Parrotfish (Scaridae) feed by biting stony corals. To investigate how their teeth endure the associated contact stresses, we examine the chemical composition, nano- and microscale structure, and the mechanical properties of the steephead parrotfish Chlorurus microrhinos tooth. Its enameloid is a fluorapatite (Ca(PO)F) biomineral with outstanding mechanical characteristics: the mean elastic modulus is 124 GPa, and the mean hardness near the biting surface is 7.3 GPa, making this one of the stiffest and hardest biominerals measured; the mean indentation yield strength is above 6 GPa, and the mean fracture toughness is ∼2.5 MPa·m, relatively high for a highly mineralized material. This combination of properties results in high abrasion resistance. Fluorapatite X-ray absorption spectroscopy exhibits linear dichroism at the Ca L-edge, an effect that makes peak intensities vary with crystal orientation, under linearly polarized X-ray illumination. This observation enables polarization-dependent imaging contrast mapping of apatite, a method to quantitatively measure and display nanocrystal orientations in large, pristine arrays of nano- and microcrystalline structures. Parrotfish enameloid consists of 100 nm-wide, microns long crystals co-oriented and assembled into bundles interwoven as the warp and the weave in fabric and therefore termed fibers here. These fibers gradually decrease in average diameter from 5 μm at the back to 2 μm at the tip of the tooth. Intriguingly, this size decrease is spatially correlated with an increase in hardness.

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Recent research efforts to combat marine biofouling have focused on foul-release coatings that are not harmful for the marine environment. Inspired by nature, Slippery Lubricant Infused Porous Surfaces (SLIPS) is a surface modification technology platform with excellent anti-adhesive and antifouling capacities. Pre-commercial coatings based on the SLIPS concept have demonstrated promising results as an environmentally friendly strategy to combat marine biofouling. Here, we investigated the resistance against marine biofouling of a range of recently developed, biocide-free SLIPS commercial coatings. The fouling resistance performance was evaluated both in the lab and in the field by conducting multi-month immersion tests in high-fouling pressure environments. In the lab, we show that the coatings are able to largely deter settlement of marine mussels -one of the most invasive marine biofouling organisms-and to weaken their interfacial adhesion strength. The key design parameter of slippery coatings to minimize fouling is the thickness of the entrapped lubricant overlayer, which can be assessed through depth-sensing nanoindentation measurements. We find that the surface energy (i.e. hydrophobic vs. hydrophilic), on the other hand, does not significantly influence the antifouling performance of these coatings in lab-scale studies. After immersion in the field in stagnant waters, all coatings exhibited efficient foul-release capacity against macrofoulers, whereas under stronger hydrodynamic flow conditions, only weakly attached biofilms were detected with a bacterial community composition that is independent on the surface energy. These results suggest that these large-scale paintable coatings exhibit a strong marine biofouling resistance with low maintenance costs, which represents an important advantage from a commercial application perspective.

Liquid metal droplets, such as eutectic gallium–indium (EGaIn), are important in many research areas, such as soft electronics, catalysis, and energy storage. Droplet contact on solid surfaces is typically achieved without control over the applied force and without optimizing the wetting properties in different environments (e.g., in air or liquid), resulting in poorly defined contact areas. In this work, we demonstrate the direct manipulation of EGaIn microdroplets using an atomic force microscope (AFM) to generate repeated, on-demand making and breaking of contact on self-assembled monolayers (SAMs) of alkanethiols. The nanoscale positional control and feedback loop in an AFM allow us to control the contact force at the nanonewton level and, consequently, tune the droplet contact areas at the micrometer length scale in both air and ethanol. When submerged in ethanol, the droplets are highly nonwetting, resulting in hysteresis-free contact forces and minimal adhesion; as a result, we are able to create reproducible geometric contact areas of 0.8–4.5 μm2 with the alkanethiolate SAMs in ethanol. In contrast, there is a larger hysteresis in the contact forces and larger adhesion for the same EGaIn droplet in air, which reduced the control over the contact area (4–12 μm2). We demonstrate the usefulness of the technique and of the gained insights in EGaIn contact mechanics by making well-defined molecular tunneling junctions based on alkanethiolate SAMs with small geometric contact areas of between 4 and 12 μm2 in air, 1 to 2 orders of magnitude smaller than previously achieved.

The evolution success of crustaceans is largely due to the diversification of their mineralized exoskeletons and hunting appendages, which exhibit a large palette of morphometric characteristics that have adapted to meet particular functions. We explored the "snapper claw" of the pistol shrimp, which is used to generate cavitation bubbles and strike prey. Our multi-scale structure-property relationship study reveals that the snapper claw is more brittle than other fast raptorial appendages - such as the stomatopod dactyl club - because it is not directly subjected to direct contact forces during action. This study implies that when higher mechanical stresses are needed to meet the function, the internal structure is built of a more complex architecture that allows to mitigate internal structural damage.

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Despite the economic and ecological importance of corals’ skeletal structure, as well as their predicted vulnerability to future climate change, few studies have examined the skeletal mechanical properties at the nanoscale. As climate change is predicted to alter coral growth and physiology, as well as increase mechanical stress events (e.g., bioerosion, storm frequency), it is crucial to understand how skeletal mechanical properties change with environmental conditions. Moreover, while material properties are intimately linked to the chemical composition of the skeleton, no previous study has examined mechanical properties alongside carbonate geochemical composition. Using Porites coral cores from a wide range of reef environments (Thailand, Singapore, Taiwan), we correlated coral’s micro-mechanical properties with chemical composition. In contrast to previous mechanical measurements of reef-building corals, we document unprecedented variability in the hardness, stiffness, and micro-cracking stress of Porites corals across reef environments, which may significantly decrease the structural integrity of reef substrate. Corals from environments with low salinity and high sedimentation had higher organic content and fractured at lower loads, suggesting that skeletal organic content caused enhanced embrittlement. Within individual coral cores, we observed seasonal variability in skeletal stiffness, and a relationship between high sea surface temperature, increased stiffness, and high-density. Regionally, lower Sr/Ca and higher Mg/Ca coincided with decreased stiffness and hardness, which is likely driven by increased amorphous calcium carbonate and skeletal organic content. If the coral is significantly embrittled, as measured here in samples from Singapore, faster erosion is expected. A decrease in skeletal stiffness will decrease the quality of reef substrate, enhance the rate of bioerosion by predators and borers, and increase colony dislodgement, resulting in widespread loss of structural complexity.

The stomatopod is a fascinating animal that uses its weaponized appendage dactyl clubs for breaking mollusc shells. Dactyl clubs are a well studied example of biomineralized hierarchical structures. Most research has focused on the regions close to the action, namely the impact region and surface composed of chitin and apatite crystallites. Further away from the site of impact, the club has lower mineralization and more amorphous phases; these areas have not been as actively studied as their highly mineralized counterparts. This work focuses on the side of the club, in what is known as the periodic and striated regions. A combination of laboratory micro-computed tomography, synchrotron X-ray diffraction mapping and synchrotron X-ray fluorescence mapping has shown that the mineral in this region undergoes the transition from an amorphous to a crystalline phase in some, but not all, clubs. This means that this side region can be mineralized by either an amorphous phase, calcite crystallites or a mixture of both. It was found that when larger calcite crystallites form, they are organized (textured) with respect to the chitin present in this biocomposite. This suggests that chitin may serve as a template for crystallization when the side of the club is fully mineralized. Further, calcite crystallites were found to form as early as 1 week after moulting of the club. This suggests that the side of the club is designed with a significant safety margin that allows for a variety of phases, i.e. the club can function independently of whether the side region has a crystalline or amorphous mineral phase.