Perovskite hydroxide-based laccase mimics with controllable activity for environmental remediation and biosensing.

Constructing relatively inexpensive nanomaterials to simulate the catalytic performance of laccase is of great significance in recent years. Although research on improving laccase-like activity by regulating ligands of copper (amino acids or small organic molecules, etc.) have achieved remarkable success. There are few reports on improving laccase-like activity by adjusting the composition of metal Cu. Here, we used perovskite hydroxide AB(OH)6 as a model to evaluate the relationship between Cu based alloys and their laccase-like activity. We found that when the Cu/Mn alloy ratio of the perovskite hydroxide A point is greater than 1, the laccase-like activity of the binary alloy perovskite hydroxide is higher than that of the corresponding single Cu. Based on the measurements of XPS and ICP-MS, we deduced that the improvements of laccase-like activity mainly attribute to the ratio of Cu+/Cu2+and the content of Cu. Moreover, two types of substrates (toxic pollutants and catechol neurotransmitters) were used to successfully demonstrated such nanozymes' excellent environmental protecting function and biosensing property. This work will provide a novel approach for the construction and application of laccase-like nanozymes in the future.

Fe3O4 nanoparticles entrapped in the inner surfaces of N-doped carbon microtubes with enhanced biomimetic activity.

Tubular structured composites have attracted great interest in catalysis research owing to their void-confinement effects. In this work, we synthesized a pair of hollow N-doped carbon microtubes (NCMTs) with Fe3O4 nanoparticles (NPs) encapsulated inside NCMTs (Fe3O4@NCMTs) and supported outside NCMTs (NCMTs@Fe3O4) while keeping other structural features the same. The impact of structural effects on the catalytic activities was investigated by comparing a pair of hollow-structured nanocomposites. It was found that the Fe3O4@NCMTs possessed a higher peroxidase-like activity when compared with NCMTs@Fe3O4, demonstrating structural superiority of Fe3O4@NCMTs. Based on the excellent peroxidase-like catalytic activity and stability of Fe3O4@NCMTs, an ultra-sensitive colorimetric method was developed for the detection of H2O2 and GSH with detection limits of 0.15 µM and 0.49 µM, respectively, which has potential application value in biological sciences and biotechnology.

Nanozymes with biomimetically designed properties for cancer treatment.

Nanozymes, as a type of nanomaterials with enzymatic catalytic activity, have demonstrated tremendous potential in cancer treatment owing to their unique biomedical properties. However, the heterogeneity of tumors and the complex tumor microenvironment pose significant challenges to the in vivo catalytic efficacy of traditional nanozymes. Drawing inspiration from natural enzymes, scientists are now using biomimetic design to build nanozymes from the ground up. This approach aims to replicate the key characteristics of natural enzymes, including active structures, catalytic processes, and the ability to adapt to the tumor environment. This achieves selective optimization of nanozyme catalytic performance and therapeutic effects. This review takes a deep dive into the use of these biomimetically designed nanozymes in cancer treatment. It explores a range of biomimetic design strategies, from structural and process mimicry to advanced functional biomimicry. A significant focus is on tweaking the nanozyme structures to boost their catalytic performance, integrating them into complex enzyme networks similar to those in biological systems, and adjusting functions like altering tumor metabolism, reshaping the tumor environment, and enhancing drug delivery. The review also covers the applications of specially designed nanozymes in pan-cancer treatment, from catalytic therapy to improved traditional methods like chemotherapy, radiotherapy, and sonodynamic therapy, specifically analyzing the anti-tumor mechanisms of different therapeutic combination systems. Through rational design, these biomimetically designed nanozymes not only deepen the understanding of the regulatory mechanisms of nanozyme structure and performance but also adapt profoundly to tumor physiology, optimizing therapeutic effects and paving new pathways for innovative cancer treatment.

Biomimetic peroxidase MOF-Fe promotes bone defect repair by inhibiting TfR2 and activating the BMP2 pathway.

BACKGROUND: Large bone defects pose a clinical treatment challenge; inhibiting transferrin receptor 2 (TfR2), which is involved in iron metabolism, can promote osteogenesis. Iron-based metal-organic frameworks (MOF-Fe) particles not only inhibit TfR2 but also serve as biomimetic catalysts to remove hydrogen peroxide in reactive oxygen species (ROS); excess ROS can disrupt the normal functions of osteoblasts, thereby hindering bone regeneration. This study explored the potential effects of MOF-Fe in increasing osteogenic activity and clearing ROS. METHODS: In vitro experiments were performed to investigate the osteogenic effects of MOF-Fe particles and assess their impact on cellular ROS levels. To further validate the role of MOF-Fe in promoting bone defect repair, we injected MOF-Fe suspensions into the femoral defects of SD rats and implanted MOF-Fe-containing hydrogel scaffolds in rabbit cranial defect models and observed their effects on bone healing. RESULTS: In vitro, the presence of MOF-Fe significantly increased the expression levels of osteogenesis-related genes and proteins compared to those in the control group. Additionally, compared to those in the untreated control group, the cells treated with MOF-Fe exhibited a significantly increased ability to remove hydrogen peroxide from ROS and generate oxygen and water within the physiological pH range. In vivo experiments further confirmed the positive effect of MOF-Fe in promoting bone defect repair. CONCLUSION: This study supports the application of MOF-Fe as an agent for bone regeneration, particularly for mitigating ROS and activating the bone morphogenetic protein (BMP) pathway, demonstrating its potential value.

Highly oriented hydrogels for tissue regeneration: design strategies, cellular mechanisms, and biomedical applications.

Many human tissues exhibit a highly oriented architecture that confers them with distinct mechanical properties, enabling adaptation to diverse and challenging environments. Hydrogels, with their water-rich "soft and wet" structure, have emerged as promising biomimetic materials in tissue engineering for repairing and replacing damaged tissues and organs. Highly oriented hydrogels can especially emulate the structural orientation found in human tissue, exhibiting unique physiological functions and properties absent in traditional homogeneous isotropic hydrogels. The design and preparation of highly oriented hydrogels involve strategies like including hydrogels with highly oriented nanofillers, polymer-chain networks, void channels, and microfabricated structures. Understanding the specific mechanism of action of how these highly oriented hydrogels affect cell behavior and their biological applications for repairing highly oriented tissues such as the cornea, skin, skeletal muscle, tendon, ligament, cartilage, bone, blood vessels, heart, etc., requires further exploration and generalization. Therefore, this review aims to fill that gap by focusing on the design strategy of highly oriented hydrogels and their application in the field of tissue engineering. Furthermore, we provide a detailed discussion on the application of highly oriented hydrogels in various tissues and organs and the mechanisms through which highly oriented structures influence cell behavior.

Energy consumption during insect flight and bioinspiration for MAV design: A review.

The excellent biological characteristics of insects provide an important source of inspiration for designing micro air vehicles (MAVs). Insect flight is an incredibly complex and energy-intensive process. Unique insect flight muscles and contraction mechanisms enable flapping at high frequencies. Moreover, the metabolic rate during flight can reach hundreds of times the resting state. Understanding energy consumption during flight is crucial for designing efficient biomimetic aircraft. This paper summarizes the structures and contraction mechanisms of insect flight muscles, explores the underlying metabolic processes, and identifies methods for energy substrate identification and detection, and discusses inspiration for biomimetic MAV design. This paper reviews energy consumption during insect flight, promotes the understanding of insect bioenergetics, and applies this information to the design of MAVs.

Mechanical design principles of avian eggshells for survivability.

Biological materials exhibit complex structure-property relationships which are designed by nature's evolution over millions of years. Unlocking the fundamental physical principles behind these relationships is crucial for creating bioinspired materials and structures with advanced functionalities. The eggshell is a remarkable example with a well-designed structure to balance the trade-off as it provides mechanical protection while still being easy for hatching. In this study, we investigate the underlying mechanical design principles of chicken eggshells under various loading conditions through a combination of experiments and simulations. The unique geometry and structure of the eggshell play a critical role in achieving an excellent balance between mechanical toughness and ease of hatching. The effects of eggshell membranes are elucidated to tune the mechanical properties of the eggshell to further enhance this balance. Moreover, a mechanics-based three-index model is proposed based on these design principles, suggesting the optimal eggshell thickness design to improve survivability across a broad range of avian species with varying egg sizes. The survivability-design relationships hold great potential for the development of improved structural materials for applications in sports safety equipment and the packaging industry. STATEMENT OF SIGNIFICANCE: The fundamental physical principles underlying the complex structure-property relationships in biological materials are uncovered in this study, with a particular focus on chicken eggshells as a prime example. Through the investigation of their mechanical design, we reveal the critical role of eggshell geometry and structure in achieving a balance between toughness and ease of hatching. Specifically, the crack resting effect is observed, making the eggshell easier to break from the inside than from the outside. Additionally, we explore the influence of eggshell membranes on this balance, contributing to the enhancement of the eggshell's mechanical properties. For the first time, we propose a three-index model that uncovers the underlying principles governing the evolution of eggshell thickness. This model suggests optimal thickness designs for diverse avian species, with the goal of enhancing egg survivability. These findings can guide the development of improved structural materials with advanced functionalities, enabling greater safety and efficiency in a wide range of applications.

Artificial structural proteins: Synthesis, assembly and material applications.

Structural proteins have evolved over billions of years and offer outstanding mechanical properties, such as resilience, toughness and stiffness. Advances in modular protein engineering, polypeptide modification, and synthetic biology have led to the development of novel biomimetic structural proteins to perform in biomedical and military fields. However, the development of customized structural proteins and assemblies with superior performance remains a major challenge, due to the inherent limitations of biosynthesis, difficulty in mimicking the complexed macroscale assembly, etc. This review summarizes the approaches for the design and production of biomimetic structural proteins, and their chemical modifications for multiscale assembly. Furthermore, we discuss the function tailoring and current applications of biomimetic structural protein assemblies. A perspective of future research is to reveal how the mechanical properties are encoded in the sequences and conformations. This review, therefore, provides an important reference for the development of structural proteins-mimetics from replication of nature to even outperforming nature.

Gas Evolution as a Tool to Study Reaction Kinetics Under Biomimetic Conditions.

The field of bioorthogonal chemistry is rapidly growing, presenting successful applications of organic and transition metal-catalysed reactions in cells and living systems (in vivo). The development of such reactions typically proceeds through many iterative steps focused on biocompatibility and fast reaction kinetics to ensure product formation. However, obtaining kinetic data, even under simulated biological (biomimetic) conditions, remains a challenge due to substantial concentrations of salts and biomolecules hampering the use of typically employed solution-phase analytical techniques. In this study, we explored the suitability of gas evolution as a probe to study kinetics under biomimetic conditions. As proof of concept, we show that the progress of two transition metal-catalysed bioorthogonal chemical reactions can be accurately monitored, regardless of the complexity of the medium. As such, we introduce a protocol to gain more insight into the performance of a catalytic system under biomimetic conditions to further progress iterative catalyst development for in vivo applications.

Injectable extracellular matrix-mimetic hydrogel based on electrospun Janus fibers.

To date, the reported injectable hydrogels have failed to mimic the fibrous architecture of the extracellular matrix (ECM), limiting their biological effects on cell growth and phenotype. Additionally, they lack the micro-sized pores present within the ECM, which is unfavorable for the facile transport of nutrients and waste. Herein, an injectable ECM-mimetic hydrogel (IEMH) was fabricated by shortening and dispersing Janus fibers capable of self-curling at body temperature into pH 7.4 phosphate buffer solution. The IEMH could be massively prepared through a side-by-side electrospinning process combined with ultraviolet irradiation. The IEMHs with only 5 wt% fibers could undergo sol-gel transition at body temperature to become solid gels with desirable stability, sturdiness, and elasticity and self-healing ability. In addition, they possessed notable pseudoplasticity, which is beneficial to injection at room temperature. The results obtained from characterization analysis via scanning electron microscopy, total internal reflection fluorescence microscopy, nuclear magnetic resonance spectroscopy, and Fourier-transform infrared spectroscopy indicate that their sol-gel transition under physiological conditions stems from the synergistic action of the tight entanglements between thermally-induced self-curling fibers and the hydrophobic interaction between the fibers. An MTT assay using C2C12 myoblast cells was performed to examine the in vitro cytotoxicity of IEMHs for biomedical applications, and the cell viability was found to be more than 95%.

Directing the Encapsulation of Single Cells with DNA Framework Nucleator-Based Hydrogel Growth.

Encapsulating individual mammalian cells with biomimetic materials holds potential in ex vivo cell culture and engineering. However, current methodologies often present tradeoffs between homogeneity, stability, and cell compatibility. Here, inspired by bacteria that use proteins stably anchored on their outer membranes to nucleate biofilm growth, we develop a single-cell encapsulation strategy by using a DNA framework structure as a nucleator (DFN) to initiate the growth of DNA hydrogels under cell-friendly conditions. We find that among the tested structures, the tetrahedral DFN can evenly and stably reside on cell membranes, effectively initiating hybridization chain reactions which generate homogeneously dense yet flexible single-cell encapsulation for diverse cell lines. The encapsulation persists for up to 72 hours in a serum-containing cell culture environment, representing a ~70-fold improvement compared to encapsulations mediated by single-stranded DNA nucleators. The metabolism and proliferation of the encapsulated cells are suppressed, but can be restored to the original efficiencies upon release, suggesting the superior cell compatibility of the encapsulation. We also find that compared to naked cells, the encapsulated cells exhibit a lower autophagy level after undergoing mechanical stress, suggesting the protective effect of the DNA encapsulation. This method may provide a new tool for ex vivo cell engineering.

Access to Advanced Functional Materials through Postmodification of Biomimetic Assemblies via Click Chemistry.

The design, synthesis, and fabrication of functional nanomaterials with specific properties remain a long-standing goal for many scientific fields. The self-assembly of sequence-defined biomimetic synthetic polymers presents a fundamental strategy to explore the chemical space beyond biological systems to create advanced nanomaterials. Moreover, subsequent chemical modification of existing nanostructures is a unique approach for accessing increasingly complex nanostructures and introducing functionalities. Of these modifications, covalent conjugation chemistries, such as the click reactions, have been the cornerstone for chemists and materials scientists. Herein, we highlight some recent advances that have successfully employed click chemistries for the postmodification of assembled one-dimensional (1D) and two-dimensional (2D) nanostructures to achieve applications in molecular recognition, mineralization, and optoelectronics. Specifically, biomimetic nanomaterials assembled from sequence-defined macromolecules such as peptides and peptoids are described.

Single-atom nanozymes with peroxidase-like activity: A review.

Single-atom nanozymes (SANs) are nanomaterials-based nanozymes with atomically dispersed enzyme-like active sites. SANs offer improved as well as tunable catalytic activity. The creation of extremely effective SANs and their potential uses have piqued researchers' curiosity due to their advantages of cheap cost, variable catalytic activity, high stability, and large-scale production. Furthermore, SANs with uniformly distributed active centers and definite coordination structures offer a distinctive opportunity to investigate the structure-activity correlation and control the geometric and electrical features of metal centers. SANs have been extensively explored in photo-, thermal-, and electro-catalysis. However, SANs suffer from the following disadvantages, such as efficiency, non-mimicking of the 3-D complexity of natural enzymes, limited and narrow range of artificial SANs, and biosafety aspects. Among a quite limited range of artificial SANs, the peroxidase action of SANs has attracted significant research attention in the last five years with the aim of producing reactive oxygen species for use in cancer therapy, and water treatment among many other applications. In this review, we explore the recent progress of different SANs as peroxidase mimics, the role of the metal center in enzymatic activity, possible prospects, and underlying limitations in real-time applications.

Advances in the application of metal oxide nanozymes in tumor detection and treatment.

Natural enzymes play an important role to support the regular life activities of the human body. However, the application conditions of natural enzymes are harsh and there are limitations in their use. As artificial enzymes, nanozymes possess the substrate specificity of natural enzymes. Due to the advantages of low cost, good stability and strong catalytic properties, nanozymes hold a wide range of applications in the fields of sensing, chemical, food and medicine. Some of the more common ones are noble metal nanozymes, metal oxide nanozymes and carbon-based nanozymes. Among them, metal oxide nanozymes have attracted much attention because of their decent fixity, exceedingly good physicochemical properties and other advantages. Today, malignant tumors pose a great danger to the human body and are a serious threat to human health. However, traditional treatments have more side effects, and finding new treatment modalities is particularly important for tumor treatment. For example, enzyme therapy can be used to catalyze reactions in the body to achieve tumor treatment. Nanozymes can exert enzymatic activity and effectively treat malignant tumors through catalysis and synergy, and have made certain progress. This paper reviews the detection and application of metal oxide nanozymes in tumor detection and treatment in recent years and provides an outlook on their future application and development.

Electrospinning of biomimetic materials with fibrinogen for effective early-stage wound healing.

Electrospun biomimetic materials based on polyester of natural origin poly-3-hudroxybutyrate (PHB) modified with hemin (Hmi) and fibrinogen (Fbg) represent a great interest and are potentially applicable in various fields. Here, we describe formulation of the new fibrous PHB-Fbg and PHB-Hmi-Fbg materials with complex structure for biomedical application. The average diameter of the fibers was 3.5 µm and 1.8 µm respectively. Hmi presence increased porosity from 80 % to 94 %, significantly reduced the number of defects, ensured the formation of a larger number of open pores, and improved mechanical properties. Hmi presence significantly improved the molding properties of the material. Hmi facilitated effective Fbg adsorption on the of the PHB wound-healing material, ensuring uniform localization of the protein on the surface of the fibers. Next, we evaluated cytocompatibility, cell behavior, and open wound healing in mice. The results demonstrated that PHB-Fbg and PHB-Hmi-Fbg electrospun materials had pronounced properties and may be promising for early-stage wound healing - the PHB-Hmi-Fbg sample accelerated wound closure by 35 % on the 3rd day, and PHB-Hmi showed 45 % more effective wound closure on the 15th day.

Single-layer semiconductor-decorated flexible 2D protein nanosheets by engineered anchoring for efficient photocatalytic hydrogen production.

Protein self-assembly can be accurately manipulated to form ordered nanostructures through various supramolecular forces. This strategy is expected to make significant breakthroughs in the field of new biomimetic functional materials. Specifically, the construction of photocatalytic systems on two-dimensional (2D) flexible protein nanosheets meets a great challenge. We introduce a synthetic methodology for creating single-layer semiconductor-decorated protein 2D materials under mild conditions with enhanced light-driven hydrogen production. This approach employs a bioengineered green fluorescent protein (E4P) with the addition of a Cd-binding peptide, enabling precise control of the assembly of CdS quantum dots (QDs) on the protein's surface. Consequently, we obtained 4.3 nm-thin single-layer 2D protein nanosheets with substantial surface areas ideal for accommodating CdS QDs. By orthogonal incorporation of metal-binding peptides and supramolecular coordination, significantly enhancing the overall photocatalytic efficiency. Our findings demonstrate the potential for stable and efficient hydrogen production, highlighting the adaptability and biocompatibility of protein scaffolds for photocatalysis.

Mutable Collagenous Tissue: A Concept Generator for Biomimetic Materials and Devices.

Echinoderms (starfish, sea-urchins and their close relations) possess a unique type of collagenous tissue that is innervated by the motor nervous system and whose mechanical properties, such as tensile strength and elastic stiffness, can be altered in a time frame of seconds. Intensive research on echinoderm 'mutable collagenous tissue' (MCT) began over 50 years ago, and over 20 years ago, MCT first inspired a biomimetic design. MCT, and sea-cucumber dermis in particular, is now a major source of ideas for the development of new mechanically adaptable materials and devices with applications in diverse areas including biomedical science, chemical engineering and robotics. In this review, after an up-to-date account of present knowledge of the structural, physiological and molecular adaptations of MCT and the mechanisms responsible for its variable tensile properties, we focus on MCT as a concept generator surveying biomimetic systems inspired by MCT biology, showing that these include both bio-derived developments (same function, analogous operating principles) and technology-derived developments (same function, different operating principles), and suggest a strategy for the further exploitation of this promising biological resource.

pH-Stimulated Response Gating for Mimic Cytochrome C Transport on Biomimetic Asymmetric Nanochannels.

Proteins are vital components in cells, biological tissues, and organs, playing a pivotal role in growth and developmental processes in living organisms. Cytochrome C (Cyt C) is a class of heme proteins found in almost all life and is involved in cellular energy metabolic processes such as respiration, mainly as electron carriers or terminal reductases. It binds cardiolipin in the inner mitochondrial membrane, leading to apoptosis. It is a challenge to design a simple and effective artificial system to mimic the complex Cyt C biological transport process. In this paper, an asymmetric biomimetic pH-driven protein gate is described by introducing arginine (Arg) at one end of an hourglass-shaped nanochannel. The nanochannel shows a sensitive protonation-driven protein gate that can be "off" at pH = 7 and "on" at pH = 2. Further studies show that differences in the binding of Arg and Cyt C at different levels of protonation lead to different switching behaviors within the nanochannels, which in turn lead to different surface charges within the nanochannels. It can be used for detecting Cyt C and as an excellent and robust gate for developing integrated circuits and nanoelectronic logic devices.

Biomimetic Wearable Sensors: Emerging Combination of Intelligence and Electronics.

Owing to the advancement of interdisciplinary concepts, for example, wearable electronics, bioelectronics, and intelligent sensing, during the microelectronics industrial revolution, nowadays, extensively mature wearable sensing devices have become new favorites in the noninvasive human healthcare industry. The combination of wearable sensing devices with bionics is driving frontier developments in various fields, such as personalized medical monitoring and flexible electronics, due to the superior biocompatibilities and diverse sensing mechanisms. It is noticed that the integration of desired functions into wearable device materials can be realized by grafting biomimetic intelligence. Therefore, herein, the mechanism by which biomimetic materials satisfy and further enhance system functionality is reviewed. Next, wearable artificial sensory systems that integrate biomimetic sensing into portable sensing devices are introduced, which have received significant attention from the industry owing to their novel sensing approaches and portabilities. To address the limitations encountered by important signal and data units in biomimetic wearable sensing systems, two paths forward are identified and current challenges and opportunities are presented in this field. In summary, this review provides a further comprehensive understanding of the development of biomimetic wearable sensing devices from both breadth and depth perspectives, offering valuable guidance for future research and application expansion of these devices.

Modeling the 3-dimensional structure of the silkworm's spinning apparatus in silk production.

The silk-spinning process of the silkworms transforms the liquid silk solution to a solid state under mild conditions, making it an attractive model for bioinspiration However, the precise mechanism behind silk expulsion remains largely unknown. Here we selected the silkworms as representative models to investigate the silk-spinning mechanism. We used serial block-face scanning electron microscopy (SBF-SEM) to reconstruct the three-dimensional structures of the spinnerets in silkworms at various stages and with different gene backgrounds. By comparing the musculature and duct deformation of these spinneret models during the spinning process, we were able to simulate the morphological changes of the spinneret. Based on the results, we proposed three essential factors for silkworm spinning: the pressure generated by the silk gland, the opening duct, and the pulling force generated by head movement. Understanding the silkworm spinning process provides insights into clarify the fluid-ejecting mechanism of a group of animals. Moreover, these findings are helpful to the development of biomimetic spinning device that mimics the push-and-pull dual-force system in silkworms. STATEMENT OF SIGNIFICANCE: The silkworms' spinning system produces fibers under mild conditions, making it an ideal candidate for bioinspiration. However, the mechanism of silk expulsion is unknown, and the three-dimensional structure of the spinneret is still uncertain. In this study, we reconstructed a detailed 3-dimensional model of the spinneret at near-nanometer resolution, and for the first time, we observed the changes that occur before and during the silk-spinning process. Our reconstructed models suggested that silkworms have the ability to control the spinning process by opening or closing the spinning duct. During the continuously spinning period, both the pressure generated by the silk gland and the pulling force resulting from head movement work in tandem to expel the silk solution. We believe that gaining a full understanding of the spinning process steps can advance our ability to spin synthetic fibers with properties comparable to those of native fibers by mimicking the natural spinning process.