Surface chemistry of the ladybird beetle adhesive foot fluid across various substrates

Nature has coevolved highly adaptive and reliable bioadhesives across a multitude of animal species. Much attention has been paid in recent years to selectively mimic these adhesives for the improvement of a variety of technologies. However, very few of the chemical mechanisms that drive these natural adhesives are well understood. Many insects combine hairy feet with a secreted adhesive fluid, allowing for adhesion to considerably rough and slippery surfaces. Insect adhesive fluids have evolved highly specific compositions which are consistent across most surfaces and optimize both foot adhesion and release in natural environments. For example, beetles are thought to have adhesive fluids made up of a complex molecular mixture containing both hydrophobic and hydrophilic parts. We hypothesize that this causes the adhesive interface to be dynamic, with molecules in the fluid selectively organizing and ordering at surfaces with complimentary hydrophobicity to maximize adhesion. In this study, we examine the adhesive fluid of a seven-spotted ladybird beetle with a surface-sensitive analytical technique, sum frequency generation spectroscopy, as the fluid interacts with three substrates of varied wettabilities. The resulting spectra present no evidence of unique molecular environments between hydrophilic and hydrophobic surfaces but exhibit significant differences in the ordering of hydrocarbons. This change in surface interactions across different substrates correlates well with traction forces measured from beetles interacting with substrates of increasing hydrophobicities. We conclude that insect adhesion is dependent upon a dynamic molecular-interfacial response to an environmental surface.