Nano-ZnO-modified hydroxyapatite whiskers with enhanced osteoinductivity for bone defect repair.

Hydroxyapatite (HA) whisker (HAw) represents a distinct form of HA characterized by its high aspect ratio, offering significant potential for enhancing the mechanical properties of bone tissue engineering scaffolds. However, the limited osteoinductivity of HAw hampers its widespread application. In this investigation, we observed HAw-punctured osteoblast membranes and infiltrated the cell body, resulting in mechanical damage to cells that adversely impacted osteoblast proliferation and differentiation. To address this challenge, we developed nano-zinc oxide particle-modified HAw (nano-ZnO/HAw). Acting as a reinforcing and toughening agent, nano-ZnO/HAw augmented the compressive strength and ductility of the matrix materials. At the same time, the surface modification with nano-ZnO particles improved osteoblast differentiation by reducing the mechanical damage from HAw to cells and releasing zinc ion, the two aspects collectively promoted the osteoinductivity of HAw. Encouragingly, the osteoinductive potential of 5% nano-ZnO/HAw and 10% nano-ZnO/HAw was validated in relevant rat models, demonstrating the efficacy of this approach in promoting new bone formation in vivo. Our findings underscore the role of nano-ZnO particle surface modification in enhancing the osteoinductivity of HAw from a physical standpoint, offering valuable insights into the development of bone substitutes with favorable osteoinductive properties while simultaneously bolstering matrix material strength and toughness.

3D printed zirconia used as dental materials: a critical review.

In view of its high mechanical performance, outstanding aesthetic qualities, and biological stability, zirconia has been widely used in the fields of dentistry. Due to its potential to produce suitable advanced configurations and structures for a number of medical applications, especially personalized created devices, ceramic additive manufacturing (AM) has been attracting a great deal of attention in recent years. AM zirconia hews out infinite possibilities that are otherwise barely possible with traditional processes thanks to its freedom and efficiency. In the review, AM zirconia's physical and adhesive characteristics, accuracy, biocompatibility, as well as their clinical applications have been reviewed. Here, we highlight the accuracy and biocompatibility of 3D printed zirconia. Also, current obstacles and a forecast of AM zirconia for its development and improvement have been covered. In summary, this review offers a description of the basic characteristics of AM zirconia materials intended for oral medicine. Furthermore, it provides a generally novel and fundamental basis for the utilization of 3D printed zirconia in dentistry.

Biodegradability and Cytocompatibility of 3D-Printed Mg-Ti Interpenetrating Phase Composites.

Orthopedic hybrid implants combining both titanium (Ti) and magnesium (Mg) have gained wide attraction nowadays. However, it still remains a huge challenge in the fabrication of Mg-Ti composites because of the different temperatures of Ti melting point and pure Mg volatilization point. In this study, we successfully fabricated a new Mg-Ti composite with bi-continuous interpenetrating phase architecture by infiltrating Mg melt into Ti scaffolds, which were prepared by 3D printing and subsequent acid treatment. We attempted to understand the 7-day degradation process of the Mg-Ti composite and examine the different Mg2+ concentration composite impacts on the MC3T3-E1 cells, including toxicity, morphology, apoptosis, and osteogenic activity. CCK-8 results indicated cytotoxicity and absence of the Mg-Ti composite during 7-day degradation. Moreover, the composite significantly improved the morphology, reduced the apoptosis rate, and enhanced the osteogenic activity of MC3T3-E1 cells. The favorable impacts might be attributed to the appropriate Mg2+ concentration of the extracts. The results on varying Mg2+ concentration tests indicated that Mg2+ showed no cell adverse effect under 10-mM concentration. The 8-mM group exhibited the best cell morphology, minimum apoptosis rate, and maximum osteogenic activity. This work may open a new perspective on the development and biomedical applications for Mg-Ti composites.

On the damage tolerance of 3-D printed Mg-Ti interpenetrating-phase composites with bioinspired architectures.

Bioinspired architectures are effective in enhancing the mechanical properties of materials, yet are difficult to construct in metallic systems. The structure-property relationships of bioinspired metallic composites also remain unclear. Here, Mg-Ti composites were fabricated by pressureless infiltrating pure Mg melt into three-dimensional (3-D) printed Ti-6Al-4V scaffolds. The result was composite materials where the constituents are continuous, mutually interpenetrated in 3-D space and exhibit specific spatial arrangements with bioinspired brick-and-mortar, Bouligand, and crossed-lamellar architectures. These architectures promote effective stress transfer, delocalize damage and arrest cracking, thereby bestowing improved strength and ductility than composites with discrete reinforcements. Additionally, they activate a series of extrinsic toughening mechanisms, including crack deflection/twist and uncracked-ligament bridging, which enable crack-tip shielding from the applied stress and lead to "Γ"-shaped rising fracture resistance R-curves. Quantitative relationships were established for the stiffness and strengths of the composites by adapting classical laminate theory to incorporate their architectural characteristics.

Cytotoxicity and Bonding Property of Bioinspired Nacre-like Ceramic-Polymer Composites.

For clinical applications, non-cytotoxicity and good bonding property of dental restorative materials are the most essential and important. The aim of this study was to evaluate the potential for clinical applications of two novel bioinspired nacre-like ceramic (yttria-stabilized zirconia)-polymer (polymethyl methacrylate) composites in terms of the cytotoxicity and bonding property. The relative growth rates (24 h) of the Lamellar and Brick-and-mortar composites measured by CCK8 were 102.93%±0.04 and 98.91%±0.03, respectively. According to the results of cytotoxicity and proliferation experiments, the two composites were not cytotoxic to human periodontal ligament fibroblasts (HPDLFs) in vitro. Both composites exhibited improved bonding strength as compared to the Control group (Vita In-Ceram YZ). As the polymer content in the composite material increases, its bonding strength also increases, which enhances the application potential of the material in the field of dental restoration. Meanwhile, by controlling the direction of loading force in the shear test, the effect of microstructure on the bonding strength of anisotropic composites was studied. After sandblasted, the bonding strengths of the Lamellar group in the longitudinal and transverse shear directions were 17.56±1.56 MPa and 18.67±1.92 MPa, respectively, while of the Brick-and-mortar group were 16.36±1.30 MPa and 16.99±1.67 MPa, respectively. The results showed that the loading direction had no significant effect on the bonding strength of the composites.

An Amorphous Peri-Implant Ligament with Combined Osteointegration and Energy-Dissipation.

Progress toward developing metal implants as permanent hard-tissue substitutes requires both osteointegration to achieve load-bearing support, and energy-dissipation to prevent overload-induced bone resorption. However, in existing implants these two properties can only be achieved separately. Optimized by natural evolution, tooth-periodontal-ligaments with fiber-bundle structures can efficiently orchestrate load-bearing and energy dissipation, which make tooth-bone complexes survive extremely high occlusion loads (>300 N) for prolonged lifetimes. Here, a bioinspired peri-implant ligament with simultaneously enhanced osteointegration and energy-dissipation is presented, which is based on the periodontium-mimetic architecture of a polymer-infiltrated, amorphous, titania nanotube array. The artificial ligament not only provides exceptional osteoinductivity owing to its nanotopography and beneficial ingredients, but also produces periodontium-similar energy dissipation due to the complexity of the force transmission modes and interface sliding. The ligament increases bone-implant contact by more than 18% and simultaneously reduces the effective stress transfer from implant to peri-implant bone by ≈30% as compared to titanium implants, which as far as is known has not previously been achieved. It is anticipated that the concept of an artificial ligament will open new possibilities for developing high-performance implanted materials with increased lifespans.

Wood-Inspired Cement with High Strength and Multifunctionality.

Taking lessons from nature offers an increasing promise toward improved performance in man-made materials. Here new cement materials with unidirectionally porous architectures are developed by replicating the designs of natural wood using a simplified ice-templating technique in light of the retention of ice-templated architectures by utilizing the self-hardening nature of cement. The wood-like cement exhibits higher strengths at equal densities than other porous cement-based materials along with unique multifunctional properties, including effective thermal insulation at the transverse profile, controllable water permeability along the vertical direction, and the easy adjustment to be water repulsive by hydrophobic treatment. The strengths are quantitatively interpreted by discerning the effects of differing types of pores using an equivalent element approach. The simultaneous achievement of high strength and multifunctionality makes the wood-like cement promising for applications as new building materials, and verifies the effectiveness of wood-mimetic designs in creating new high-performance materials. The simple fabrication procedure by omitting the freeze-drying treatment can also promote a better efficiency of ice-templating technique for the mass production in engineering and may be extended to other material systems.

3D printed Mg-NiTi interpenetrating-phase composites with high strength, damping capacity, and energy absorption efficiency.

It is of significance, but still remains a key challenge, to simultaneously enhance the strength and damping capacities in metals, as these two properties are often mutually exclusive. Here, we provide a multidesign strategy for defeating such a conflict by developing a Mg-NiTi composite with a bicontinuous interpenetrating-phase architecture through infiltration of magnesium melt into three-dimensionally printed Nitinol scaffold. The composite exhibits a unique combination of mechanical properties with improved strengths at ambient to elevated temperatures, remarkable damage tolerance, good damping capacities at differing amplitudes, and exceptional energy absorption efficiency, which is unprecedented for magnesium materials. The shape and strength after deformation can even be largely recovered by heat treatment. This study offers a new perspective for the structural and biomedical applications of magnesium.

Interfacial toughening effect of suture structures.

Suture interfaces are one of the most common architectural designs in natural material-systems and are critical for ensuring multiple functionalities by providing flexibility while maintaining connectivity. Despite intensive studies on the mechanical role of suture structures, there is still a lack of understanding on the fracture mechanics of suture interfaces in terms of their interactions with impinging cracks. Here we reveal an interfacial toughening effect of suture structures by means of "excluding" cracks away from interfaces based on a dimensionless micro-mechanical model for single-leveled and hierarchical suture interfaces with triangular-shaped suture teeth. The effective stress-intensity driving forces for crack deflection along, versus penetration through, an interface at first impingement and on subsequent kinking are formulated and compared with the corresponding resistances. Quantitative criteria are established for discerning the cracking modes and fracture resistance of suture interfaces with their dependences on sutural tooth sharpness and interfacial toughness clarified. Additionally, the effects of structural hierarchy are elucidated through a consideration of hierarchical suture interfaces with fractal-like geometries. This study may offer guidance for designing bioinspired suture structures, especially for toughening materials where interfaces are a key weakness. STATEMENT OF SIGNIFICANCE: Suture interfaces are one of the most common architectural material designs in biological systems, and are found in a wide range of species including armadillo osteoderms, boxfish armor, pangolin scales and insect cuticles. They are designed to provide flexibility while maintaining connectivity. Despite many studies on the mechanical role of suture structures, there is still little understanding of their role in terms of interactions with impinging cracks. Here we reveal an interfacial toughening effect of suture structures by means of "excluding" cracks away from interfaces based on a dimensionless micro-mechanical model for single-leveled and hierarchical suture interfaces with triangular-shaped suture teeth. Quantitative criteria are established for discerning the cracking mode and fracture resistance of the interfaces with their dependences on sutural tooth sharpness and interfacial toughness clarified.

Nature-Inspired Nacre-Like Composites Combining Human Tooth-Matching Elasticity and Hardness with Exceptional Damage Tolerance.

Making replacements for the human body similar to natural tissue offers significant advantages but remains a key challenge. This is pertinent for synthetic dental materials, which rarely reproduce the actual properties of human teeth and generally demonstrate relatively poor damage tolerance. Here new bioinspired ceramic-polymer composites with nacre-mimetic lamellar and brick-and-mortar architectures are reported, which resemble, respectively, human dentin and enamel in hardness, stiffness, and strength and exhibit exceptional fracture toughness. These composites are additionally distinguished by outstanding machinability, energy-dissipating capability under cyclic loading, and diminished abrasion to antagonist teeth. The underlying design principles and toughening mechanisms of these materials are elucidated in terms of their distinct architectures. It is demonstrated that these composites are promising candidates for dental applications, such as new-generation tooth replacements. Finally, it is believed that this notion of bioinspired design of new materials with unprecedented biologically comparable properties can be extended to a wide range of material systems for improved mechanical performance.

Multiscale Toughening Mechanisms in Biological Materials and Bioinspired Designs.

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.

Adaptive structural reorientation: Developing extraordinary mechanical properties by constrained flexibility in natural materials.

Seeking strategies to enhance the overall combinations of mechanical properties is of great significance for engineering materials, but still remains a key challenge because many of these properties are often mutually exclusive. Here we reveal from the perspective of materials science and mechanics that adaptive structural reorientation during deformation, which is an operating mechanism in a wide variety of composite biological materials, functions more than being a form of passive response to allow for flexibility, but offers an effective means to simultaneously enhance rigidity, robustness, mechanical stability and damage tolerance. As such, the conflicts between different mechanical properties can be "defeated" in these composites merely by adjusting their structural orientation. The constitutive relationships are established based on the theoretical analysis to clarify the effects of structural orientation and reorientation on mechanical properties, with some of the findings validated and visualized by computational simulations. Our study is intended to give insight into the ingenious designs in natural materials that underlie their exceptional mechanical efficiency, which may provide inspiration for the development of new man-made materials with enhanced mechanical performance. STATEMENT OF SIGNIFICANCE: It is challenging to attain certain combinations of mechanical properties in man-made materials because many of these properties - for example, strength with toughness and stability with flexibility - are often mutually exclusive. Here we describe an effective solution utilized by natural materials, including wood, bone, fish scales and insect cuticle, to "defeat" such conflicts and elucidate the underlying mechanisms from the perspective of materials science and mechanics. We show that, by adaptation of their structural orientation on loading, composite biological materials are capable of developing enhanced rigidity, strength, mechanical stability and damage tolerance from constrained flexibility during deformation - combinations of attributes that are generally unobtainable in man-made systems. The design principles extracted from these biological materials present an unusual yet potent new approach to guide the development of new synthetic composites with enhanced combinations of mechanical properties.

Multiscale designs of the chitinous nanocomposite of beetle horn towards an enhanced biomechanical functionality.

Operating mainly as a type of weapon, the beetle horn develops an impressive mechanical efficiency based on chitinous materials to maximize the injury to opponent and simultaneously minimize the damage to itself and underlying brain under stringent loading conditions. Here the cephalic horn of the beetle Allomyrina dichotoma is probed using multiscale characterization combined with finite element simulations to explore the origins of its biomechanical functionality from the perspective of materials science. The horn is revealed to be highly regulated from the macroscopic shape, geometry, and connection with the body to the meso- and microscopic architecture, moisture content, and chemical and structural characteristics. Varying kinds of gradients are integrated at all length-scales. Such designs are demonstrated to benefit the mechanical performance by mitigating stress concentrations, retarding crack propagation, and modulating local properties to better adapt to stress. Enhanced rigidity, robustness and stability are additionally generated from the constrained flexibility endowed by the nanocomposite plywood structure through the reorientation of chitin nanofibrils within the proteinaceous matrix. These findings shed light on the intriguing materials-design strategies of nature in creating synergy of offence and persistence. They may even offer inspiration for the synthesis of high-performance materials and structures, in particular beams to resist bending and torsion.

Hydration-induced nano- to micro-scale self-recovery of the tooth enamel of the giant panda.

The tooth enamel of vertebrates comprises a hyper-mineralized bioceramic, but is distinguished by an exceptional durability to resist impact and wear throughout the lifetime of organisms; however, enamels exhibit a low resistance to the initiation of large-scale cracks comparable to that of geological minerals based on fracture mechanics. Here we reveal that the tooth enamel, specifically from the giant panda, is capable of developing durability through counteracting the early stage of damage by partially recovering its innate geometry and structure at nano- to micro- length-scales autonomously. Such an attribute results essentially from the unique architecture of tooth enamel, specifically the vertical alignment of nano-scale mineral fibers and micro-scale prisms within a water-responsive organic-rich matrix, and can lead to a decrease in the dimension of indent damage in enamel introduced by indentation. Hydration plays an effective role in promoting the recovery process and improving the indentation fracture toughness of enamel (by ∼73%), at a minor cost of micro-hardness (by ∼5%), as compared to the dehydrated state. The nano-scale mechanisms that are responsible for the recovery deformation, specifically the reorientation and rearrangement of mineral fragments and the inter- and intra-prismatic sliding between constituents that are closely related to the viscoelasticity of organic matrix, are examined and analyzed with respect to the structure of tooth enamel. Our study sheds new light on the strategies underlying Nature's design of durable ceramics which could be translated into man-made systems in developing high-performance ceramic materials. STATEMENT OF SIGNIFICANCE: Tooth enamel plays a critical role in the function of teeth by providing a hard surface layer to resist wear/impact throughout the lifetime of organisms; however, such enamel exhibits a remarkably low resistance to the initiation of large-scale cracks, of hundreds of micrometers or more, comparable to that of geological minerals. Here we reveal that tooth enamel, specifically that of the giant panda, is capable of partially recovering its geometry and structure to counteract the early stages of damage at nano- to micro-scale dimensions autonomously. Such an attribute results essentially from the architecture of enamel but is markedly enhanced by hydration. Our work discerns a series of mechanisms that lead to the deformation and recovery of enamel and identifies a unique source of durability in the enamel to accomplish this function. The ingenious design of tooth enamel may inspire the development of new durable ceramic materials in man-made systems.

On the Materials Science of Nature's Arms Race.

Biological material systems have evolved unique combinations of mechanical properties to fulfill their specific function through a series of ingenious designs. Seeking lessons from Nature by replicating the underlying principles of such biological materials offers new promise for creating unique combinations of properties in man-made systems. One case in point is Nature's means of attack and defense. During the long-term evolutionary "arms race," naturally evolved weapons have achieved exceptional mechanical efficiency with a synergy of effective offense and persistence-two characteristics that often tend to be mutually exclusive in many synthetic systems-which may present a notable source of new materials science knowledge and inspiration. This review categorizes Nature's weapons into ten distinct groups, and discusses the unique structural and mechanical designs of each group by taking representative systems as examples. The approach described is to extract the common principles underlying such designs that could be translated into man-made materials. Further, recent advances in replicating the design principles of natural weapons at differing lengthscales in artificial materials, devices and tools to tackle practical problems are revisited, and the challenges associated with biological and bioinspired materials research in terms of both processing and properties are discussed.

Enhanced protective role in materials with gradient structural orientations: Lessons from Nature.

UNLABELLED: Living organisms are adept at resisting contact deformation and damage by assembling protective surfaces with spatially varied mechanical properties, i.e., by creating functionally graded materials. Such gradients, together with multiple length-scale hierarchical structures, represent the two prime characteristics of many biological materials to be translated into engineering design. Here, we examine one design motif from a variety of biological tissues and materials where site-specific mechanical properties are generated for enhanced protection by adopting gradients in structural orientation over multiple length-scales, without manipulation of composition or microstructural dimension. Quantitative correlations are established between the structural orientations and local mechanical properties, such as stiffness, strength and fracture resistance; based on such gradients, the underlying mechanisms for the enhanced protective role of these materials are clarified. Theoretical analysis is presented and corroborated through numerical simulations of the indentation behavior of composites with distinct orientations. The design strategy of such bioinspired gradients is outlined in terms of the geometry of constituents. This study may offer a feasible approach towards generating functionally graded mechanical properties in synthetic materials for improved contact damage resistance. STATEMENT OF SIGNIFICANCE: Living organisms are adept at resisting contact damage by assembling protective surfaces with spatially varied mechanical properties, i.e., by creating functionally-graded materials. Such gradients, together with multiple length-scale hierarchical structures, represent the prime characteristics of many biological materials. Here, we examine one design motif from a variety of biological tissues where site-specific mechanical properties are generated for enhanced protection by adopting gradients in structural orientation at multiple length-scales, without changes in composition or microstructural dimension. The design strategy of such bioinspired gradients is outlined in terms of the geometry of constituents. This study may offer a feasible approach towards generating functionally-graded mechanical properties in synthetic materials for improved damage resistance.

Intrinsic hierarchical structural imperfections in a natural ceramic of bivalve shell with distinctly graded properties.

Despite the extensive investigation on the structure of natural biological materials, insufficient attention has been paid to the structural imperfections by which the mechanical properties of synthetic materials are dominated. In this study, the structure of bivalve Saxidomus purpuratus shell has been systematically characterized quantitatively on multiple length scales from millimeter to sub-nanometer. It is revealed that hierarchical imperfections are intrinsically involved in the crossed-lamellar structure of the shell despite its periodically packed platelets. In particular, various favorable characters which are always pursued in synthetic materials, e.g. nanotwins and low-angle misorientations, have been incorporated herein. The possible contributions of these imperfections to mechanical properties are further discussed. It is suggested that the imperfections may serve as structural adaptations, rather than detrimental defects in the real sense, to help improve the mechanical properties of natural biological materials. This study may aid in understanding the optimizing strategies of structure and properties designed by nature, and accordingly, provide inspiration for the design of synthetic materials.