Reversible Adhesion Research Articles

Sticky organisms create underwater biological adhesives driven by interactions between EGF- and GlcNAc- containing polysaccharides

Marine and terrestrial organisms often utilise EGF/EGF-like domains in wet adhesives, yet their roles in adhesion remain unclear. Here, we investigate the Barbatia virescense byssal system and uncover an oxidation-independent, reversible, and robust adhesion mechanism where EGF/EGF-like domain tandem repetitions in adhesive proteins bind robustly to GlcNAc-based biopolymer. EGF/EGF-like-domain-containing proteins demonstrate over three-fold superior underwater adhesion to chitosan compared to the well-known strongest wet-adhesive proteins, mefp-5, and suckerin, when adhering to mica in an surface forces apparatus-based measurement. Additionally, as the degree of acetylation of chitosan decreases from 20.0 to 5.34%, the underwater adhesion energy between mefp-2 and chitosan decreases from |Wad | ≈ 41.80 to 12.92 ± 0.40 mJm−2. This finding highlights the importance of GlcNAc over GlcN in binding with EGF to formulate effective underwater adhesives, expanding our understanding of underwater adhesion and supporting EGF’s functional role in biomedical wet adhesive interfaces, hydrogels, and chitosan applications.

Research on advanced photoresponsive azobenzene hydrogels with push-pull electronic effects: a breakthrough in photoswitchable adhesive technologies.

Smart materials that adapt to various stimuli, such as light, hold immense potential across many fields. Photoresponsive molecules like azobenzenes, which undergo E-Z photoisomerization when exposed to light, are particularly valuable for applications in smart coatings, light-controlled adhesives, and photoresists in semiconductors and integrated circuits. Despite advances in using azobenzene moieties for stimuli-responsive adhesives, the role of push-pull electronic effects in regulating reversible adhesion remains largely unexplored. In this study, we investigate for the first time photo-controlled hydrogel adhesives of azobenzene with different push-pull electronic groups. We synthesized the monomers 4-methoxyazobenzene acrylate (ABOMe), azobenzene acrylate (ABH), and 4-nitroazobenzene acrylate (ABNO2), and examined their effects on reversible adhesion properties. By incorporating these azobenzene monomers into acrylamide, dialdehyde-functionalized poly(ethylene glycol), and [3-(methacryloylamino)propyl]-trimethylammonium chloride, we prepared ABOMe, ABH, and ABNO2 ionic hydrogels. Our research findings demonstrate that only the ABOMe ionic hydrogel exhibits reversible adhesion. This is due to its distinct transition state mechanism compared to ABH and ABNO2, which enables efficient E-Z photoisomerization and drives its reversible adhesion properties. Notably, the ABOMe ionic hydrogel reveals an outstanding skin adhesion strength of 360.7 ± 10.1 kPa, surpassing values reported in current literature. This exceptional adhesion is attributed to Schiff base reactions, monopole-quadrupole interactions, π-π interactions, and hydrogen bonding with skin amino acids. Additionally, the ABOMe hydrogel exhibits excellent reversible self-healing capabilities, significantly enhancing its potential for injectable medical applications. This research underscores the importance of integrating multifunctional properties into a single system, opening new possibilities for innovative and durable adhesive materials.

Adhesion of a nematic elastomer cylinder.

Reversible dry adhesion is exploited by lizards and insects in nature, and is of interest to robotics and bio-medicine. In this paper, we use numerical simulation to study how the soft elasticity of liquid crystal elastomers can affect its adhesion and provide a technological opportunity. Liquid crystal elastomers are cross-linked elastomer networks with liquid crystal mesogens incorporated into the main or side chain. Polydomain liquid crystalline (nematic) elastomers exhibit unusual mechanical properties like soft elasticity, where the material deforms at nearly constant stress, due to the reorientation of mesogens. Our study reveals that the soft elasticity of nematic elastomers dramatically affects the interfacial stress distribution at the interface of a nematic elastomer cylinder adhered to a rigid substrate. The stress near the edge of the nematic cylinder under tensile load deviates from the singular behavior predicted for linear elastic materials, and the maximum normal stress reduces dramatically. This suggests that nematic elastomers should display extremely high, but controllable adhesion, consistent with the available experimental observations.

Shape Memory Vitrimer for Reversible Dry Adhesion Enabled by Multiscale Reprocessing and Shape Fixing

Shape Memory Vitrimer for Reversible Dry Adhesion Enabled by Multiscale Reprocessing and Shape Fixing

Fabricating a SFMA/BAChol/PAA/ZnCl2 Hydrogel with Excellent Versatile Comprehensive Properties and Stable Sensitive Freezing-Tolerant Conductivity for Wearable Sensors.

Flexible wearable sensors have obtained tremendous interest in various fields and conductive hydrogels are a promising candidate. Nevertheless, the insufficient mechanical properties, the low electrical conductivity and sensitivity, and the limited functional properties prevent the development of hydrogels as wearable sensors. In this study, an SFMA/BAChol/PAA/ZnCl2 hydrogel was fabricated with high mechanical strength and versatile comprehensive properties. Specifically, the obtained hydrogel displayed excellent adhesion and mechanical stability, cryophylactic ability, stable sensitive freezing-tolerant conductivity, and feasible electrical conduction under a wide temperature range, demonstrating the high application potential as a flexible wearable sensor for movement behavior surveillance, even under harsh environments. Furthermore, the mechanical strength of the hydrogel could easily be regulated by varying the copolymer content. The molecular mechanisms of the hydrogel formation and the reversible adhesion during the wet-dry transition were proposed. The non-covalent interactions, including the electrostatic interaction, hydrogen bond interaction and hydrophobic association, and coordination interaction, were dynamically presented in the hydrogel network and hence supported the versatile comprehensive properties of the hydrogel. This study provides a strategy for designing novel hydrogels to promote the development of flexible sensors with stable sensitive freezing-tolerant conductivity.

An Environmentally Stable, Biocompatible, and Multilayered Wound Dressing Film with Reversible and Strong Adhesion.

Reversible adhesives for wound care improve patient experiences by permitting reuse and minimizing further tissue injury. Existing reversible bandages are vulnerable to water and can undergo unwanted deformation during removal and readdressing procedures. Here, a biocompatible, multilayered, reversible wound dressing film that conforms to skin and is waterproof is designed. The inner layer is capable of instant adhesion to various substrates upon activation of the dynamic boronic ester bonds by water; intermediate hydrogel layer and outer silicone backing layer can enhance the dressing's elasticity and load distribution for adhesion, and the silicone outer layer protects the dressing from exposure to water. The adhesive layer is found to be biocompatible with mouse skin. Skin injuries on the mouse skin heal more rapidly with the film compared to no dressing controls. Evaluations of the film on skin of freshly euthanized minipigs corroborate the findings in the mouse model. The film remains attached to skins without delamination despite subjecting to various degrees of deformation. Exposure to water softens the film to allow removal from the skin without pulling any hair off. The multilayered design considers soft mechanics in each layer and will offer new insights to improve wound dressing performance and patient comfort.

A chondroitin sulfate-based temperature-responsive hydrogel with antimicrobial properties for epidermal wound repair in diabetic patients

Preventing wound infection and avoiding secondary damage to wounds during dressing changes represents a significant clinical challenge. Developing wound dressings that mitigate wound infections and facilitate peel-on-demand property may solve the problem. In this study, a temperature-responsive hydrogel with antimicrobial and on-demand peeling properties was proposed. Basing on the Schiff-base reaction, a gelatin/oxidized chondroitin sulfate (GelOCS@Ag) hydrogel loaded with silver nanoparticles was synthesized via the straightforward amalgamation of gelatin, chondroitin sulfate, and silver nanoparticles. The resultant hydrogel exhibited commendable tensile, recovery, and temperature-responsive properties, effectively reconciling the dichotomy between adhesion and reversible adhesion, and thereby achieving the desired effect of on-demand peeling. Specifically, the adhesion strength of the GelOCS@Ag hydrogel reached 12.7 kPa at body temperature, in stark contrast to a mere 1.2 kPa at 10℃, facilitating easy detachment from the wound surface. Furthermore, the hydrogel exhibited potent antimicrobial properties and demonstrated excellent cytocompatibility. The GelOCS@Ag hydrogel has promising applications within the realm of wound dressings.

Custom-shaped malleable, recyclable and reversible structural adhesives based on vanillin polyimine vitrimers

A series of polyimine vitrimers were prepared from a synthesized dialdehyde derivative of vanillin. This derivative was then crosslinked with two different ratios of amines (Jeffamine T403 and m-xylylenediamine), forming imine bonds responsible for the exchange reactions. This process resulted in three distinct materials which exhibited glass transition temperatures (Tgs) ranging from 20 to 60 °C, along with good thermal stability, and strong mechanical and thermomechanical properties.Their dynamicity resulted in a fast relaxation rate achieving a complete relaxation in less than 15 min at 140 °C. Additionally, the polyimines could be mechanically recycled up to three times without significant loss in their final properties, demonstrating the possible enhancement of their lifespan. Moreover, they could be chemically recycled under mild conditions through acid hydrolysis or transamination, which significantly contributes towards a better circular economy. Furthermore, these vitrimers were tested as reversible structural adhesives, achieving initial lap-shear strength values of 12.4 MPa and up to 97 % of efficiency after re-bonding, highlighting their huge potential for industrial applications. Due to their pre-cured state, these adhesives were malleable, which allow them to be custom-shaped into different complex shapes. Finally, these imine materials showed outstanding self-welding capabilities with the repaired versions showing comparable performance to the original.

Exploring α-Lipoic Acid Based Thermoplastic Silicone Adhesive: Towards Sustainable and Green Recycling.

Considering the demand for the construction of a sustainable future, it is essential to endow the conventional thermoset silicone adhesive with reuse capability and recyclability. Although various research attempts have been made by incorporating reversible linkages, developing sustainable silicone adhesives by natural linkers is still challenging, as the interface between the natural linker and the silicone is historically difficult. We exploited the possibility of utilizing α-lipoic acid, a natural linker, to construct a sustainable silicone adhesive. Via the simultaneous ring-opening reaction between the COOH and epoxide-functionalized silicone and the polymerization of the α-lipoic acid, the resulting network exhibited dynamic properties. The shear strength of the LASA90 presented strong adhesion (up to 88 kPa) on various substrates including steel, aluminum, PET, and PTFE. Meanwhile, reversible adhesion was shown multiple times under mild heating conditions (80 °C). The rheology, TG-DTA, DSC, and 1H NMR showed that the degradation of the LASA occurred at 150 °C via the retro-ROP of the five-membered disulfide ring, indicating their recyclability after usage. Conclusively, we envision that a silicone adhesive based on α-lipoic acid as a natural linker is more sustainable than conventional silicone thermosets because of its desired properties, strong adhesion, reversibility, and on-demand heat degradation.

Design Strategy, On-Demand Control, and Biomedical Engineering Applications of Wet Adhesion.

The adhesion of tissues to external devices is fundamental to numerous critical applications in biomedical engineering, including tissue and organ repair, bioelectronic interfaces, adhesive robotics, wearable electronics, biomedical sensing and actuation, as well as medical monitoring, treatment, and healthcare. A key challenge in this context is that tissues are typically situated in aqueous and dynamic environments, which poses a bottleneck to further advancements in these fields. Wet adhesion technology (WAT) presents an effective solution to this issue. In this review, we summarize the three major design strategies and control methods of wet adhesion, comprehensively and systematically introducing the latest applications and advancements of WAT in the field of biomedical engineering. First, single adhesion mechanism under the frameworks of the three design strategies is systematically introduced. Second, control methods for adhesion are comprehensively summarized, including spatiotemporal control, detachment control, and reversible adhesion control. Third, a systematic summary and discussion of the latest applications of WAT in biomedical engineering research and education were presented, with a particular focus on innovative applications such as tissue-electronic interface devices, ingestible devices, end-effector components, in vivo medical microrobots, and medical instruments and equipment. Finally, opportunities and challenges encountered in the design and development of wet adhesives with advanced adhesive performance and application prospects are discussed.

Harnessing Extreme Internal Damping in Polyrotaxane‐Incorporated Liquid Crystal Elastomers for Pressure‐Sensitive Adhesives

AbstractLiquid crystal elastomers (LCEs) exhibit extraordinary energy dissipation due to their unique viscoelastic response, resulting from the rotation of mesogens under mechanical stress. While recent studies demonstrate the LCE‐based pressure‐sensitive adhesives (PSAs) by exploiting the enhanced damping, all previous studies have focused on LCEs with covalent crosslinks. Here, a new class of PSAs is developed by integrating movable polyrotaxane crosslinkers into an LCE matrix (PRx‐LCEs). Dynamic viscoelastic measurements reveal that PRx‐LCE exhibits a remarkably high energy dissipation, as indicated by a large tan δ. Interestingly, the secondary tan δ peak associated with LCE damping is more pronounced than the primary peak of the glass transition. The exceptional energy dissipation in PRx‐LCE results in superior adhesion strength (≈1864 N m−1), which is 3.5 times higher than conventional LCEs and 13 times higher than commercial PSAs in the peel test. Additionally, PRx‐LCEs demonstrate thermally reversible adhesion, enabling clean removal at elevated temperatures. Furthermore, the sliding effect in PRx‐LCE enhances both deformability and stress relaxation under load, resulting in deeper indentation, and superior adhesion during the probe tack test. The combination of LCE and slidable crosslinks provides robust and switchable adhesion, making them promising for applications in biomedical engineering, display, and semiconductor industries.

Hydrogen-Bonded Supramolecular Network Enabled Gentle Reprogramming of Liquid Crystal Elastomer toward Evolutionary Robot.

In nature, many organisms augment chances of survival by reprogramming their structures to evolving environment, among which sea squirts being a prime example. Such reprogramming has been demonstrated in liquid crystal elastomer (LCE) actuator assembled with heat assistance. However, the required temperature being higher than the actuation temperature limits its application. Here, we reported a hydrogen-bonded supramolecular network LCE to construct soft modular and reprogrammable actuator by assembling with a gentle heat treatment. Leveraging the Michael addition reaction, we introduced hydrogen bonding to the LCE matrix with functionalized pyridine monomers. Experimental and molecular dynamics modeling proved the efficient dynamic hydrogen bond exchange at 60 °C, significantly lower than the actuating temperature of the LCE. This gave rise to the reversible and robust adhesion of the same collection of LCE modules capable of being built into different bilayers and performing various morphing upon a short thermal stimulation. Therefore, we demonstrated that these comparatively weak cross-links enabled reconfiguration of the LCE actuator. With the developed hydrogen-bonding LCEs, we built proof-of-concept modular reprogrammable robot, performing crawling, sailing, and microcircuit repair tasks. This bioinspired and efficient method for evolutionary LCE robot offers a viable path for further development of intelligent actuators sustainable in complex environments.

Hydrogen‐Bonded Supramolecular Network Enabled Gentle Reprogramming of Liquid Crystal Elastomer toward Evolutionary Robot

AbstractIn nature, many organisms augment chances of survival by reprogramming their structures to evolving environment, among which sea squirts being a prime example. Such reprogramming has been demonstrated in liquid crystal elastomer (LCE) actuator assembled with heat assistance. However, the required temperature being higher than the actuation temperature limits its application. Here, we reported a hydrogen‐bonded supramolecular network LCE to construct soft modular and reprogrammable actuator by assembling with a gentle heat treatment. Leveraging the Michael addition reaction, we introduced hydrogen bonding to the LCE matrix with functionalized pyridine monomers. Experimental and molecular dynamics modeling proved the efficient dynamic hydrogen bond exchange at 60 °C, significantly lower than the actuating temperature of the LCE. This gave rise to the reversible and robust adhesion of the same collection of LCE modules capable of being built into different bilayers and performing various morphing upon a short thermal stimulation. Therefore, we demonstrated that these comparatively weak cross‐links enabled reconfiguration of the LCE actuator. With the developed hydrogen‐bonding LCEs, we built proof‐of‐concept modular reprogrammable robot, performing crawling, sailing, and microcircuit repair tasks. This bioinspired and efficient method for evolutionary LCE robot offers a viable path for further development of intelligent actuators sustainable in complex environments.

Thermoreversible Apparel Adhesives to Enable Sustainable Garment Assembly

AbstractOver 90 million tons of fabric waste are generated annually by the apparel industry and there exists an urgent need to develop innovative approaches for the recycling of garments. Reversible adhesives can both enable the automation of labor‐intensive assembly processes and facilitate fabric recycling for a circular apparel economy. Herein, an adhesive formulation based on thermoreversible Diels–Alder chemistry has been developed via the combination of a furan‐functionalized methacrylate copolymer (F) with a bismaleimide (M). To establish the fine balance between adhesion strength and reversible bonding, an extensive screening on the optimal composition and molar mass of F is conducted. Methyl, 2‐ethylhexyl, and lauryl methacrylate are used to tune the Tg of F copolymers, whereas H‐bonding monomers such as methacrylic acid and 2‐hydroxyethyl methacrylate are utilized to strengthen the adhesive and improve its interactions with cotton. Following the optimization of F composition, F molecular weight, and M crosslinker, the scaled‐up thermoreversible adhesive is studied by rheometry and successfully dispensed via an automated assembly platform. The adhered fabrics are tested for the required shear and peel strength and then separated for fabric recycling by a short heat treatment followed by a simple solvent wash to remove adhesive residues.

Precision-induced localized molten liquid metal stamps for damage-free transfer printing of ultrathin membranes and 3D objects

Transfer printing, a crucial technique for heterogeneous integration, has gained attention for enabling unconventional layouts and high-performance electronic systems. Elastomer stamps are typically used for transfer printing, where localized heating for elastomer stamp can effectively control the transfer process. A key challenge is the potential damage to ultrathin membranes from the contact force of elastic stamps, especially with fragile inorganic nanomembranes. Herein, we present a precision-induced localized molten technique that employs either laser-induced transient heating or hotplate-induced directional heating to precisely melt solid gallium (Ga). By leveraging the fluidity of localized molten Ga, which provides gentle contact force and exceptional conformal adaptability, this technique avoids damage to fragile thin films and improves operational reliability compared to fully liquefied Ga stamps. Furthermore, the phase transition of Ga provides a reversible adhesion with high adhesion switchability. Once solidified, the Ga stamp hardens and securely adheres to the micro/nano-membrane during the pick-up process. The solidified stamp also exhibits the capability to maneuver arbitrarily shaped objects by generating a substantial grip force through the interlocking effects. Such a robust, damage-free, simply operable protocol illustrates its promising capabilities in transfer printing diverse ultrathin membranes and objects on complex surfaces for developing high-performance unconventional electronics.

Chirality differences of three borneols contribute to controlling Escherichia coli biofilm formation by chemotaxis mediating movement

SummaryEscherichia coli (E. coli) biofilm is the major cause of its high lethality in foodborne illness. Controlling E. coli biofilm formation is a critical way to reduce foodborne diseases. Here, chiral borneol isomers (L‐borneol, D‐borneol, and isoborneol) were identified as E. coli chemorepellents, which reduced reversible adhesion at the initial stage of biofilm formation. Borneols directly inhibited biofilm production and their inhibitory capacities were associated with the chiral stereochemical structures (L‐borneol > D‐borneol > isoborneol). A transcriptomic study revealed the inhibitory mechanism of borneols was attributed to the bacterial motility intention and motility energy system. The most effective isomer, L‐borneol, reduced bacterial energy metabolism and increased E. coli chemotaxis motility intention through the up‐regulation of genes associated with flagellar assembly and bacterial chemotaxis pathways. This work demonstrates that borneols are biofilm inhibitors and supports the potential of borneols as a stereochemical antimicrobial strategy to reduce foodborne pathogenic bacterial contamination.

Ionic aggregates induced room temperature autonomous self-healing elastic tape for reducing ankle sprain

Traditional kinesiology tape (KT) is an elastic fabric tape that clinicians and sports trainers widely use for managing ankle sprains. However, inadequate mechanical properties, adhesive strength, water resistance, and micro-damage generation could affect the longevity of the tape on the skin during physical activity and sweating. Therefore, autonomous room-temperature self-healing elastomers with robust mechanical properties and adequate adhesion to the skin are highly desirable to replace traditional KT. Ionic aggregates were introduced into the polymer matrix via electrostatic attraction between polymer colloid and polyelectrolyte to achieve such elastic tape. These ionic aggregates act as physical crosslink points to enhance mechanical properties and dissociate at room temperature to provide self-healing functions. The obtained elastic tape possesses a tensile strength of 3.7 MPa, elongation of 940 %, toughness of 16.6 MJ∙m−3, and self-healing efficiency of 90 % for 2 h at room temperature. It also exhibits adequate reversible adhesion on the skin via van der Waals force and electrostatic interaction in both dry and wet conditions. The new elastic tapes have great potential in biomedical engineering for preventing and rehabilitating ankle sprain.

Flexible Organic Molecular Single Crystal-Based Triboelectric Device as a Self-Powered Tactile Sensor.

Triboelectric nanogenerators (TENGs) have proven to be effective at converting mechanical energy into electrical power, making them a viable technology for operating self-powered electronic devices used in medical diagnostics and environmental monitoring. In the present study, we demonstrate the utility of the flexible single crystals of an organic compound for the fabrication of a TENG as a self-powered tactile sensor. Triboelectrification was attained in single crystals as a result of surface functionalization with positively and negatively charged moieties, viz. Zn2+ and F-, respectively, which resulted in a variable surface potential and reversible adhesion through electrostatic interaction and induction phenomena. TENG incorporating the single crystals showed an output voltage of 2.4 V, a current density of ∼2.2 μA/m2, and a power density of ∼850 mW/m2 and was capable of charging commercial capacitors thereby ensuring its ability to be used as a self-powered touch sensor. Capitalizing on these features, a self-powered tactile sensor was fabricated to demonstrate limb movements. The excellent mechano-electric sensitivity (∼102 mV/kPa until 6 kPa range) and response time (∼38 ms) establish the viability of flexible organic single crystals for mechanical energy harvesting and biosensing applications that could pave the way for their utilization as biomedical wearable devices.

Branched Oligomer-Based Reversible Adhesives Enabled by Controllable Self-Aggregation.

Supramolecular adhesion material systems based on small molecules have shown great potential to unite the great contradiction between strong adhesion and reversibility. However, these material systems suffer from low adhesion strength/narrow adhesion span, limited designability, and single interaction due to fewer covalent bond content and action sites in small molecules. Herein, an ultrahigh-strength and large-span reversible adhesive enabled by a branched oligomer controllable self-aggregation strategy is developed. The dense covalent bonds present in the branched oligomers greatly enhance adhesion strength without compromising reversibility. The resulting adhesive exhibits a large-span reversible adhesion of ≈140 times, switching between ultra-strong and tough adhesion strength (5.58MPa and 5093.92Nm-1) and ultralow adhesion (0.04MPa and 87.656Nm-1) with alternating temperature. Moreover, reversible dynamic double cross-linking endows the adhesive with stable reversible adhesion transitions even after 100 cycles. This reversible adhesion property can also be remotely controlled via a voltage of 8V, with a loading voltage duration of 45s. This work paves the way for the design of reversible adhesives with long-span outstanding properties using covalent polymers and offers a pathway for the rational design of high-performance adhesives featuring both robust toughness and exceptional reversibility.

In Situ Triggered Self-Contraction Bioactive Microgel Assembly Accelerates Diabetic Skin Wound Healing by Activating Mechanotransduction and Biochemical Pathway.

Chronic nonhealing skin wounds, characterized by reduced tissue contractility and inhibited wound cell survival under hyperglycemia and hypoxia, present a significant challenge in diabetic care. Here, an advanced self-contraction bioactive core-shell microgel assembly with robust tissue-adhesion (SMART-EXO) is introduced to expedite diabetic wound healing. The SMART-EXO dressing exhibits strong, reversible adhesion to damaged tissue due to abundant hydrogen and dynamic coordination bonds. Additionally, the core-shell microgel components and dynamic coordination bonds provide moderate rigidity, customizable self-contraction, and an interlinked porous architecture. The triggered in situ self-contraction of the SMART-EXO dressing enables active, tunable wound contraction, activating mechanotransduction in the skin and promoting the optimal fibroblast-to-myofibroblast conversion, collagen synthesis, and angiogenesis. Concurrently, the triggered contraction of SMART-EXO facilitates efficient loading and on-demand release of bioactive exosomes, contributing to re-epithelialization and wound microenvironment regulation in diabetic mice. RNA-seq results reveal the activation of critical signaling pathways associated with mechanosensing and exosome regulation, highlighting the combined biomechanical and biochemical mechanisms. These findings underscore SMART-EXO as a versatile, adaptable solution to the complex challenges of diabetic wound care.