Molecular Changes in Spider Viscid Glue As a Function of Relative Humidity Revealed Using Infrared Spectroscopy.

Spider aggregate glue can absorb moisture from the atmosphere to reduce its viscosity and become tacky. The viscosity at which glue adhesion is maximized is remarkably similar across spider species, even though that viscosity is achieved at very different relative humidity (RH) values matching their diverse habitats. However, the molecular changes in the protein structure and the bonding state of water (both referred to here as molecular structure) with respect to the changes in RH are not known. We use attenuated total reflectance-infrared (ATR-IR) spectroscopy to probe the changes in the molecular structure of glue as a function of RH for three spider species from different habitats. We find that the glue retains bound water at lower RH and absorbs liquid-like water at higher RH. The absorption of liquid-like water at high RH plasticizes the glue and explains the decrease in glue viscosity. The changes to protein conformations as a function RH are either subtle or not detectable by IR spectroscopy. Importantly, the molecular changes are reversible over multiple cycles of RH change. Further, separation of glue constituents results in a different humidity response as compared to pristine glue, supporting the standing hypothesis that the glue constituents have a synergistic association that makes spider glue a functional adhesive. The results presented in this study provide further insights into the mechanism of the humidity-responsive adhesion of spider glue.