A Hollow Foldecture with Truncated Trigonal Bipyramid Shape from the Self‐Assembly of an 11‐Helical Foldamer

The creation of self‐assembling microscale architectures that possess new and useful physical properties remains a significant challenge. Herein we report that an 11‐helical foldamer self‐assembles in a controlled manner to form a series of 3D foldectures with unusual three‐fold symmetrical shapes that are distinct from those generated from 12‐helical foldamers. The foldamer packing motif was revealed by powder X‐ray diffraction technique, and provides an important link between the molecular‐level symmetry and the microscale morphologies. The utility of foldectures with hollow interiors as robust and well‐defined supramolecular hosts was demonstrated for inorganic, organic, and even protein guests. This work will pave the way for the design of functional foldectures with greater 3D shape diversity and for the development of biocompatible delivery vehicles and containment vessels.     

Metal‐Free Hydrosilylation Polymerization by Borane Catalyst

The first example of metal‐free hydrosilylation polymerization between dienes and disilanes is developed by using a borane catalyst, B(C₆F₅)₃ to replace precious transition‐metal‐based systems. Under the easy‐to‐handle and mild conditions, a step‐growth polymerization of two readily available diene and disilane units was achieved with high degrees of polymerization. Various combinations of dienes and disilanes produced polycarbosilanes with a broad range of structures and properties.     

Boron‐Based Drug Design

The use of the element boron, which is not generally observed in a living body, possesses a high potential for the discovery of new biological activity in pharmaceutical drug design. In this account, we describe our recent developments in boron‐based drug design, including boronic acid containing protein tyrosine kinase inhibitors, proteasome inhibitors, and tubulin polymerization inhibitors, and ortho‐carborane‐containing proteasome activators, hypoxia‐inducible factor 1 inhibitors, and topoisomerase inhibitors. Furthermore, we applied a closo‐dodecaborate as a water‐soluble moiety as well as a boron‐10 source for the design of boron carriers in boron neutron capture therapy, such as boronated porphyrins and boron lipids for a liposomal boron delivery system.     

In-Depth TEM Investigation on Structural Inhomogeneity within a Primary LixNi0.835Co0.15Al0.015O2 Particle: Origin of Capacity Decay during High-Rate Discharge

The structural stability of cathode materials during electrochemical reactions, in particular, under high-rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi_0.835Co_0.15Al_0.015O₂ (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro- and nano-scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni-rich cathode materials.     

Highly Mesoporous Metal-Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo- and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal-organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo- and biocatalytic components. This was shown by one-pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]-catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

Analysis of Voice and Quantitative Measurement of Glottal Gap After Thyroplasty Type I in the Treatment of Unilateral Vocal Paralysis

Thyroplasty type I is one of several surgical treatments in which improving the voice of unilateral vocal fold paralysis is the ultimate objective. The goal of the surgery is the medialization of the paralyzed vocal fold. The purpose of this study is to evaluate the effectiveness of thyroplasty type I through acoustical analysis, aerodynamic measures, and quantitative videostroboscopic measurements. We report on 20 patients with unilateral vocal cord paralysis who underwent thyroplasty type I. We performed preoperative and postoperative video image analysis (normalized glottal gap area) and computer-assisted voice analysis (fundamental frequency, jitter, shimmer, noise-to-harmonic ratio, mean phonation time, mean flow rate, mean subglottic pressure) in all patients. The glottal gap was significantly reduced after thyroplasty type I. Postoperative voice quality was characterized by an improved pitch and amplitude pertubation (jitter and shimmer), phonation time (mean phonation time), and subglottic pressure (mean subglottic pressure). Thyroplasty type I is an effective method for regaining glottal closure and vocal function.     

Efficiency comparison of subcritical OTEC power cycle using various working fluids

This paper presents an investigation into the thermal efficiency and main component size of the subcritical ocean thermal energy conversion (OTEC) power cycle using various working fluids under different operation conditions. The analysis procedure was performed with a simulation program written in Engineering Equation Solver. With the given analysis conditions, efficiencies of three types of working fluids were evaluated and compared. It was found that the thermal efficiencies of the subcritical OTEC power cycle depend strongly on the evaporating and condensing temperature, and turbine efficiency, while not roughly depending on superheating degrees and pump efficiencies. With a thorough grasp of these results, an efficient OTEC power cycle can be designed. R717 and R404A yielded the highest and lowest thermal efficiencies among the wet fluids, and R22 showed the largest efficiency among the dry fluids. For the iso-entropic fluids, R245fa provided the highest thermal efficiency. In comparison of main component sizes, R404A and R744 had the largest and smallest condenser size, respectively. Also, R744 exhibited the smallest evaporator size, and R404A and R227ea show the largest size. And R744 and R245fa gave the largest and smallest pump size, respectively. From the results of thermal efficiency and main components for various working fluids in the OTEC power cycle, R717 in the subcritical OTEC power cycle is the preferred working fluid, except for its toxicity and flammability.     

A phase-field model for elastically anisotropic polycrystalline binary solid solutions

A phase-field model for modeling the diffusional processes in an elastically anisotropic polycrystalline binary solid solution is described. The elastic interactions due to coherency elastic strain are incorporated by solving the mechanical equilibrium equation using an iterative-perturbation scheme taking into account elastic modulus inhomogeneity stemming from different grain orientations. We studied the precipitate interactions among precipitates across a grain boundary and grain boundary segregation–precipitate interactions. It was shown that the local pressure field from one coherent precipitate influences the shape of precipitates in other grains. The local pressure distribution due to primary coherent precipitates near the grain boundary leads to inhomogeneous solute distribution along the grain boundary, resulting in non-uniform distribution of secondary nuclei at the grain boundary.     

Green route fast synthesis and characterization of chemical bath deposited nanocrystalline ZnS buffer layers

Zinc sulphide (ZnS) thin films are deposited using chemical bath deposition method on the glass substrates in an aqueous alkaline reaction bath of zinc acetate and thiourea along with non-toxic complexing agent tri-sodium citrate at 95 °C. The results show noteworthy improvement in the growth rate of the deposited ZnS thin films and thickness of the film increases with the deposition time. From X-ray diffraction patterns, it is found that the ZnS thin films exhibit hexagonal polycrystalline phase reflecting from (101) and (0016) planes. The high resolution transmission electron microscopy studies confirmed the formation of hexagonal phase from the d-value calculation which was 0.3108 nm. X-ray photoelectron spectroscopy reveals that the Zn–S bonding energy is at 1022.5 and 162.1 eV for Zn 2p_3/2 and S 2p_1/2 states, respectively. Field emission scanning electron microscopy study shows that deposited thin films are highly uniform, with thin thickness and completely free from large ZnS clusters which usually form in aqueous solutions. Atomic force microscopy investigates that root mean square values of the ZnS thin films are from 3 to 4.5 nm and all the films are morphologically smooth. Energy dispersive spectroscopy shows that the ZnS thin films are relatively stoichiometric having Zn:S atomic ratio of 55:45. It is shown by ultraviolet–visible spectroscopy that ～90% transmittance and ～10% absorbance for the ZnS films in the visible region, which is significantly higher than that reported elsewhere and the band gap energy of the ZnS films is found to be 3.76, 3.74, and 3.71 eV, respectively.