On-Demand Manufacturing Capabilities of Mussels Enable Robust Adhesion to Geometrically Complex Surfaces.

Marine mussels have the remarkable ability to adhere to a variety of natural and artificial surfaces under hostile environmental conditions. Although the molecular composition of mussel adhesives has been well studied, a mechanistic understanding of the physical origins of mussels' impressive adhesive strength remains elusive. Here, we investigated the role of substrate geometry in the adhesive performance of mussels. Experimentally, we created substrates with differing surface properties using 3D printing and laser drilling and introduced these to mussels, which in turn adhered to the engineered surfaces via plaque-thread byssal structures. Tensile testing with in situ imaging was conducted to quantify the adhesion strength of the mussel plaques, and the microstructures of the mechanically deformed plaques were characterized using scanning electron microscopy. Our results reveal that the geometry of the surfaces has no significant impact on the detachment force and the strain, whereas the change in adhesion area leads to a different adhesion stress. Ultrastructural analysis confirms the expected presence of an open-cell foamy network coated with the cuticle. The observed detachment dynamics and failure mechanisms do vary depending on the substrate properties, suggesting the presence of substrate-dependent nonuniform stress distributions at the interface. Together, these results show mussels' remarkable ability to adapt to differing physical conditions and demonstrate the importance of the on-demand and in situ manufacturing of the stiff cuticle and relatively compliant adhesive interlayer. The resultant composite structure avoids the formation of prestress during the formation of the adhesive joint, provides conformability to the surface, and helps compensate for local bending interactions to maintain adhesive strength. Our findings suggest forward design strategies to improve adhesive performance on complex surfaces.

Effects of sea water pH on marine mussel plaque maturation.

Marine mussel plaques are an exceptional model for wet adhesives. Despite advances in understanding their protein composition and strategies for molecular bonding, the process by which these soluble proteins are rapidly processed into load-bearing structures remains poorly understood. Here, we examine the effects of seawater pH on the time evolution of the internal microstructures in plaques harvested from Mytilus californianus. Experimentally, plaques deposited by mussels on glass and acrylic surfaces were collected immediately after foot retraction without plaque separation from the surface, placed into pH-adjusted artificial seawater for varying times, and characterized using scanning electron microscopy and tensile testing. We found a pH dependent transition from a liquid-like state to a porous solid within 30 min for pH ≥ 6.7; these plaques are load-bearing. By contrast, samples maintained at pH 3.0 showed no porosity and no measurable strength. Interestingly, we found cuticle development within 15 min regardless of pH, suggesting that cuticle formation occurs prior to pore assembly. Our results suggest that sea water infusion after deposition by and disengagement of the foot is critical to the rapid formation of internal structures, which in turn plays an important role in the plaques' mechanical performance.