Well‐defined,environment‐friendly synthesis of polypeptides based on phosgene‐free transformation of amino acids into urethane derivatives and their applications

In this study, both naturally occurring and artificial amino acids were successfully transformed into the corresponding urethane derivatives using diphenyl carbonate. The urethanes thus prepared could be efficiently cyclized into amino acid N‐carboxyanhydrides (NCAs) without the requirement of phosgene. In addition, the presence of primary amines converted the urethane derivatives into NCAs and initiated the ring‐opening polymerization of the in situ formed NCAs, allowing for the well‐defined synthesis of polypeptides. These polypeptides contained initiating ends functionalized by an amine‐derived residue and propagating ends bearing the reactive amino group. By precise control of the structures of the polypeptides, various polypeptide conjugates such as block copolymers and graft copolymers were successfully synthesized as designed, and their applications in antifouling coatings against proteins, drug delivery systems and biosensors were demonstrated. © 2019 Society of Chemical Industry     

Thermal Spray Using a High-Frequency Pulse Detonation Combustor Operated in the Liquid-Purge Mode

Experiments on thermal spray by pulsed detonations at 150 Hz were conducted. Two types of pulse detonation combustors were used, one operated in the inert gas purge (GAP) mode and the other in the liquid-purge (LIP) mode. In both modes, all gases were supplied in the valveless mode. The GAP mode is free of moving components, although the explosive mixture is unavoidably diluted with the inert gas used for the purge of the hot burned gas. In the LIP mode, pure fuel-oxygen combustion can be realized, although a liquid-droplet injector must be actuated cyclically. The objective of this work was to demonstrate a higher spraying temperature in the LIP mode. First, the temperature of CoNiCrAlY particles heated by pulsed detonations was measured. As a result, the spraying temperature in the LIP mode was higher than that in the GAP mode by about 1000 K. Second, the temperature of yttria-stabilized zirconia (YSZ) particles, whose melting point was almost 2800 °C, heated by pulsed detonations in the LIP mode was measured. As a result, the YSZ particles were heated up to about 2500 °C. Finally, a thermal spray experiment using YSZ particles was conducted, and a coating with low porosity was successfully deposited.     

Development of Sensor and Control Systems of a Wearable Robot to Walk on a Step

The goal of our study is to develop a system for walking on a step using a wearable robot. Our system consists of (1) sensing of a step from the movement of the walker, (2) detection of the foot placement state related to the step, and (3) generation of gait patterns of climbing and stepping down for the step. In the generation of gait patterns for the step, toe trajectories are generated according to the height of the step to avoid collision of the swinging leg with the step. The hip trajectory is generated by an optimization technique that minimizes the sum of the joint angular jerk of the robot subject to constraints on the hip position and the velocity at toe liftoff. Each joint angle trajectory is calculated from the generated trajectories by means of inverse kinematic equations. We investigated the feasibility of the proposed sensor and control systems for two steps with different heights.     

Multi-scale parallel finite element analyses of LDH sheet formability tests based on crystallographic homogenization method

A multi-scale parallel finite element (FE) procedure based on the crystallographic homogenization method was applied to the LDH sheet formability test analysis. For the multi-scale structure, two scales are considered. One is a microscopic polycrystal structure and the other is a macroscopic elastic plastic continuum. The analysis code can predict the formability of sheet metal in macro-scale, simultaneously the crystal texture and hardening evolutions in the micro-scale (Nakamachi E et al. Int J Plasticity 2007;23:450-8). Since huge computation time is required for the nonlinear dynamic multi-scale FE analysis, parallel computing technique based on domain partitioning of FE model for macro-continuum is introduced into the multi-scale code using the message passing interface (MPI) library and PC cluster (Kuramae H et al. In: Proceedings of the eighth international conference on computational plasticity, Part 1, 2005. p. 622-5). The explicit time stepping solution scheme in the nonlinear multi-scale FE dynamic problem is well-suited for parallel computing on distributed memory environment such as PC cluster because solving simultaneous equation is not required. We measured crystal morphologies of four automotive sheet metals, aluminum alloy sheet metals A6022-T43 and A5182-O, an asymmetrically rolled aluminum alloy sheet metal A6022-ASR, and mild steel HC220YD, by using the scanning electron microscope (SEM) with electron back scattered diffraction (EBSD) analyses, and defined a three-dimensional representative volume element (RVE) of micro polycrystal structure, which satisfy the periodicity condition of crystal orientation distribution. We evaluate not only macroscopic formability of the automotive sheet metals by the multi-scale LDH test analysis, but also microcrystalline texture evolution during plastic deformation. Furthermore, a relationship between the macroscopic formability and the microcrystal texture evolution was discussed through looking at multi-scale FE results. It is concluded that the mild steel HC220YD was the highest formability than the aluminum alloy sheet metals because of remaining and generating the γ-fiber texture, such as {1 1 1}〈1 1 0〉-{1 1 1}〈1 1 2〉 orientations, during plastic deformation.     

Cationic polymerization behavior of β‐methylglycidyl ether derivatives and physical properties of their cationically cured materials

β‐Methylglycidyl ethers have been applied to Electrical and Electronic adhesives. However, there is no report about the detailed polymerization behavior and physical properties of their cured products. Hence, we investigated cationic polymerization behavior of bisphenol A di(β‐methylglycidyl) ether (Me‐BADGE) and physical properties of the cured products containing Me‐BADGE. DSC analysis suggested that Me‐BADGE could be cured completely at lower temperature than bisphenol A diglycidyl ether (BADGE). Physical properties were analyzed by dynamic viscoelastic analysis. Glass transition temperature (T_g) of BADGE homopolymer was 194°C. In contrast, the copolymer of BADGE (50 wt %) with Me‐BADGE (50 wt %) showed T_g at 124°C. According to the data of E’ and tan δ, crosslink density of the cured products decreased with increasing the Me‐BADGE content. The analysis of cationic polymerization of monofunctional β‐methylglycidyl ether suggested that the cationic polymerization proceeded not only through oxonium cation but also through carbocation formed by ring‐opening reaction of oxonium cation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42377.     

Biosynthesis of Trehangelin in Polymorphospora rubra K07–0510: Identification of Metabolic Pathway to Angelyl‐CoA

Trehangelins are trehalose angelates discovered from endophytic actinomycete Polymorphospora rubra K07‐0510. We identified the trehangelin biosynthetic gene cluster, including genes that encode a glycoside hydrolase‐like protein (thgC), α‐amylase (thgD), 3‐ketoacyl‐ACP synthase III (thgI), 3‐ketoacyl‐ACP reductase (thgK), enoyl‐CoA hydratase (thgH) and acyl transferase (thgJ). Heterologous expression of thgH, thgI, thgJ and thgK confirmed the importance of these genes in the biosynthesis of trehangelin A. Enzymatic activity studies showed that ThgI catalyses the condensation of acetyl‐CoA and methylmalonyl‐CoA to 2‐methylacetoacetyl‐CoA (MAA‐CoA), ThgK catalyses NADPH‐dependent reduction of MAA‐CoA to 3‐hydroxy‐2‐methylbutyryl‐CoA (HMB‐CoA) and ThgH catalyses the dehydration of HMB‐CoA to angelyl‐CoA (AN‐CoA). This is the first report on the elucidation of the enzymatic formation of AN‐CoA.     

Study on prevention of angular distortion in fillet-welded T-joint by welding with a trailing reverse-side gas heating

Reduction or control of angular distortion without additional processes is demanded because it takes a lot of time and effort to correct the angular distortion of fillet-welded T-joints. In this study, the reduction or control of angular distortion of both sides of a fillet-welded T-joint by welding with trailing reverse-side gas heating was investigated through a welding experiment and its numerical simulation. First, the effect of gas heating position and intensity on the reduction in angular distortion was experimentally investigated using a gas burner. The results showed that angular distortion became smallest when reverse-side heating using the gas burner was located 50 mm backward of the welding torch. Also, the concentrated gas flame with increased propane and oxygen gas flow was effective for reducing angular distortion. It was clarified that the angular distortion could be controlled completely with an appropriate reverse-side gas heating condition. Next, the numerical simulation model of welding and gas heating was constructed based on comparison with the measured temperature histories and angular distortion. Through the numerical simulation of welding with a trailing reverse-side gas, more detailed understanding of the effect of gas heating condition on reduction in angular distortion was developed. In addition, it was confirmed that the gas heating position for the smallest angular distortion is dependent on the temperature distribution along the thickness of the flange plate.