Tooth enamel comprises parallel microscale and nanoscale ceramic columns or prisms interlaced with a soft protein matrix. This structural motif is unusually consistent across all species from all geological eras. Such invariability-especially when juxtaposed with the diversity of other tissues-suggests the existence of a functional basis. Here we performed ex vivo replication of enamel-inspired columnar nanocomposites by sequential growth of zinc oxide nanowire carpets followed by layer-by-layer deposition of a polymeric matrix around these. We show that the mechanical properties of these nanocomposites, including hardness, are comparable to those of enamel despite the nanocomposites having a smaller hard-phase content. Our abiotic enamels have viscoelastic figures of merit (VFOM) and weight-adjusted VFOM that are similar to, or higher than, those of natural tooth enamels-we achieve values that exceed the traditional materials limits of 0.6 and 0.8, respectively. VFOM values describe resistance to vibrational damage, and our columnar composites demonstrate that light-weight materials of unusually high resistance to structural damage from shocks, environmental vibrations and oscillatory stress can be made using biomimetic design. The previously inaccessible combinations of high stiffness, damping and light weight that we achieve in these layer-by-layer composites are attributed to efficient energy dissipation in the interfacial portion of the organic phase. The in vivo contribution of this interfacial portion to macroscale deformations along the tooth's normal is maximized when the architecture is columnar, suggesting an evolutionary advantage of the columnar motif in the enamel of living species. We expect our findings to apply to all columnar composites and to lead to the development of high-performance load-bearing materials.
A systematic approach has been followed in the development of a high-efficiency hybrid photovoltaic device that has a combination of poly(3-hexylthiophene) (P3HT), [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and silver nanowires (Ag NWs) in the active layer using the bulk heterojunction concept. The active layer is modified by utilizing a binary solvent system for blending. In addition, the solvent evaporation process after spin-coating is changed and an Ag NWs is incorporated to improve the performance of the hybrid photovoltaic device. Hybrid photovoltaic devices were fabricated by using a 1:0.7 weight ratio of P3HT to PCBM in a 1:1 weight ratio of o-dichlorobenzene and chloroform solvent mixture, in the presence and absence of 20 wt % of Ag NWs. We also compared the photovoltaic performance of Ag NWs embedded in P3HT:PCBM to that of silver nanoparticles (Ag NPs). Atomic force microscopy, scanning electron microscopy, transmittance electron microscopy, UV-visible absorption, incident photon-to-current conversion efficiency, and time-of-flight measurements are performed in order to characterize the hybrid photovoltaic devices. The optimal hybrid photovoltaic device composed of Ag NWs generated in this effort exhibits a power conversion efficiency of 3.91%, measured by using an AM 1.5G solar simulator at 100 mW/cm(2) light illumination intensity.
Enzyme inhibitors are ubiquitous in all living systems, and their biological inhibitory activity is strongly dependent on their molecular shape. Here, we show that small zinc oxide nanoparticles (ZnO NPs)-pyramids, plates, and spheres-possess the ability to inhibit activity of a typical enzyme β-galactosidase (GAL) in a biomimetic fashion. Enzyme inhibition by ZnO NPs is reversible and follows classical Michaelis-Menten kinetics with parameters strongly dependent on their geometry. Diverse spectroscopic, biochemical, and computational experimental data indicate that association of GAL with specific ZnO NP geometries interferes with conformational reorganization of the enzyme necessary for its catalytic activity. The strongest inhibition was observed for ZnO nanopyramids and compares favorably to that of the best natural GAL inhibitors while being resistant to proteases. Besides the fundamental significance of this biomimetic function of anisotropic NPs, their capacity to serve as degradation-resistant enzyme inhibitors is technologically attractive and is substantiated by strong shape-specific antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA), endemic for most hospitals in the world.
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