color-changing range of smart FPHs to almost cover the whole visible spectrum. Then, to closely mimic the multifunctional behaviors of chameleons and cephalopods, we further develop efficient strategies to introduce supramolecular interactions or heterogeneously integrating smart FPHs with other soft materials with disparate functions, producing a number of multifunctional fluorescent polymeric hydrogel systems. These robust FPHs can find many frontier applications, including bioinspired synergistic color/shape switchable hydrogel actuators/robots, smart systems with on-demand fluorescent patterning capacities for displaying or information encryption, as well as robust chemosensors for important food or environmental analytes. We expect that the discussion presented in this Account would promote better understanding of the discoloration systems in nature, and advance the development of bioinspired color-changing materials.

A Urease-Containing Fluorescent Hydrogel for Transient Information Storage.

The improper handling of decrypted information can lead to the leakage of confidential data. Thus, there is increasing interest in the development of self-erasing decrypted data. Herein, we report a urease-containing fluorescent hydrogel for multistage information security protection. Information can be input into the fluorescent hydrogel, which is based on the protonated 4-(N,N-dimethylaminoethylene) amino-N-allyl-1,8-naphthalimide (DEAN-H+ ) and doped with urease, using metal ions, such as Zn2+ that coordinate with DEAN. Upon exposure to urea, urease produces NH3 , which reduces the fluorescence of the hydrogel. In the presence of urea, metal-coordinated hydrogel fluorescence decreases more slowly than the fluorescence of the hydrogel alone, revealing the information. The displayed information is then automatically erased within a few minutes. This work opens up a new insights in designing and fabricating information storage materials.

Aggregation-Induced Emissive Carbon Dots Gels for Octopus-Inspired Shape/Color Synergistically Adjustable Actuators.

Some living organisms such as the octopus have fantastic abilities to simultaneously swim away and alter body color/morphology for disguise and self-protection, especially when there is a threat perception. However, it is still quite challenging to construct artificial soft actuators with octopus-like synergistic shape/color change and directional locomotion behaviors, but such systems could enhance the functions of soft robotics dramatically. Herein, we proposed to utilize unique hydrophobic carbon dots (CDs) with rotatable surficial groups to construct the aggregation-induced emission (AIE) active glycol CDs polymer gel, which could be further employed to be interfacially bonded to an elastomer to produce anisotropic bilayer soft actuator. When putting the actuator on a water surface, glycol spontaneously diffused out from the gel layer to allow water intake, resulting in a color change from a blue dispersion fluorescence to red AIE and a shape deformation, as well as a large surface tension gradient that can promote its autonomous locomotion. Based on these findings, artificial soft swimming robots with octopus-like synergistic shape/color change and directional swimming motion were demonstrated. This study provides an elegant strategy to develop advanced multi-functional bio-inspired intelligent soft robotics.

Ionic Strength and Thermal Dual-Responsive Bilayer Hollow Spherical Hydrogel Actuator.

As one of the most promising intelligent materials, polymeric hydrogel actuators could produce reversible shape change upon external stimuli. Although complex shape deformation from 2D to 3D have been achieved, the realization of actuating behavior from 3D to 3D is still a significant challenge. Herein, an effective strategy to develop a novel bilayer hollow spherical hydrogel actuator is proposed. Through immersing a Ca2+ incorporated gelatin core into alginate solution, an ionic-strength-responsive alginate layer will be formed along the gelatin core via alginate-Ca2+ crosslinks, and then another thermo-responsive alginate-poly(2-(dimethylamino)ethyl methacrylate)(Alg-PDMAEMA) layer is introduced to achieve a bilayer hydrogel with ionic strength and temperature dual responsiveness. A hollow hydrogel capsule could be obtained if a spherical gelatin core is applied, and it could produce complex shape deformations from 3D to 3D upon the trigger of ionic strength and temperatures changes. The present work may offer new inspirations for the development of novel intelligent polymeric hydrogel actuators.

pH and Thermo Dual-Responsive Fluorescent Hydrogel Actuator.

As one of the most important smart materials, fluorescent hydrogel actuators can produce both color and shape changes under external stimuli. In the present work, an effective approach to develop a novel fluorescent hydrogel actuator with pH and thermo dual responsiveness is proposed. Through incorporating pH-responsive perylene tetracarboxylic acid (PTCA), which is a typical fluorescent moiety with aggregation-caused quenching (ACQ) effect, into an anisotropic poly(N-isopropylacrylamide)-polyacrylamide (PNIPAm-PAAm) structure, the obtained hydrogel exhibits stable thermoresponsive shape deformation and switchable fluorescence performance upon a pH trigger. Therefore, fluorescence-quenching-based and actuation-based information can be revealed when exposed to UV light and immersed into warm water, respectively. Moreover, the thermoresponsive actuating behavior can be applied to further hide the fluorescence-quenching-based images. The present work may provide new insights into the design and preparation of novel stimuli-responsive hydrogel actuators.

Bioinspired Synergistic Fluorescence-Color-Switchable Polymeric Hydrogel Actuators.

Many living organisms have amazing control over their color, shape, and morphology for camouflage, communication, and even reproduction in response to interplay between environmental stimuli. Such interesting phenomena inspire scientists to develop smart soft actuators/robotics via integrating color-changing functionality based on polymer films or elastomers. However, there has been no significant progress in synergistic color-changing and shape-morphing capabilities of life-like material systems such as hydrogels. Herein, we reported a new class of bioinspired synergistic fluorescence-color-switchable polymeric hydrogel actuators based on supramolecular dynamic metal-ligand coordination. Artificial hydrogel apricot flowers and chameleons have been fabricated for the first time, in which simultaneous color-changing and shape-morphing behaviors are controlled by the subtle interplay between acidity/alkalinity, metal ions, and temperature. This work has made color-changeable soft machines accessible and is expected to hold wide potential applications in biomimetic soft robotics, biological sensors, and camouflage.

Shape Memory Hydrogels with Simultaneously Switchable Fluorescence Behavior.

Realization of shape memory process in polymeric hydrogels at ambient condition is a significant development to shape memory materials. The sound understanding of the dynamic shape memory process is fundamentally important but limited. Here, a novel shape memory hydrogel with simultaneously switchable fluorescence behavior is developed. The hydrogel is prepared by incorporating a pH-responsive fluorescent molecule, perylene tetracarboxylic acid, into chitosan-based hydrogel, and the assembly and disassembly of chitosan chains into microcrystals upon the trigger of pH are applied as reversible crosslinks to achieve shape memory effect. Therefore, the formation and disassociation of microcrystalline chitosan, and the switchable fluorescence performance happen concurrently, which bring convenience to monitoring the shape memory process by fluorescent imaging. Moreover, the erasable fluorescence behavior also gives the hydrogel potential applications in information storage.

A Novel Anisotropic Hydrogel with Integrated Self-Deformation and Controllable Shape Memory Effect.

Although shape memory polymers have been highlighted widely and developed rapidly, it is still a challenging task to realize complex temporary shapes automatically in practical applications. Herein, a novel shape memory hydrogel with the ability of self-deformation is presented. Through constructing an anisotropic poly(acrylic acid)-polyacrylamide (PAAc-PAAm) structure, the obtained hydrogel exhibits stable self-deformation behavior in response to pH stimulus, and the shapes that formed automatically can be fixed by the coordination between carboxylic groups and Fe3+ ; therefore, self-deformation and shape memory behaviors are integrated in one system. Moreover, the magnitude of auto-deformation and shape memory could be adjusted with the concentration of corresponding ions, leading to programmable shape memory and shape recovery processes.

Supramolecular shape memory hydrogels: a new bridge between stimuli-responsive polymers and supramolecular chemistry.

Supramolecular shape memory hydrogels (SSMHs) refer to shape memory polymers, in which temporary shapes are stabilized by reversible crosslinks such as supramolecular interactions and dynamic covalent bonds. Following a brief introduction of the conventional shape memory polymers (SMPs), this tutorial review is focused to summarize the recent advancement in various reversible crosslinks employed to construct SSMHs (supramolecular interactions and dynamic covalent bonds) and different shape memory behaviors (dual and triple shape memory effects). In addition, current challenges and future perspectives in this field are also discussed to suggest a new developing direction.

Dual-Mode Hydrogels with Structural and Fluorescent Colors toward Multistage Secure Information Encryption.

Constructing an anti-counterfeiting material with non-interference dual optical modes is an effective way to improve information security. However, it remains challenging to achieve multistage secure information encryption due to the limited stimulus responsiveness and color tunability of the current dual-mode materials. Herein, a dual-mode hydrogel with both independently tunable structural and fluorescent colors toward multistage information encryption, is reported. In this hydrogel system, the rigid lamellar structure of poly(dodecylglyceryl itaconate) (pDGI) formed by shear flow-induced self-assembly provides the restricted domains wherein monomers undergo polymerization to form a hydrogel network, producing structural color. The introduction of fluorescent monomer 6-acrylamidopicolinate (6APA) as a complexation site provides the possibility of fluorescent color formation. The hydrogel's angle-dependent structural color can be controlled by adjusting the crosslinking density and water content. Additionally, the fluorescence color can be modulated by adjusting the ratio of lanthanide ions. Information of dual-mode can be displayed separately in different channels and synergistically overlayed to read the ultimate message. Thus, a multistage information encryption system based on this hydrogel is devised through the programed decryption process. This strategy holds tremendous potential as a platform for encrypting and safeguarding valuable and authentic information in the field of anti-counterfeiting.

Water-sensitive fluorescent microgel inks to produce verifiable information for highly secured anti-counterfeiting.

The decryption and verification of encrypted information via a simple and efficient method is always difficult and challenging in the field of information security. Herein, a series of water-sensitive fluorescent microgels are fabricated for highly secured anti-counterfeiting with authenticity identification. The initial negatively charged microgels (MG) are made up of N-isopropylacrylamide (NIPAM), acrylic acid (AAc) and anthracen-9-yl acrylate (9-ANA, blue fluorescent monomer). The prepared MGs can bind cationic fluorescent dyes such as 5-aminofluorescein (FITC, green fluorescent dye) and rhodamine B (Rh B, red fluorescent dye) via electrostatic interaction, emitting multi-fluorescent colors based on the fluorescence resonance energy transfer (FRET) process. Furthermore, the fluorescence colors of MG-derived systems can be rapidly changed by swelling in water, which can block the FRET process and change the aggregation state of dyes. With the assistance of inkjet printing, multi-color security patterns can be designed and encoded, which can be revealed by UV irradiation and further verified by water stimulation. This study has pioneered a novel strategy to verify the authenticity of decrypted information, which greatly improves the security level of information.

Editorial for Special Issue: Advances in Smart and Tough Hydrogels.

Smart hydrogels possess both intelligent and responsive properties, which are designed to exhibit specific responses to external stimuli such as changes in temperature, pH, or the presence of specific ions/counterions, making them "smart" or "responsive" materials [...].

Regulating Aggregated Structures in Organohydrogels for On-Demand Information Encryption.

As one of the most promising candidates for dynamic information storage, intelligent gels with tunable optical properties under external stimuli have received great attention. The implementation of transparency variation for information display is a favorable and versatile strategy but still faces the challenge of on-demand encryption-decryption. Herein, an optical tunable organohydrogel is prepared, which has interpenetrating heterogeneous networks consisting of hydrophilic poly(N,N-dimethylacrylamide) (PDMA) and hydrophobic polyoctadecyl methacrylate (PSMA). The long alkane side chains of PSMA endow the organohydrogel with the capacity of crystallization-melting transitions under the stimulus of heat, accompanied by transparent-opaque switching. In addition, the variations of transparency can also be achieved by water-induced hydrophobic association and microphase separation, resulting from the unique heterogeneous networks of the organohydrogel. Based on the abovementioned two aggregated structures, various pieces of information can be loaded on the organohydrogel by light writing or water printing with the assistance of masks. The coded information can be encrypted and decrypted by solvent replacement and temperature switching. This elaborately designed organohydrogel can act as an effective communication platform with an improved security level and ignite the sparks of developing novel information storage materials.

Light-Writing and Projecting Multicolor Fluorescent Hydrogels for On-Demand Information Display.

Intelligent rewritable display systems have been long expected to reduce the heavy consumption of single-use or transient devices in the age of Internet-of-Things. However, it remains challenging to construct such systems with integrated functionality of remote control, rapid activation, multicolor and multimode display. Herein, by learning from the unique multilayer arrangement of chromatophores in chameleon skins, a promising kind of rewritable hydrogel multicolor systems is presented that can combine the merits of near-infrared (NIR) light-writing and projecting modes for on-demand information display. Specifically, the systems have typical multilayer layout consisting of poly(dimethylsiloxane) (PDMS)-sealed carbon nanotubes (CNTs) film as photothermal control unit and embedded fluorescent hydrogels as multicolor display unit, in which thermoresponsive hydrogel is constrained within non-responsive hydrogel. Such rational structure design results in the establishment of one promising display mechanism via the cascading "light trigger-heat generation-fluorescence output" process. On this basis, rapid and reversible hand-written display of arbitrary information is achieved within 5 s. Also, sustainable light-projecting display of predesigned multicolor patterns is demonstrated due to the multilayer design that ensures easy patterning of photothermal control or hydrogel display layer. This study brings functional-integrated merits for novel rewritable display systems and open new possibility to construct high-end products for information display/transmission.

Organohydrogel Actuators with Adjustable Stimulus Responsiveness for On-Demand Morphing.

Hydrogel actuators showing shape morphing in response to external stimuli are of significant interest for their applications in soft robots, artificial muscles, etc. However, there is still a lack of hydrogel actuators with adjustable stimulus responsiveness for on-demand driving. In this study, an organohydrogel actuator was prepared by a two-step interpenetrating method, resulting in the coexistence of poly(N-isopropylacrylamide-co-4-(2-sulfoethyl)-1-(4-vinylbenzyl) pyridinium betaine) (p(NIPAM-SVBP)) hydrophilic networks and poly(lauryl methacrylate) (pLMA) hydrophobic networks with gradient distribution. In the initial state, the organohydrogel actuator can be driven globally under thermal stimulation. Owing to the unique alkali-chromic performance of SVBP, the organohydrogel actuator can be endowed with photothermal properties and actuate locally under the stimulus of NIR light. More importantly, the organohydrogel will return to the original colorless state after being treated with acid solution. Our work provides a new insight into designing and fabricating novel actuators with adjustable stimulus responsiveness for on-demand morphing.

Transcranial Acoustic Metamaterial Parameters Inverse Designed by Neural Networks.

Objective: The objective of this work is to investigate the mapping relationship between transcranial ultrasound image quality and transcranial acoustic metamaterial parameters using inverse design methods. Impact Statement: Our study provides insights into inverse design methods and opens the route to guide the preparation of transcranial acoustic metamaterials. Introduction: The development of acoustic metamaterials has enabled the exploration of cranial ultrasound, and it has been found that the influence of the skull distortion layer on acoustic waves can be effectively eliminated by adjusting the parameters of the acoustic metamaterial. However, the interaction mechanism between transcranial ultrasound images and transcranial acoustic metamaterial parameters is unknown. Methods: In this study, 1,456 transcranial ultrasound image datasets were used to explore the mapping relationship between the quality of transcranial ultrasound images and the parameters of transcranial acoustic metamaterials. Results: The multioutput parameter prediction model of transcranial metamaterials based on deep back-propagation neural network was built, and metamaterial parameters under transcranial image evaluation indices are predicted using the prediction model. Conclusion: This inverse big data design approach paves the way for guiding the preparation of transcranial metamaterials.

Recent Progress in Smart Polymeric Gel-Based Information Storage for Anti-Counterfeiting.

Information security protection has a tremendous impact on human life, social stability and national security, leading to the rapid development of anti-counterfeiting materials and related techniques. However, the traditional stored information on hard or dry media is often static and lacks functions, which makes it challenging to deal with increasing and powerful counterfeiting technologies. Modified intelligent polymeric gels exhibit color changes and shape morphing under external stimuli, which give them great potential for applications in information storage. This paper provides an overview of the latest progress in polymeric gel-based information storage materials in relation to counterfeiting. Following a brief introduction of anti-counterfeiting materials, the preparation methods for intelligent gels with adjustable colors (e.g., chemical colors and physical colors) and various encryption/decryption modes involving dimensions and diverse colors are outlined. Finally, the challenges and prospects for information storage and anti-counterfeiting based on smart gels are discussed.

Supramolecular Assembly of Shape Memory and Actuating Hydrogels for Programmable Shape Transformation.

The deformable diversity of organisms in nature has inspired the development of bionic hydrogel actuators. However, the anisotropic structures of hydrogel actuators cannot be altered after the fabrication process, which restricts hydrogel actuators to provide complex and diverse shape deformations. Herein, we propose a dual programming method to generate numerous anisotropic structures from initial isotropic gelatin-containing hydrogels; the isotropic hydrogel blocks could be first assembled into anisotropic structures based on the coil-triple helix transition of gelatin, and then, the assembled hydrogels could further be fixed into various temporary anisotropies, so that they can produce complex and diverse deformations under the stimulation of pH. In addition, the shape programming and deformation behaviors are reversible. This dual programming method provides more potential for the application of hydrogel actuators in soft robots and bionics.