Tooth enamel, renowned for its high stiffness, hardness, and viscoelasticity, is an ideal model for designing biomimetic materials, but accurate replication of complex hierarchical organization of high-performance biomaterials in scalable abiological composites is challenging. We engineered an enamel analog with the essential hierarchical structure at multiple scales through assembly of amorphous intergranular phase (AIP)–coated hydroxyapatite nanowires intertwined with polyvinyl alcohol. The nanocomposite simultaneously exhibited high stiffness, hardness, strength, viscoelasticity, and toughness, exceeding the properties of enamel and previously manufactured bulk enamel-inspired materials. The presence of AIP, polymer confinement, and strong interfacial adhesion are all needed for high mechanical performance. This multiscale design is suitable for scalable production of high-performance materials.

Currently, the development of semiconducting metal oxide (SMO)-based gas sensors with innovative modification and three-dimensional (3D) structural designs has become a significant scientific interest due to their potential for addressing key technological challenges. Herein, gas sensing devices based on the 3D hierarchical monoclinic-type structural Sb-doped WO₃ (HMSW) gas sensing material were successfully constructed by ordered assembly of urchin-like monoclinic-type structural (P2/m) Sb-doped WO_2.72 (W₁₈O₄₉) (UMSW) nanocrystals and nanowires. The crystalline microstructure, composition, morphological characteristics, and possible growth mechanisms were systematically investigated. The results of the gas sensor measurements, performed simultaneously on multiple samples, indicated that the 3D HMSW material has superior sensitivity (S = 122) and high selectivity to ppm-level NO₂ at 30 °C with a significantly larger response than the best-reported values from other WO₃-based gas sensors fabricated so far. All the results clearly demonstrate that the combined effects of abundant structural defects derived from Sb doping modification, reduced band gap, and 3D hierarchical microstructure synergistically play a key role in the NO₂ gas sensing performance. Such excellent gas sensing performance foresees the great potential application of 3D hierarchical structural WO₃-based sensors for fast and effective detection of toxic gases that can aid in human health and public safety.

Tooth enamel, and especially the outer tooth enamel, is a load-resistant shell that benefits mastication but is easily damaged, driving the need for enamel-restorative materials with comparable properties to restore the mastication function and protect the teeth. Synthesizing an enamel analog that mimics the components and hierarchical structure of natural tooth enamel is a promising way to achieve these comparable mechanical properties, but it is still challenging to realize. Herein, we fabricate a hierarchical enamel analog with comparable stiffness, hardness, and viscoelasticity as natural enamel by incorporating three hierarchies of outer tooth enamel based on hierarchical assembly of enamel-like hydroxyapatite hybrid nanowires with polyvinyl alcohol as a matrix. This enamel analog possesses enamel-similar inorganic components and a nanowire-microbundle-macroarray hierarchical structure. It exhibits toughness of 19.80 MPa m^1/2, which is 3.4 times higher than natural tooth enamel, giving it long-term fatigue durability. This hierarchical design is promising for scalable production of enamel-restorative materials and for optimizing the mechanical performance of engineering composites.