Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Synthesis of lupeol derivatives and their antileishmanial and antitrypanosomal activities

The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by ¹H NMR, ¹³C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC₅₀ = 12.48 μg/mL) and the lowest cytotoxic derivative (CC₅₀ = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase.     

Eye-safe compact scanning LIDAR technology

A 1.5-μm eye-safe, 3-D scanning, and compact Mie LIght Detection and Ranging (LIDAR) is presented. The transmitter of the LIDAR is based on a KTA optical parameter oscillator (OPO) resonator. For detecting return signals, an InGaAs APD is used. The all solid-state OPO laser transmitter has the feature of small volume and lightweight, which allows a 165-lb compact eye-safe scanning LIDAR to be constructed. A system simulation using our own model was conducted to direct the system development. A method to solve the problem with small active area APD detectors was developed and described. The preliminary field-test measurement results indicated that the LIDAR has the capability to detect aerosols and clouds in lower atmospheres up to three dimensions.     

Micromachining of circular ring microstructure by femtosecond laser pulses

In this paper, integration of interference phenomenon into femtosecond laser micromachining was reported as the femtosecond laser pulses were reshaped spatially to perform ablation. The generation of circular interference pattern was demonstrated by overlapping infrared femtosecond laser pulses. The interference pattern was subsequently focused on a copper substrate to ablate microstructures of concentric circular rings. The present technique is expected to open up new applications in the areas of rapid fabrication of micro-Fresnel lenses, hybrid microlenses and lens arrays.     

Character of the thermal motion of water molecules according to the data on quasielastic incoherent scattering of slow neutrons

The paper discusses the applicability of quasi-crystalline approximation to describing the thermal motion of water molecules in their normal and supercooled states. The problem is subjected to the critical analysis of experimental data on incoherent scattering of slow neutrons based on theories developed by Singwi-Sjolander [1] and Oskotsky [2] modified to duly take into account the limited applicability range of diffusion approximation. The applicability conditions of quasi-crystalline approximation are shown to be consistently satisfied only when water is in supercooled state and within a narrow temperature range above the melting temperature.     

Approximate inverse computation using Frobenius inner product

Parallel preconditioners are presented for the solution of general linear systems of equations. The computation of these preconditioners is achieved by orthogonal projections related to the Frobenius inner product. So, min_M∈??∥AM?I∥ _F and matrix M₀∈?? corresponding to this minimum (?? being any vectorial subspace of ??_n(?)) are explicitly computed using accumulative formulae in order to reduce computational cost when subspace ?? is extended to another one containing it. Every step, the computation is carried out taking advantage of the previous one, what considerably reduces the amount of work. These general results are illustrated with the subspace of matrices M such that AM is symmetric. The main application is developed for the subspace of matrices with a given sparsity pattern which may be constructed iteratively by augmenting the set of non‐zero entries in each column. Finally, the effectiveness of the sparse preconditioners is illustrated with some numerical experiments. Copyright © 2002 John Wiley & Sons, Ltd.