Touch initiated on-demand adhesion on rough surfaces.

Reversible adhesion with on-demand attachment and detachment is used by many animals for their locomotion. However, achieving robust and switchable adhesion on rough surfaces in artificial adhesives remains a significant challenge. Here, we present a snail mucus-inspired touch-initiate adhesive (TIA), showing robust adhesions on various surfaces. TIA is a polymeric hydrogel photo-cured with the presence of supersaturated sodium acetate (NaAc) in the precursor solution. TIA is soft and flexible at room temperature, allowing it to form conformal contact with objects with various surfaces. The contact with the target surface immediately initiates the crystallization of TIA, increasing the elastic modulus of TIA by an order of magnitude. The increased modulus and the interlocking with the target surfaces thus results in an adhesion strength up to 465.56 ± 84.05 kPa. TIA can be easily detached from the surface by heating to a temperature above 58 °C, showing an adhesion strength of 12.71 ± 2.73 kPa. The detached TIA, even cooled down to and kept at room temperature, is readily used for the subsequent adhesion. The study here not only provides a highly adhesive material for on-demand attachment to various surfaces, but also proposes a new design strategy to compose smart materials.

Bioinspired Touch-Responsive Hydrogels for On-Demand Adhesion on Rough Surfaces.

Reversible adhesives are widely needed in our daily lives and industrial applications. However, robust and switchable adhesion on rough surfaces with on-demand attachment and detachment remains highly challenging. Here, we report a snail-mucus-inspired touch-responsive hydrogel (TRH), whose universal and robust adhesion is triggered by simple contact with the attaching surface. TRH is composed of a polymeric hydrogel and saturated sodium acetate (NaAc) and is prepared by one-pot synthesis. At room temperature, TRH remains in an amorphous and soft state, which allows it to conformally adapt to rough surfaces. The contact with the target surface triggers the crystallization of NaAc, which increases the modulus of TRH by an order of magnitude and interlocks with the target surfaces, achieving an adhesion of up to 204.84 ± 53.98 kPa. Upon heating, TRH returns to a soft state, facilitating easy detachment with adhesion of 5.12 ± 1.34 kPa. Meanwhile, the detached TRH is ready for the next adhesion without the need to be maintained at high temperature. TRH finds applications as a smart material for light-triggered adhesion switching, information encryption, and temperature sensors.

Micropillar with Radial Gradient Modulus Enables Robust Adhesion and Friction.

The gradient modulus in beetle setae plays a critical role in allowing it to stand and walk on natural surfaces. Mimicking beetle setae to create a modulus gradient in microscale, especially in the direction of setae radius, can achieve reliable contact and thus strong adhesion. However, it remains highly challenging to achieve modulus gradient along radial directions in setae-like structures. Here, polydimethylsiloxane (PDMS) micropillar with radial gradient modulus, (termed GM), is successfully constructed by making use of the polymerization inhibitor in the photosensitive resin template. GM gains adhesion up to 84 kPa, which is 2.3 and 4.7 times of soft homogeneous micropillars (SH) and hard homogeneous micropillars (HH), respectively. The radial gradient modulus facilitates contact formation on various surfaces and shifts stress concentration from contact perimeter to the center, resulting in adhesion enhancement. Meanwhile, GM achieves strong friction of 8.1 mN, which is 1.2 and 2.6 times of SH and HH, respectively. Moreover, GM possesses high robustness, maintaining strong adhesion and friction after 400 cycles of tests. The work here not only provides a robust structure for strong adhesion and friction, but also establishes a strategy to create modulus gradient at micron-scale.

Highly Antibacterial and Self-Healing Janus Fabric for Effective Body Moisture/Thermal Management and Durable Waterproof.

Despite the development of many functional fabrics, they are unable to meet practical needs due to their monolithic functions and low durability. Therefore, a multifunctional waterborne polyurethane nanodroplet containing disulfide bonds (WSPU) was synthesized using a simple and environmentally friendly approach. The functional WSPU nanodroplet coating endowed fabrics with a variety of properties, including exceptional hydrophobicity, antibacterial properties, self-healing at room temperature, directional transport, etc. The functionalized fabric demonstrated durable mechanical and chemical stabilities due to the combined effects of disulfide bond reconstruction and hydrophobic chain migration. It exhibited the ability to regain its hydrophobic properties at room temperature after 50 friction cycles were performed without requiring external stimulation. Furthermore, the fabric maintained a water contact angle above 140°, even after being subjected to washing, boiling, and immersion in acid and alkali solutions. In addition, as a result of the fabric's Janus-like wettability, it performed various functions in accordance with varying weather conditions, in terms of wearing comfort and breathability. In hot weather or during exercise, the Janus fabric with the hydrophilic side facing outward enhances the process of sweat-directed perspiration, resulting in a notable cooling effect. On rainy days, the Janus fabric, when positioned with the hydrophobic side facing outward, exhibited excellent waterproof performance. This study presents an opportunity to explore the development of multifunctional fabrics through the combined effects of several functions.

Robust and Elevated Adhesion and Anisotropic Friction in a Bioinspired Bridged Micropillar Array.

Bioinspired structured adhesives have promising applications in the fields of robotics, electronics, medical engineering, and so forth. The strong adhesion and friction as well as the durability of bioinspired hierarchical fibrillar adhesives are essential for their applications, which require fine submicrometer structures to stay stable during repeated use. Here, we develop a bioinspired bridged micropillars array (BP), which realizes a 2.18-fold adhesion and a 2.02-fold friction as compared to that of poly(dimethylsiloxane) (PDMS) original micropillar arrays. The aligned bridges offer BP strong anisotropic friction. The adhesion and friction of BP can be finely regulated by changing the modulus of the bridges. Moreover, BP shows strong adaptability to surface curvature (ranging from 0 to 800 m-1), excellent durability over 500 repeating cycles of attachment/detachment, and self-cleaning ability. This study presents a novel approach for designing robust structured adhesives with strong and anisotropic friction, which may find applications in areas such as climbing robots and cargo transportation.

Gradient Micropillar Array Inspired by Tree Frog for Robust Adhesion on Dry and Wet Surfaces.

The strong adhesion on dry and wet surfaces and the durability of bioinspired hierarchical fibrillar adhesives are critical for their applications. However, the critical design for the strong adhesion normally depends on fine sub-micron structures which could be damaged during repeat usage. Here, we develop a tree frog-inspired gradient composite micropillars array (GP), which not only realizes a 2.3-times dry adhesion and a 5.6-times wet adhesion as compared to the pure polydimethylsiloxane (PDMS) micropillars array (PP), but also shows excellent durability over 200 repeating cycles of attachment/detachment and self-cleaning ability. A GP consists of stiffer tips and softer roots by incorporating gradient dispersed CaCO3 nanoparticles in PDMS micropillar stalks. The modulus gradient along the micropillar height facilitates the contact formation and enhances the maximum stress during the detaching. The study here provides a new design strategy for robust adhesives for practical applications in the fields of robotics, electronics, medical engineering, etc.

Switchable Adhesion on Curved Surfaces Mimicking the Coordination of Radial-Oriented Spatular Tips and Motion of Gecko Toes.

Bio-inspired structured adhesives have promising applications in many fields, like biomedicine, robotics, and aerospace. However, achieving robust and switchable adhesion in structured adhesives on non-planar surfaces remains highly challenging. Inspired by the gripping and rolling motions of gecko toes, a strong and switchable adhesive, which comprises a pillar array with radial-oriented spatular tips and is named as PROST, is developed. PROST possesses a robust adhesion on flat surfaces and doubles its adhesion on curved surfaces. Moreover, in situ and fast adhesion switching of PROST on flat/curved surfaces in dry and wet conditions has been realized by solvent stimulation, mimicking the bending locomotion of gecko toes. The work here provides a new strategy for designing controllable adhesion on curved substrates.

Fast Self-Assembly of Photonic Crystal Hydrogel for Wearable Strain and Temperature Sensor.

Structural colors from photonic crystals (PCs) have attracted emerging attention in the research area of wearable sensors. Conventional self-assembly of PC takes days to weeks. Here, a fast self-assembly method of PC with horizontal precipitation of silica nanoparticles (NPs) in a polydimethylsiloxane fence, which can be completed within 1-4 h depending on the fence parameters, is introduced. The resultant PC exhibits tunable structural colors in the entire visible spectrum. With infiltration of composite hydrogels containing acrylic acid, acrylamide, chitosan, and carbon nanotubes (CNTs) into the gaps of NPs to form an inverse opal PC, a structural color hydrogel that can quickly respond to different stimuli, including strain and temperature, is obtained. Moreover, with the addition of CNTs, the composite PC hydrogel can also output an electronic signal together with optical color changes. Based on these extraordinary responsive behaviors, the PC hydrogel sensor for quantitative feedback to external stimuli of stretching, bending, pressing, and thermal stimuli, with brilliant color change and electronic signal outputs simultaneously, is demonstrated. This fast-assembled PC hydrogel with excellent responsive properties has great potential for applications in wearable devices, mechanical sensors, temperature sensors, and colorimetric displays.

Responsive hydrogel-based microneedle dressing for diabetic wound healing.

Wound healing is a critical challenge in diabetic patients, mainly due to long-term dysglycemia and its related pathological complications. Subcutaneous insulin injection represents a typical clinical solution, while the low controllability of insulin administration commonly leads to a result far from the optimal therapeutic effect. In this work, we developed a glucose-responsive insulin-releasing hydrogel for microneedle dressing fabrication and then investigated its effects on diabetic wound healing. The hydrogel system was composed of biocompatible gelatin methacrylate (GelMa), glucose-responsive monomer 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid (AFPBA) and gluconic insulin (G-insulin), and the Gel-AFPBA-ins hydrogel-based microneedle dressing was developed by replicating PDMS molds. The resultant hydrogel microneedle dressing exhibited adequate mechanical properties, high biocompatibility, glucose-responsive insulin release behavior upon exposure to different glucose solutions, and potent adhesion to the skin compared to hydrogels without microstructures. The microneedle dressing could accelerate the diabetic wound healing process with decreased inflammatory reaction, enhanced collagen deposition on the regenerated tissue sites, and improved blood glucose control in animals. Therefore, the glucose-responsive insulin-releasing hydrogel microneedle dressing is effective in diabetic wound management and has potential for treatment of other chronic skin injuries.

Tree frog-inspired nanopillar arrays for enhancement of adhesion and friction.

Bioinspired structure adhesives have received increasing interest for many applications, such as climbing robots and medical devices. Inspired by the closely packed keratin nanopillars on the toe pads of tree frogs, tightly arranged polycaprolactone nanorod arrays are prepared by mold process and chemical modification. Nanorod arrays show enhanced adhesion and friction on both smooth and rough surfaces compared to the arrays with hexagonal micropillars. The bonding of nanorods results in a larger stiffness of the nanorod surface, contributing mainly to friction rather than adhesion. The results suggest the function of closely packed keratin nanopillars on the toe pad of tree frogs and offer a guiding principle for the designing of new structured adhesives with strong attaching abilities.

Adhesion Enhancement of Micropillar Array by Combining the Adhesive Design from Gecko and Tree Frog.

It has long been demonstrated the gecko-inspired micropillar array with T-shape tips possesses the best adhesion performance of a given material. The further enhancement of the adhesion performances of T-shape micropillars can offer redundant adhesion to compensate for the inevitable improper contacts. Here, the array of T-shape polydimethylsiloxane (PDMS) micropillars is incorporated with gradient dispersed calcium carbonate nanoparticles in the micropillar stalk, termed as T-shape gradient micropillars (TG), possessing the modulus gradient with stiff tip and soft root. The gradient modulus in TG facilitates the contact formation and regulates the stress at the detaching interface, resulting in a 4.6 times adhesion and 2.4 times friction as compared with the pure PDMS T-shape micropillar arrays. The study here provides a new design strategy for the super-strong structured dry adhesives.

Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs.

Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization-solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.

Reversible Structure Engineering of Bioinspired Anisotropic Surface for Droplet Recognition and Transportation.

Surfaces with tunable liquid adhesion have aroused great attention in past years. However, it remains challenging to endow a surface with the capability of droplet recognition and transportation. Here, a bioinspired surface, termed as TMAS, is presented that is inspired by isotropic lotus leaves and anisotropic butterfly wings. The surface is prepared by simply growing a triangular micropillar array on the pre-stretched thin poly(dimethylsiloxane) (PDMS) film. The regulation of mechanical stress in the PDMS film allows the fine tuning of structural parameters of the micropillar array reversibly, which results in the instantaneous, in situ switching between isotropic and various degrees of anisotropic droplet adhesions, and between strong adhesion and directional sliding of water droplets. TMAS can thus be used for robust droplet transportation and recognition of acids, bases, and their pH strengths. The results here could inspire the design of robust sensor techniques.

Thermoinduced Crystallization-Driven Self-Assembly of Bioinspired Block Copolymers in Aqueous Solution.

Delicate control over architectures via crystallization-driven self-assembly (CDSA) in aqueous solution, particularly combined with external stimuli, is rare and challenging. Here, we report a stepwise CDSA process thermally initiated from amphiphilic poly(N-allylglycine)-b-poly(N-octylglycine) (PNAG-b-PNOG) conjugated with thiol-terminated triethylene glycol monomethyl ethers ((PNAG-g-EG3)-b-PNOG) in aqueous solution. The diblock copolymers show a reversible thermoresponsive behavior with nearly identical cloud points in both heating and cooling runs. In contrast, the morphology transition of the assemblies is irreversible upon a heating-cooling cycle because of the presence of a confined domain arising from crystalline PNOG, which allows for the achievement of different nanostructured assemblies by the same polymer. We demonstrated that the thermoresponsive property of PNAG-g-EG3 initiates assembly kinetically that is subsequently promoted by crystallization of PNOG thermodynamically. The irreversible morphology transition behavior provides a convenient platform for comparing the cellular uptake efficiency of nanostructured assemblies with various morphologies that are otherwise similar.

Tree Frog-Inspired Micropillar Arrays with Nanopits on the Surface for Enhanced Adhesion under Wet Conditions.

Inspired by the nanoconcave top of epidermal cells on tree frogs' toe pads, an array of composite micropillars with nanopits on the surface (CPp) has been designed. Polystyrene (PS) nanoparticles are mixed with polydimethylsiloxane (PDMS) and serve as the template for nanopits on the PS/PDMS composite micropillars. CPp shows much larger wet adhesion compared to the arrays of micropillars without nanopits. Under a certain loading force, most of the liquid between CPp and the counterpart surface is squeezed out, so the liquid that remained in nanopits forms multiple nanoscale liquid bridges within the contact area of a single micropillar. Moreover, a large loading force could squeeze part of the liquid out of nanopits, resulting in the suction effect during the pull-off. The multiple liquid bridges, the suction effect, and the solid direct contact thus contribute to strong wet adhesion, which could be ∼36.5 times that of tree frogs' toe pads. The results suggest the function of nanoconcaves on the toe pad of tree frogs and offer a new design strategy for structured adhesives to gain strong wet adhesion.

Reversible Adhesion via Light-Regulated Conformations of Rubber Chains.

Bio-inspired reversible adhesives have attracted great attention because of their promising applications in the electronic, biomedical, and robotic fields. Here, to achieve in situ reversible adhesion, a new concept is demonstrated by modulating the conformations of polydimethylsiloxane (PDMS) chains. The new adhesive, termed BGPP, is composed of the graphene/PDMS composite (GP) as the backing layer and PDMS as the micropillar array. The photothermal effect of graphene under UV irradiation heats up the micropillars, resulting in an increase in the chain conformations of PDMS and thus the contact points with the counterpart surface. The more contact points together with the alignment of PDMS chains during the shearing result in an adhesion much higher than that without UV irradiation. The adhesion switching thus does not rely on the changing of the contact area, and so the macroscopic deformation of structures is avoided. The results suggest a new design principle for light-controllable structured adhesive, which could be conceptualized into other rubbery materials.

A smart hydrogel system for visual detection of glucose.

Glucose sensing is of vital importance due to the growing number of diabetes. In this study, we developed a visual detecting approach for glucose sensing based on a smart hydrogel system, by assembling of a photo-crosslinkable hydrogel and a pH-responsive nanogel, respectively. The hydrogel system showed fast response and high sensitivity to glucose in the physiological ranges, and enabled a visual detection of glucose both in vitro in glucose solutions and in vivo in diabetic mouse models. In normoglycemic state, the hydrogels showed large swelling, resulting in a large shape but with weak color or fluorescence intensity of the hydrogels. In hyperglycemic state, the hydrogels exhibited less swelling, resulting in a small shape but with strong color or fluorescence intensity of the hydrogels. Based on the observation of the size change and intensity change of the hydrogels, we can visual the glucose levels by either colorimetry or fluorescence imaging. This hydrogel system provides a novel means for visual detection of glucose. Our study broadens the current applications of hydrogels, extending their potentials in clinical diagnosis of diabetes or glucose-related analysis.

Charge-Determined LCST/UCST Behavior in Ionic Polypeptoids.

Stimuli-responsive polymers have received increasing interest for a variety of applications. Here, we report a series of unique charge-determined thermoresponsive polypeptoids synthesized by a combination of ring-opening polymerization and click chemistry. The LCST-type and UCST-type behavior is mainly dominated by the charge state on the side chain. Further, the phase transition temperature highly depends on the degree of polymerization, the side-chain architecture, the pH value, and so on. The obtained polypeptoid solutions exhibit good stability against temperature and salt concentration. To our knowledge, this report presents the first charge-determined LCST/UCST-type polymer from identical homopolymer backbone that displays a wide range of tunable cloudy points in aqueous media. We propose the hydrogen-bonding interaction plays a critical part on the solution behavior. These features make polypeptoids ideal candidates for highly designable stimuli-responsive polymeric materials.