For the increasing demand of soft materials with wide ranges of applications, hydrogels have been developed exhibiting variety of functions (e.g., stretchable, self-healing, stimuli-responsive, and etc.). So far, add-in components such as inorganic nanoparticles, carbon materials, clays, and many others to main polymers have been used to achieve various unique functions of hydrogels. The multicomponent hydrogel systems often exhibit batch-dependent inconsistent results and problems in multicomponent mixings, require labors during preparations, and accompany unpredictable cross-talk between the added components. Here, we developed 'single polymeric component', alginate-boronic acid (alginate-BA) hydrogel to overcome the aforementioned problems. It exhibits unprecedented multifunctionalities simultaneously, such as high stretchability, self-healing, shear-thinning, pH- and glucose-sensitivities, adhesive properties, and reshaping properties. Multifunctionalities of alginate-BA hydrogel is resulted from the reversible inter- and intramolecular interactions by dynamic equilibrium of boronic acid-diol complexation and dissociation, which was proved by single molecule level Atomic Force Microscopy (AFM) pulling experiments. We also found that the alginate-BA gel showed enhanced in vivo retentions along gastrointestinal (GI) tract. Our findings suggest that rational polymer designs can result in minimizing the number of a participating component for multifunctional hydrogels, instead of increasing complexity by adding various additional components.

A new insect-cuticle- and fruit-browning-mimetic film exhibiting simultaneous self-healing and self-sealing properties only by ambient oxygen without external stimuli is developed. The film is formed at the liquid/air interface via crosslinking of phenolic compounds and poly(amine) chains. The film can be self-healed over a hundred times under ambient air at room temperature without exogenous materials and stimuli.

Since the first report of underwater adhesive proteins of marine mussels in 1981, numerous studies have reported mussel-inspired synthetic adhesive polymers. However, none of them have developed up to human-level translational studies. Here, we report a sticky polysaccharide that effectively promotes hemostasis from animal bleeding models to first-in-human hepatectomy. We found that the hemostatic material instantly generates a barrier layer that seals hemorrhaging sites. The barrier is created within a few seconds by in situ interactions with abundant plasma proteins. Therefore, as long as patient blood contains proper levels of plasma proteins, hemostasis should always occur even in coagulopathic conditions. To date, insufficient tools have been developed to arrest coagulopathic bleedings originated from genetic disorders, chronic diseases, or surgical settings such as organ transplantations. Mussel-inspired adhesion chemistry described here provides a useful alternative to the use of fibrin glues up to a human-level biomedical application.

In general, mechanical properties and gelation kinetics exhibit a positive correlation with the amount of gelation reagents used. Similarly, for catechol-containing hydrogels, which have attracted significant attention, because of their unique dual properties of cohesion and adhesion, increased amounts of cross-linking agents, such as organic oxidants and/or transition metals (Fe3+), result in enhanced mechanical strength and more rapid gelation kinetics. Here, we report a new metal–ligand cross-linking chemistry, inspired by mussels and ascidians, that defies the aforementioned conventional stoichiometric concept. When a small amount of vanadium is present in the catechol-functionalized polymer solution (i.e., [V] ≪ [catechol]), organic radicals are rapidly generated that trigger the gelation reaction. However, when a large amount of the ion is added to the same solution (i.e., [V] ≫ [catechol]), the catechol remains chemically intact by coordination that inhibits gelation. Thus, a large amount of cross-linking agent is not necessary to prepare mechanically strong, biocompatible hydrogels using this system. This new chemistry may provide insight into the biological roles of vanadium and its interaction with catechol-containing molecules (i.e., determination of the liquid state versus the solid state). Excess amounts of vanadium ([V] ≫ [catechol]) coordinate with catechol, which may result in a liquid state for ascidian blood, whereas excess amounts of catechol ([V] ≪ [catechol]) generate an organic radical-mediated chemical reaction, which may result in solid-state conversion of the mussel byssal threads.

Mussel-inspired adhesive coatings on biomedical devices have attracted significant interest due to their unique properties such as substrate independency and high efficiency. The key molecules for mussel-inspired adhesive coatings are catechol and amine groups. Along with the understanding of catechol chemistry, chitosan-catechol has also been developed as a representative mussel-inpired adhesive polymer that contains catechol and amine groups for adhesiveness. Herein, we demonstrated the direct writability of chitosan-catechol as a bioink for 3D printing, one of the additive techniques. The use of chitosan-catechol bioink results in the formation of 3D constructs in normal culture media via rapid complexation of this bioink with serum proteins; in addition, the metal/catechol combination containing tiny amounts of vanadyl ions, in which the ratio of metal to catechol is 0.0005, dramatically enhances the mechanical strength and printability of the cell-encapsulated inks, showing a cell viability of approximately 90%. These findings for mussel-inspired bioinks will be a promising way to design a biocompatible 3D bioink cross-linked without any external stimuli.

Vitamins are non‐toxic compounds that perform a variety of biological functions and also available in a large quantity. Other than the usage as food supplements, few attempts have been made to use them as functional materials. In this study, we report that vitamin B6, pyridoxal 5′‐phosphate (PLP), is a multi‐functional molecule for oxide surface chemistry. PLP‐immobilized surfaces exhibit superhydrophilicity and even hemophilicity, enhancing proliferation, migration, and differentiation of mammalian cells. Unlike existing molecules used so far in surface modification, PLP has an intrinsic chemical reactivity toward biomacromolecules due to the presence of the aldehyde group. In fact, RGD peptide is covalently tethered onto PLP surfaces directly in one step without any chemical activation. Furthermore, PLP‐functionalized implant device showed rapid bone healing. As vitamin B6 is a FDA approved molecule for human usage, the surface chemistry of vitamin B6 potentially allows a fast route for surface functionalized medical devices into clinic.

M13 bacteriophage (phage) was engineered for the use as a versatile template for preparing various nanostructured materials via genetic engineering coupled to enzymatic chemical conversions. First, we engineered the M13 phage to display TyrGluGluGlu (YEEE) on the pVIII coat protein and then enzymatically converted the Tyr residue to 3,4-dihydroxyl-l-phenylalanine (DOPA). The DOPA-displayed M13 phage could perform two functions: assembly and nucleation. The engineered phage assembles various noble metals, metal oxides, and semiconducting nanoparticles into one-dimensional arrays. Furthermore, the DOPA-displayed phage triggered the nucleation and growth of gold, silver, platinum, bimetallic cobalt-platinum, and bimetallic iron-platinum nanowires. This versatile phage template enables rapid preparation of phage-based prototype devices by eliminating the screening process, thus reducing effort and time.

This study reports polysaccharide-based fibers that can be utilized as biocompatible functional sutures. Fibers are spontaneously formed by spinning at the interface between two oppositely charged polysaccharide solutions. Unlike the common belief that polysaccharide fibers prepared by electrostatic interactions would exhibit weak mechanical strength, it is demonstrated that fibers spun at the interface between two droplets of positively charged chitosan and negatively charged heparin can exhibit high mechanical strength through spontaneous wet-state fusion of interfiber strands at a spinning wheel. Dry solidification results in multistranded fibers that were ≈100 µm in diameter with a tensile strength of ≈220 MPa. Post fibrous manipulation yields various morphology with straight or twisted fibers, fabrics, or springs. To demonstrate application of the fiber, it is applied as a medical suture. As heparin has a unique ability to bind adeno-associated virus (AAV), a therapeutic, biocompatible suture exhibiting localized AAV-mediated gene delivery function can be prepared. This study shows that multistrand fusion of fibers, formed by weak, electrostatic interactions and followed by drying solidification counterintuitively results in mechanically strong, functional fibers with various potential applications.