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Over hundreds of millions of years, organisms have evolved architected structures via precise control over hierarchically assembled components, including the integration of dissimilar materials. One such example is found in the radula system of chitons, intertidal mollusks that feed on algae growing on the rock. Their radula consists of multiple rows of ultrahard teeth, each integrated with a foldable belt-like substrate via a stiff, yet flexible stylus, which is essential for efficient rasping during the feeding process. Here, we investigate the nano and micro-scale components and architectures as well as regional mechanical properties of the stylus, and their subsequent role during the rasping of Cryptochiton stelleri. Three important factors were determined to contribute to the regio-specific stiffness of the stylus: the presence of mineral components, highly oriented chitinous fibers, and a chemically cross-linked protein matrix. All these factors are varied throughout the stylus. There is a high mineral content on the trailing edge close to the tooth and a cross-linked matrix on the leading edge, both with orientational specific oriented chitin fibers that provide force transduction to the tooth. Conversely, there is a significant lack of mineral or cross-linked matrix in the proximal end as well as a low degree of fiber orientation, resulting in a flexible region that can accommodate torsion and flexure during rasping. Understanding the graded composite structure of the stylus and applying this unique design to various engineering fields such as soft robotics, biotechnology, and the medical industry, can inspire the production of high-performance materials.

The relationship between diet, bite performance, and tooth structure is a topic of common interest for ecologists, biologists, materials scientists, and engineers. The highly specialized group of biters found in Serrasalmidae offers a unique opportunity to explore their functional diversity. Surprisingly, the piranha, whose teeth have a predominantly cutting function and whose main diet is soft flesh, is capable of exerting a greater bite force than a similarly sized pacu, who feeds on a hard durophagous diet. Herein, we expand our understanding of diet specialization in the Serrasalmidae family by investigating the influence of elemental composition and hierarchical structure on the local mechanical properties, stress distribution, and deformation mechanics of teeth from piranha (Pygocentrus nattereri) and pacu (Colossoma macropomum). Microscopic and spectroscopic analyses combined with nanoindentation and finite element simulations are used to probe the hierarchical features to uncover the structure-property relationships in piranha and pacu teeth. We show that the pacu teeth support a durophagous diet through its broad cusped-shaped teeth, thicker-irregular enameloid, interlocking interface of the dentin-enameloid junction, and increased hardness of the cuticle layer due to the larger concentrations of iron present. Comparatively, the piranha teeth are well suited for piercing due to their conical-shape which we report as having the greatest stiffness at the tip and evenly distributed enameloid. STATEMENT OF SIGNIFICANCE: The hierarchical structure and local mechanical properties of the piranha and pacu teeth are characterized and related to their feeding habits. Finite element models of the anterior teeth are generated to map local stress distribution under compressive loading. Bioinspired designs from the DEJ interface are developed and 3D printed. The pacu teeth are hierarchically structured and have local mechanical properties more suitable to a durophagous diet than the piranha. The findings here can provide insight into the design and fabrication of layered materials with suture interfaces for applications that require compressive loading conditions.

Magnetotactic bacterium, Magnetospirillum magneticum, produces biogenic magnetic nanoparticles termed magnetosomes, which are primarily composed of a magnetite core and a surrounding lipid bilayer membrane. We have fabricated human transmembrane protein-magnetosome complexes by genetic engineering with embedding the transmembrane proteins of interest, in particular G protein-coupled receptors (GPCRs), in the magnetosome membrane. The magnetosomes provide a promising platform for high throughput ligand screening towards drug discovery, and this is a critical advantage of the magnetosome display system beyond conventional membrane platforms such as liposomes and lipid nano-discs. However, the human GPCRs expressed on the magnetosomes were not fully functionalized in bacterial membranes the most probably due to the lack of essential phospholipids such as phosphatidylcholine (PC) for GPCR functionalization. To overcome this issue, we expressed two types of PC-producing enzymes, phosphatidylcholine synthase (PCS) and phosphatidylethanolamine N-methyltransferase (PMT) in M. magneticum. As a result, generation and incorporation of PC in cell- and magnetosome-membranes were demonstrated. To the best of our knowledge, M. magneticum is the second bacterial species which had the PC-incorporated lipid membrane by genetic engineering. Subsequently, a GPCR, thyroid-stimulating hormone receptor (TSHR) and PCS were simultaneously expressed. We found that PC in the magnetosome membrane assisted the binding of TSHR and its ligand, indicating that the genetic approach demonstrated in this study is useful to enhance the function of the GPCRs displayed on the magnetosomes.

The influx and efflux of water in biological structures actuates reversible deformation and recovery processes that are crucial for mechanical functions in plants and animals. These processes utilize various mechanochemical mechanisms: swelling directed by the arrangement of cellulosic microfibrils in a bilayer construct, which generates different deformation patterns; lignification gradients; hierarchical foam-like inner structures, some of which also include swelling by hygroscopic cellulose inner cell layer; turgor pressure, which is activated by osmosis and acts at the cellular level, generating reversible motions. In this Review, we present representatives of each of these four mechanisms: pine cones, wheat awns, the twisted opening of Bauhinia pods and the seed of the stork’s bill; the resurrection plant; ice plant seed capsules and carrotwood seed pod; the wilting and redressing of plant stems. Natural polymeric materials produced by animals can also exhibit hydration-driven shape and strength recovery: bird feathers and hair are prime examples. Spider silk — a non-keratinous biopolymer — also exhibits humidity-driven reversible deformation. After describing these animal-based mechanisms, we outline bioinspired applications to actuate multifunctional and biocompatible smart materials, and indicate future directions of research with potential for new bioinspired designs. The influx and efflux of water in biological structures leads to reversible deformation, which has important functions in plants (for example, in seed protection and dispersal) and animals (for example, in the recovery of the strength and shape of feathers, and for reversible changes in silk and hair). Here the authors review the main hydration-induced deformation mechanisms and highlight applications inspired by these processes.

Biologically composites offer inspiration for the design of next generation structural materials due to their hierarchical microstructure that allows for, low density, and combination of high stiffness and toughness, currently unmatched by engineering technologies. Here, we investigate biomimetic composite materials that feature the laminated helicoidal architecture of fibers characteristic of the arthropod cuticle, specific to the mantis shrimp, but utilize either glass or Kevlar fibers, with epoxy or urethane matrix materials, to examine their role in impact energy dissipation. Drop weight impact test revealed epoxy-matrix composites exhibited the highest peak load on impact and showed larger degrees of external damage such as delamination and fiber breakage as compared to the urethane-based composites. Moreover, the helicoidal panels, showed a significant reduction in dent depth and better residual compressive strength as compared to the quasi-isotropic design. These findings provide useful insight into the variation of reinforcement and matrix materials for the helicoidal architecture and how it affects the delocalization of damage and improves residual strength.

Joining dissimilar materials such as plastics and metals in engineered structures remains a challenge1. Mechanical fastening, conventional welding and adhesive bonding are examples of techniques currently used for this purpose, but each of these methods presents its own set of problems2 such as formation of stress concentrators or degradation under environmental exposure, reducing strength and causing premature failure. In the biological tissues of numerous animal and plant species, efficient strategies have evolved to synthesize, construct and integrate composites that have exceptional mechanical properties3. One impressive example is found in the exoskeletal forewings (elytra) of the diabolical ironclad beetle, Phloeodes diabolicus. Lacking the ability to fly away from predators, this desert insect has extremely impact-resistant and crush-resistant elytra, produced by complex and graded interfaces. Here, using advanced microscopy, spectroscopy and in situ mechanical testing, we identify multiscale architectural designs within the exoskeleton of this beetle, and examine the resulting mechanical response and toughening mechanisms. We highlight a series of interdigitated sutures, the ellipsoidal geometry and laminated microstructure of which provide mechanical interlocking and toughening at critical strains, while avoiding catastrophic failure. These observations could be applied in developing tough, impact- and crush-resistant materials for joining dissimilar materials. We demonstrate this by creating interlocking sutures from biomimetic composites that show a considerable increase in toughness compared with a frequently used engineering joint.

Microorganisms, in the most hyperarid deserts around the world, inhabit the inside of rocks as a survival strategy. Water is essential for life, and the ability of a rock substrate to retain water is essential for its habitability. Here we report the mechanism by which gypsum rocks from the Atacama Desert, Chile, provide water for its colonizing microorganisms. We show that the microorganisms can extract water of crystallization (i.e., structurally ordered) from the rock, inducing a phase transformation from gypsum (CaSO4·2H2O) to anhydrite (CaSO4). To investigate and validate the water extraction and phase transformation mechanisms found in the natural geological environment, we cultivated a cyanobacterium isolate on gypsum rock samples under controlled conditions. We found that the cyanobacteria attached onto high surface energy crystal planes ({011}) of gypsum samples generate a thin biofilm that induced mineral dissolution accompanied by water extraction. This process led to a phase transformation to an anhydrous calcium sulfate, anhydrite, which was formed via reprecipitation and subsequent attachment and alignment of nanocrystals. Results in this work not only shed light on how microorganisms can obtain water under severe xeric conditions but also provide insights into potential life in even more extreme environments, such as Mars, as well as offering strategies for advanced water storage methods.

Over hundreds of millions of years, organisms have derived specific sets of traits in response to common selection pressures that serve as guideposts for optimal biological designs. A prime example is the evolution of toughened structures in disparate lineages within plants, invertebrates, and vertebrates. Extremely tough structures can function much like armor, battering rams, or reinforcements that enhance the ability of organisms to win competitions, find mates, acquire food, escape predation, and withstand high winds or turbulent flow. From an engineering perspective, biological solutions are intriguing because they must work in a multifunctional context. An organism rarely can be optimally designed for only one function or one environmental condition. Some of these natural systems have developed well-orchestrated strategies, exemplified in the biological tissues of numerous animal and plant species, to synthesize and construct materials from a limited selection of available starting materials. The resulting structures display multiscale architectures with incredible fidelity and often exhibit properties that are similar, and frequently superior, to mechanical properties exhibited by many engineered materials. These biological systems have accomplished this feat through the demonstrated ability to tune size, morphology, crystallinity, phase, and orientation of minerals under benign processing conditions (i.e., near-neutral pH, room temperature, etc.) by establishing controlled synthesis and hierarchical 3D assembly of nano- to microscaled building blocks. These systems utilize organic-inorganic interactions and carefully controlled microenvironments that enable kinetic control during the synthesis of inorganic structures. This controlled synthesis and assembly requires orchestration of mineral transport and nucleation. The underlying organic framework, often consisting of polysaccharides and polypeptides, in these composites is critical in the spatial and temporal regulation of these processes. In fact, the organic framework is used not only to provide transport networks for mineral precursors to nucleation sites but also to precisely guide the formation and phase development of minerals and significantly improve the mechanical performance of otherwise brittle materials.Over the past 15 years, we have focused on a few of these extreme performing organisms, (Wang

Biomineralization is an elaborate process that controls the deposition of inorganic materials in living organisms with the aid of associated proteins. Magnetotactic bacteria mineralize magnetite (Fe

Simultaneous saccharification and fermentation (SSF) is effective for minimizing sugar inhibition during high solids fermentation of biomass solids to ethanol. However, fungal enzymes used during SSF are optimal between 50 and 60 °C, whereas most fermentative yeast, such as Saccharomyces cerevisiae, do not tolerate temperatures above 37 °C. Kluyveromyces marxianus variant CBS 6556 is a thermotolerant eukaryote that thrives at 43 °C, thus potentially serving as a promising new host for SSF operation in biorefineries. Here, we attempt to leverage the thermotolerance of the strain to demonstrate the application of CBS 6556 in a high solids (up to 20 wt% insoluble solid loading) SSF configuration to understand its capabilities and limitations as compared to a proven SSF strain, S. cerevisiae D5A. For this study, we first pretreated hardwood poplar chips using Co-Solvent Enhanced Lignocellulosic Fractionation (CELF) to remove lignin and hemicellulose and to produce cellulose-enriched pretreated solids for SSF. Our results demonstrate that although CBS 6556 could not directly outperform D5A, it demonstrated similar tolerance to high gravity sugar solutions, superior growth rates at higher temperatures and higher early stage ethanol productivity. We discovered that CBS 6556’s membrane was particularly sensitive to higher ethanol concentrations causing it to suffer earlier fermentation arrest than D5A. Cross-examination of metabolite data between CBS 6556 and D5A and cell surface imaging suggests that the combined stresses of high ethanol concentrations and temperature to CBS 6556’s cell membrane was a primary factor limiting its ethanol productivity. Hence, we believe K. marxianus to be an excellent host for future genetic engineering efforts to improve membrane robustness especially at high temperatures in order to achieve higher ethanol productivity and titers, serving as a viable alternative to D5A.

We report the biological synthesis of titania that is integrated into the silica-based cell walls of a titanium-resistant diatom

Iron is an essential micronutrient for most living organisms, including cyanobacteria. These microorganisms have been found in Earth's driest polar and non-polar deserts, including the Atacama Desert, Chile. Iron-containing minerals were identified in colonized rock substrates from the Atacama Desert, however, the interactions between microorganisms and iron minerals remain unclear. In the current study, we determined that colonized gypsum rocks collected from the Atacama Desert contained both magnetite and hematite phases. A cyanobacteria isolate was cultured on substrates consisting of gypsum with embedded magnetite nanoparticles. Transmission electron microscopy imaging revealed a significant reduction in the size of magnetite nanoparticles due to their dissolution, which occurred around the microbial biofilms. Concurrently, hematite was detected, likely from the oxidation of the magnetite nanoparticles. Higher cell counts and production of siderophores were observed in cultures with magnetite nanoparticles suggesting that cyanobacteria were actively acquiring iron from the magnetite nanoparticles. Magnetite dissolution and iron acquisition by the cyanobacteria was further confirmed using large bulk magnetite crystals, uncovering a survival strategy of cyanobacteria in these extreme environments.

In response to Wierzchos et al. (1) regarding the mechanism of water extraction from gypsum rock by desert colonizing microorganisms (2), we provide details that refute their incorrect assessments. We carefully selected areas without microorganism colonies that only contained gypsum, as confirmed by X-ray diffraction (XRD), for our culture experiments. Raman is useful for localized analysis of phase on surfaces, but here, it is complementary to XRD, which provides sample-wide detection (3, 4). Furthermore, selected area electron diffraction (SAED) confirms anhydrite, exhibiting arcs at 0.347 ± 0.003 nm and 0.278 ± 0.002 nm [(200) and (211) planes, respectively] with a [01−1] zone axis (Fig. 1 A and B ). The closest reflection for gypsum, the (130) plane, was not observed. SAED and fast Fourier transform (FFT) show twofold symmetry of the arcs, while the gypsum (130) plane exhibits fourfold symmetry, which was not observed. Finally, the crystal morphology of gypsum (monoclinic) was observably different from anhydrite (orthorhombic) (Fig. 1 C − F ). Thus, XRD, high-resolution … [↵][1]1To whom correspondence may be addressed. Email: david.k{at}uci.edu. [1]: #xref-corresp-1-1

The semicrystalline protein structure and impressive mechanical properties of major ampullate (MA) spider silk make it a promising natural alternative to polyacrylonitrile (PAN) fibers for carbon fiber manufacture. However, when annealed using a similar procedure to carbon fiber production, the tensile strength and Young’s modulus of MA silk decrease. Despite this, MA silk fibers annealed at 600 °C remain stronger and tougher than similarly annealed PAN but have a lower Young’s modulus. Although MA silk and PAN graphitize to similar extents, annealing disrupts the hydrogen bonding that controls crystal alignment within MA silk. Consequently, unaligned graphite crystals form in annealed MA silk, causing it to weaken, while graphite crystals in PAN maintain alignment along the fiber axis, strengthening the fibers. These shortcomings of spider silk when annealed provide insights into the selection and design of future alternative carbon fiber precursors.

Dickinsonia is one of the oldest macroscopic metazoans in the fossil record. Determining the biological characters of this extinct taxon is critical to our understanding of the early evolution of life. Preservation of abundant specimens from the Ediacara Member (Rawnsley Quartzite), South Australia, in a variety of taphonomic states allows the unparalleled opportunity to compare the biomechanical responses of Dickinsonia tissue to various forces with those typical of modern organisms. Dickinsonia are found as lifted, transported, folded, rolled, ripped, and expanded or contracted individuals, while maintaining diagnostic morphology. This suite of characters indicates that Dickinsonia was composed of material that was flexible, difficult to rip, and capable of elastic and plastic deformation. While none of these traits are diagnostic of a single biomaterial component, we find many similarities with modern biopolymers, particularly collagen, keratin, and elastin. Maintenance of significant relief following complete tearing suggests that Dickinsonia was composed of relatively thick tissues, signifying higher oxygen requirements than previously hypothesized. The ability to be transported and still be preserved as recognizable fossils is unique amongst the Ediacara Biota and demonstrates that Dickinsonia was a taphonomic elite. Combined with discovery in multiple environmental settings, this indicates that the absence of Dickinsonia represents the likely extinction of this organism prior to the Nama assemblage, possibly due to a decrease in the global availability of oxygen in the latest Ediacaran.

The equine hoof has been considered as an efficient energy absorption layer that protects the skeletal elements from impact when galloping. In the present study, the hierarchical structure of a fresh equine hoof wall and the energy absorption mechanisms are investigated. Tubules are found embedded in the intertubular matrix forming the hoof wall at the microscale. Both tubules and intertubular areas consist of keratin cells, in which keratin crystalline intermediate filaments (IFs) and amorphous keratin fill the cytoskeletons. Cell sizes, shapes and IF fractions are different between tubular and intertubular regions. The structural differences between tubular and intertubular areas are correlated to the mechanical behavior of this material tested in dry, fresh and fully hydrated conditions. The stiffness and hardness in the tubule areas are higher than that in the intertubular areas in the dry and fresh samples when loaded along the hoof wall; however, once the samples are fully hydrated, the intertubular areas become stiffer than the tubular areas due to higher water absorption in these regions. The compression behavior of hoof in different loading speed and directions are also examined, with the isotropy and strain-rate dependence of mechanical properties documented. In the hoof walls, mechanistically the tubules serve as a reinforcement, which act to support the entire wall and prevent catastrophic failure under compression and impact loading. Elastic buckling and cracking of the tubules are observed after compression along the hoof wall, and no shear-banding or severe cracks are found in the intertubular areas even after 60% compression, indicating the highly efficient energy absorption properties, without failure, of the hoof wall structure. STATEMENT OF SIGNIFICANCE: The equine hoof wall is found to be an efficient energy absorbent natural polymer composite. Previous studies showed the microstructure and mechanical properties of the hoof wall in some perspective. However, the hierarchical structure of equine hoof wall from nano- to macro-scale as well as the energy absorption mechanisms at different strain rates and loading orientations remains unclear. The current study provides a thorough characterization of the hierarchical structure as well as the correlation between structure and mechanical behaviors. Energy dissipation mechanisms are also identified. The findings in the current research could provide inspirations on the designs of impact resistant and energy absorbent materials.

Beetles possess a set of highly modified and tanned forewings, elytra, which are lightweight yet rigid and tough. Immediately after eclosion, the elytra are initially thin, pale and soft. However, they rapidly expand and subsequently become hardened and often dark, resulting from both pigmentation and sclerotization. Here, we identified changes in protein composition during the developmental processes of the elytra in the Japanese rhinoceros beetle, Trypoxylus dichotomus. Using mass spectrometry, a total of 414 proteins were identified from both untanned and tanned elytra, including 31 cuticular proteins (CPs), which constitute one of the major components of insect cuticles. Moreover, CPs containing Rebers and Riddiford motifs (CPR), the most abundant CP family, were separated into two groups based on their expression and amino acid sequences, such as a Gly-rich sequence region and Ala-Ala-Pro repeats. These protein groups may play crucial roles in elytra formation at different time points, likely including self-assembly of chitin nanofibers that control elytral macro and microstructures and dictate changes in other properties (i.e., mechanical property). Clarification of the protein functions will enhance the understanding of elytra formation and potentially benefit the development of lightweight materials for industrial and biomedical applications. STATEMENT OF SIGNIFICANCE: The beetle elytron is a light-weight natural bio-composite which displays high stiffness and toughness. This structure is composed of chitin fibrils and proteins, some of which are responsible for architectural development and hardening. This work, which involves insights from molecular biology and materials science, investigated changes in proteomic, architectural, and localized mechanical characteristics of elytra from the Japanese rhinoceros beetle to understand molecular mechanisms driving elytra development. In the present study, we identified a set of new protein groups which are likely related to the structural development of elytra and has potential for new pathways for processing green materials.

Genetic analysis of single-cells is widely recognized as a powerful tool for understanding cellular heterogeneity and obtaining genetic information from rare populations. Recently, many kinds of single-cell isolation systems have been developed to facilitate single-cell genetic analysis. However, these systems mainly target non-adherent cells or cells in a cell suspension. Thus, it is still challenging to isolate single-adherent cells of interest from a culture dish using a microscope. We had previously developed a single-cell isolation technique termed "gel-based cell manipulation" (GCM). In GCM, single-cells could be visualized by photopolymerizable-hydrogel encapsulation that made it easier to isolate the single-cells. In this study, GCM-based isolation of single-adherent cancer cells from a culture dish was demonstrated. Single-adherent cells were encapsulated in a photopolymerizable hydrogel using a microscope and isolated with high efficiency. Furthermore, whole genome amplification and sequencing for the isolated single-adherent cell could be achieved. We propose that the GCM-based approach demonstrated in this study has the potential for efficient analysis of single-adherent cells at the genetic level.

We report the biological synthesis of titania that is integrated into the silica-based cell walls of a titanium-resistant diatom, Fistulifera solaris. Titania is deposited across the diatom cell wa...

To survive in terrestrial and aquatic environments, spiders often rely heavily on their silk. The vast majority of silks that have been studied are from orb-web or cob-web weaving species, leaving the silks of water-associated spiders largely undescribed. We characterize transcripts, proteins, and silk fibres from the semi-aquatic spider Dolomedes triton. From silk gland RNAseq libraries, we report 18 silk transcripts representing four categories of known silk protein types: aciniform, ampullate, pyriform, and tubuliform. Proteomic and structural analyses (scanning electron microscopy, energy dispersive X-ray spectrometry, contact angle) of the D. triton submersible egg sac reveal similarities to silks from aquatic caddisfly larvae. We identified two layers in D. triton egg sacs, notably a highly hydrophobic outer layer with a different elemental composition compared to egg sacs of terrestrial spiders. These features may provide D. triton egg sacs with their water repellent properties.

The Bouligand structure in some arthropods is a hierarchical composite comprised of a helicoidal arrangement of strong fibers in a weak matrix. In this study, we focus on the Bouligand structure present in the dactyl club of the smashing mantis shrimp due to its exceptional capability to withstand repetitive high-energy impact without catastrophic failure. We carry out a combined computational and experimental approach to investigate the high damage resistance of the Bouligand structure through a biomimetic composite material. This is studied by performing specific fracture experiments on the helicoidal composites specimens, where it was found that crack twisting, driven by the fiber architecture, is the main fracture mechanisms. This crack twisting mechanism competes with other alternative mechanisms such as crack branching and delamination, delaying catastrophic failure. The main mechanism of crack twisting is studied through specifically designed specimens in which the crack propagation path is controlled. Further quantification of the toughening mechanisms and crack growth rate is analyzed with analytical and finite element models. The biomimetic helicoidal composites are shown to have improved fracture resistance as the crack twists mainly driven by the increase in crack surface area and fracture mode mixity. Our analysis allowed us to study the effect of crack front shape, stress distribution and energy dissipation mechanisms.

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

This paper explores whether the photochromic reaction of a molecule embedded in a polymer film can affect its surface adhesion properties, as measured by shear strength and delamination in water. The adherence of polystyrene (PS) to glass was chosen as a model system. Two commercially available photochromes—a spiropyran derivative 1′,3′-dihydro-1′,3′,3′-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2′-(2H)-indole]) (SP) and a diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene (DAE)—are studied in detail. Both photochromic reactions can significantly enhance the adhesion of PS to a glass surface. The most dramatic results were obtained for PS/SP films, whose shear strength increased by a factor of 7 while the delamination rate was suppressed by at least 2 orders of magnitude after exposure to UV light. The enhanced polymer adhesion could only be partially reversed, even after extended exposure to visible light completely regenerated the UV-absorbing isomer. Na...

Gastropods shells have evolved to resist the threat of increasingly stronger predators that smash, peal, and crush their shells. Their shells are most commonly constructed from a crossed lamellar microstructure, which consists of an exquisitely architected arrangement of aragonitic mineral and organic encompassing at least four orders of hierarchy. It is this careful control of mineral and organic placement within the entire crossed lamellar structure that yields a four-order of magnitude increase in fracture toughness versus abiotic aragonite. We investigated the effect of differing microstructural orientations on their influence of inter-3rd order lamellar fracture behavior using nanoindentation from the inner layer of the Strombus gigas shell. We observed a significant influence of lamella (plank) orientation and nanoindenter probe on the mechanical properties. The ±45° arrangement of mineral planks found within biological crossed lamellar composites provides a significant enhancement of isotropic resistance to penetration by sharp objects such as jaws and claws. In addition, the ±45° arrangement is able to resist higher loads before failure. This combination of features from the crossed lamellar architecture helped enable species with this shell structure to survive predation for hundreds of millions of years and will also help provide insights into designs of future generations of composites.

Nature utilizes the available resources to construct lightweight, strong and tough materials under constrained environmental conditions. The impact surface of the fast-striking dactyl club from the mantis shrimp is an example of one such composite material; the shrimp has evolved the capability to localize damage and avoid catastrophic failure from high-speed collisions during its feeding activities. Here we report that the dactyl club of mantis shrimps contains an impact-resistant coating composed of densely packed (about 88 per cent by volume) ~65-nm bicontinuous nanoparticles of hydroxyapatite integrated within an organic matrix. These mesocrystalline hydroxyapatite nanoparticles are assembled from small, highly aligned nanocrystals. Under impacts of high strain rates (around 104 s−1), particles rotate and translate, whereas the nanocrystalline networks fracture at low-angle grain boundaries, form dislocations and undergo amorphization. The interpenetrating organic network provides additional toughening, as well as substantial damping, with a loss coefficient of around 0.02. An unusual combination of stiffness and damping is therefore achieved, outperforming many engineered materials. A coating made from densely packed hydroxyapatite particles in an organic matrix endows the dactyl club of mantis shrimps with high stiffness and energy damping.

Joining dissimilar materials such as plastics and metals in engineered structures remains a challenge

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., atomic- to 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.

Nanostructured amorphous silica in rice plants (biosilica or plant opal) plays an important role in plant growth related to food production. However, the same silica has a structural supporting role as well that has not been uncovered. The current study focuses on the structural design of the two main types of biosilicas in rice plants for the improvement of their mechanical properties. One structural motif is plate-like silicas, which cover most of the surfaces of leaf blades. Another is fan-shaped silicas, which are aligned inside leaf blades, providing a stiff backbone. These biosilica structures consist of 10–100 nm diameter nanoparticles. The mechanical properties, such as hardness and Young's modulus, of the biosilicas are associated with their relative density. Thus, the rice plant mechanics is inferred to be designed by changing the packing of the nanoparticles. Silica plates consisting of loosely packed particles have relatively low density and high flexibility enabling coverage of leaf blade surfaces, while fan-shaped silicas, which consist of tightly packed nanoparticles, are rigid to support the leaf blades as a backbone.

The remarkable mechanical properties observed in biological composite materials relative to those of their individual constituents distinguish them from common engineering materials. Some naturally occurring high-performance ceramics, like the external veneer of the Chiton ( Cryptochiton stelleri ) tooth, have been shown to have superior hardness and impressive abrasion resistance properties. The mechanical performance of the chiton tooth has been attributed to a hierarchical arrangement of nanostructured magnetite rods surrounded with organic material. While nanoindentation tests provide useful information about the overall performance of this biological composite, understanding the key microstructural features and energy dissipation mechanisms at small scales remains a challenging task. We present a combined experimental/numerical approach to elucidate the role of material deformation in the rods, debonding at the rod interfaces and the influence of energy dissipation mechanisms on the ability of the microstructure to distribute damage under extreme loading conditions. We employ a 3D finite element-based micromechanical model to simulate the nanoindentation tests performed in geological magnetite and cross-sections of the chiton tooth. This proposed model is capable of capturing the inelastic deformation of the rods and the failure of their interfaces, while damage, fracture and fragmentation of the mineralized rods is assessed using a probabilistic function. Our results show that these natural materials achieve their abrasion resistant properties by controlling the interface strength between rods, alleviating the tensile stress on the rods near the indentation tip and therefore decreasing the probability of catastrophic failure without significantly sacrificing resistance to penetration. The understanding of these competing energy dissipating mechanisms provides a path to the prediction of new combination of materials. In turns, these results suggest certain guidelines for abrasion resistance rod-like microstructures in composites with high volume fraction of brittle minerals or ceramics with tailored performance for specific applications.

Chitons are herbivorous invertebrates that use rows of ultrahard magnetite-based teeth connected to a flexible belt (radula) to rasp away algal deposits growing on and within rocky outcrops along coastlines around the world. Each tooth is attached to the radula by an organic structure (stylus) that provides mechanical support during feeding. However, the underlying structures within the stylus, and their subsequent function within the chiton have yet to be investigated. Here, we investigate the macrostructural architecture, the regional material and elemental distribution and subsequent nano-mechanical properties of the stylus from the Northern Pacific dwelling Cryptochiton stelleri. Using a combination of μ-CT imaging, optical and electron microscopy, as well as elemental analysis, we reveal that the stylus is a highly contoured tube, mainly composed of alpha-chitin fibers, with a complex density distribution. Nanoindentation reveals regiospecific and graded mechanical properties that can be correlated with both the elemental composition and material distribution. Finite element modeling shows that the unique macroscale architecture, material distribution and elemental gradients have been optimized to preserve the structural stability of this flexible, yet robust functionally-graded fiber-reinforced composite tube, providing effective function during rasping. Understanding these complex fiber-based structures offers promising blueprints for lightweight, multifunctional and integrated materials.

This study investigates UV irradiation-induced cell settling, followed by cell aggregation, of the oleaginous diatom Fistulifera solaris. Cell settling was observed after 24 h of cultivation following UV irradiation. The highest cell settling rate was obtained at a light intensity of 10 mJ/cm2. The cell settling was induced by irradiating with UV (254 nm), but was ineffective with light of other wavelengths (474 or 620 nm). The settling response was not observed in other microalgae, such as Chlamydomonas reinhardtii and Phaeodactylum tricornutum, with the same treatment, suggesting that this response was specific to F. solaris. The optical and SEM images revealed the occurrence of cell aggregation with the UV treatment, resulting in the subsequent cell settling. Although there was no significant change in the lipid, protein, and sugar content, secreted acidic polysaccharide was found in the F. solaris cell culture following UV irradiation. Therefore, this polysaccharide was considered likely to be the cell aggregation-inducing factor. The energy consumption of this UV-induced cell settling for cell recovery method was estimated to be approximately 0.77 × 10−1 kWh/m3, which is lower than the energy consumption of existing methods. Therefore, this method could be applied for harvesting F. solaris cells from large-scale cultures.

Uniform TiO2 nanospheres from hollow, core–shell and mesoporous structures have been synthesized using quasi-nano-sized carbonaceous spheres as templates. The TiO2 nanospheres formed after calcination at 400 °C are composed of ∼7 nm nanoparticles and the shells of the hollow TiO2 nanospheres are as thin as a single layer of nanoparticles. The ultrafine nanoparticles endow the hollow and mesoporous TiO2 nanospheres with short lithium ion diffusion paths leading to high discharge specific capacities of 211.9 and 196.0 mA h g−1 at a current rate of 1 C (167.5 mA g−1) after 100 cycles, and especially superior discharge specific capacities of 125.9 and 113.4 mA h g−1 at a high current rate of up to 20 C. The hollow and mesoporous TiO2 nanospheres also show superior cycling stability with long-term discharge capacities of 103.0 and 110.2 mA h g−1, respectively, even after 3000 cycles at a current rate of 20 C.

Wave propagation was investigated in the Bouligand-like structure from within the dactyl club of the Stomatopod, a crustacean that is known to smash their heavily shelled preys with high accelerations. We incorporate the layered nature in a unitary material cell through the propagator matrix formalism while the periodic nature of the material is considered via Bloch boundary conditions as applied in the theory of solid state physics. Our results show that these materials exhibit bandgaps at frequencies related to the stress pulse generated by the impact of the dactyl club to its prey, and therefore exhibiting wave filtering in addition to the already known mechanisms of macroscopic isotropic behavior and toughness., 19 pages, 7 figures, In press, Acta Biomaterialia (2015)

Identifying the most appropriate polymorph of active pharmaceutical ingredients is one of the important steps in drug development, since their bioactivities are largely dependent on their solid forms. However, the sample preparation for the characterization of crystal forms is time-consuming and requires large quantities of sample. Here, we introduce a microfluidic device-based method to prepare a sub-millimeter-sized single aspirin crystal from a small quantity of material. For the crystal preparation, a device equipped with a solution flow system and temperature controller was placed under the microscope. To use the device, concentration–temperature phase diagrams were generated, and regions where dominant nucleation or crystal growth with specific directions were clearly determined. By observing time-dependent changes of crystal number and size with solution temperature, a pathway to grow a single crystal of aspirin was determined and applied to prepare a sub-millimeter-sized crystal from 250 μg of asp...

Many biomineralized organisms have evolved highly oriented nanostructures to perform specific functions. One key example is the abrasion-resistant rod-like microstructure found in the radular teeth of Chitons (Cryptochiton stelleri), a large mollusk. The teeth consist of a soft core and a hard shell that is abrasion resistant under extreme mechanical loads with which they are subjected during the scraping process. Such remarkable mechanical properties are achieved through a hierarchical arrangement of nanostructured magnetite rods surrounded with α-chitin. We present a combined biomimetic approach in which designs were analyzed with additive manufacturing, experiments, analytical and computational models to gain insights into the abrasion resistance and toughness of rod-like microstructures. Staggered configurations of hard hexagonal rods surrounded by thin weak interfacial material were printed, and mechanically characterized with a cube-corner indenter. Experimental results demonstrate a higher contact resistance and stiffness for the staggered alignments compared to randomly distributed fibrous materials. Moreover, we reveal an optimal rod aspect ratio that lead to an increase in the site-specific properties measured by indentation. Anisotropy has a significant effect (up to 50%) on the Young's modulus in directions parallel and perpendicular to the longitudinal axis of the rods, and 30% on hardness and fracture toughness. Optical microscopy suggests that energy is dissipated in the form of median cracks when the load is parallel to the rods and lateral cracks when the load is perpendicular to the rods. Computational models suggest that inelastic deformation of the rods at early stages of indentation can vary the resistance to penetration. As such, we found that the mechanical behavior of the system is influenced by interfacial shear strain which influences the lateral load transfer and therefore the spread of damage. This new methodology can help to elucidate the evolutionary designs of biomineralized microstructures and understand the tolerance to fracture and damage of chiton radular teeth.

The denticle caps of chiton teeth exhibit the largest hardness and stiffness among any biological minerals in the world. They consist of a composite structure of highly oriented crystalline nanorods of magnetite surrounded by a veneer of organic. The ultrahard teeth of the chiton are the first reported example of biologically formed magnetite, and its formation mechanisms have been of great interest to researchers for decades. Recently, using modern nanomechanical characterization techniques, it was shown that chiton teeth exhibit the largest hardness and stiffness of any biological mineral. The predicted abrasion resistance of chiton teeth against a blunt contact was reported to be even higher than that of zirconia. Therefore, the elucidation of chiton teeth synthetic processes could help us learn how to develop novel abrasion-resistant materials and environmentally benign processes for the production of iron oxides and other nanostructured materials. In order to understand the chiton teeth formation, proteomic analyses of tooth proteins as well as detailed structural analyses of mature and developing teeth were conducted. Based on the results obtained from these analyses, we discuss the underlying mechanisms of iron oxide biomineralization in chiton teeth.

Woodpeckers peck at trees without any reported brain injury despite undergoing high impact loads. Amongst the adaptations allowing this is a highly functionalized impact-absorption system consisting of the head, beak, tongue and hyoid bone. This study aims to examine the anatomical structure, composition, and mechanical properties of the skull to determine its potential role in energy absorption and dissipation. An acorn woodpecker and a domestic chicken are compared through micro-computed tomography to analyze and compare two- and three-dimensional bone morphometry. Optical and scanning electron microscopy with energy dispersive X-ray spectroscopy are used to identify the structural and chemical components. Nanoindentation reveals mechanical properties along the transverse cross-section, normal to the direction of impact. Results show two different strategies: the skull bone of the woodpecker shows a relatively small but uniform level of closed porosity, a higher degree of mineralization, and a higher cortical to skull bone ratio. Conversely, the chicken skull bone shows a wide range of both open and closed porosity (volume fraction), a lower degree of mineralization, and a lower cortical to skull bone ratio. This structural difference affects the mechanical properties: the skull bones of woodpeckers are slightly stiffer than those of chickens. Furthermore, the Young's modulus of the woodpecker frontal bone is significantly higher than that of the parietal bone. These new findings may be useful to potential engineered design applications, as well as future work to understand how woodpeckers avoid brain injury.

Highly oriented epitaxial rutile titanium dioxide (TiO

The Bouligand structure, which is found in many biological materials, is a hierarchical architecture that features uniaxial fiber layers assembled periodically into a helicoidal pattern. Many studies have highlighted the high damage-resistant performance of natural and biomimetic Bouligand structures. One particular species that utilizes the Bouligand structure to achieve outstanding mechanical performance is the smashing Mantis Shrimp, Odontodactylus Scyllarus (or stomatopod). The mantis shrimp generates high speed, high acceleration blows using its raptorial appendage to defeat highly armored preys. The load-bearing part of this appendage, the dactyl club, contains an interior region [16] that consists of a Bouligand structure. This region is capable of developing a significant amount of nested twisting microcracks without exhibiting catastrophic failure. The development and propagation of these microcracks are a source of energy dissipation and stress relaxation that ultimately contributes to the remarkable damage tolerance properties of the dactyl club. We develop a theoretical model to provide additional insights into the local stress intensity factors at the crack front of twisting cracks formed within the Bouligand structure. Our results reveal that changes in the local fracture mode at the crack front leads to a reduction of the local strain energy release rate, hence, increasing the necessary applied energy release rate to propagate the crack, which is quantified by the local toughening factor. Ancillary 3D simulations of the asymptotic crack front field were carried out using a J-integral to validate the theoretical values of the energy release rate and the local stress intensity factors.

We have investigated the effects of crystal structure and size of Li[Ni1/3Co1/3Mn1/3]O2 (L333) cathodes on the performance of lithium-ion batteries. Cation ordering and particle sizes were determined as a function of annealing temperature with subsequent electrochemical performance monitored by cyclic voltammetry (CV) and charge–discharge testing. With increasing annealing temperature, L333 exhibits a greater cation ordering, which subsequently benefitted cell performance. However, higher annealing temperatures yielded larger crystal sizes, which resulted in a decrease in high rate discharge capacity and a significant capacity fade. This is attributed to an increase in lattice parameter and volume expansion during cycling, with the largest crystal sizes displaying the most significant structural changes due to the lower strain accommodation.

We report the synthesis of ultrathin carbon coatings on polycrystalline LiFePO4 via solution deposition and subsequent annealing. The annealing temperature was systematically investigated with polymer systems on LiFePO4 nanostructures. The crystal structures, sizes, and morphologies were monitored and analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Micro-Raman and TEM were used to interrogate the carbon coatings after heat-treatments. Electrochemical performance of coated materials was investigated by cyclic voltammograms (CVs) and galvanostatic charge–discharge analysis. The olivine structured LiFePO4 remained stable up to 600 °C but underwent a rapid reduction reaction from LiFePO4 to Fe2P above 700 °C. The good compatibility between polyethylene glycol (PEG) and the surface of LiFePO4 enabled the formation of core–shell structure, which was transformed into a thin carbon coating on LiFePO4 after annealing. Both PEG and sucrose carbon-based sources yielded high-quality carbon...

Four fluorinated derivatives of 9-anthracene carboxylic acid (9AC), a molecule that shows a reversible photomechanical response in its crystal form, have been synthesized and characterized. The spectroscopic properties and crystal structures of 4-fluoro-9-anthracene carboxylic acid (4F-9AC), 2-fluoro-9-anthracene carboxylic acid (2F-9AC), 10-fluoro-9-anthracene carboxylic acid (10F-9AC), and 2,6-difluoro-9-anthracene carboxylic acid (2,6DF-9AC) are all very similar to those of 9AC. However, their photomechanical properties vary widely. 405 nm light was used to induce [4 + 4] photodimerization and a mechanical response in crystalline microneedles and ribbons. Both the photodimer dissociation rate and the mechanical recovery varied by more than an order of magnitude, with 4F-9AC exhibiting the most rapid recovery time, on the order of 30 s. Nanoindentation measurements show that this crystal has a slightly reduced elastic modulus and a significantly reduced hardness, making it less brittle than the 9AC crys...

Chiton are marine mollusks who use heavily mineralized and ultrahard teeth to feed on epilithic and endolithic algae on intertidal rocks. To fulfi ll this function, chiton teeth must be tough and wear-resistant. Impressive mechanical properties are achieved in the chiton tooth through a hierarchically arranged composite structure consisting of a hard shell of organic-encased and highly oriented nanostructured magnetite rods that surround a soft core of organicrich iron phosphate. Microscopic and spectroscopic analyses combined with fi nite element simulations are used to probe the ultrastructural features and uncover structure‐mechanical property relationships in the fully mineralized teeth of the gumboot chiton Cryptochiton stelleri . By understanding the effects of the nanostructured architecture within the chiton tooth, abrasionresistant materials can be developed for tooling and machining applications, as well as coatings for equipment and medical implants.

Over millions of years, the crustacean exoskeleton has evolved into a rigid, tough, and complex cuticle that is used for structural support, mobility, protection of vital organs, and defense against predation. The crustacean cuticle is characterized by a hierarchically arranged chitin fiber scaffold, mineralized predominately by calcium carbonate and/or calcium phosphate. The structural organization of the mineral and organic within the cuticle occurs over multiple length scales, resulting in a strong and tough biological composite. Here, the ultrastructural details observed in three species of crustacean are reviewed: the American lobster (Homarus americanus), the edible crab (Cancer pagurus), and the peacock mantis shrimp (Odontodactylus scyllarus). The Review concludes with a discussion of recent advances in the development of biomimetics with controlled organic scaffolding, mineralization, and the construction of nanoscale composites, inspired by the organization and formation of the crustacean cuticle.