Water-assisted strong underwater adhesion via interfacial water removal and self-adaptive gelation.

In nearly all cases of underwater adhesion, water molecules typically act as a destroyer. Thus, removing interfacial water from the substrate surfaces is essential for forming super-strong underwater adhesion. However, current methods mainly rely on physical means to dislodge interfacial water, such as absorption, hydrophobic repulsion, or extrusion, which are inefficient in removing obstinate hydrated water at contact interface, resulting in poor adhesion. Herein, we present a unique means of reversing the role of water to assist in realizing a self-strengthening liquid underwater adhesive (SLU-adhesive) that can effectively remove water at contact interface. This is achieved through multiscale physical-chemical coupling methods across millimeter to molecular levels and self-adaptive strengthening of the cohesion during underwater operations. As a result, strong adhesion over 1,600 kPa (compared to ~100 to 1,000 kPa in current state of the art) can be achieved on various materials, including inorganic metal and organic plastic materials, without preloading in different environments such as pure water, a wide range of pH solutions (pH = 3 to 11), and seawater. Intriguingly, SLU-adhesive/photothermal nanoparticles (carbon nanotubes) hybrid materials can significantly reduce the time required for complete curing from 24 h to 40 min using near-infrared laser radiation due to unique thermal-response of the chemical reaction rate. The excellent adhesion property and self-adaptive adhesion procedure allow SLU-adhesive materials to demonstrate great potential for broad applications in underwater sand stabilization, underwater repair, and even adhesion failure detection as a self-reporting adhesive. This concept of "water helper" has potential to advance underwater adhesion and manufacturing strategies.

Robust and Lubricating Interface Semi-Interpenetrating Network on Inert Polymer Substrates Enabled by Subsurface-Initiated Polymerization.

Lubricating hydrogel coatings on inert rubber and plastic surfaces significantly reduce friction and wear, thus enhancing material durability and lifespan. However, achieving optimal hydration lubrication typically requires a porous polymer network, which unfortunately reduces their mechanical strength and limits their applicability where robust durability and wear-resistance are essential. In the research, a hydrogel coating with remarkable wear resistance and surface stability is developed by forming a semi-interpenetrating polymer network with polymer substrate at the interface. By employing a good solvent swelling method, monomers, and photoinitiators are embedded within the substrates' subsurface, followed by in situ polymerization under ultraviolet light, creating a robust semi-interpenetrating and entangled network structure. This approach, offering a thicker energy-dissipating layer, outperforms traditional surface modifications in wear resistance while preserving anti-fatigue, hydrophilicity, oleophobicity, and other properties. Adaptable to various rubber and plastic substrates by using suitable solvents, this method provides an efficient solution for creating durable, lubricating surfaces, broadening the potential applications in multiple industries.

Design of Stretchable and Conductive Self-Adhesive Hydrogels as Flexible Sensors by Guar-Gum-Enabled Dynamic Interactions.

The limited elasticity and inadequate bonding of hydrogels made from guar gum (GG) significantly hinder their widespread implementation in personalized wearable flexible electronics. In this study, we devise GG-based self-adhesive hydrogels by creating an interpenetrating network of GG cross-linked with acrylic, 4-vinylphenylboronic acid, and Ca2+. With the leverage of the dynamic interactions (hydrogen bonds, borate ester bonds, and coordination bonds) between -OH in GG and monomers, the hydrogel exhibits a high stretchability of 700%, superior mechanical stress of 110 kPa, and robust adherence to several substrates. The adhesion strength of 54 kPa on porcine skin is obtained. Furthermore, the self-adhesive hydrogel possesses stable conductivity, an elevated gauge factor (GF), and commendable durability. It can be affixed to the human body as a strain sensor to obtain precise monitoring of human movement behavior. Our research offers possibilities for the development of GG-based hydrogels and applications in wearable electronics and medical monitoring.

Functional Zwitterionic Polyurethanes: State-of-the-Art Review.

Recent advancements in bioengineering and medical devices have been greatly influenced and dominated by synthetic polymers, particularly polyurethanes (PUs). PUs offer customizable mechanical properties and long-term stability, but their inherent hydrophobic nature poses challenges in practically biological application processes, such as interface high friction, strong protein adsorption, and thrombosis. To address these issues, surface modifications of PUs for generating functionally hydrophilic layers have received widespread attention, but the durability of generated surface functionality is poor due to irreversible mechanical wear or biodegradation. As a result, numerous researchers have investigated bulk modification techniques to incorporate zwitterionic polymers or groups onto the main or side chains of PUs, thereby improving their hydrophilicity and biocompatibility. This comprehensive review presents an extensive overview of notable zwitterionic PUs (ZPUs), including those based on phosphorylcholine, sulfobetaine, and carboxybetaine. The review explores their wide range of biomedical applications, from blood-contacting devices to antibacterial coatings, fouling-resistant marine coatings, separation membranes, lubricated surfaces, and shape memory and self-healing materials. Lastly, the review summarizes the challenges and future prospects of ZPUs in biological applications.

A Fluorescent Hydrogel with AIE Emission for Dehydration-Visualizable Wearable Sensors.

Hydrogel-based wearable sensors eventually experience dehydration, which negatively impacts their function, leading to decreased sensitivity. Monitoring the real-time water retention rate and sensing performance of wearable flexible sensors without dismantling them remains a significant difficulty. In this study, a molecule having aggregation-induced emission (AIE) properties in an aqueous environment has been developed and produced, which can combine with anionic guar gum and acrylic acid to create an AIE hydrogel. Wearable sensing electronic devices have the capability to track motion signals at various joints of the human body. Additionally, they can effectively and visually monitor dehydration status during extended periods of operation. The fluorescence intensity of the hydrogel is primarily influenced by the level of aggregation of luminous monomers inside the network. This level of aggregation is predominantly governed by the hydrogel's water retention rate. Hence, the extended duration of hydrogel dehydration can be manifested through alterations in their fluorescence characteristics, which are employed for strain sensing. This approach enables users to assess the water retention of hydrogels with greater efficiency, eliminating the requirement for disassembling them from the completed electrical gadget. In summary, the use of AIE-based fluorescent hydrogels will advance the progress of intelligent wearable electronics.

Bioinspired simultaneous regulation in fluorescence of AIEgen-embedded hydrogels.

The development of stimuli-responsive functional fluorescent hydrogels is of great significance for the realization of artificial intelligence. In the present work, we design and synthesize a stimulus-responsive hydrogel embedded with an aggregation-induced emission (AIE) monomer, in which the fluorescence brightness and intensity can be tuned. The hydrogel embedded with tetraphenylethene-grafted-poly[3-sulfopropyl methacrylate potassium salt] (TPE-PSPMA) as the functional element is prepared by the radical polymerization method. Among them, the TPE core exhibits adaptive fluorescence ability through the AIE effect, while the PSPMA chain provides tunable hydrophilic properties under an external stimulus. The effect of different cationic surfactants with different lengths of hydrophobic tails on the fluorescence properties of TPE-PSPMA in solution is systematically investigated. With cationic surfactants, such as cetyltrimethylammonium bromide (CTAB), the fluorescence intensity is gradually tuned from 1059 to 4623. And the fluorescence intensities increase with the growth of hydrophobic tails of surfactants, which results from hydrophobicity-induced electrostatic interactions among surfactants and polymer chains. Furthermore, an obvious tunable fluorescence feature of hydrogel copolymerized TPE-PSPMA is realized, resulting from the change of brightness and the dynamic increase of fluorescence intensity (from 1031 to 3138) for the hydrogel immersed in CTAB solution with different soaking times. Such a typical fluorescence-regulated behavior can be attributed to the AIE of the TPE-PSPMA chain and the electrostatic interaction between the surfactant and the anionic polymer chain. The designed TPE-PSPMA-based hydrogel is responsive to stimuli, inspiring the development of intelligent systems such as soft robots and smart wearables.

A Strong and Double-sided Self-Adhesive Hydrogel Sensor.

Flexible self-adhesive hydrogel sensors are attracting considerable concerns in recent years. However, creating a self-adhesive hydrogel sensor with excellent mechanical properties remains to be challenging. Herein, a double-sided self-adhesive hydrogel capable of strain sensor with high strength is demonstrated by penetration strategy. The middle poly(acrylic acid)-polyacrylamide/Fe3+ (PAA-PAM/Fe3+ ) tough layer endows the double-sided self-adhesive hydrogel with high mechanical properties, while the bilateral poly[2-(methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide-polyacrylamide (PSBMA-PAM) adhesive layers are used to ensure excellent adhesiveness on diverse substrates. The tough layer of the double-sided self-adhesive hydrogel sensor shows a strong interface bonding force against the adhesive layer. The double-sided self-adhesive hydrogel sensor enables excellent adhesiveness on diverse substrates. More importantly, it can accurately detect different strains and human motions as a self-adhesive hydrogel strain sensor. This work manifests a new route of structural design to develop a self-adhesive hydrogel sensor with excellent mechanical properties that is suitable for a wide range of applications.

Bioinspired Polysaccharide Derivative with Efficient and Stable Lubrication for Silicon-Based Devices.

It is becoming increasingly important to synthesize efficient biomacromolecule lubricants suitable for medical devices. Even though the development of biomimetic lubricants has made great progress, the current system suitable for hydrophobic silicone-based medical devices is highly limited. In this work, we synthesize one kind of novel polysaccharide-derived macromolecule lubricant of chitosan (CS) grafted polyethylene glycol (PEG) chains and catechol groups (CT) (CS-g-PEG-g-CT). CS-g-PEG-g-CT shows good adsorption ability by applying quantitative analysis of quartz crystal microbalance (QCM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and confocal fluorescence imaging technique, as well as the typical shear-thinning feature. CS-g-PEG-g-CT exhibits low and stable coefficients of friction (COFs) (0.01-0.02) on polydimethylsiloxane (PDMS) surfaces at a wide range of mass concentrations in diverse media including pure water, physiological saline, and PBS buffer solution and is even tolerant to various normal loads and sliding frequencies for complex pressurizing or shearing environments. Subsequently, systematic surface characterizations are used to verify the dynamic attachment ability of the CS-g-PEG-g-CT lubricant on the loading/shearing process. The lubrication mechanism of CS-g-PEG-g-CT can be attributed to the synergy of strong adsorption from catechol groups to form a uniform assembly layer, excellent hydration effect from PEG chains, and typical shear-thinning feature to dissipate viscous resistance. Surprisingly, CS-g-PEG-g-CT exhibits efficient lubricity on silicone-based commercial contact lenses and catheters. The current macromolecule lubricant demonstrates great real application potential in the fields of medical devices and disease treatments.

Successive Redox-Reaction-Triggered Interface Radical Polymerization for Growing Hydrogel Coatings on Diverse Substrates.

Growing lubricating hydrogel coatings in controllable manners on diverse material surfaces demonstrates promising applications. Here, a surface modification method is reported for in situ growing hydrogel coatings onto surfaces of diverse substrates in the absence of UV assistance. It is performed by decorating substrates with a universal mussel-inspired synthetic adhesive with catechol groups. Upon being immersed in reaction solution, these groups can assist substrate bonding and in situ capture and reduce Fe3+ into Fe2+ for decomposing S2 O8 2- into SO4 - ⋅ catalytically at the interface to initiate interface polymerization of monomers. As a result, hydrogel coatings with controllable thickness could be grown on surfaces of arbitrary substrates to change their surface characteristics regardless of materials size, category, geometry and transparency, implying considerable potential in surface engineering.

Repeatedly Regenerating Mechanically Robust Polymer Brushes from Persistent Initiator Coating (PIC).

In this study, a novel surface initiated polymerization (SIP) method was developed from organic-inorganic hybrid persistent initiator coating (PIC) that embeds initiator molecules into inorganic silica sol-gel layer. Comparing with traditional silane initiator surface that prepared by chemical vapor deposition (CVD) method, the PIC can effectively improve the mechanical stability of initiator that was able to endure ten-thousand times of friction cycles. Besides, it allows polymer grafting from sub-surface and so the grafted brushes, poly 3-sulfopropyl methacrylate potassium salt (pSPMA) on the PIC were also much more wear-resisting than those prepared by the traditional ways. More importantly, the PIC could still trigger new polymerization reaction when the grafted brushes were worn off. In addition, the PIC is universal and can be covered on different substrates including glass, metals and plastics, etc. to realize functionalization of these materials. The approach may pave technological way for the application of surface grafted polymer brushes.

Bioinspired 3D Printed Locomotion Devices Based on Anisotropic Friction.

Anisotropic friction plays a key role in natural systems, particularly for realizing the purpose of locomotion and strong attachment for the survival of organisms. Of particular interest, here, is the observation that friction anisotropy is promoted numerous times by nature, for example, by wild wheat awn for its targeted and successful seed anchorage and dispersal. Such feature is, however, not fully exploited in man-made systems, such as microbots, due to technical limitations and lack of full understanding of the mechanisms. To unravel the complex dynamics occurring in the sliding interaction between anisotropic microstructured surfaces, the friction induced by asymmetric plant microstructures is first systematically investigated. Inspired by this, anisotropic polymer microactuators with three-dimensional (3D) printed microrelieves are then prepared. By varying geometric parameters, the capability of microactuators to generate strong friction anisotropy and controllable motion in remotely stretched cylindrical tubes is investigated. Advanced theoretical models are proposed to understand and predict the dynamic behavior of these synthetic systems and to shed light on the parameters and mechanisms governing their behavior. Finally, a microbot prototype is developed and cargo transportation functions are successfully realized. This research provides both in-depth understanding of anisotropic friction in nature and new avenues for developing intelligent actuators and microbots.

Mussel-Inspired One-Step Fabrication of Ultralow-Friction Coatings on Diverse Biomaterial Surfaces.

Low-friction and hydrophilic surfaces have critical applications in biomedical devices and implants. Existing methods to achieve such surfaces, for example, grafting polymer brushes, usually suffer from tedious steps and harsh reaction conditions, which limit practical applications. In this work, we propose a set of versatile ultralow-friction coatings applicable for diverse biomaterial surfaces via a one-step simple codeposition strategy with dopamine and hydrophilic monomers. The polymer coatings show ultralow-friction performance together with hydrophilic feature and antifouling property. The coefficient of friction of the as-prepared coating can be as low as 0.003 in pure water. The coating also provides superior and stable lubrication in biological fluids due to antifouling capability. Furthermore, the versatility of this strategy allows fabrication of multiple lubricious polymer coatings with different hydrophilic monomers and on diverse material surfaces. The typical application of this low-friction coating on a medical catheter was further demonstrated, which dramatically improved surface wettability and reduced friction of the outer surface of the catheter. In view of the versatility and remarkable lubrication ability, the multifunctional coatings may find important applications in biomedical devices and implants.

Promoting Lubricity and Antifouling Properties by Supramolecular-Recognition-Based Surface Grafting.

In the supramolecular host-guest system, the host molecule selectively identifies the guest and forms the inclusion complex with the guest molecule. In this study, the physicochemical properties of solid surfaces were regulated by the interfacial supramolecular recognition. The host-guest interaction between ß-cyclodextrin and guest molecules, including adamantaneacetic acid, sodium dodecyl sulfonate, and a copolymer of 2-methacryloyloxy-2-methyladamantane and 3-sulfopropyl methacrylate potassium salt, was introduced onto the silicon substrate to construct supramolecular composite surfaces. After the assembly of hydrophilic guest molecules on the host surface, the wettability, aqueous lubrication, and anti-algae cell adhesion properties of the supramolecular composite surfaces were improved. This strategy of host-guest interfacial supramolecular recognition provides a new route to prepare aqueous lubrication and antifouling materials.

Bio-Inspired Design and Fabrication of Micro/Nano-Brush Dual Structural Surfaces for Switchable Oil Adhesion and Antifouling.

The underwater superoleophobic surfaces play a significant role in anti-oil contamination, marine antifouling, etc. Inspired by the Gecko's feet and its self-cleaning property, a hierarchical structure composed of poly (acrylic acid) gel micro-brushes is designed by the liquid-infused method. This surface exhibits underwater superoleophobicity with very low oil adhesion. It is then modified with stimuli-responsive polymer nano-brushes via surface-initiated atom transfer radical polymerization from the embedded initiator. The micro/nano-brush dual structural surfaces can switch the underwater oil adhesion between low and high while keeping the superoleophobicity. The antifouling properties against algae attachment under different mediums are also investigated to show a strong link between oleophobicity and antibiofouling property. The model surface will be very useful in directing the design of marine self-cleaning coatings to both living and non-living species.

Tuning the Hydration and Lubrication of the Embedded Load-Bearing Hydrogel Fibers.

One of the most prominent properties of hydrogels is their excellent hydrolubrication that derives from the strong hydration of the gel network. However, excessive hydration makes hydrogels exhibit a very poor mechanical property, which limits their practical applications. Here, we prepared a novel composite surface of hydrogel nanofibers embedded in an anodic aluminum oxide substrate which exhibited both excellent lubrication and a high load-bearing capacity. Through the copolymerization of acrylic acid and 3-sulfopropyl methacrylate potassium salt, the gel network swelled sufficiently in aqueous solution and caused high osmotic pressure repulsion to bear heavy loads and hence exhibited excellent aqueous lubrication (µ ≈ 0.01). Notably, the friction coefficient of gels showed no dependence on the load in the experiment, whereas it was strongly influenced by the sliding velocity. Additionally, both electrolyte solution and ionic surfactants affect the conformation of the polymer chains, which results in a significant impact on the friction properties of hydrogel fibers.

UV-Triggered Surface-Initiated Polymerization from Colorless Green Tea Polyphenol-Coated Surfaces.

A facile and versatile approach to constructing colorless surface coatings based on green tea polyphenols is reported, which can further act as a photoinitiating layer to initiate radical polymerization. These colorless green tea polyphenol coatings are capable of successfully photografting polymer brushes, and the resulting polymer brush patterns show spatial shape adjustability by masked UV irradiation. Both surface modifications and photografted polymer brushes do not alter the original color of the substrates. This method could be promising for the development of surface modifications.

Astringent Mouthfeel as a Consequence of Lubrication Failure.

Herein, we systematically investigate the origin of astringent mouthfeel when we eat unripe fruits, drink coffee or tea, from the perspective of lubrication by simulating the dynamic weak interaction on the tongue with model protein (mucoprotein, MP) and polyphenolic compounds (tannic acid, TA). Astringency was due to the protein-mediated lubrication failure when encountering polyphenolic molecules that normally exist, for example in unripe fruits, coffee, tea. The underlying molecular mechanism of oral tribology is widely present in nature and enables us to engineer a tongue-like polyacrylamide composite hydrogel that exhibits high TA sensitivity and to develop a scientific strategy for catching slippery fish using TA-containing gloves. These results provide novel and useful insights into the failure of biological boundary lubrication on soft tissue surface with the adsorbed proteins.

Gecko-inspired but chemically switched friction and adhesion on nanofibrillar surfaces.

Chemically switched friction nano-fibrillar surfaces (SiNWAs-PSPMA & SiNWAs-PMAA arrays) can be constructed by finely decorating ordered Si nanowire arrays with responsive polymer brushes. As expected, these surfaces sense humidity or pH smartly and show reversible friction switching, based on swelling and shrinking of the polymer brushes, which is successfully monitored by AFM in liquid media.

Bioinspired Interfacial Friction Control: From Chemistry to Structures to Mechanics.

Organisms in nature have evolved a variety of surfaces with different tribological properties to adapt to the environment. By studying, understanding, and summarizing the friction and lubrication regulation phenomena of typical surfaces in nature, researchers have proposed various biomimetic friction regulation theories and methods to guide the development of new lubrication materials and lubrication systems. The design strategies for biomimetic friction/lubrication materials and systems mainly include the chemistry, surface structure, and mechanics. With the deepening understanding of the mechanism of biomimetic lubrication and the increasing application requirements, the design strategy of multi-strategy coupling has gradually become the center of attention for researchers. This paper focuses on the interfacial chemistry, surface structure, and surface mechanics of a single regulatory strategy and multi-strategy coupling approach. Based on the common biological friction regulation mechanism in nature, this paper reviews the research progress on biomimetic friction/lubrication materials in recent years, discusses and analyzes the single and coupled design strategies as well as their advantages and disadvantages, and describes the design concepts, working mechanisms, application prospects, and current problems of such materials. Finally, the development direction of biomimetic friction lubrication materials is prospected.

Novel biomimetic macromolecules system for highly efficient lubrication, ROS scavenging and osteoarthritis treatment.

The early stages of osteoarthritis (OA) in the joints are typically characterized by two key factors: the dysfunction of articular cartilage lubrication and inflammation resulting from the excessive production of reactive oxygen species (ROS). Synthetic injectable macromolecular materials present great potential for preventing the progression of early OA. In this study, to mimic the excellent lubricity of brush-like aggregates found in natural synovial fluid, we develop a novel macromolecular biolubricant (CS-PS-DA) by integrating adhesion and hydration groups onto backbone of natural biomacromolecules. CS-PS-DA exhibits a strong affinity for cartilage surfaces, enabling the formation of a stable lubrication layer at the sliding interface of degraded cartilages to restore joint lubrication performance. In vitro results from ROS scavenging and anti-inflammatory experiments indicate the great advantage of CS-PS-DA to decrease the levels of proinflammatory cytokines by inhibiting ROS overproduction. Finally, in vivo rats OA model demonstrates that intra-cavitary injection of CS-PS-DA could effectively resist cartilage wear and mitigated inflammation in the joints. This novel biolubricant provides a new and timely strategy for the treatment of OA.