Evidence that gecko setae are coated with an ordered nanometre-thin lipid film.

The fascinating adhesion of gecko to virtually any material has been related to surface interactions of myriads of spatula at the tips of gecko feet. Surprisingly, the molecular details of the surface chemistry of gecko adhesion are still largely unknown. Lipids have been identified within gecko adhesive pads. However, the location of the lipids, the extent to which spatula are coated with lipids, and how the lipids are structured are still open questions. Lipids can modulate adhesion properties and surface hydrophobicity and may play an important role in adhesion. We have therefore studied the molecular structure of lipids at spatula surfaces using near-edge X-ray absorption fine structure imaging. We provide evidence that a nanometre-thin layer of lipids is present at the spatula surfaces of the tokay gecko (Gekko gecko) and that the lipids form ordered, densely packed layers. Such dense, thin lipid layers can effectively protect the spatula proteins from dehydration by forming a barrier against water evaporation. Lipids can also render surfaces hydrophobic and thereby support the gecko adhesive system by enhancement of hydrophobic-hydrophobic interactions with surfaces.

Structure of Keratins in Adhesive Gecko Setae Determined by Near-Edge X-ray Absorption Fine Structure Spectromicroscopy.

Geckos have the astonishing ability to climb on vertical surfaces due to the adhesive properties of fibrous setae at the tips of their toe pads. While the adhesion mechanism principle, based on van der Waals interactions of myriads of spatula located at the outermost end of the setal arrays, has been studied extensively, there are still open questions about the chemistry of gecko setae. The gecko adhesive system is based on keratin fibrils assembled to support the entire setal structure. At the same time, the structure and alignment of keratin molecules within the ultrafine spatula tissue, which can support the enormous mechanical strain, still remain unknown. We have studied the molecular structure of gecko spatula using near-edge X-ray absorption fine structure (NEXAFS) imaging. We indeed found that the setae consist of a ß-sheet structure aligned with the adhesion direction of the setae. Such alignment may provide mechanical stability to the setae and resistance to wear across different length scales.