Diatom Silica/Polysaccharide Elastomeric Hydrogels: Adhesion and Interlocking Synergy.

The addition of particles during the sol-to-gel conversion process generally enhances the mechanical properties of the resulting hydrogels. However, the impact of the addition of porous particles during such a process remains an open question. Herein, we report hydrogel-to-elastomer conversions by natural porous particles called diatom frustule silica, namely, Melosira nummuloides. The surface pores provide mechanical interlocking points for polymers that are reinforced by gelation. The most critical aspect when choosing polymeric materials is the presence of water-resistant adhesion moieties, such as catechol, along a polymer chain, such as chitosan. Without catechol, no sol-to-gel conversion is observed; thus, no elastomeric hydrogel is produced. The resulting hybrid gel reveals reversible compressibility up to a 60% strain and high stretchability even up to ∼400% in area. Further, in vivo study demonstrates that the hybrid composite gel can be used as a therapeutic for pressure-induced ulcers. The synergy of chemical adhesion and physical chain entanglement via pores provides a way to fabricate a new class of 100% water-based elastomeric materials.

Mussel-inspired poly(γ-gl utamic acid)/nanosilicate composite hydrogels with enhanced mechanical properties, tissue adhesive properties, and skin tissue regeneration.

It was demonstrated herein that the adhesive property of catechol-functionalized nanocomposite hydrogel can be enhanced by tuning the cohesive strength due to the secondary crosslinking between catechol and synthetic bioactive nanosilicate, viz. Laponite (LP). The nanocomposite hydrogel consists of the natural anionic poly(γ-glutamic acid) (γ-PGA), which was functionalized with catechol moiety, and incorporated with disk-structured LP. The dual-crosslinked hydrogel was fabricated by enzymatic chemical crosslinking of catechol in the presence of horseradish peroxidase (HRP) and H2O2, and physical crosslinking between γ-PGA-catechol conjugate and LP. The PGADA/LP nanocomposite hydrogels with catechol moieties showed strong adhesiveness to various tissue layers and demonstrated an excellent hemostatic properties. These PGADA/LP nanocomposite hydrogels are potentially applied for injectable tissue engineering hydrogels, tissue adhesives, and hemostatic materials. STATEMENT OF SIGNIFICANCE: Recently, many attempts have been performed to manufacture high-performance tissue adhesives using synthetic and natural polymer-based materials. In order to apply in various biological substrates, commercially available tissue adhesives should have an improved adhesive property in wet conditions. Here, we designed a mussel-inspired dual crosslinked tissue adhesive that meets most of conditions as an ideal tissue adhesive. The designed tissue adhesive is composed of poly(γ-glutamic acid)-dopamine conjugate (PGADA)-gluing macromer, horseradish peroxidase (HRP)/hydrogen peroxide (H2O2)-enzymatic crosslinker, and Laponite (LP)-additional physical crosslinking nanomaterial. The PGADA hydrogel has tunable physicochemical properties by controlling the LP concentration. Furthermore, this dual crosslinked hydrogel shows strong tissue adhesive property, regardless of the tissue types. Specially the PGADA hydrogel has tissue adhesive strength four times higher than commercial bioadhesive. This dual crosslinked PGADA hydrogel with improved tissue adhesion property is a promising biological tissue adhesive for various tissue type in surgical operation.

Diatom Bio-Silica and Cellulose Nanofibril for Bio-Triboelectric Nanogenerators and Self-Powered Breath Monitoring Masks.

The application of biodegradable and biocompatible materials to triboelectric nanogenerators (TENGs) for harvesting energy from motions of the human body has been attracting significant research interest. Herein, we report diatom bio-silica as a biomaterial additive to enhance the output performance of cellulose nanofibril (CNF)-based TENGs. Diatom frustules (DFs), which are tribopositive bio-silica having hierarchically porous three-dimensional structures and high surface area, have hydrogen bonds with CNFs, resulting in enhanced electron-donating capability and a more roughened surface of the DF-CNF composite film. Hence, DFs were applied to form a tribopositive composite film with CNFs. The DF-CNF biocomposite film is mechanically strong, electron-rich, low-cost, and frictionally rough. The DF-CNF TENG showed an output voltage of 388 V and time-averaged power of 85.5 mW/m2 in the contact-separation mode with an efficient contact area of 4.9 cm2, and the generated power was sufficient for instantaneous illumination of 102 light-emitting diodes. In addition, a cytotoxicity study and biocompatibility tests on rabbit skin suggested that the DF-CNF composite was biologically safe. Moreover, a practical application of the DF-CNF TENG was examined with a self-powered smart mask for human breathing monitoring. This study not only suggests high output performance of biomaterial-based TENGs but also presents the diverse advantages of the DFs in human body-related applications such as self-powered health monitoring masks, skin-attachable power generators, and tactile feedback systems.

Enzymatically Cross-Linked Poly(γ-glutamic acid) Hydrogel with Enhanced Tissue Adhesive Property.

Enzymatic cross-linking of polymer-catechol conjugates in the presence of horseradish peroxidase (HRP) and H2O2 has emerged as an important method to fabricate in situ-forming, injectable hydrogels. Subsequently, tissue adhesion studies using catechol-containing polymers were extensively reported. However, because of the presence of numerous variables such as polymer concentration, oxidizing agent/enzyme, and stoichiometry, the design of the polymer with optimized tissue adhesive property is still challenging. In this study, a poly(γ-glutamic acid) (γ-PGA)-dopamine (PGADA) conjugate was synthesized, and in situ hydrogels were fabricated via enzymatic cross-linking of a catechol moiety. To optimize the tissue adhesive property of the PGADA hydrogel, the effect of various factors, such as polymer concentration, catechol substitution degree (DS), HRP concentration, and H2O2 content, on the gelation behavior and mechanical strength was investigated. The gelation behavior of PGADA hydrogels was characterized using a rheometer and rotational viscometer. Also, the possibility of its use as a tissue adhesive was examined by evaluating the tissue adhesion strength in vitro and ex vivo.

Localization of Phenolic Compounds at an Air-Solid Interface in Plant Seed Mucilage: A Strategy to Maximize Its Biological Function?

Given a low concentration of phenols in the naturally occurring aqueous lubricant (mucilage) from hydrated seeds, their biological functions should be severely limited. Here, we introduce an undisclosed natural strategy that enables maximization of phenolic functions through exposing the phenols at the air-seed solid interface. Our findings not only offer a new perspective on plant reproduction physiology but also provide insights into an innovative design of lubricating biomaterials with additional phenolic functions.