Bioinspired Supramolecular Photonic Composites: Construction and Emerging Applications.

Living organisms have evolved fascinating structural colors to survive in complex natural environments. Artificial photonic composites developed by imitating the structural colors of organisms are applied in displaying, sensing, biomedicine, and many other fields. As emerging materials, photonic composites mediated by supramolecular chemistry, namely, supramolecular photonic composites, are designed and constructed to meet emerging application needs and challenges. This review mainly introduces the constructive strategies, properties, and applications of supramolecular photonic composites. First, constructive strategies of supramolecular photonic composites are summarized, including the introduction of supramolecular polymers into colloidal photonic array templates, coassembly of colloidal particles (CPs) with supramolecular polymers, self-assembly of soft CPs, and compounding photonic elastomers with functional substances via supramolecular interactions. Supramolecular interactions endow photonic composites with attractive properties, such as stimuli-responsiveness and healability. Subsequently, the unique optical and mechanical properties of supramolecular photonic composites are summarized, and their applications in emerging fields, such as colorful coatings, real-time and visual motion monitoring, and biochemical sensors, are introduced. Finally, challenges and perspectives in supramolecular photonic composites are discussed. This article provides general strategies and considerations for the design of photonic materials based on supramolecular chemistry.

Bioinspired Photonic Ionogels as Interactively Visual Ionic Skin with Optical and Electrical Synergy.

With the ever-growing demands for flexible smart interactive electronics, it remains highly desirable yet challenging to design and fabricate interactive ionic skin with multiple signal synergistic outputs. Herein, high-performance photonic ionogels (PIGs) with excellent stability and synergy sensitivity are designed by locking a non-volatile and non-hygroscopic ionic liquid (IL), that is, 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([EMIm][TFSI]), into photonic elastomers based on polymer networks of poly(ethylene glycol) phenyl ether acrylate (PEGPEA). Through manipulating the degree of crosslinking, PIGs exhibit high sensitivity that can output distinct and intuitive color change in visual with the mechanochromic sensitivity of ≈1.76 nm per percent strain and clear electrical signal with the gauge factor of 1, in response to a tiny stretch of millimeter scale. Thanks to the stable photonic elastomers and IL employed, the PIGs developed in this study exhibit good performance under harsh and complex environmental conditions, including high/low temperature (from -35 °C to 100 °C), dry/wet air, and high vacuum. This study provides a novel strategy for developing integrated, stable, and multifunctional photonic ionogels for ionic skin sensors and flexible interactive devices with synergistically optical and electrical output.

Structurally-colored adhesives for sensitive, high-resolution, and non-invasive adhesion self-monitoring.

Polymeric adhesives are critical in many applications, from daily life to implantable devices and soft robotics. Monitoring adhesion in a real-time and convenient manner before premature failure is essential yet challenging. Herein, we present structurally-colored adhesives for sensitive, high-resolution, and non-invasive adhesion self-monitoring via distinct color change for detecting subtle deformation and debonding. The structurally-colored adhesives are designed by integrating one-dimensional photonic nanochains into exemplified acrylate-copolymer-based adhesives and demonstrate distinct color-changing capability through a unique tilting mechanism of nanochains under shear. Our structurally-colored adhesives can be customized as pressure-sensitive and structural adhesives, exhibiting ultrafast response (<60 ms), high sensitivity, and high resolution (~120 µm). Moreover, predicting adhesion states and premature failure can be achieved assisted by imaging systems and machine learning algorithms with an average accuracy of up to 97.2%. Our structurally-colored adhesives are expected to offer a practical paradigm for structural health monitoring in the Internet of Things era.

Colloidal Photonic Composites with a Long-Range Order by Hot-Pressing Polymer Brush-Grafted Silica Colloids.

Colloidal photonic composites (CPCs) are unique optical materials that combine flexible and responsive polymers with colloidal photonic crystals, and they have promising applications in colorful displays, optical anticounterfeiting, and visual sensors. However, conventional self-assembly strategies for constructing CPCs via solvent evaporation have faced limitations due to the meticulous regulation required during the evaporation process and typically long preparation durations. Here, we present an external force method to achieve a long-range ordered arrangement in CPCs by hot-pressing poly(2-[[(butylamino)carbonyl]oxy]ethyl acrylate (PBCOE)) brush-grafted silica colloidal particles (SiO2-g-PBCOE). We show that the hot-pressing conditions (i.e., temperature and pressure) and the silica volume fraction (φsilica) of the SiO2-g-PBCOE colloidal particles play crucial roles in determining their ordering and optical properties. By optimization of the hot-pressing temperature up to 100 °C and pressure of 5 MPa, a long-range ordered arrangement of SiO2-g-PBCOE colloidal particles with a φsilica of 20.3% can be achieved. For the effect of structural features, our findings reveal that SiO2-g-PBCOE colloidal particles featuring a higher φsilica are more prone to obtain a long-range ordered arrangement compared to a lower φsilica under hot-pressing conditions at relatively low temperature and pressure (50 °C and 5 MPa), which is mainly attributed to the chain entanglement and hydrogen bonding interactions induced by grafted longer polymer brushes, leading to additional energy inputs and weakening the ordering. Significantly, the critical φsilica (φc) of SiO2-g-PBCOE colloidal particles is discerned, strongly influencing the optical properties of the hot-pressed films. Specifically, a hot-pressed SiO2-g-PBCOE film with a critical φsilica of 29.3% displays enhanced optical properties characterized by intensified reflection peaks, narrowed full width at half-maximum (FWHM), and brilliant structural colors. Notably, in this work, we reveal the mechanism of hot-pressing-driven core-shell colloidal particle ordering and the key factors affecting the ordering of colloidal particles, i.e., chain entanglement and hydrogen-bonding interactions, which play a crucial role in obtaining CPCs with controllable structures. Moreover, angle-dependent structural color is observed in the hot-pressed SiO2-g-PBCOE film with a φsilica content of 29.3% due to the unique attributes of the highly ordered arrangement, while the films exhibit mechanochromic properties due to chain entanglement and hydrogen bonding interactions. This work provides valuable insights into the rapid construction of highly ordered CPCs and establishes a solid foundation for external force-assisted ordering of colloidal particles.

Scalable production of structurally colored composite films by shearing supramolecular composites of polymers and colloids.

Structurally colored composite films, composed of orderly arranged colloids in polymeric matrix, are emerging flexible optical materials, but their production is bottlenecked by time-consuming procedures and limited material choices. Here, we present a mild approach to producing large-scale structurally colored composite films by shearing supramolecular composites composed of polymers and colloids with supramolecular interactions. Leveraging dynamic connection and dissociation of supramolecular interactions, shearing force stretches the polymer chains and drags colloids to migrate directionally within the polymeric matrix with reduced viscous resistance. We show that meter-scale structurally colored composite films with iridescence color can be produced within several minutes at room temperature. Significantly, the tunability and diversity of supramolecular interactions allow this shearing approach extendable to various commonly-used polymers. This study overcomes the traditional material limitations of manufacturing structurally colored composite films by shearing method and opens an avenue for mildly producing ordered composites with commonly-available materials via supramolecular strategies.

Bioinspired Colloidal Photonic Composites: Fabrications and Emerging Applications.

Organisms in nature have evolved unique structural colors and stimuli-responsive functions for camouflage, warning, and communication over millions of years, which are essential to their survival in harsh conditions. Inspired by these characteristics, colloidal photonic composites (CPCs) composed of colloidal photonic crystals embedded in the polymeric matrix are artificially prepared and show great promise in applications. This review focuses on the summary of building blocks, i.e., colloidal particles and polymeric matrices, and constructive strategies from the perspective of designing CPCs with robust performance and specific functionality. Furthermore, their state-of-the-art applications are also discussed, including colorful coatings, anti-counterfeiting, and regulation of photoluminescence, especially in the field of visualized sensing. Finally, current challenges and potential for future developments in this field are discussed. The purpose of this review is not only to clarify the design principle for artificial CPCs but also to serve as a roadmap for the exploration of next-generation photonic materials.

Solvent-Responsive Invisible Photonic Patterns with High Contrast for Fluorescence Emission Regulation and Anti-Counterfeiting.

Invisible photonic patterns (IPPs) are photonic materials that can display hidden patterns under external stimulation and are attractive in anti-counterfeiting devices and information storage. In this work, we report a solvent-responsive invisible photonic pattern (SRIPP) with high contrast by polymerizing two monomers of acrylamide (AAm) and poly(ethylene glycol) methacrylate (PEGMA) with different solubility parameters in different regions of poly(hydroxyethyl methacrylate) photonic gels. The two regions with different solvent responsiveness can shrink and swell in the same environment, thus causing the colors of different regions of photonic gel to shift in opposite directions from the initial state. As a result, the contrast of photonic patterns is significantly improved, increasing naked-eye visualization. In addition, by introducing fluorescent substances into the photonic gel and adjusting the photonic band gap (PBG) of photonic gels, we realize the regulation of fluorescence emission and display of fluorescence patterns by utilizing different PBGs on the SRIPP. Dynamic solvent responsiveness patterns and fluorescence patterns are integrated into a photonic gel, showing great potential in information storage and multiple-mode anti-counterfeiting applications.

Composite Polyelectrolyte Photothermal Hydrogel with Anti-biofouling and Antibacterial Properties for the Real-World Application of Solar Steam Generation.

Solar steam generation provides a promising and low-cost solution for freshwater production in energy scarcity areas. However, in real-world applications, evaporators are easily affected by microorganism contamination in source water, causing surface corrosion, structural damage, or even invalidation. Developing anti-biofouling and antibacterial evaporators is significant for long-term stable freshwater production. Herein, a composite polyelectrolyte photothermal hydrogel consisting of sulfobetaine methacrylate (SBMA), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC), and polypyrrole (PPy) with anti-biofouling and antibacterial properties is developed. Crediting sufficient ammonium groups and zwitterionic segments, the optimized polyelectrolyte hydrogel exhibits an ∼90% antibacterial ratio against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) and effectively controls biological contamination. Under 1.0 kW m-2 solar irradiation, a rapid water evaporation rate of ∼1.690 kg m-2 h-1 and a high solar-to-evaporation efficiency of ∼95.94% are achieved with the photothermal hydrogel. We show that a lab-made setup integrated with the hydrogel can realize ∼0.455 kg m-2 h-1 freshwater production from seawater under natural sunlight. Moreover, the hydrogel exhibits excellent durability with a stable evaporation rate of ∼1.617 kg m-2 h-1 in real seawater for over 6 weeks, making it fullhearted in the real-world application of solar steam generation.

Cationic Photothermal Hydrogels with Bacteria-Inhibiting Capability for Freshwater Production via Solar-Driven Steam Generation.

Solar-driven steam generation has been recognized as a sustainable and low-cost solution to freshwater scarcity using abundant solar energy. To harvest freshwater, various interfacial evaporators with rational designs of photothermal materials and structures have been developed concentrating on increasing the evaporation rate in the past few years. However, pathogenic microorganism accumulation on the evaporators by long-duration contact with natural water resources may lead to the deterioration of water transportation and the reduction of the evaporation rate. Here, we develop cationic photothermal hydrogels (CPHs) based on [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC) and photothermal polypyrrole (PPy) with bacteria-inhibiting capability for freshwater production via solar-driven steam generation. A rapid water evaporation rate of 1.592 kg m-2 h-1 under simulated solar irradiation is achieved with CPHs floating on the water surface. Furthermore, we find that CPHs possess nearly 100% antibacterial performance against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The significant bacteria-inhibiting capability is mainly attributed to the large number of ammonium groups on the CPH network. Moreover, we show that CPHs exhibit good applicability with stable evaporation in natural lake water over 2 weeks, and the number of bacteria in purified lake water is significantly reduced. The device based on CPHs can achieve ∼0.49 kg m-2 h-1 freshwater production from lake water under natural sunlight. This study provides an attractive strategy for the evaporator to inhibit biological contamination and a potential way for long-term stable freshwater production from natural water resources in practical application.

Fluorescent Metallosupramolecular Elastomers for Fast and Ultrasensitive Humidity Sensing.

Fluorescent supramolecular polymers that can respond to subtle external stimuli to generate luminescence signals are promising in a wide range of applications, including probes, anti-counterfeiting materials, and sensors. However, complicated preparative procedures, limited responsive speed, and relatively low sensitivity still limit their practical sensing applications. Herein, we report europium-containing metallosupramolecular (PU-Eu) elastomers for fast and ultrasensitive humidity sensing by employing hygroscopic polyurethane (PU), whose urethane groups can coordinate with europium ions (Eu3+), emitting a strong luminescent signal by ligand-to-metal energy transfer. The variant of the coordination bond strength triggered by external humidity imparts the PU-Eu elastomer with a fast (∼1.1 s) and ultrasensitive response to the humid condition, where the external humidity increases by ∼1% and the corresponding fluorescence intensity will drop by ∼421.98 a.u. By a dip-coating process, PU-Eu elastomers can be conveniently coated on a hydrophilic and porous cellulose acetate nanofiber membrane, and the resulting composite membrane can achieve real-time and reversible monitoring of environmental humidity and human respiration. Given the versatility of PU-Eu elastomers, this study provides a low-cost and facile route of obtaining fluorescent metallosupramolecular polymers for fast and ultrasensitive humidity sensing.

Moist-Induced Electricity Generation by Electrospun Cellulose Acetate Membranes with Optimized Porous Structures.

Harvesting energy from moist in the atmosphere has recently been demonstrated as an effective manner for a portable power supply to meet the ever-increasing demands of energy consumption. Porous materials are shown to have great potential in moist-induced electricity generation. Herein, we report moist-induced electricity generation by electrospun cellulose acetate (CA) membranes with optimized porous structures. We show that the pore size and porosity of CA membranes can be readily tuned via a facile compression and annealing process, and the effect of pore features on the output voltages can thus be investigated systematically. We find that, at a relatively high porosity, the electricity-generation performance can be further enhanced by constructing a smaller pore to form more nanochannels. Porous CA membranes, with an optimized porosity of 52.6% and a pore diameter less than 250 nm, are prepared to construct moist-induced electricity generators, which can be applied as breath sensors and can power up calculator operation. The current study provides insights for the construction of porous materials with different pore characteristics for moist-induced electricity generation, especially in the exploration of more efficient and low-cost porous materials for large-scale practical application of the portable power supply.

Metallosupramolecular Photonic Elastomers with Self-Healing Capability and Angle-Independent Color.

Photonic elastomers that can change colors like a chameleon have shown great promise in various applications. However, it still remains a challenge to produce artificial photonic elastomers with desired optical and mechanical properties. Here, the generation of metallosupramolecular polymer-based photonic elastomers with tunable mechanical strength, angle-independent structural color, and self-healing capability is reported. The photonic elastomers are prepared by incorporating isotropically arranged monodispersed SiO2 nanoparticles within a supramolecular elastomeric matrix based on metal coordination interaction between amino-terminated poly(dimethylsiloxane) and cerium trichloride. The photonic elastomers exhibit angle-independent structural colors, while Young's modulus and elongation at break of the as-formed photonic elastomers reach 0.24 MPa and 150%, respectively. The superior elasticity of photonic elastomers enables their chameleon-skin-like mechanochromic capability. Moreover, the photonic elastomers are capable of healing scratches or cuts to ensure sustainable optical and mechanical properties, which is crucial to their applications in wearable devices, optical coating, and visualized force sensing.