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The adhesive strategy of the gecko relies on foot pads composed of specialized keratinous foot-hairs called setae, which are subdivided into terminal spatulae of approximately 200 nm (ref. 1). Contact between the gecko foot and an opposing surface generates adhesive forces that are sufficient to allow the gecko to cling onto vertical and even inverted surfaces. Although strong, the adhesion is temporary, permitting rapid detachment and reattachment of the gecko foot during locomotion. Researchers have attempted to capture these properties of gecko adhesive in synthetic mimics with nanoscale surface features reminiscent of setae; however, maintenance of adhesive performance over many cycles has been elusive, and gecko adhesion is greatly diminished upon full immersion in water. Here we report a hybrid biologically inspired adhesive consisting of an array of nanofabricated polymer pillars coated with a thin layer of a synthetic polymer that mimics the wet adhesive proteins found in mussel holdfasts. Wet adhesion of the nanostructured polymer pillar arrays increased nearly 15-fold when coated with mussel-mimetic polymer. The system maintains its adhesive performance for over a thousand contact cycles in both dry and wet environments. This hybrid adhesive, which combines the salient design elements of both gecko and mussel adhesives, should be useful for reversible attachment to a variety of surfaces in any environment.
In physiological fluids and seawater, adhesion of synthetic polymers to solid surfaces is severely limited by high salt, pH, and hydration, yet these conditions have not deterred the evolution of effective adhesion by mussels. Mussel foot proteins provide insights about adhesive adaptations: Notably, the abundance and proximity of catecholic Dopa (3,4-dihydroxyphenylalanine) and lysine residues hint at a synergistic interplay in adhesion. Certain siderophores—bacterial iron chelators—consist of paired catechol and lysine functionalities, thereby providing a convenient experimental platform to explore molecular synergies in bioadhesion. These siderophores and synthetic analogs exhibit robust adhesion energies (E(ad) ≥-15 millijoules per square meter) to mica in saline pH 3.5 to 7.5 and resist oxidation. The adjacent catechol-lysine placement provides a "one-two punch," whereby lysine evicts hydrated cations from the mineral surface, allowing catechol binding to underlying oxides.
Achieving strong adhesion between wet materials (i.e., tissues and hydrogels) is challenging. Existing adhesives are weak, toxic, incompatible with wet and soft surfaces, or restricted to specific functional groups from the wet materials. The approach reported here uses biocompatible polymer chains to achieve strong adhesion and retain softness, but requires no functional groups from the wet materials. In response to a trigger, the polymer chains form a network, in topological entanglement with the two polymer networks of the wet materials, stitching them together like a suture at the molecular scale. To illustrate topological adhesion, pH is used as a trigger. The stitching polymers are soluble in water in one pH range but form a polymer network in another pH range. Several stitching polymers are selected to create strong adhesion between hydrogels in full range of pH, as well as between hydrogels and various porcine tissues (liver, heart, artery, skin, and stomach). The adhesion energy above 1000 J m-2 is achieved when the stitching polymer network elicits the hysteresis in the wet materials. The molecular suture can be designed to be permanent, transient, or removable on-demand. The topological adhesion may open many opportunities in complex and diverse environments.
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