Programming hydrogel adhesion with engineered polymer network topology.

Hydrogel adhesion that can be easily modulated in magnitude, space, and time is desirable in many emerging applications ranging from tissue engineering and soft robotics to wearable devices. In synthetic materials, these complex adhesion behaviors are often achieved individually with mechanisms and apparatus that are difficult to integrate. Here, we report a universal strategy to embody multifaceted adhesion programmability in synthetic hydrogels. By designing the surface network topology of a hydrogel, supramolecular linkages that result in contrasting adhesion behaviors are formed on the hydrogel interface. The incorporation of different topological linkages leads to dynamically tunable adhesion with high-resolution spatial programmability without alteration of bulk mechanics and chemistry. Further, the association of linkages enables stable and tunable adhesion kinetics that can be tailored to suit different applications. We rationalize the physics of polymer chain slippage, rupture, and diffusion at play in the emergence of the programmable behaviors. With the understanding, we design and fabricate various soft devices such as smart wound patches, fluidic channels, drug-eluting devices, and reconfigurable soft robotics. Our study presents a simple and robust platform in which adhesion controllability in multiple aspects can be easily integrated into a single design of a hydrogel network.

Overcoming the adhesion paradox and switchability conflict on rough surfaces with shape-memory polymers.

Smart adhesives that can be applied and removed on demand play an important role in modern life and manufacturing. However, current smart adhesives made of elastomers suffer from the long-standing challenges of the adhesion paradox (rapid decrease in adhesion strength on rough surfaces despite adhesive molecular interactions) and the switchability conflict (trade-off between adhesion strength and easy detachment). Here, we report the use of shape-memory polymers (SMPs) to overcome the adhesion paradox and switchability conflict on rough surfaces. Utilizing the rubbery-glassy phase transition in SMPs, we demonstrate, through mechanical testing and mechanics modeling, that the conformal contact in the rubbery state followed by the shape-locking effect in the glassy state results in the so-called rubber-to-glass (R2G) adhesion (defined as making contact in the rubbery state to a certain indentation depth followed by detachment in the glassy state), with extraordinary adhesion strength (>1 MPa) proportional to the true surface area of a rough surface, overcoming the classic adhesion paradox. Furthermore, upon transitioning back to the rubbery state, the SMP adhesives can detach easily due to the shape-memory effect, leading to a simultaneous improvement in adhesion switchability (up to 103, defined as the ratio of the SMP R2G adhesion to its rubbery-state adhesion) as the surface roughness increases. The working principle and the mechanics model of R2G adhesion provide guidelines for developing stronger and more switchable adhesives adaptable to rough surfaces, thereby enhancing the capabilities of smart adhesives, and impacting various fields such as adhesive grippers and climbing robots.

Fast, strong, and reversible adhesives with dynamic covalent bonds for potential use in wound dressing.

Adhesives typically fall into two categories: those that have high but irreversible adhesion strength due to the formation of covalent bonds at the interface and are slow to deploy, and others that are fast to deploy and the adhesion is reversible but weak in strength due to formation of noncovalent bonds. Synergizing the advantages from both categories remains challenging but pivotal for the development of the next generation of wound dressing adhesives. Here, we report a fast and reversible adhesive consisting of dynamic boronic ester covalent bonds, formed between poly(vinyl alcohol) (PVA) and boric acid (BA) for potential use as a wound dressing adhesive. Mechanical testing shows that the adhesive film has strength in shear of 61 N/cm2 and transcutaneous adhesive strength of 511 N/cm2, generated within 2 min of application. Yet the film can be effortlessly debonded when exposed to excess water. The mechanical properties of PVA/BA adhesives are tunable by varying the cross-linking density. Within seconds of activation by water, the surface boronic ester bonds in the PVA/BA film undergo fast debonding and instant softening, leading to conformal contact with the adherends and reformation of the boronic ester bonds at the interface. Meanwhile, the bulk film remains dehydrated to offer efficient load transmission, which is important to achieve strong adhesion without delamination at the interface. Whether the substrate surface is smooth (e.g., glass) or rough (e.g., hairy mouse skin), PVA/BA adhesives demonstrate superior adhesion compared to the most widely used topical skin adhesive in clinical medicine, Dermabond.

Fabrication of an Ultrastrong Formaldehyde-Free Wood Adhesive with an Organic-Inorganic Cross-Linking Network.

The wood industry faces challenges in producing eco-friendly, high-performance, and formaldehyde-free adhesives. In this study, carboxylated styrene-butadiene rubber (XSBR) was blended with polyamidoamine-epichlorohydrin (PAE) resin, and a controlled amount of CaCO3 powder was incorporated to create an adhesive with exceptional strength. The resulting three-layer plywood demonstrated remarkable dry and wet shear strengths of 3.09 and 2.36 MPa, respectively, and of 2.27 MPa after boiling water tests, comparable to that of phenolic resins. Additionally, the adhesive exhibited strong adhesion across various materials including glass, metal, etc. This exceptional performance was due to two primary factors: (1) the high-density chemical cross-linking reaction and the physical entanglement between XSBR and PAE; (2) the organic-inorganic hybrid involving metal ion complexation developed by CaCO3, which fostered molecular chain connections and enhanced the adhesive-material interface. These findings offer valuable references for further research in the field of wood adhesives.

Harnessing Biomimicry for Controlled Adhesion on Material Surfaces.

Nature serves as an abundant wellspring of inspiration for crafting innovative adhesive materials. Extensive research is conducted on various complex forms of biological attachment, such as geckos, tree frogs, octopuses, and mussels. However, significant obstacles still exist in developing adhesive materials that truly replicate the behaviors and functionalities observed in living organisms. Here, an overview of biological organs, structures, and adhesive secretions endowed with adhesion capabilities, delving into the intricate relationship between their morphology and function, and potential for biomimicry are provided. First, the design principles and mechanisms of adhesion behavior and individual organ morphology in nature are summarized from the perspective of structural and size constraints. Subsequently, the value of engineered and bioinspired adhesive materials through selective application cases in practical fields is emphasized. Then, a forward-looking gaze on the conceivable challenges and associated opportunities in harnessing biomimetic strategies and biological materials for advancing adhesive material innovation is highlighted and cast.

Machine Learning-Based Shear Optimal Adhesive Microstructures with Experimental Validation.

Bioinspired fibrillar structures are promising for a wide range of disruptive adhesive applications. Especially micro/nanofibrillar structures on gecko toes can have strong and controllable adhesion and shear on a wide range of surfaces with residual-free, repeatable, self-cleaning, and other unique features. Synthetic dry fibrillar adhesives inspired by such biological fibrils are optimized in different aspects to increase their performance. Previous fibril designs for shear optimization are limited by predefined standard shapes in a narrow range primarily based on human intuition, which restricts their maximum performance. This study combines the machine learning-based optimization and finite-element-method-based shear mechanics simulations to find shear-optimized fibril designs automatically. In addition, fabrication limitations are integrated into the simulations to have more experimentally relevant results. The computationally discovered shear-optimized structures are fabricated, experimentally validated, and compared with the simulations. The results show that the computed shear-optimized fibrils perform better than the predefined standard fibril designs. This design optimization method can be used in future real-world shear-based gripping or nonslip surface applications, such as robotic pick-and-place grippers, climbing robots, gloves, electronic devices, and medical and wearable devices.

Preload-Induced Switchable Adhesion.

Animals with robust attachment abilities commonly exhibit stable attachment and convenient detachment. However, achieving an efficient attachment-detachment function in bioinspired adhesives is challenging owing to the complexity and delay of actuators. In this study, a class of multilayer adhesives (MAs) comprising backing, middle, and bottom layers is proposed to realize rapid switching by only adjusting the preload. At low preload, the MAs maintain intimate contact with the substrate. By contrast, a sufficiently large preload results in significant deformation of the middle layer, causing underside buckling and reducing adhesion. By optimizing the structural parameters of the MAs, a high switching ratio (up to 136×) can be achieved under different preloads. Furthermore, the design of the MAs incorporates a film-terminated structure, which prevents the embedding of dirt particles, simplifies cleaning, and maintains the separation and uprightness of the microstructures. Consequently, the MAs demonstrate practical potential for simple and efficient transportation applications, as they achieve switchable adhesion through their structure, exhibiting a high switching ratio and fast switching.

Green and Low-Cost Alkali-Polyphenol Synergetic Self-Catalysis System Access to Fast Gelation of Self-Healable and Self-Adhesive Conductive Hydrogels for Self-Powered Triboelectric Nanogenerators.

Biomass-based hydrogels have attracted great attention in flexible and sustainable self-powered power sources but struggled to fabricate in a green, high-efficiency, and low-cost manner. Herein, a novel and facile alkali-polyphenol synergetic self-catalysis system is originally employed for the fast gelation of self-healable and self-adhesive lignin-based conductive hydrogels, which can be regarded as hydrogel electrodes of flexible triboelectric nanogenerators (TENGs). This synergy self-catalytic system comprises aqueous alkali and polyphenol-containing lignin, in which alkali-activated ammonium persulfate (APS) significantly accelerates the generation of radicals and initiates the polymerization of monomers, while polyphenol acts as a stabilizer to avoid bursting polymerization from inherent radical scavenging ability. Furthermore, multiple hydrogen bonds between lignin biopolymers and polyacrylamide (PAM) chains impart lignin-based hydrogels with exceptional adhesiveness and self-healing properties. Intriguingly, the alkaline conditions not only contribute to the solubility of lignin but also impart superior ionic conductivity of lignin-based hydrogel that is applicable to flexible TENG in self-powered energy-saving stair light strips, which holds great promise for industrial applications of soft electronics.

Deformation-Resistant Underwater Adhesion in a Wide Salinity Range.

Conventional adhesives experience reduced adhesion when exposed to aqueous environments. The development of underwater adhesives capable of forming strong and durable bonds across various wet substrates is crucial in biomedical and engineering domains. Nonetheless, limited emphasis placed on retaining high adhesion strengths in different saline environments, addressing challenges such as elevated osmotic pressure and spontaneous dimensional alterations. Herein, a series of ionogel-based underwater adhesives are developed using a copolymerization approach that incorporates "dynamic complementary cross-linking" networks. Synergistic engineering of building blocks, cross-linking networks, pendant groups and counterions within ionogels ensures their adhesion and cohesion in brine spanning a wide salinity range. A high adhesion strength of ≈3.6 MPa is attained in freshwater. Gratifyingly, steady adhesion strengths exceeding 3.3 MPa are retained in hypersaline solutions with salinity ranging from 50 to 200 g kg-1, delivering one of the best-performing underwater adhesives suitable for diverse saline solutions. A combination of outstanding durability, reliability, deformation resistance, salt tolerance, and self-healing properties showcases the "self-contained" underwater adhesion. This study shines light on the facile fabrication of catechol-free ionogel-based adhesives, not merely boosting adhesion strengths in freshwater, but also broadening their applicability across various saline environments.

Supramolecular/Dynamic Covalent Design of High-Performance Pressure-Sensitive Adhesive from Natural Low-Molecular-Weight Compounds.

Adhesive materials have played an essential role in the history of humanity. Natural adhesives composed of low-molecular-weight monomers have been overshadowed by modern petroleum-based glues. With the development of green economy, the demand for eco-friendly materials has increased. Herein, two natural biocompatible compounds, namely thioctic acid (TA) and malic acid (MA), are selected to prepare a high-performance pressure-sensitive adhesive poly[TA-MA]. This adhesive can be quantitatively obtained via a simple mixing and heating process. Poly[TA-MA] shows interesting and useful properties, including reversible flexibility, high elongation, and good self-healing, owing to its dynamic polymerization pattern and reversible cross-linking behavior. Poly[TA-MA] exhibits excellent adhesion performance under various extreme conditions, such as at low temperatures and in hot water. High values of shear strength (3.86 MPa), peel strength (7.90 N cm-1), loop tack (10.60 N cm-1), tensile strength (1.02 MPa), and shear resistance (1628 h) demonstrate the strong adhesive effect of poly[TA-MA]. Additionally, TA can be regenerated in the monomer forms from poly[TA-MA] with high recovery rate (>90%). Meanwhile, strong anti-bacterial behavior of poly[TA-MA] is recorded. This study not only reported a new pressure-sensitive adhesive but also fully displayed the feasibility of using natural small molecules to achieve robust surface adhesion.

Underwater Adhesives from Redox-Responsive Polyplexes of Thiolated Polyamide Polyelectrolytes.

We report the fabrication of optically clear underwater adhesives using polyplexes of oppositely charged partially-thiolated polyamide polyelectrolytes (TPEs). The thiol content of the constituent PEs was varied to assess its influence on the adhesive properties of the resulting glues. These catechol-free, redox-responsive TPE-adhesives were formulated in aquo and exhibited high optical transparency and strong adhesion even on submerged or moist surfaces of diverse polar substrates such as glass, aluminium, wood, and bone pieces. The adhesives could be cured under water through oxidative disulphide crosslinking of the constituent TPEs. The polyamide backbone provided multi-site H-bonding interactions with the substrates while the disulphide crosslinking provided the cohesive strength to the glue. Strong adhesion of mammalian bones (load bearing capacity upto 7 kg/cm2 ) was achieved using the adhesive containing 30 mol % thiol residues. Higher pH and use of oxidants such as povidone-iodine solution enhanced the curing rate of the adhesives, and so did the use of Tris buffer instead of Phosphate buffer. The porous architecture of the adhesive and its progressive degradation in aqueous medium over the course of three weeks bode well for diverse biomedical applications where temporary adhesion of tissues is required.

Chemical Design of Supramolecular Reversible Adhesives for Promising Applications.

Supramolecular reversible adhesives have garnered significant attention due to their potential applications in various fields. These adhesives exhibit remarkable properties such as reversible adhesion, self-healing, and high flexibility. This concept aims to present a comprehensive overview of the current research progress in developing supramolecular reversible adhesives. Firstly, the fundamentals of supramolecular chemistry and the principles underlying the design and synthesis of reversible adhesive systems are discussed. Next, the concept focuses on characterizing the reversible adhesion strength of supramolecular adhesive systems that have been developed. The adhesion performance of supramolecular reversible adhesives is summarized, highlighting their unique characteristics and promising applications. Finally, the challenges and future perspectives in the field of supramolecular reversible adhesives are discussed. The comprehensive overview provided in this concept aims to inspire further research and innovation in this exciting field.

Oral Patch/Film for Drug Delivery-Current Status and Future Prospects.

In recent years, there has been extensive research into drug delivery systems aimed at enhancing drug utilization while minimizing drug toxicities. Among these systems, oral patches/films have garnered significant attention due to their convenience, noninvasive administration, ability to bypass hepatic first-pass metabolism, thereby enhancing drug bioavailability, and their potential to ensure good compliance, particularly among special patient populations. In this review, from the perspective of the anatomical characteristics of the oral cavity and the advantages and difficulties of oral drug delivery, we illustrate the design ideas, manufacturing techniques, research methodologies, and the essential attributes of an ideal oral patch/film. Furthermore, the applications of oral patches/films in both localized and systemic drug delivery were discussed. Finally, we offer insights into the future prospects of the oral patch/film, aiming to provide valuable reference for the advancement of oral localized drug delivery systems.

Aesthetic outcome of intermediate closure versus intermediate closure followed by 2-octyl cyanoacrylate: A randomized evaluator-blinded split-wound comparative effectiveness trial.

BACKGROUND: Dermatologic surgeons are increasingly using surgical adhesives in their practice. Studies comparing sutured wounds to those that utilize a combination of suturing and skin adhesive have not been previously conducted. OBJECTIVE: To compare the cosmetic outcome and patient wound care satisfaction of an intermediate suture closure with an intermediate suture closure followed by the application of 2-octyl cyanoacrylate (2-OCA). METHODS: Fifty patients were enrolled in a randomized, evaluator-blinded, split-scar study. Following intermediate sutured closure of a surgical defect, one side of the wound was randomized to receive an additional application of 2-OCA. After 3 months, the scar was assessed using the POSAS tool and patients reported wound care preferences. RESULTS: As the primary outcome measure, the mean sum of observer POSAS was 12.80 for sutured closure alone versus 12.40 for sutured closures followed by 2-OCA (P = .49). LIMITATIONS: Single-center study of a relatively homogenous population. CONCLUSION: Although there were no significant differences in scar cosmesis, both patients and observers tended to prefer the side with an additional application of 2-OCA in most POSAS components, in overall opinion, and in patient wound care satisfaction. Dermatologic surgeons may add this to their practice without sacrificing scar outcomes or patient satisfaction.

High-Performance Dopamine-Based Supramolecular Bio-Adhesives.

The need for wound closure or surgical procedures has been commonly met by the application of sutures. Unfortunately, these are often invasive or subject to contamination. Alternative solutions are offered by surgical adhesives that can be applied and set without major disruption; a new class of supramolecular-based adhesives provides potential solutions to some of these challenges. In this study, a series of polymers utilizing dopamine as a self-assembling unit are synthesized. It is found that these motifs act as extremely effective adhesives, with control over the mechanical strength of the adhesion and materials' tensile properties enabled by changing monomer feed ratios and levels of cross-linking. These materials significantly outperform commercially available bio-adhesives, showing yield strengths after adhesion at least two times higher than that of BioGlue and Tisseel, as well as the ability to re-adhere with significant recovery of adhesion strength. Promisingly, the materials are shown to be non-cytotoxic, with cell viability > 90%, and able to perform in aqueous environments without significant loss in strength. Finally, the removal of the materials, is possible using benign organic solvents such as ethanol. These properties all demonstrate the effectiveness of the materials as potential bio-adhesives, with potential advantages for use in surgery.

A Mesostructure Multivariant-Assembly Reinforced Ultratough Biomimicking Superglue.

The imitation of mussels and oysters to create high-performance adhesives is a cutting-edge field. The introduction of inorganic fillers is shown to significantly alter the adhesive's properties, yet the potential of mesoporous materials as fillers in adhesives is overlooked. In this study, the first report on the utilization of mesoporous materials in a biomimetic adhesive system is presented. Incorporating mesoporous silica nanoparticles (MSN) profoundly enhances the adhesion of pyrogallol (PG)-polyethylene imine (PEI) adhesive. As the MSN concentration increases, the adhesion strength to glass substrates undergoes an impressive fivefold improvement, reaching an outstanding 2.5 mPa. The adhesive forms an exceptionally strong bond, to the extent that the glass substrate fractures before joint failure. The comprehensive tests involving various polyphenols, polymers, and fillers reveal an intriguing phenomenon-the molecular structure of polyphenols significantly influences adhesive strength. Steric hindrance emerges as a crucial factor, regulating the balance between π-cation and charge interactions, which significantly impacts the multicomponent assembly of polyphenol-PEI-MSN and, consequently, adhesive strength. This groundbreaking research opens new avenues for the development of novel biomimetic materials.

Effect of Lignin Structure Characteristics on the Performance of Lignin Based Phenol Formaldehyde Adhesives.

As the second most abundant biopolymer, lignin remains underutilized in various industrial applications. Various forms of lignin generated from different methods affect its physical and chemical properties to a certain extent. To promote the broader commercial utilization of currently available industrial lignins, lignin sulfonate (SL), kraft lignin (KL), and organosolv lignin (OL) are utilized to partially replace phenol in the synthesis of phenol formaldehyde (PF) adhesives. The impact of lignin production process on the effectiveness of lignin-based phenolic (LPF) adhesives is examined based on the structural analysis of the selected industrial lignin. The results show that OL has more phenolic hydroxyl groups, lower molecular weight, and greater number of reactive sites than the other two types of lignins. The maximum replacement rate of phenol by OL reaches 70% w/w, resulting in organosolv lignin phenolic (OLPF) adhesives with a viscosity of 960 mPa·s, a minimal free formaldehyde content of 0.157%, and a shear strength of 1.84 MPa. It exhibits better performance compared with the other two types of lignin-based adhesives and meets the requirements of national standards.

Efficacy of Endoscopic Tissue Adhesive in Patients with Gastrointestinal Tumor Bleeding.

BACKGROUND: Gastrointestinal tumors bleeding remains a significantly clinical challenge due to its resistance to conventional endoscopic hemostasis methods. While the efficacy of endoscopic tissue adhesives (ETA) in variceal bleeding has been established, its role in gastrointestinal tumor bleeding (GITB) remains ambiguous. AIMS: This study aims to assess the feasibility and effectiveness of ETA in the treatment of GITB. METHODS: The study enrolled 30 patients with GITB who underwent hemostasis through Histoacryl® tissue glue injection. Hemostasis success rates, ETA-related adverse events, and re-bleeding rates were evaluated. RESULTS: ETA application achieved successful hemostasis at all tumor bleeding sites, with immediate hemostasis observed in all 30 (100.0%) patients. Among the initially hemostasis cases, 5 patients (17.0%) experienced re-bleeding within 30 days, and the 60 day re-bleeding rate was 20.0% (6/30). Expect for one case of vascular embolism, no adverse events related with ETA application were reported. The 6 month survival was 93%. CONCLUSION: ETA demonstrated excellent immediate hemostasis success rate in GITB cases and showed promising outcomes in prevention re-bleeding.

Optical effects of graphene addition on adhesives for orthodontic lingual retainers.

The objective of this study was to determine the effects on the colour of adding increasing concentrations of graphene to orthodontic fixed retainer adhesives and to evaluate changes in optical transmission during light curing and the resultant degree of conversion. Two different types of adhesives commonly used for fixed retainers were investigated: A packable composite (Transbond) and a flowable composite (Transbond Supreme). Graphene was added to the adhesives in three different concentrations (0.01, 0.05, and 0.1 wt%). Adhesives without graphene addition were set as control groups. A Minolta colourimeter was used to measure the colour and translucency parameters. Irradiance transmitted during curing was quantified using MARC Light Collector. Fourier-transform infrared spectroscopy was used to record degree of conversion. Data were statistically analysed with the Student's t-test and one-way ANOVA with Tukey's tests (α = 0.05). The findings showed that incorporating graphene darkened the adhesive colour significantly and reduced translucency. As the graphene concentration reached 0.1 wt%, samples became opaque; yet, no adverse effect on degree of conversion was observed. The addition of graphene reduces optical transmission of lingual retainer adhesives; the effect increases with graphene concentration.

Influence of different immediate dentin sealing strategies on bond strength of indirect resin nanoceramic restorations.

In this study, we evaluated the effect of four different strategies for bonding a CAD/CAM resin nanoceramic restoration (Lava Ultimate, 3M) to the dentin surface using a universal adhesive (Scotch Bond Universal, 3M) and adhesive resin cement (RelyX Ultimate, 3M) on the shear bond strength (SBS) and failure mode. The strategies comprised: (i) immediate sealing, immediate bonding; (ii) immediate sealing, bonding after 2 weeks with provisional restoration; (iii) immediate sealing with flowable resin composite reinforcement and bonding after 2 weeks with provisional restoration; and (iv) no immediate sealing, and bonding after 2 weeks with provisional restoration. After bonding, all the specimens were thermocycled, shear tests were performed using a universal testing machine, and failure modes were determined using stereomicroscope and scanning electron microscopy. The highest mean SBS was recorded with immediate sealing, immediate bonding strategy. Most adhesive failures with exposed dentinal tubules were noted in specimens exposed to bonding after 2 weeks with no immediate sealing, which was associated with the lowest SBS. Mixed failures predominated in all immediate dentin sealing groups. Immediate sealing with universal adhesives improves SBS, particularly in the single-visit approach, which has shown significantly better performance, whereas the provisional phase has a negative effect.