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The structure–property paradox of biological tissues, in which water-rich porous structures efficiently transfer mass while remaining highly mechanically stiff, remains unsolved. Although hydrogel/sponge hybridization is the key to understanding this phenomenon, material incompatibility makes this a challenging task. Here we describe hydrogel/sponge hybrids (hydrospongels) that behave as both ultrastiff water-rich gels and reversibly squeezable sponges. The self-organizing network of cyano-p-aramid nanofibres holds approximately 5,000 times more water than its solid content. Hydrospongels, even at a water concentration exceeding 90 wt%, are hard as cartilage with an elastic modulus of 50−80 MPa, and are 10–1,000 times stiffer than typical hydrogels. They endure a compressive strain above 85% through poroelastic relaxation and hydrothermal pressure at 120 °C. This performance is produced by amphiphilic surfaces, high rigidity and an interfibrillar, interaction-driven percolating network of nanofibres. These features can inspire the development of future biofunctional materials.

Mussel periostracum, a nonliving multifunctional gel that covers the rigid inorganic shells of mussels, provides protection against mechanical impacts, biofouling, and corrosion in harsh ocean environments. The inner part of the periostracum, which emerges from biological tissues, functions as a natural interface between tissue and inorganic materials. The periostracum shows significant potential for application in implantable devices that provide interfaces; however, this system remains unexplored. In this study, we revealed that the inner periostracum performs graded mechanical functions and efficiently dissipates energy to accommodate differences in stiffness and stress types on both sides. On the tissue end, the lightly pigmented periostracum exhibits extensibility and energy dissipation under repetitive tension. This process was facilitated by the slipping and reassembly of β-strands in the discovered major proteins, which we named periostracin proteins. On the shell end, the highly pigmented, mineralized, and porous segment of the periostracum provided stiffness and cushioned against compressive stresses exerted by the shell valves during closure. These findings offer a novel possibilities for the design of interfaces that bridge human tissue and devices.

The load-bearing proteins in mussel holdfasts rely on condensed tris-catecholato-Fe3+coordination complexes for their toughness and shock-absorbing properties, and this feature has been successfully translated into synthetic materials with short-term high-performance properties. However, oxidation of catecholic DOPA (3,4-dihydroxyphenylalanine) remains a critical impediment to achieving materials with longer-lasting performance. Here, following the natural mussel pathway for protein processing, we explore how DOPA oxidation impacts coacervation of mussel foot protein-1 (mfp-1) and its capacity for phase-specific metal uptake in vitro. Without metal, DOPA oxidation changed the rheological properties (i.e., viscosity, loss, and storage moduli) of mfp-1 coacervate droplets. However, oxidation-dependent changes were recovered with dithiothreitol (DTT), completely restoring the behavior of mfp-1 coacervates prior to oxidation. With metal, mfp-1 coacervates exhibited gel-like behavior with high viscosity and cohesive forces by forming recognizable bis- and tris-catecholato-Fe complexes, linked to increased energy dissipation and toughness of byssus. These results indicate that Fe3+-mediated conversion of liquid–liquid phase-separated polymers into metal-coordinated networks is thorough and rapid, and DTT effectively maintains redox integrity. Our study provides much-needed improvements for processing catechol-functionalized polymers into high-performance materials.

Gluing dynamic, wet biological tissue is important in injury treatment yet difficult to achieve. Polymeric adhesives are inconvenient to handle due to rapid cross-linking and can raise biocompatibility concerns. Inorganic nanoparticles adhere weakly to wet surfaces. Herein, an aqueous suspension of guanidinium-functionalized chitin nanoparticles as a biomedical adhesive with biocompatible, hemostatic, and antibacterial properties is developed. It glues porcine skin up to 3000-fold more strongly (30 kPa) than inorganic nanoparticles at the same concentration and adheres at neutral pH, which is unachievable with mussel-inspired adhesives alone. The glue exhibits an instant adhesion (2 min) to fully wet surfaces, and the glued assembly endures one-week underwater immersion. The suspension is lowly viscous and stable, hence sprayable and convenient to store. A nanomechanic study reveals that guanidinium moieties are chaotropic, creating strong, multifaceted noncovalent bonds with proteins: salt bridges comprising ionic attraction and bidentate hydrogen bonding with acidic moieties, cation−π interactions with aromatic moieties, and hydrophobic interactions. The adhesion mechanism provides a blueprint for advanced tissue adhesives.

We investigated the photophysical interactions between CdSe/CdS quantum dots (QDs) and a conjugated polymer (CP, P3HT). The photoluminescence intensity of P3HT in the QDs/P3HT hybrid system is significantly enhanced compared to that of the neat P3HT system. We found via transient absorption spectroscopy that the energy level differences at the interfaces between P3HT and QDs resulted in delayed relaxation dynamics of the P3HT singlet (S1) excitons and suppressed polaron formation. Thus, the radiative recombination of the S1excitons occurs frequently in the hybrid system than in the neat P3HT system. Our findings on the CP-based hybrid system may provide important information to improve the efficiencies of optoelectronic devices, such as organic light-emitting diodes.

We investigated the photophysical interaction between a conjugated polymer (CP) and a plasmonic gold nanoparticle (Au NP) using transient absorption spectroscopy. We prepared a hybrid system containing CP-stabilized Au NPs by reducing a Au precursor directly with a thiol-terminated poly(3-hexylthiophene) surfactant (P3HT-SH), with the unreacted P3HT-SH chains used as an organic matrix. The P3HT attached to the Au NPs plays two critical roles in our hybrid system: it suppresses exciton quenching from the P3HT matrix to Au NPs (the spacer role) and relays hot electrons induced by surface plasmon resonance of Au NPs to P3HT (the bridge role). Thus, singlet excitons are more slowly relaxed in our hybrid system than those in a neat P3HT film. Our findings may provide important information for development of the high-efficiency hybrid optoelectronic devices.

Plastic packaging effectively protects foods from mechanical, microbial, and chemical damage, but oxygen can still permeate these plastics, degrading foods. Improving the gas barrier usually requires metallic or halogenated polymeric coatings; however, both cause environmental concerns and metallic coatings block visible light and electromagnetic signals. This paper reports a design of a highly flexible, visible light and radio frequency transparent coating on commercial poly(ethylene terephthalate) (PET) film. Nanoscale blending was achieved between negatively charged cellulose nanofibers and positively charged chitin nanowhiskers by employing spray-assisted layer-by-layer assembly. Synergetic interplay between these highly crystalline nanomaterials results in a flexible film with superior barrier characteristics. The oxygen transmission rate was below 0.5 mL m–2day–1. Moreover, this coating maintains its performance even when exposed to common hazards such as bending stress and hydration. The coating also notably reduces the haziness of PET with a negligible loss of transparency and provides effective inhibition of antibacterial growth. This “crab-on-a-tree” nanocoating holds high potential for biorenewable and optical and radio frequency transparent packaging applications.

Although biodegradable membranes are essential for effective bone repair, severe loss of mechanical stability because of rapid biodegradation, soft tissue invasion, and excessive immune response remain intrinsically problematic. Inspired by the exoskeleton-reinforcing strategy found in nature, we have produced a Ti-infiltrated chitin nanofibrous membrane. The membrane employs vapor-phase infiltration of metals, which often occurs during metal oxide atomic layer deposition (ALD) on organic substrates. This metal infiltration manifests anomalous mechanical improvement and stable integration with chitin without cytotoxicity and immunogenicity. The membrane exhibits both impressive toughness (∼13.3 MJ·m–3) and high tensile strength (∼55.6 MPa), properties that are often mutually exclusive. More importantly, the membrane demonstrates notably enhanced resistance to biodegradation, remaining intact over the course of 12 weeks. It exhibits excellent osteointegrative performance and suppresses the immune response to pathogen-associated molecular pattern molecules indicated by IL-1β, IL-6, and granulocyte-macrophage colony-stimulating factor expression. We believe the excellent chemico-biological properties achieved with ALD treatment can provide insight for synergistic utilization of the polymers and ALD in medical applications.

Aramid nanofibers (ANFs), typically produced by exfoliating aramid microfibers (Kevlar) in alkaline media, exhibit excellent mechanical properties and have therefore attracted increased attention as nanoscale building blocks. However, the preparation of aramid microfibers involves laborious and hazardous processes, which limits the industrial-scale use of ANFs. This work describes a facile and direct monomer-to-ANF synthesis via an as-synthesized intermediate low-molecular-weight poly(p-phenylene terephthalamide) (PPTA) without requiring the environmentally destructive acids and high-order shearing processes. Under the employed conditions, PPTA immediately dissociates and self-assembles into ANFs within a time period of 15 h, which is much shorter than the time of 180 h (not including the Kevlar preparation time) required for the Kevlar-to-ANF conversion. Interestingly, the fabricated ANFs exhibit nanoscale dimensions and thermoplastic polyurethane (TPU) reinforcing effects similar to those of Kevlar-derived ANFs; i.e., a 1.5-fold TPU toughness improvement and a maximum ultimate tensile strength of 84 MPa are achieved at an ANF content of only 0.04 wt %. Remarkable reinforcement ability investigated by comprehensive analytical data comes from ANFs, which disturb ordered hydrogen bonding in hard segments and induce strain hardening along the elongation pathway. Thus, the developed approach paves the way to industrial-scale production of ANFs and related nanocomposites.

We describe robustly anchored triblock copolymers that adopt loop conformations on surfaces and endow them with unprecedented lubricating and antifouling properties. The triblocks have two end blocks with catechol-anchoring groups and a looping poly(ethylene oxide) (PEO) midblock. The loops mediate strong steric repulsion between two mica surfaces. When sheared at constant speeds of ∼2.5 μm/s, the surfaces exhibit an extremely low friction coefficient of ∼0.002–0.004 without any signs of damage up to pressures of ∼2–3 MPa that are close to most biological bearing systems. Moreover, the polymer loops enhance inhibition of cell adhesion and proliferation compared to polymers in the random coil or brush conformations. These results demonstrate that strongly anchored polymer loops are effective for high lubrication and low cell adhesion and represent a promising candidate for the development of specialized high-performance biomedical coatings.

Mussels survive by strongly attaching to a variety of different surfaces, primarily subsurface rocks composed of metal oxides, through the formation of coordinative interactions driven by protein-based catechol repeating units contained within their adhesive secretions. From a chemistry perspective, catechols are known to form strong and reversible complexes with metal ions or metal oxides, with the binding affinity being dependent on the nature of the metal ion. As a result, catechol binding with metal oxides is reversible and can be broken in the presence of a free metal ion with a higher stability constant. It is proposed to exploit this competitive exchange in the design of a new strategy for the formation, removal, and reformation of surface coatings and self-assembled monolayers (SAM) based on catechols as the adhesive unit. In this study, catechol-functionalized tri(ethylene oxide) (TEO) was synthesized as a removable and recoverable self-assembled monolayer (SAM) for use on oxides surfaces. Attachment and detachment of these catechol derivatives on a variety of surfaces was shown to be reversible and controllable by exploiting the high stability constant of catechol to soluble metal ions, such as Fe(III). This tunable assembly based on catechol binding to metal oxides represents a new concept for reformable coatings with applications in fields ranging from friction/wettability control to biomolecular sensing and antifouling.

Although hydrogels are promising transdermal patches, they face spatiotemporal problems related to controlled drug release. From the “spatio” perspective, hydrogels are not malleable, therefore they do not fully contact curved skin, such as that found on the nose and fingers. From the “temporal” perspective, the internal network of a hydrogel retards cargo release. Herein, a malleable and rapid‐cargo‐releasing poly(vinyl alcohol)‐borax hydrogel that embeds freely mobile poly(hydroxyethyl methacrylate) (PHEMA) micelles is prepared. The in situ polymerization of PHEMA within the matrix produces large compound micelle particles that are not bound by the matrix. The micelles act as expellers by sweeping out cargo upon exposure to wet conditions through a concentration gradient. The hydrogel embedded with the micellar cargo‐expellers delivers a 25‐fold larger 3‐min release quantity of Nile Red (a model cargo) than the control hydrogel. The particles absorb mechanical shocks and the dynamic borate‐diol bonds engender the hydrogel with self‐healing properties, which results in a hydrogel that tightly contacts highly curved skin. Moreover, the hydrogel shows no toxicity in in vivo and skin irritation tests. This malleable hydrogel will inspire novel prompt skin‐patch systems for pharmaceutical and cosmetics purposes. An extremely malleable, stretchable, self‐healable, and biocompatible poly(vinyl alcohol)‐borax hydrogel embedded with free poly(hydroxyethyl methacrylate) micelles is designed for prompt therapeutic transdermal patches, in which the free micelles satisfy the conditions of perfect skin contact and rapid cargo release as a stress absorbent and an expelling “conveyor belt,” respectively.

In article number 2000876, Sung Yeon Hwang, Dongyeop X. Oh, Jeyoung Park, and co‐workers fabricate a malleable and rapid‐cargo‐releasing poly(vinyl alcohol)‐borax hydrogel that embeds freely mobile poly(hydroxyethyl methacrylate) micelles. Upon exposure to wet conditions, the micelle particles escaping from the hydrogel act as a “conveyor belt” to effectively expel the cargo into the external environment.