The Impact of Substrate Temperature on the Adhesion Strength of Electroplated Copper on an Al-Doped ZnO/Si System.

This research, which involved a comprehensive methodology, including depositing electroplated copper on a copper seed layer and Al-doped ZnO (AZO) thin films on textured silicon substrates using DC magnetron sputtering with varying substrate heating, has yielded significant findings. The study thoroughly investigated the effects of substrate temperature (Ts) on copper adhesion strength and morphology using the peel force test and electron microscopy. The peel force test was conducted at angles of 90°, 135°, and 180°. The average adhesion strength was about 0.2 N/mm for the samples without substrate heating. For the samples with substrate heating at 100 °C, the average peeling force of the electroplated copper film was about 1 N/mm. The average peeling force increased to 1.5 N/mm as the substrate heating temperature increased to 200 °C. The surface roughness increases as the annealing temperature of the Cu/AZO/Si sample increases. These findings not only provide a reliable and robust method for applying AZO transparent conductive films onto silicon solar cells but also underscore its potential to significantly enhance the efficiency and durability of solar cells significantly, thereby instilling confidence in the field of solar cell technology.

Biosustainable Multiscale Transparent Nanocomposite Films for Sensitive Pressure and Humidity Sensors.

Light weight, thinness, transparency, flexibility, and insulation are the key indicators for flexible electronic device substrates. The common flexible substrates are usually polymer materials, but their recycling is an overwhelming challenge. Meanwhile, paper substrates are limited in practical applications because of their poor mechanical and thermal stability. However, natural biomaterials have excellent mechanical properties and versatility thanks to their organic-inorganic multiscale structures, which inspired us to design an organic-inorganic nanocomposite film. For this purpose, a bio-inspired multiscale film was developed using cellulose nanofibers with abundant hydrophilic functional groups to assist in dispersing hydroxyapatite nanowires. The thickness of the biosustainable film is only 40 µm, and it incorporates distinctive mechanical properties (strength: 52.8 MPa; toughness: 0.88 MJ m-3) and excellent optical properties (transmittance: 80.0%; haze: 71.2%). Consequently, this film is optimal as a substrate employed for flexible sensors, which can transmit capacitance and resistance signals through wireless Bluetooth, showing an ultrasensitive response to pressure and humidity (for example, responding to finger pressing with 5000% signal change and exhaled water vapor with 4000% signal change). Therefore, the comprehensive performance of the biomimetic multiscale organic-inorganic composite film confers a prominent prospect in flexible electronics devices, food packaging, and plastic substitution.

Efficacy of the newly designed "SkyWalker" robot compared to the MAKO robotic system in primary total knee arthroplasty: a one-year follow-up study.

PURPOSE: Robot-assisted surgical systems for performing total knee arthroplasty (TKA) have gained significant attention. This study was designed to compare the surgical outcomes in primary TKA surgery between the recently developed "SkyWalker" robot system and the more commonly used MAKO robot. METHODS: A total of 75 patients undergoing primary TKA surgery by the same surgical team were included in this study, with 30 patients in the "SkyWalker" group and 45 patients in the "MAKO" group. We documented the osteotomy plan for both robotic systems. The lower limb alignment angles were evaluated by postoperative radiographic assessment. The operation time, estimated blood loss, postoperative hospital stays, and changes in laboratory indexes were collected during hospitalization. In addition, a comparative evaluation of knee functional assessments and complications was conducted during six month and one year follow-ups. RESULTS: There were no significant differences between the two groups in terms of the accuracy of restoring lower limb alignment, estimated blood loss, or operation time. The knee function assessments at six months and one year postoperatively were similar in both groups. Except for day three after surgery, the level of interleukin-6 (IL-6) and the change in IL-6 (∆IL-6) from preoperative baseline were higher in the "SkyWalker" group than in the MAKO group (median: 20.53 vs. 14.17, P=0.050 and median: 17.30 vs. 10.09, P=0.042, respectively). Additionally, one patient from the MAKO group underwent revision surgery at nine months postoperatively due to ongoing periprosthetic discomfort. CONCLUSIONS: The newly developed "SkyWalker" robot showed comparable efficacy to the MAKO robot in terms of lower limb alignment accuracy and postoperative six month and one year follow-up of clinically assessed resumption of knee function.

Fluorapatite nanorod arrays with enamel-like bundle structure regulated by iron ions.

Pigmented rodent tooth enamel is mainly composed of parallel hydroxyapatite nanorods and a small amount of organic matrix. These hydroxyapatite nanorods tend to be carbonated and contain traces of iron, fluorine, and magnesium. The pigmented rodent tooth enamel which contains trace iron is stronger and more resistant to acid corrosion than unpigmented rodent enamel, which could provide inspiration for the preparation and synthesis of high performance and corrosion resistant artificial materials. However, the regulatory role and mechanical enhancement of iron ions in enamel growth are unclear. Here, we synthesized enamel-like fluorapatite nanorod arrays in vitro using a mineralization technique at room-temperature. To investigate the regulatory effect of iron ions on the fluorapatite nanorod arrays (FAP-Fe), the phosphate solution is slowly transfused dropwise in the calcium ion solution, and different concentrations of iron ions are added to the calcium ion solution in advance. We demonstrated that fluorapatite nanorod arrays (FAP) can be epitaxially grown from amorphous calcium phosphate nanoparticles and iron ions can improve the microstructure of FAP nanorod arrays and obtain the same enamel bundle structure as the natural enamel. Moreover, high concentration of iron ions can inhibit the crystallization of fluorapatite. The FAP-Fe nanorod arrays controlled by 0.02 mM Fe3+ have good mechanical properties. Their hardness is 1.34 ± 0.02 GPa and Young's modulus is 65.3 ± 0.4 GPa, respectively. This work is helpful to understand the role of trace elements in natural enamel in the regulation of enamel formation and to provide a theoretical foundation for the preparation of high strength artificial composites, which can play a greater role in the fields of biological alternative materials, anti-oil coating, oil/water separation, anti-bioadhesion and so on.

Bioinspired Additive Manufacturing of Hierarchical Materials: From Biostructures to Functions.

Throughout billions of years, biological systems have evolved sophisticated, multiscale hierarchical structures to adapt to changing environments. Biomaterials are synthesized under mild conditions through a bottom-up self-assembly process, utilizing substances from the surrounding environment, and meanwhile are regulated by genes and proteins. Additive manufacturing, which mimics this natural process, provides a promising approach to developing new materials with advantageous properties similar to natural biological materials. This review presents an overview of natural biomaterials, emphasizing their chemical and structural compositions at various scales, from the nanoscale to the macroscale, and the key mechanisms underlying their properties. Additionally, this review describes the designs, preparations, and applications of bioinspired multifunctional materials produced through additive manufacturing at different scales, including nano, micro, micro-macro, and macro levels. The review highlights the potential of bioinspired additive manufacturing to develop new functional materials and insights into future directions and prospects in this field. By summarizing the characteristics of natural biomaterials and their synthetic counterparts, this review inspires the development of new materials that can be utilized in various applications.

Bioprocess inspired formation of calcite mesocrystals by cation-mediated particle attachment mechanism.

Calcite mesocrystals were proposed, and have been widely reported, to form in the presence of polymer additives via oriented assembly of nanoparticles. However, the formation mechanism and the role of polymer additives remain elusive. Here, inspired by the biomineralization process of sea urchin spine comprising magnesium calcite mesocrystals, we show that calcite mesocrystals could also be obtained via attachment of amorphous calcium carbonate (ACC) nanoparticles in the presence of inorganic zinc ions. Moreover, we demonstrate that zinc ions can induce the formation of temporarily stabilized amorphous nanoparticles of less than 20 nm at a significantly lower calcium carbonate concentration as compared to pure solution, which is energetically beneficial for the attachment and occlusion during calcite growth. The cation-mediated particle attachment crystallization significantly improves our understanding of mesocrystal formation mechanisms in biomineralization and offers new opportunities to bioprocess inspired inorganic ions regulated materials fabrication.

Sustained visual attentional load modulates audiovisual integration in older and younger adults.

Previous studies have shown that attention influences audiovisual integration (AVI) in multiple stages, but it remains unclear how AVI interacts with attentional load. In addition, while aging has been associated with sensory-functional decline, little is known about how older individuals integrate cross-modal information under attentional load. To investigate these issues twenty older adults and 20 younger adults were recruited to conduct a dual task including a multiple object tracking (MOT) task, which manipulated sustained visual attentional load, and an audiovisual discrimination task, which assesses AVI. The results showed that response times were shorter and hit rate was higher for audiovisual stimuli than for auditory or visual stimuli alone and in younger adults than in older adults. The race model analysis showed that AVI was higher under the load_3 condition (monitoring two targets of the MOT task) than under any other load condition (no-load [NL], one or three targets monitoring). This effect was found regardless of age. However, AVI was lower in older adults than younger adults under NL condition. Moreover, the peak latency was longer, and the time window of AVI was delayed in older adults compared to younger adults under all conditions. These results suggest that slight visual sustained attentional load increased AVI but that heavy visual sustained attentional load decreased AVI, which supports the claim that attention resource was limited, and we further proposed that AVI was positively modulated by attentional resource. Finally, there were substantial impacts of aging on AVI; AVI was delayed in older adults.

Bioinspired Strategy for Efficient TiO2/Au/CdS Photocatalysts Based On Mesocrystal Superstructures in Biominerals and Charge-Transfer Pathway in Natural Photosynthesis.

Natural photosynthesis involves an efficient charge-transfer pathway through exquisitely arranged photosystems and electron transport intermediates, which separate photogenerated carriers to realize high quantum efficiency. It inspires a rational design construction of artificial photosynthesis systems and the architectures of semiconductors are essential to achieve optimal performance. Of note, biomineralization processes could form various mesocrystals with well-ordered superstructures for unique optical applications. Inspired by both natural photosynthesis and biomineralization, we construct a ternary superstructure-based mesocrystal TiO2 (meso-TiO2)/Au/CdS artificial photosynthesis system by a green photo-assisted method. The well-ordered superstructure of meso-TiO2 and efficient charge-transfer pathway among the three components are crucial for retarding charge recombination. As a result, the meso-TiO2/Au/CdS photocatalyst displays enhanced visible light-driven photocatalytic hydrogen evolution (4.60 mmol h-1 g-1), which is 3.2 times higher than that of commercial TiO2 (P25)/Au/CdS with disordered TiO2 nanocrystal aggregates (1.41 mmol h-1 g-1). This work provides a promising bioinspired design strategy for photocatalysts with an improved solar conversion efficiency.

Mechanically Reinforced Artificial Enamel by Mg2+-Induced Amorphous Intergranular Phases.

Amorphous intergranular phases in mature natural tooth enamel are found to provide better adhesion and could dramatically affect their mechanical performance as a structure reinforcing phase. This study successfully synthesized an amorphous intergranular phase enhanced fluorapatite array controlled by Mg2+ (FAP-M) at room temperature. Furthermore, atom probe tomography (APT) observation presents that Mg2+ is enriched at grain boundaries during the assembly of enamel-like fluorapatite arrays, leading to the formation of intergranular phases of Mg-rich amorphous calcium phosphate (Mg-ACP). APT results also demonstrated that the segregation of Mg2+ caused the chemical gradient in nanocrystalline attachment and realignment under the drive of inherent surface stress. These results indicate that the amorphous intergranular phases served like glue to connect each nanorod to reinforce the enamel-like arrays. Therefore, the as-received FAP-M artificial enamel exhibits excellent mechanical properties, with hardness and Young's modulus of 2.90 ± 0.13 GPa and 67.9 ± 3.4 GPa, which were ∼8.3 and 2.2 times higher than those of FAP arrays without controlled by Mg2+, respectively.

Room-temperature growth of fluorapatite/CaCO3 heterogeneous structured composites inspired by human tooth.

Organisms can synthesize heterogeneous structures with excellent mechanical properties through mineralization, the most typical of which are teeth. The tooth is an extraordinarily resilient bi-layered material that is composed of external enamel perpendicular to the tooth surface and internal dentin parallel to the tooth surface. The synthesis of enamel-like heterostructures with good mechanical properties remains an elusive challenge. In this study, we applied a biomimetic mineralization method to grow fluorapatite/CaCO3 (FAP/CaCO3) heterogeneous structured thin films that mimic their biogenic counterparts found in teeth through a three-step pathway: coating a polymer substrate, growing a layered calcite film, and mineralization of a fluorapatite columnar array on the calcite layer. The synthetic heterostructure composites combine well and exhibit good mechanical properties comparable to their biogenic counterparts. The FAP/CaCO3 heterogeneous structured composite exhibits excellent mechanical properties, with a hardness and Young's modulus of 1.99 ± 0.02 GPa and 47.5 ± 0.6 GPa, respectively. This study provides a reasonable new idea for unique heterogeneous structured materials designed at room temperature.

Mineralization generates megapascal contractile stresses in collagen fibrils.

During bone formation, collagen fibrils mineralize with carbonated hydroxyapatite, leading to a hybrid material with excellent properties. Other minerals are also known to nucleate within collagen in vitro. For a series of strontium- and calcium-based minerals, we observed that their precipitation leads to a contraction of collagen fibrils, reaching stresses as large as several megapascals. The magnitude of the stress depends on the type and amount of mineral. Using in-operando synchrotron x-ray scattering, we analyzed the kinetics of mineral deposition. Whereas no contraction occurs when the mineral deposits outside fibrils only, intrafibrillar mineralization generates fibril contraction. This chemomechanical effect occurs with collagen fully immersed in water and generates a mineral-collagen composite with tensile fibers, reminiscent of the principle of reinforced concrete.

Nanocage Ferritin Reinforced Polyacrylamide Hydrogel for Wearable Flexible Strain Sensors.

Biocomposite hydrogels are promising for applications in wearable flexible strain sensors. Nevertheless, the existing biocomposite hydrogels are still hard to meet all requirements, which limits the practical application. Here, inspired by the structure and composition of natural ferritin, we design a PAAm-Ferritin hybrid hydrogel through a facile method. Ferritin is uniformly distributed in the cross-linking networks and acts as a nanocage spring model, leading to the enhanced tensile strength of the hydrogel. The fracture stress is 99 kPa at 1400% maximum elongation. As fabricated PAAm-Ferritin hybrid hydrogels exhibit high toughness and low elastic modulus (21 kPa). The PAAm-Ferritin hybrid hydrogels present excellent biocompatibility and increased conductivity compared with PAAm hydrogel. Impressively, as a wearable flexible strain sensor, the PAAm-Ferritin hybrid hydrogels have high sensitivity (gauge factor = 2.06), excellent reliability, and cycling stability. This study indicates the feasibility of utilizing ferritin to synthesize functional materials, which is conducive to expanding the use of protein synthesis of materials technology and application fields.

Growth of mineralized collagen films by oriented calcium fluoride nanocrystal assembly with enhanced cell proliferation.

Bone is a highly calcified tissue with 60 wt% inorganic components. It is made up of mineralized collagen fibrils, where the platelet-like hydroxyapatite nanocrystals deposit within the collagen fibrils in an oriented manner. Inspired by the special structure and biological activity of bone, we realize the intrafibrillar mineralization of collagen films with oriented calcium fluoride nanocrystals in vitro. Amorphous calcium fluoride (ACF) precursors are generated by polyacrylic acid through polymer-induced liquid precursor processes. The precursors are ready to infiltrate and fill the gap zones laterally and then diffuse to occupy the whole space inside the collagen longitudinally. Finally, the fully mineralized collagen fibrils exhibit a single-crystal-like structure after transforming precursors to co-oriented nanocrystals under the influence of arranged collagen molecules. Expanding the collagen mineralization from 1D fibrils to 2D films, the growth of mineralized areas on the films with a reaction-limited behavior is found. The kinetic rate of growth is around 0.2-0.3 µm min-1, which depends on the pH of the solution. Furthermore, the mineralized collagen films exhibit an enhanced ability of cell proliferation over the pure collagen matrices. Understanding the mineralization of artificial collagen-based scaffolds may have broad promising potentials for bone tissue regeneration and repair in the future.

Bioprocess-inspired synthesis of multilayered chitosan/CaCO3 composites with nacre-like structures and high mechanical properties.

The formation of natural structures found in biological systems is wonderful and can be completed at ambient temperatures in contrast to artificial technologies wherein harsh conditions are common prerequisites. A new research direction, "bioprocess inspired manufacturing", is proposed for fabricating advanced materials with novel structures and functions. Nacre consists of an ordered multilayer structure of crystalline calcium carbonate lamellae separated by organic layers exhibiting mechanical toughness, which transcends that of its constituent components. Inspired by the nacre formation process, a microscale additive manufacturing mineralization method is proposed for achieving a multilayered organic-inorganic layered structure. In this work, layered calcite was synthesized on the surface of chitosan (CS) films at room temperature under the coordinated control of magnesium ions (Mg2+) and polyacrylic acid (PAA). The CS films and layered calcite are sequentially assembled in a layer-by-layer deposition approach to form an organic-inorganic hybrid structure. The nacre-like chitosan/CaCO3 (CS/CaCO3) composites exhibit high transparency and underwater superoleophobicity. Impressively, the hardness (2.35 ± 0.03 GPa) and Young's modulus (58.1 ± 0.5 GPa) of the as-prepared (CS/CaCO3) composites are comparable to those of their biological counterparts. This study provides a rational bioprocess-inspired room-temperature mineralization method to develop advanced composite materials with good performance.

Hydroxyapatite-reinforced alginate fibers with bioinspired dually aligned architectures.

Biological materials have excellent mechanical properties due to their organized structures from nano- to macro-scale. Artificial manufacture of materials with anisotropic microstructures still remains challenging. We described a stress-induced method to fabricate anisotropic alginate fibers. Organic-inorganic composite fibers were obtained by incorporating aligned hydroxyapatite (HAP) nanowires into the alginate fiber. Detailed structural characterization revealed the bone-like structure of the HAP-reinforced alginate fibers. Tensile test results showed that the maximum Young's modulus and tensile strength were 4.3 GPa and 153.8 MPa, respectively. A multiscale reinforcing mechanism is proposed after the discussion of the structure-property relationship: highly ordered and compacted nanofibrils aligned along the longitudinal direction at the microscale, and two kinds of alginate gels with different mechanical behaviors at the nanoscale coexisted (acidic alginate gel and calcium-alginate gel). This work validates the effectiveness of the bioinspired fabrication strategy, which inspires further manufacturing and optimization of materials for diverse applications.

Bioprocess-Inspired Room-Temperature Synthesis of Enamel-like Fluorapatite/Polymer Nanocomposites Controlled by Magnesium Ions.

Tooth enamel is composed of arrayed fluorapatite (FAP) or hydroxyapatite nanorods modified with Mg-rich amorphous layers. Although it is known that Mg2+ plays an important role in the formation of enamel, there is limited research on the regulatory role of Mg2+ in the synthesis of enamel-like materials. Therefore, we focus on the regulatory behavior of Mg2+ in the fabrication of biomimetic mineralized enamel-like structural materials. In the present study, we adopt a bioprocess-inspired room-temperature mineralization technique to synthesize a multilayered array of enamel-like columnar FAP/polymer nanocomposites controlled by Mg2+ (FPN-M). The results reveal that the presence of Mg2+ induced the compaction of the array and the formation of a unique Mg-rich amorphous-reinforced architecture. Therefore, the FPN-M array exhibits excellent mechanical properties. The hardness (2.42 ± 0.01 GPa) and Young's modulus (81.5 ± 0.6 GPa) of the as-prepared FPN-M array are comparable to those of its biological counterparts; furthermore, the enamel-like FPN-M array is translucent. The hardness and Young's modulus of the synthetic array of FAP/polymer nanocomposites without Mg2+ control (FPN) are 0.51 ± 0.04 and 43.5 ± 1.6 GPa, respectively. The present study demonstrates a reliable bioprocess-inspired room-temperature fabrication technique for the development of advanced high-performance composite materials.

Rapid collagen-directed mineralization of calcium fluoride nanocrystals with periodically patterned nanostructures.

Collagen fibrils present periodic structures, which provide space for intrafibrillar growth of oriented hydroxyapatite nanocrystals in bone and contribute to the good mechanical properties of bone. However, there are not many reports focused on bioprocess-inspired synthesis of non-native inorganic materials inside collagen fibrils and detailed forming processes of crystals inside collagen fibrils remain poorly understood. Herein, the rapid intrafibrillar mineralization of calcium fluoride nanocrystals with a periodically patterned nanostructure is demonstrated. The negatively charged calcium fluoride precursor phase infiltrates collagen fibrils through the gap zones creating an intricate periodic mineralization pattern. Later, the nanocrystals initially filling the gap zones only expand gradually into the remaining space within the collagen fibrils. Mineralized tendons with organized calcium fluoride nanocrystals acquire mechanical properties (indentation elastic modulus ∼25.1 GPa and hardness ∼1.5 GPa) comparable or even superior to those of native human dentin and lamellar bone. Understanding the mineral growth processes in collagen may facilitate the development of tissue engineering and repairing.

Bioinspired 3D Printable, Self-Healable, and Stretchable Hydrogels with Multiple Conductivities for Skin-like Wearable Strain Sensors.

Bioinspired hydrogels have promising prospects in applications such as wearable devices, human health monitoring equipment, and soft robots due to their multifunctional sensing properties resembling natural skin. However, the preparation of intelligent hydrogels that provide feedback on multiple electronic signals simultaneously, such as human skin receptors, when stimulated by external contact pressure remains a substantial challenge. In this study, we designed a bioinspired hydrogel with multiple conductive capabilities by incorporating carbon nanotubes into a chelate of calcium ions with polyacrylic acid and sodium alginate. The bioinspired hydrogel consolidates self-healing ability, stretchability, 3D printability, and multiple conductivities. It can be fabricated as an integrated strain sensor with simultaneous piezoresistive and piezocapacitive performances, exhibiting sensitive (gauge factor of 6.29 in resistance mode and 1.25 kPa-1 in capacitance mode) responses to subtle pressure changes in the human body, such as finger flexion, knee flexion, and respiration. Furthermore, the bioinspired strain sensor sensitively and discriminatively recognizes the signatures written on it. Hence, we expect our ideas to provide inspiration for studies exploring the use of advanced hydrogels in multifunctional skin-like smart wearable devices.

Mineralization of calcium phosphate induced by a silk fibroin film under different biological conditions.

Silk fibroin is a promising biomaterial that has been used for tissue engineering applications. However, the influence of silk fibroin on the mineralization of calcium phosphate in different biological environments has not been discussed before. In this work, we fabricated organized silk fibroin film as the organic framework and amorphous calcium phosphate (ACP) deposited on the films as precursors. The transformation pathways and morphology of ACP was then studied in both enzyme and PBS (phosphate buffer saline) solutions. While only hydroxyapatite (HA) crystals formed in enzyme solution, a mixture of tricalcium phosphate (TCP) and HA crystals were obtained in PBS solution, which can be related to the variations of the content of silk fibroin and pH of the solution. Therefore, silk fibroin films can have an important effect on the mineralization process of calcium phosphate in different biological environments. In addition, cell cultivation experiments show that the silk films after mineralization promoted osteogenesis and exhibited good biocompatibility.

Particle-attachment crystallization facilitates the occlusion of micrometer-sized Escherichia coli in calcium carbonate crystals with stable fluorescence.

Inspired from the occlusion of macromolecules in mineral crystals during the biomineralization process, the occlusion mechanism of functional guest species into a host matrix is gradually revealed in artificial systems. However, the guest species within calcite crystals are limited to the nanometer scale. Herein, using amorphous calcium carbonate (ACC) as a precursor and taking advantage of the crystallization of vaterite by the attachment of ACC nanoparticles, micrometer-sized modified Escherichia coli (E. coli) was incorporated into vaterite crystals. The occlusion content of bacteria within the vaterite crystal could reach up to 16 wt%. On the contrary, the occlusion of E. coli into calcite crystals, which proceeded via ion-by-ion addition growth, was only confined to the surface layer. Through modifying the surface structure or chemical composition of bacteria, the strong interaction between the surface of the bacteria and calcium carbonate has proved to be the key factor for successful occlusion. Interestingly, the genetically modified green fluorescent protein (GFP)-E. coli/vaterite composites exhibited stable fluorescence for more than six months with little attenuation and the lifetime could be more than 1.2 µs. It was demonstrated that a combination of the amorphous precursor crystallization pathway and a suitable surface structure of the foreign species can significantly enhance the occlusion efficiency of micrometer-sized species in crystals.