Biomimetic material development takes inspiration from biological materials and organisms that possess extraordinary properties or appearance, such as excellent mechanical strength and toughness, self-cleaning, self-healing, brilliant colours, etc., to develop materials and products with advanced capabilities. One such remarkable inspiring source is nacre which forms the inner layer of shells and is commonly known as the mother of pearls. Nacre consists of 95 vol% brittle inorganic minerals (CaCO3), and 5% organic polymers as the brick-and-mortar structure, yet exhibits a work of fracture that is ca. 3000 times higher than that of pure constituent minerals. Mimicking nacre, an ideal combination of high strength, and high fracture toughness, paves the way for the production of alternative, sustainable high performance, structural and functional materials. Recent research advances have led to the fabrication of nacre-inspired hierarchical structured fibres, films, and bulk composite materials. This review discusses the chemistry of nacre formation, the details of brick-and-mortar structure, and the strengthening and deformation mechanism. Furthermore, we present a broad overview of recent trends and developments in synthesis processes and applications of nacre-inspired materials. We put emphasis on hierarchical composites with a brief discussion on artificial carbonates synthesized by mimicking the natural formation of nacre. 

A review of nacre-inspired materials: chemistry, strengthening-deformation mechanism, synthesis, and applications

In the search for new biotechnological advances, increasing attention is currently being paid to the development of magnetic nanoplatforms loaded with enzymes, since, on the one hand, they can be recovered and reused, and on the other hand, they improve their catalytic activity and increase their stability, avoiding processes such as aggregation or autolysis. In this review, we evaluate a series of key parameters governing the enzyme–nanoparticle immobilization phenomena from a thermodynamic and kinetic point of view. We also focus on the use of magnetite nanoparticles (MNPs) as multifunctional vectors able to anchor enzymes, summarize the most relevant aspects of functionalization and immobilization and, finally, describe some recent and relevant applications of the enzyme–MNP hybrids as biocatalysts with especial emphasis on cancer therapy.

/pdf/enzyme-iron-oxide-nanoassemblies-a-review-of-immobilization-2peo3s53.pdf

Enzyme–Iron Oxide Nanoassemblies: A Review of Immobilization and Biocatalytic Applications

Protective materials are essential for personal, electronic, and military defenses owing to their efficient impact-resistant and energy-absorbing properties. Inspired by the bottom-up fabrication process and energy dissipation mechanism of natural organisms with hierarchical structures, we demonstrated a self-wrinkled photo-curing coating as a new protective material for enhancing the anti-impact property of the substrates. Owing to the self-assembly of polydimethylsiloxane (PDMS) containing polymeric photoinitiator on the surface, the liquid coating formulation was photo-cured by one-step UV irradiation with simultaneous generation of self-wrinkled surface morphology and a gradient cross-linked architecture. The maximum impact resistance height (hmax) of the glass substrate coated with plain coating increased from 120 to 180 cm when coated with wrinkled gradient coating. Furthermore, the Young's modulus, fracture stress, and toughness of the wrinkled gradient coating film improved from 39.6 MPa, 2.4 MPa, and 74.1 MJ/cm3 to 235.0 MPa (∼5× increase), 18.5 MPa (∼6.6× increase), and 845.0 MJ/cm3 (∼10.8× increase) compared to the pure coating film as reference. The theoretical simulation and experimental results proved that the surface self-wrinkled morphology and intrinsic hierarchical architecture contribute to the energy dissipation and impact resistance of the cured coating. The photo-curing process, a bottom-up strategy, is conducted in a non-contact mode compared with nano-printing and lithography, enabling bulk materials to be engineered. 

Self-wrinkling coating for impact resistance and mechanical enhancement.

Modern material design aims to achieve multifunctionality through integrating structures in a diverse range, resulting in simple materials with embedded functions. Biological materials and organisms are typical examples of this concept, where complex functionalities are achieved through a limited material base. This review highlights the multiscale structural and functional integration of representative natural organisms and materials, as well as biomimetic examples. The impact, wear, and crush resistance properties exhibited by mantis shrimp and ironclad beetle during predation or resistance offer valuable inspiration for the development of structural materials in the aerospace field. Investigating cyanobacteria that thrive in extreme environments can contribute to developing living materials that can serve in places like Mars. The exploration of shape memory and the self-repairing properties of spider silk and mussels, as well as the investigation of sensing–actuating and sensing–camouflage mechanisms in Banksias, chameleons, and moths, holds significant potential for the optimization of soft robot designs. Furthermore, a deeper understanding of mussel and gecko adhesion mechanisms can have a profound impact on medical fields, including tissue engineering and drug delivery. In conclusion, the integration of structure and function is crucial for driving innovations and breakthroughs in modern engineering materials and their applications. The gaps between current biomimetic designs and natural organisms are also discussed.

/pdf/multifunctionality-in-nature-structure-function-2fm34uqv.pdf

Multifunctionality in Nature: Structure–Function Relationships in Biological Materials

Insects and microbial pathogens are ubiquitous and play significant roles in various biological processes, while microbial pathogens are microscopic organisms that can cause diseases in multiple hosts. Insects and microbial pathogens engage in diverse interactions, leveraging each other’s presence. Metals are crucial in shaping these interactions between insects and microbial pathogens. However, metals such as Fe, Cu, Zn, Co, Mo, and Ni are integral to various physiological processes in insects, including immune function and resistance against pathogens. Insects have evolved multiple mechanisms to take up, transport, and regulate metal concentrations to fight against pathogenic microbes and act as a vector to transport microbial pathogens to plants and cause various plant diseases. Hence, it is paramount to inhibit insect–microbe interaction to control pathogen transfer from one plant to another or carry pathogens from other sources. This review aims to succinate the role of metals in the interactions between insects and microbial pathogens. It summarizes the significance of metals in the physiology, immune response, and competition for metals between insects, microbial pathogens, and plants. The scope of this review covers these imperative metals and their acquisition, storage, and regulation mechanisms in insect and microbial pathogens. The paper will discuss various scientific studies and sources, including molecular and biochemical studies and genetic and genomic analysis.

A Comprehensive Review on the Roles of Metals Mediating Insect–Microbial Pathogen Interactions

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 (Fe3O4) nanoparticles with finely tuned morphologies in their cells. Mms6, a magnetosome membrane specific (Mms) protein isolated from the surfaces of bacterial magnetite nanoparticles, plays an important role in regulating the magnetite crystal morphology. Although the binding ability of Mms6 to magnetite nanoparticles has been speculated, the interactions between Mms6 and magnetite crystals have not been elucidated thus far. Here, we show a direct adsorption ability of Mms6 on magnetite nanoparticles in vitro. An adsorption isotherm indicates that Mms6 has a high adsorption affinity (Kd = 9.52 µM) to magnetite nanoparticles. In addition, Mms6 also demonstrated adsorption on other inorganic nanoparticles such as titanium oxide, zinc oxide, and hydroxyapatite. Therefore, Mms6 can potentially be utilized for the bioconjugation of functional proteins to inorganic material surfaces to modulate inorganic nanoparticles for biomedical and medicinal applications.

/pdf/adsorption-of-biomineralization-protein-mms6-on-magnetite-167mb0fy.pdf

Adsorption of Biomineralization Protein Mms6 on Magnetite (Fe3O4) Nanoparticles

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. Graphical Abstract

Fibrous anisotropy and mineral gradients within the radula stylus of chiton: Controlled stiffness and damage tolerance in a flexible biological composite

A comprehensive understanding of phytoplankton diversity is valuable for assessing an environment of interest as phytoplankton are primary producers in various aquatic food webs. Microscopic analyses are useful for diversity assessment based on characteristic cell morphologies. However, phylogenetic classification based solely on morphology requires an extremely high level of expertise. The genetic approach is another option for evaluating phytoplankton diversity; however, it cannot reveal morphological information. To integrate these two approaches, an original technology was developed, that is referred to as microcavity array (MCA)/gel‐based cell manipulation (GCM). The model experiments using monocultures of various phytoplankton indicated that the efficiencies of cell recovery and isolation of single‐cell plankton were dependent on cell size and shape. Cells with widths larger than the cavity width showed high level of recovery and isolation efficiency. Subsequent whole‐genome amplification (WGA) of isolated single‐cell plankton provided a sufficient amount (≈30 μg) of WGA products for genetic analyses. Furthermore, it is showed that MCA/GCM could directly analyze phytoplankton in ocean water obtained from Suruga Bay, Japan, without any cumbersome pretreatment. These results indicate that MCA/GCM technology is a powerful tool for elucidating the phytoplankton diversity in marine environment.

Single‐cell genotyping of phytoplankton from ocean water by gel‐based cell manipulation

ConspectusOver 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 , Adv. Funct. Mater. 2013, 23, 2908; Weaver , Science 2012, 336, 1275; Huang , Nat. Mater. 2020, 19, 1236; Rivera , Nature 2020, 586, 543) investigating not only their ultrastructural features and mechanical properties but in some cases, how these assembled structures are mineralized. In specific instances, comparative analyses of multiscale structures have pinpointed which design principles have arisen convergently; when more than one evolutionary path arrives at the same solution, we have a good indication that it is the best solution. This is required for survival under extreme conditions. Indeed, we have found that there are specific architectural features that provide an advantage toward survival by enabling the ability to feed effectively or to survive against predatory attacks. In this Account, we describe 3 specific design features, nanorods, helicoids, and nanoparticles, as well as the interfaces in fiber-reinforced biological composites. We not only highlight their roles in the specific organisms but also describe how controlled syntheses and hierarchical assembly using organic (i.e., often chitinous) scaffolds lead to these integrated macroscale structures. Beyond this, we provide insight into multifunctionality: how nature leverages these existing structures to potentially add an additional dimension toward their utility and describe their translation to biomimetic materials used for engineering applications.

Nanoarchitecture Tough Biological Composites from Assembled Chitinous Scaffolds.

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Adsorption of Biomineralization Protein Mms6 on Magnetite (Fe3O4) Nanoparticles

Fibrous anisotropy and mineral gradients within the radula stylus of chiton: Controlled stiffness and damage tolerance in a flexible biological composite

Single‐cell genotyping of phytoplankton from ocean water by gel‐based cell manipulation

Nanoarchitecture Tough Biological Composites from Assembled Chitinous Scaffolds.