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Nature has evolved efficient strategies to synthesize complex mineralized structures that exhibit exceptional damage tolerance. One such example is found in the hypermineralized hammer-like dactyl clubs of the stomatopods, a group of highly aggressive marine crustaceans. The dactyl clubs from one species, Odontodactylus scyllarus, exhibit an impressive set of characteristics adapted for surviving high-velocity impacts on the heavily mineralized prey on which they feed. Consisting of a multiphase composite of oriented crystalline hydroxyapatite and amorphous calcium phosphate and carbonate, in conjunction with a highly expanded helicoidal organization of the fibrillar chitinous organic matrix, these structures display several effective lines of defense against catastrophic failure during repetitive high-energy loading events.

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Two-dimensional (2D) crystalline materials possess unique structural, mechanical, and electronic properties1,2, which have rendered them highly attractive in many applications3-5. Although there have been advances in preparing 2D materials that consist of one or few atomic/molecular layers6,7, bottom-up assembly of 2D crystalline materials remains a considerable challenge and an active area of development8-10. Even more challenging is the design of dynamic 2D lattices that can undergo large-scale motions without loss of crystallinity. Dynamicity in porous 3D crystalline solids has been exploited for stimuli-responsive functions and adaptive behavior11-13. As in the case of such 3D materials, integrating flexibility/adaptiveness into crystalline 2D lattices would greatly broaden the functional scope of 2D materials. Here we report the self-assembly of unsupported, 2D protein lattices with precise spatial arrangements and patterns through a readily accessible design strategy. Three single- or double-point mutants of the C4 symmetric protein RhuA were designed to assemble via different modes of intermolecular interactions (single disulfide, double disulfide and metal coordination) into crystalline 2D arrays. Owing to the flexibility of the single disulfide interactions, the lattices of one of the variants (C98RhuA) are essentially defect-free and undergo substantial but fully correlated changes in molecular arrangement, giving coherently dynamic 2D molecular lattices. Notably, C98RhuA lattices possess a Poisson's ratio of −1, the lowest thermodynamically possible value for an isotropic material.

Biological materials found in Nature such as nacre and bone are well recognized as light-weight, strong, and tough structural materials. The remarkable toughness and damage tolerance of such biological materials are conferred through hierarchical assembly of their multiscale (i.e., atomicto macroscale) architectures and components. Herein, the toughening mechanisms of different organisms at multilength scales are identified and summarized: macromolecular deformation, chemical bond breakage, and biomineral crystal imperfections at the atomic scale; biopolymer fibril reconfiguration/deformation and biomineral nanoparticle/nanoplatelet/ nanorod translation, and crack reorientation at the nanoscale; crack deflection and twisting by characteristic features such as tubules and lamellae at the microscale; and structure and morphology optimization at the macroscale. In addition, the actual loading conditions of the natural organisms are different, leading to energy dissipation occurring at different time scales. These toughening mechanisms are further illustrated by comparing the experimental results with computational modeling. Modeling methods at different length and time scales are reviewed. Examples of biomimetic designs that realize the multiscale toughening mechanisms in engineering materials are introduced. Indeed, there is still plenty of room mimicking the strong and tough biological designs at the multilength and time scale in Nature.

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Nacre, the iridescent material in seashells, is one of many natural materials employing hierarchical structures to achieve high strength and toughness from relatively weak constituents. Incorporating these structures into composites is appealing as conventional engineering materials often sacrifice strength to improve toughness. Researchers hypothesize that nacre's toughness originates within its brick-and-mortar-like microstructure. Under loading, bricks slide relative to each other, propagating inelastic deformation over millimeter length scales. This leads to orders-of-magnitude increase in toughness. Here, we use in situ atomic force microscopy fracture experiments and digital image correlation to quantitatively prove that brick morphology (waviness) leads to transverse dilation and subsequent interfacial hardening during sliding, a previously hypothesized dominant toughening mechanism in nacre. By replicating this mechanism in a scaled-up model synthetic material, we find that it indeed leads to major improvements in energy dissipation. Ultimately, lessons from this investigation may be key to realizing the immense potential of widely pursued nanocomposites.

A fibrous herringbone-modified helicoidal architecture is identified within the exocuticle of an impact-resistant crustacean appendage. This previously unreported composite microstructure, which features highly textured apatite mineral templated by an alpha-chitin matrix, provides enhanced stress redistribution and energy absorption over the traditional helicoidal design under compressive loading. Nanoscale toughening mechanisms are also identified using high load nanoindentation and in-situ TEM picoindentation. A Sinusoidally-Architected Helicoidal BiocompositeBy Nicholas A. Yaraghi, Nicolás Guarín-Zapata, Lessa K. Grunenfelder, Eric Hintsala, Sanjit Bhowmick, Jon M. Hiller, Mark Betts, Edward L. Principe, Jae-Young Jung, Leigh Sheppard, Richard Wuhrer, Joanna McKittrick, Pablo D. Zavattieri Keywords: (Composites, Toughness, Impact, Biomineral, Ultrastructure) Submitted to 3 Biologically mineralized composites offer inspiration for the design of next generation structural materials due to their low density, high strength and toughness currently unmatched by engineering technologies. [1][2][3][4][5][6][7][8][9] Such properties are based on the ability for the organism to utilize structural organics and acidic proteins to guide and control the mineralization process to yield hierarchical architectures with well-defined compositional gradients.One notable example is the highly developed raptorial appendage, or dactyl, of the stomatopods, a group of aggressive marine crustaceans that use these structures for feeding upon hard-shelled and soft-bodied prey. [10][11][12][13][14] The dactyls of the "smashers", those that feed primarily on hard-shelled prey, (see Figure 1A) takes the form of a bulbous club ( Figure 1B), which is used to smash through mollusk shells, crab exoskeletons, and other tough mineralized structures with tremendous force and speed. [11][12][13][14][15][16] Achieving accelerations over 10,000g and reaching speeds of 23 m/s from rest, the dactyl strike is recognized as one of the fastest and most powerful impacting events observed in Nature. [11,12] The club is capable of delivering and subsequently enduring repetitive impact forces up to 1500 N and cavitation stresses without catastrophically failing, demonstrating its utility as an exceptionally damage-tolerant natural material.The origins of such a mechanical response lie in the structural design. Previous work identified the club as a multi-regional composite material containing an organic matrix composed of alpha-chitin fibers mineralized by amorphous forms of calcium carbonate and calcium phosphate as well as crystalline apatite. [17,18] These investigations revealed mechanisms responsible for providing damage-tolerance and impact-resistance to the club, which were largely attributed to the interior of the club (periodic region), identified as the primary energy-absorbing layer. [17,18] The combination of soft polymeric nanofibers and stiffer mineral provides a periodic modulus mismatch leading to crack deflection, which in co...