Alyssa Y. Stark

Surface Wettability Plays a Significant Role in Gecko Adhesion Underwater

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.

The effect of surface water and wetting on gecko adhesion

SUMMARY Despite 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 geckos adhesive toe pads may have significant consequences for the ecology and behavior of geckos living in tropical environments.

Direct evidence of phospholipids in gecko footprints and spatula- substrate contact interface detected using surface-sensitive spectroscopy

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 geckos 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.

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

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.

Self-Drying: A Gecko's Innate Ability to Remove Water from Wet Toe Pads

When the adhesive toe pads of geckos become wet, they become ineffective in enabling geckos to stick to substrates. This result is puzzling given that many species of gecko are endemic to tropical environments where water covered surfaces are ubiquitous. We hypothesized that geckos can recover adhesive capabilities following exposure of their toe pads to water by walking on a dry surface, similar to the active self-cleaning of dirt particles. We measured the time it took to recover maximum shear adhesion after toe pads had become wet in two groups, those that were allowed to actively walk and those that were not. Keeping in mind the importance of substrate wettability to adhesion on wet surfaces, we also tested geckos on hydrophilic glass and an intermediately wetting substrate (polymethylmethacrylate; PMMA). We found that time to maximum shear adhesion recovery did not differ in the walking groups based on substrate wettability (22.7±5.1 min on glass and 15.4±0.3 min on PMMA) but did have a significant effect in the non-walking groups (54.3±3.9 min on glass and 27.8±2.5 min on PMMA). Overall, we found that by actively walking, geckos were able to self-dry their wet toe pads and regain maximum shear adhesion significantly faster than those that did not walk. Our results highlight a unexpected property of the gecko adhesive system, the ability to actively self-dry and recover adhesive performance after being rendered dysfunctional by water.

Sticking to the story: outstanding challenges in gecko-inspired adhesives

ABSTRACT The natural clinging ability of geckos has inspired hundreds of studies seeking design principles that could be applied to creating synthetic adhesives with the same performance capabilities as the gecko: adhesives that use no glue, are self-cleaning and reusable, and are insensitive to a wide range of surface chemistries and roughness. Important progress has been made, and the basic mechanics of how ‘hairy’ adhesives work have been faithfully reproduced, advancing theory in surface science and portending diverse practical applications. However, after 15 years, no synthetic mimic can yet perform as well as a gecko and simultaneously meet of all the criteria listed above. Moreover, processes for the production of inexpensive and scalable products are still not clearly in view. Here, we discuss our perspective on some of the gaps in understanding that still remain; these gaps in our knowledge should stimulate us to turn to deeper study of the way in which free-ranging geckos stick to the variety of surfaces found in their natural environments and to a more complete analysis of the materials composing the gecko toe pads. Summary: High performing gecko-inspired adhesives have been the subject of extensive study for nearly 15 years. We comment on current gaps in understanding the natural system that seem critical to the design of highly functioning synthetic mimics.

The effect of temperature and humidity on adhesion of a gecko-inspired adhesive: implications for the natural system.

The adhesive system of geckos has inspired hundreds of synthetic adhesives. While this system has been used relentlessly as a source of inspiration, less work has been done in reverse, where synthetics are used to test questions and hypotheses about the natural system. Here we take such an approach. We tested shear adhesion of a mushroom-tipped synthetic gecko adhesive under conditions that produced perplexing results in the natural adhesive system. Synthetic samples were tested at two temperatures (12 °C and 32 °C) and four different humidity levels (30%, 55%, 70%, and 80% RH). Surprisingly, adhesive performance of the synthetic samples matched that of living geckos, suggesting that uncontrolled parameters in the natural system, such as surface chemistry and material changes, may not be as influential in whole-animal performance as previously thought. There was one difference, however, when comparing natural and synthetic adhesive performance. At 12 °C and 80% RH, adhesion of the synthetic structures was lower than expected based on the natural system’s performance. Our approach highlights a unique opportunity for both biologists and material scientists, where new questions and hypotheses can be fueled by joint comparisons of the natural and synthetic systems, ultimately improving knowledge of both.

Faster but Not Stickier: Invasive House Geckos Can Out-Sprint Resident Mournful Geckos in Moorea, French Polynesia

Abstract The House Gecko, Hemidactylus frenatus, is one of the worlds most invasive vertebrate species and is spreading rapidly across the South Pacific, displacing other species of geckos that are native or were already resident. We studied the adhesion and locomotor capabilities of H. frenatus and the resident Lepidodactylus lugubris on the island of Moorea in French Polynesia where they are syntopic. Our goal was to determine whether H. frenatus could stick or sprint faster than L. lugubris, two types of performance measures that could underlie superiority of H. frenatus in foraging and agonistic interactions hypothesized in other studies. The clinging ability of H. frenatus and L. lugubris are comparable suggesting that the potential for sticking to vertical and over-hanging surfaces as geckos move through their environments does not differ between species. In contrast, H. frenatus have maximal sprint speeds that are approximately fourfold higher than L. lugubris, an advantage in speed that is even greater than that measured previously for the two species running on horizontal surfaces. Proposed superiority in foraging and agonistic interactions of H. frenatus compared to L. lugubris are potentially traceable to performance characteristics such as adhesion and locomotion. We demonstrate that comparatively high maximal locomotor speeds may contribute to the observed success of H. frenatus over resident geckos in French Polynesia, and possibly in other areas where they have been introduced.

Adhesive interactions of geckos with wet and dry fluoropolymer substrates

Fluorinated substrates like Teflon® (poly(tetrafluoroethylene); PTFE) are well known for their role in creating non-stick surfaces. We showed previously that even geckos, which can stick to most surfaces under a wide variety of conditions, slip on PTFE. Surprisingly, however, geckos can stick reasonably well to PTFE if it is wet. In an effort to explain this effect, we have turned our attention to the role of substrate surface energy and roughness when shear adhesion occurs in media other than air. In this study, we removed the roughness component inherent to commercially available PTFE and tested geckos on relatively smooth wet and dry fluoropolymer substrates. We found that roughness had very little effect on shear adhesion in air or in water and that the level of fluorination was most important for shear adhesion, particularly in air. Surface energy calculations of the two fluorinated substrates and one control substrate using the Tabor–Winterton approximation and the Young–Dupré equation were used to determine the interfacial energy of the substrates. Using these interfacial energies we estimated the ratio of wet and dry normal adhesion for geckos clinging to the three substrates. Consistent with the results for rough PTFE, our predictions show a qualitative trend in shear adhesion based on fluorination, and the quantitative experimental differences highlight the unusually low shear adhesion of geckos on dry smooth fluorinated substrates, which is not captured by surface energy calculations. Our work has implications for bioinspired design of synthetics that can preferentially stick in water but not in air.

MECHANICAL PROPERTIES OF THE CHITIN-CALCIUM-PHOSPHATE "CLAM SHRIMP" CARAPACE (BRANCHIOPODA: SPINICAUDATA): IMPLICATIONS FOR TAPHONOMY AND FOSSILIZATION

Spinicaudata (colloquially ‘the clam shrimp’) are freshwater branchiopod crustaceans that occur worldwide in lakes and temporary pools. The spinicaudatans are easily recognizable by their bivalved carapace which is unusual among arthropods in that it is subject to only partial molting. During ecdysis (molting), the outer surface of the carapace is not shed, resulting in the retention of the ontogenetic record of an individual through distinct growth-rings representing each molt. When this unusual feature is considered alongside the interesting chemical properties of the carapace, “clam shrimp” present an interesting biological material not seen anywhere else: a multi-laminar calcium-phosphate-chitin composite. In addition, the carapace survives numerous destructive taphonomic processes (including transport, decay, compaction, and desiccation) to become the dominant body component of Spinicaudata preserved in their 380 million year fossil record. Understanding the mechanical properties and chemical composition of this structure may not only aid in a better understanding of the evolutionary history of this group but also facilitate efforts to develop novel materials that retain functional material properties even in harsh aquatic conditions. Therefore, this study aims to provide quantitative information about the composition and mechanics of this unique and interesting biological material and help predict possible biases in the fossilization of different species of Spinicaudata to aid future palaeontological research.