Structurally Diverse Polyamines: Solid‐Phase Synthesis and Interaction with DNA

A versatile solid‐phase approach based on peptide chemistry was used to construct four classes of structurally diverse polyamines with modified backbones: linear, partially constrained, branched, and cyclic. Their effects on DNA duplex stability and structure were examined. The polyamines showed distinct activities, thus highlighting the importance of polyamine backbone structure. Interestingly, the rank order of polyamine ability for DNA compaction was different to that for their effects on circular dichroism and melting temperature, thus indicating that these polyamines have distinct effects on secondary and higher‐order structures of DNA.     

Drying of Sewage Sludge During Composting in an Updraft Dryer with the Concept of Using Self-Energy Generated Within the System

An innovative technology for sewage treatment systems is proposed. A mixture of sewage sludge and char particle is subjected to drying in the progress of composting in an updraft column. Exothermic heat generated during composting is utilized for energy of sludge drying. The char particle in the mixture contributes to enhancement of composting and drying rate. This study presents drying and composting behaviors of sludge to examine the effect of char addition. A fundamental drying experiment was carried out by hot-air heating of the sample in a small vessel. The drying characteristic curve for a mixture of sludge and char was greater than the sample of only sludge over a whole period if the drying rates were compared with the same moisture content. The drying behavior could be analyzed with a reasonable agreement by the water front receding model. The enhancement effect of drying and composting of sludge by char addition was confirmed by examination using a pilot scale of the updraft column whose volume was 50 m³. Sludge with 400% dry base (80% wet base) in moisture content could be dried successfully to lower moisture content than 67% dry base (40% wet base) only by exothermic heat during composting without supplying any auxiliary energy from the outside, and the treatment time was reduced by mixing char in sludge. The behavior was analyzed with a satisfactory agreement by a theoretical model employing moisture diffusion parameters determined from the drying characteristic curve.     

Sillimanite‐mullite transformation observed in synchrotron X‐ray diffraction experiments

High‐resolution synchrotron powder X‐ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (T_c). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson‐Mehl‐Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T≥1240°C the mullitization had the same kinetics. The activation energy E at T≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol^?1. In analysis using a time‐temperature‐transformation diagram for mullitization, a mullitization curve of ζ=1% can be described as where t is time, n is a reaction‐mechanism‐dependent parameter determined as 0.324 by JMA‐analysis, k₀ is the frequency factor, E_A is the activation energy for atomic diffusion, and represents the activation energy for nucleation. The results of fitting the data to this equation were T_c=1199°C, A=3.9×10⁶ kJ mol^?1 K^?2, E_A=605 kJ mol^?1, and k₀=3.65×10¹⁵. We conclude that the boundary between sillimanite and mullite+SiO₂ in the phase diagram is ~1200°C.     

Separation of C6H6 and C6H12 from H2 using ionic liquid/PVDF composite membrane

Ionic liquid/polyvinylidene fluoride composite membrane was successfully prepared by impregnation method and used for the separation on organic chemical hydride process. The separation factors of C₆H₆/H₂ and C₆H₁₂/H₂ in the ternary mixture system were 7500 and 300, respectively. The ionic liquid membrane showed an excellent possibility as a technology of H₂ purification in the organic chemical hydride process by removing aromatic hydrocarbon and cycloalkane simultaneously from the ternary system. © 2015 American Institute of Chemical Engineers AIChE J, 62: 624–628, 2016     

Lattice Boltzmann simulation of asymptotic longitudinal mass dispersion in reconstructed random porous media

To research macroscopic mass transport characteristics of porous media, a lattice Boltzmann method (LBM) approach was utilized to calculate asymptotic longitudinal mass dispersion. In this study, a D2Q9 model with multi‐relaxation‐time (MRT) collision operator, which is appropriate for incompressible flow with a high Péclet number without refining the lattice, was chosen. With respect to the microstructure of porous media, random placement (RP) method was applied to obtain randomly positioned particles. Based on the exhausted numerical results presented in the study, a new correlation of longitudinal mass dispersion was established. By comparing with available experimental data in the literature, reasonable agreements are observed in a wide porosity range from 0.3 to 0.7, indicating the validity of the proposed correlation. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2770–2780, 2018     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Effect of temperature on the stereoselectivity of phospholipase D toward glycerol in the transphosphatidylation of phosphatidylcholine to phosphatidylglycerol

In this study, the effect of temperature on the stereoselectivity of phospholipase D (PLD) toward the two primary hydroxyl groups of glycerol in the transphosphatidylation reaction of phosphatidylcholine to phosphatidylglycerol (PtdGro) was investigated. For this purpose, PLD from bacteria (Streptomyces septatus TH-2, S. halstedii subsp. scabies K6, and Actinomadura sp.) and cabbage were tested. At the reaction temperatures employed (0–60°C), the proportions of the two PtdGro diastereomers, namely, 1,2-dioleoyl-sn-glycero-3-phospho-3′-sn-glycerol (R,R configuration) and 1,2-dioleoyl-sn-glycero-3-phosphol-1′-sn-glycerol (R,S configuration), which were produced with PLD from Streptomyces TH-2 and Actinomadura sp., changed gradually from 50% R,R and 50% R,S at 50–60°C to 70% R,R and 30% R,S at O°C. These alterations suggested that the stereoselectivity of the bacterial PLD toward the two primary hydroxyl groups of prochiral glycerol was significantly influenced by reaction temperature. PLD from Streptomyces K6 showed relatively little effect of temperature on stereoselectivity, giving 65–69% R,R in the temperature range of 60–10°C examined. The plots of In ([R,R]/[R,S]) vs. 1/T gave good linear fits for these three bacterial PLD. No temperature effect was observed for cabbage PLD, which gave an almost equimolar mixture of the R,R and R,S diastereomers in the range from 0 to 40°C. The temperature-dependent change in enantiomeric selectivity of the bacterial PLD promises potentially profitable commercial exploitation.     

Enantio-differentiating hydrogenation of prochiral ketones over modified nickel

This article reviews the enantio-differentiating hydrogenation of prochiral ketones over a asymmetrically modified catalyst, focusing on the hydrogenation of simple prochiral alkanones. The parameters affecting catalytic activity and enantiodifferentiating ability are considerable in number, and each parameter should be optimized in order to attain a highperformance enantio-differentiating catalyst. Optimization of the parameters and the mode of enantio-differentiation are discussed and compared with the enantio-differentiating hydrogenation of β-ketoesters.     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Fluorescent imaging of endothelial glycocalyx layer with wheat germ agglutinin using intravital microscopy

Endothelial glycocalyx (GCX) is located on the apical surface of vascular endothelial cells and is composed of a negatively‐charged network of proteoglycans and glycoproteins. The GCX plays an important role in maintaining the integrity of vascular walls and preventing leakage of plasma. Therefore, degradation of the GCX is believed to lead to pathological leakage of plasma. Because the GCX is a very thin layer, its ultrastructural image has been demonstrated on electron microscope. To explore the function of the GCX, it should be visualized by a microscope in vivo. Thus, we developed in vivo visualization technique of the GCX under fluorescence microscopy using a mouse dorsal skinfold chamber (DSC) model. To label and visualize the GCX, we used fluorescein isothiocyanate (FITC)‐labeled lectin, which has a high specificity for sugar moieties. We examined the affinity of the different lectins to epivascular regions under an intravital fluorescent microscope. Among seven different lectins we examined, FITC labeled Triticum vulgaris (wheat germ) agglutinin (WGA) delineated the GCX most clearly. Binding of WGA to the GCX was inhibited by chitin hydrolysate, which contained WGA‐binding polysaccharide chains. Furthermore, the septic condition attenuated this structure, suggesting structural degradation of endothelial GCX layer. In conclusion, FITC‐labeled WGA lectin enabled visualization of endothelial GCX under in vivo fluorescence microscopy. Microsc. Res. Tech. 79:31–37, 2016. © 2015 Wiley Periodicals, Inc.