Direct Probing of Lattice-Strain-Induced Oxygen Release in LiCoO2 and Li2 MnO3 without Electrochemical Cycling.

Since the recognition of a significant oxygen-redox contribution to enhancing the capacity of Li transition-metal oxide cathodes, the oxygen release and subsequent structural variations together with capacity fading are critical issues to achieve better electrochemical performance. As most previous reports dealt with the structural degradation of cathodes after electrochemical cycling, it is fairly difficult to clarify how substantial the effect of lattice strain on the oxygen release will be while exclusively ruling out any electrochemical influences. By utilizing nanoindentation and mechanical surface polishing of single-crystal LiCoO2 and Li2 MnO3 , the local variations of both the atomic structure and oxygen content are scrutinized. Atomic-column-resolved imaging reveals that local LiM (M = Co and Mn) disordering and further amorphization are induced by mechanical strain. Moreover, substantial oxygen deficiency in the regions with these structural changes is directly identified by spectroscopic analyses. Ab initio density functional theory calculations also demonstrate energetically favorable formation of oxygen vacancies under shear strain. Providing direct evidence of oxygen release as a consequence of lattice strain, the findings in this work suggest that efficient strain relaxation will be of great significance for longevity of the anion framework in layered oxide cathodes.

Multiscale Functional Metal Architectures by Antibody-Guided Metallization of Specific Protein Assemblies in Ex Vivo Multicellular Organisms.

Biological systems consist of hierarchical protein structures, each of which has unique 3D geometries optimized for specific functions. In the past decades, the growth of inorganic materials on specific proteins has attracted considerable attention. However, the use of specific proteins as templates has only been demonstrated in relatively simple organisms, such as viruses, limiting the range of structures that can be used as scaffolds. This study proposes a method for synthesizing metallic structures that resemble the 3D assemblies of specific proteins in mammalian cells and animal tissues. Using 1.4 nm nanogold-conjugated antibodies, specific proteins within cells and ex vivo tissues are labeled, and then the nanogold acts as nucleation sites for growth of metal particles. As proof of concept, various metal particles are grown using microtubules in cells as templates. The metal-containing cells are applied as catalysts and show catalytic stability in liquid-phase reactions due to the rigid support provided by the microtubules. Finally, this method is used to produce metal structures that replicate the specific protein assemblies of neurons in the mouse brain or the extracellular matrices in the mouse kidney and heart. This new biotemplating approach can facilitate the conversion of specific protein structures into metallic forms in ex vivo multicellular organisms.

Friction Control by Deformation Mode in Nanopatterned Amorphous Carbon.

Traditionally, the manipulation of contact mechanisms has been adopted as the primary strategy to tailor the friction properties of surfaces. On the contrary, the detaching process involving the local deformation and failure at the interface has been considered relatively less important. Here, we present a new approach toward the friction control of amorphous carbon through the plasticity and resultant transition of deformation mode on nanopatterned surfaces. Depending on the topography of the nanopatterns, the mechanical responses of the surfaces alter from elastic fracture to plastic flow, through which the friction coefficient changes by a factor of 5 without manipulation of the intrinsic structure of the material.

Reversed Anionic Hofmeister Effect in Metal-Phenolic-Based Film Formation.

Although metal-phenolic species have emerged as one of the versatile material-independent-coating materials, providing attractive tools for interface engineering, mechanistic understanding of their film formation and growth still remains largely unexplored. Especially, the anions have been overlooked despite their high concentration in the coating solution. Considering that the anions are critical in the reactivity of metal-organic complex and the formation and/or property of functional materials, we investigated the anionic effects on the characteristics of film formation, such as film thickness and properties, in the Fe3+-tannic acid coating. We found that the film characteristics were strongly dictated by the counteranions (e.g., SO42-, Cl-, and Br-) of the Fe3+ ion. Specifically, the film thickness and properties (i.e., mechanical modulus, permeability, and stability) followed the reversed anionic Hofmeister series (Br- > Cl- > SO42-). Mechanistic studies suggested that more chaotropic anions, such as Br-, might induce a more widely extended structure of the Fe3+-TA complexes in the coating solution, leading to thicker, harder, but more porous films. The reversed anionic Hofmeister effect was further confirmed by the additive effects of various sodium salts (NaF, NaCl, NaBr, and NaClO4).