Although we now have thousands of studies focused on the nano-, micro-, and whole-animal mechanics of gecko adhesion on clean, dry substrates, we know relatively little about the effects of water on gecko adhesion. For many gecko species, however, rainfall frequently wets the natural surfaces they navigate. In an effort to begin closing this gap, we tested the adhesion of geckos on submerged substrates that vary in their wettability. When tested on a wet hydrophilic surface, geckos produced a significantly lower shear adhesive force (5.4 ± 1.33 N) compared with a dry hydrophilic surface (17.1 ± 3.93 N). In tests on an intermediate wetting surface and a hydrophobic surface, we found no difference in shear adhesion between dry and wet contact. Finally, in tests on polytetrafluoroethylene (PTFE), we found that geckos clung significantly better to wet PTFE (8.0 ± 1.09 N) than dry PTFE (1.6 ± 0.66 N). To help explain our results, we developed models based on thermodynamic theory of adhesion for contacting surfaces in different media and found that we can predict the ratio of shear adhesion in water to that in air. Our findings provide insight into how geckos may function in wet environments and also have significant implications for the development of a synthetic gecko mimic that retains adhesion in water.contact angle | superhydrophobicity | van der Waals | friction | bioinspired adhesive O ver the past decade, researchers have made extraordinary progress in understanding how the gecko adhesive system works (1-8). Indeed, many laboratories have tested hundreds of synthetic mimics for potential use in robotics, medicine, space, and everyday life (9-21). Although the range and performance of synthetic "gecko-tapes" are impressive, important gaps remain in our knowledge of the system and its capabilities in natural environments. Geckos are extremely diverse, constituting more than 1,400 species worldwide (22, 23). However, knowledge of the natural substrates and conditions geckos use is very limited. For example, it is likely that many species move across leaves and other plant structures that are not perfectly smooth and have variable surface chemistries (24,25). In principle, the interaction of gecko feet with such surfaces may have a significant effect on adhesion, yet gecko research has only just begun to tackle such questions (26-28). Additionally, natural surfaces are likely to become wet (especially in the tropics) and dirty, potentially reducing adhesion. Although research on the ability of geckos to remove dirt from their toes has received some attention (29,30), studies on wetting and the effect of water are limited, despite the well-known antiwetting properties of the toes, which are superhydrophobic and have a low-contact-angle hysteresis (31, 32).Somewhat surprisingly, geckos cannot stick to hydrophilic glass when it is covered with a layer of water (33). Anecdotally, this effect has been long and widely appreciated; nevertheless, the effect of water on gecko adhesion is complex. For example, a thin water ...

SUMMARYDespite profound interest in the mechanics and performance of the gecko adhesive system, relatively few studies have focused on performance under conditions that are ecologically relevant to the natural habitats of geckos. Because geckos are likely to encounter surfaces that are wet, we used shear force adhesion measurements to examine the effect of surface water and toe pad wetting on the whole-animal performance of a tropical-dwelling gecko (Gekko gecko). To test the effect of surface wetting, we measured the shear adhesive force of geckos on three substrate conditions: dry glass, glass misted with water droplets and glass fully submerged in water. We also investigated the effect of wetting on the adhesive toe pad by soaking the toe pads prior to testing. Finally, we tested for repeatability of the adhesive system in each wetting condition by measuring shear adhesion after each step a gecko made under treatment conditions. Wetted toe pads had significantly lower shear adhesive force in all treatments (0.86±0.09N) than the control (17.96±3.42N), as did full immersion in water (0.44±0.03N). Treatments with droplets of water distributed across the surface were more variable and did not differ from treatments where the surface was dry (4.72±1.59N misted glass; 9.76±2.81N dry glass), except after the gecko took multiple steps. These findings suggest that surface water and the wetting of a geckoʼs adhesive toe pads may have significant consequences for the ecology and behavior of geckos living in tropical environments.

Observers ranging from Aristotle to young children have long marvelled at the ability of geckos to cling to walls and ceilings. Detailed studies have revealed that geckos are 'sticky' without the use of glue or suction devices. Instead, a gecko's stickiness derives from van der Waals interactions between proteinaceous hairs called setae and substrate. Here, we present surprising evidence that although geckos do not use glue, a residue is transferred on surfaces as they walk-geckos leave footprints. Using matrix-free nano-assisted laser desorption-ionization mass spectrometry, we identified the residue as phospholipids with phosphocholine head groups. Moreover, interface-sensitive sum-frequency generation spectroscopy revealed predominantly hydrophobic methyl and methylene groups and the complete absence of water at the contact interface between a gecko toe pad and the substrate. The presence of lipids has never been considered in current models of gecko adhesion. Our analysis of gecko footprints and the toe pad-substrate interface has significant consequences for models of gecko adhesion and by extension, the design of synthetic mimics.

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70–90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

Lipid and protein aggregates are one of the fundamental materials of biological systems. Examples include cell membranes, insect cuticle, vertebrate epidermis, feathers, hair and adhesive structures known as ‘setae’ on gecko toes. Until recently gecko setae were assumed to be composed entirely of keratin, but analysis of footprints left behind by geckos walking on surfaces revealed that setae include various kinds of lipids. However, the arrangement and molecular-level behavior of lipids and keratin in the setae is still not known. In the present study we demonstrate, for the first time, the use of Nuclear Magnetic Resonance (NMR) spectroscopy techniques to confirm the presence of lipids and investigate their association with keratin in ‘pristine' sheds, or natural molts of the adhesive toe pad and non-adhesive regions of the skin. Analysis was also carried on the sheds after they were ‘delipidized’ to remove surface lipids. Our results show a distribution of similar lipids in both the skin and toe shed but with different dynamics at a molecular level. The present study can help us understand the gecko system both biologically and for design of synthetic adhesives, but the findings may be relevant to the characteristics of lipid-protein interactions in other biological systems.