Low-temperature chemical synthesis of intermetallic TiFe nanoparticles for hydrogen absorption

Nanosizing of TiFe hydrogen storage alloy is conducted to facilitate its activation. Here, pure intermetallic TiFe nanoparticles (45 nm) were prepared using chemical reduction of oxide precursors at 600 °C, which is the lowest temperature ever used in chemical synthesis. This was achieved using a strong reducing agent (CaH₂) in a molten LiCl. When used for hydrogen absorption, the obtained nanoparticles surprisingly exhibited almost no hydrogen absorption. The results demonstrated that TiFe nanoparticles are more difficult to activate than the bulk powder because the oxidized surface layers of the nanoparticles become stabilized, which prevents the morphological change necessary for their activation.     

Usefulness of solute elution from frozen matrix for freeze-concentration technique

A novel freeze-concentration method was proposed to use solute elution from a frozen matrix as a concentrating operation. A batch crystallizer was made up to freeze solution with a jacket cooler, and a rod heater was set at the centre of the crystallizer in order to make the solution contact with the frozen zone. Commercial apple juice was employed as a model liquid food, and the concentration behavior was investigated with the present apparatus. It was found that the concentration clearly increased with time, and the concentrate was recovered at desirable level if the temperature of the jacket and the heater were properly selected. In fact almost all the solute could be recovered from the original apple juice. The present method would mainly be governed by the solute elution from a frozen phase to a liquid phase, therefore, would not require complicated operation.     

Electrochemical properties of LiFePO4 prepared via hydrothermal route

LiFePO₄ as a cathode material for rechargeable lithium batteries was prepared by hydrothermal process at 170 °C under inert atmosphere. The starting materials were LiOH, FeSO₄, and (NH₄)₂HPO₄. The particle size of the obtained LiFePO₄ was 0.5 μm. The electrochemical properties of LiFePO₄ were characterized in a mixed solvent of ethylene carbonate and diethyl carbonate (1:1 in volume) containing 1.0 mol dm⁻³ LiClO₄. The hydrothermally synthesized LiFePO₄ exhibited a discharge capacity of 130 mA h g⁻¹, which was smaller than theoretical capacity (170 mA h g⁻¹). The annealing of LiFePO₄ at 400 °C in argon atmosphere was effective in increasing the discharge capacity. The discharge capacity of the annealed LiFePO₄ was 150 mA h g⁻¹.     

Improvement of SNAr Reaction Rate by an Electron‐Withdrawing Group in the Crosslinking of DNA Cytosine‐5 Methyltransferase by a Covalent Oligodeoxyribonucleotide Inhibitor

DNA cytosine 5‐methyltransferase (DNMT) catalyzes methylation at the C5 position of the cytosine residues in the CpG sequence. Aberrant DNA methylation patterns are found in cancer cells. Therefore, inhibition of human DNMT is an effective strategy for treating various cancers. The inhibitors of DNMT have an electron‐deficient nucleobase because this group facilitates attack by the catalytic Cys residue in DNMTs. Recently, we reported the synthesis and properties of mechanism‐based modified nucleosides, 2‐amino‐4‐halopyridine‐C‐nucleosides (d^XP), as inhibitors of DNMT. To develop a more efficient inhibitor of DNMT for oligonucleotide therapeutics, oligodeoxyribonucleotides (ODNs) containing other nucleoside analogues, which react more quickly with DNMT, are needed. Herein, we describe the design, synthesis, and evaluation of the properties of 2‐amino‐3‐cyano‐4‐halopyridine‐C‐nucleosides (d^XP^CN) and ODNs containing d^XP^CN, as more reactive inhibitors of DNMTs. Nucleophilic aromatic substitution (S_NAr) of the designed nucleosides, d^XP^CN, was faster than that of d^XP, and the ODN containing d^XP^CN effectively formed a complex with DNMTs. This study suggests that the incorporation of an electron‐withdrawing group would be an effective method to increase reactivity toward the nucleophile of the DNMTs, while maintaining high specificity.     

Transfer to fish of petroleum paraffins and organic sulfur compounds

Eels were maintained in a controlled laboratory environment in water with suspensions of crude oil. Gas chromatography of the eel flesh revealed the presence of paraffins and organic sulfur compounds whose concentration increased with rearing time.     

Enhancement of drawdown force in polypropylene containing nucleating agent

The effect of the nucleation efficiency of three commercial nucleating agents, such as 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS), sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate (SMBP), and magnesium silicate (talc), on the melt-stretching performance of isotactic polypropylene (PP) is studied. It is found that the addition of 0.5 wt % of a nucleating agent enhances the crystallization temperature and that effect is pronounced for DMDBS and SMBP. Furthermore, DMDBS is more efficient than the other tested nucleating agents in enhancing the drawdown force, defined as a force required for stretching a molten strand. Nanofibers of DMDBS, which show significant alignment in the flow direction, are responsible for the rapid crystallization of PP in the flow field leading to an increase of drawdown force. The stretched strand shows a highly oriented structure in which the α-form crystals orient to the flow direction. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47295.     

Janus Kinase Inhibitors Ameliorated Gastrointestinal Amyloidosis and Hypoalbuminemia in Persistent Dermatitis Mouse Model

Malnutrition is not only regarded as a complication of rheumatoid arthritis and inflammatory bowel disease but also that of inflammatory skin disease; however, the mechanisms and efficacy of its treatment have not been elucidated. Using a mouse model of dermatitis, we investigated the pathophysiology of malnutrition in inflammatory skin conditions and efficacy of its treatment. We employed spontaneous skin inflammation mice models overexpressing human caspase-1 in the epidermal keratinocytes. Body weight, nutrition level, and α1-antitrypsin fecal concentration were measured. The gastrointestinal tract was histologically and functionally investigated. Fluorescein isothiocyanate (FITC)-dextran was forcibly fed on an empty stomach, and plasma FITC-dextran was measured. The treatment efficacy of antibodies against tumor necrosis factor-α (TNF-α) and interleukin (IL)-α/β as well as Janus kinase (JAK) inhibitors was investigated. Compared with wild-type littermates, the inflammatory skin mice models showed a lowered body weight, reduction of serum albumin level, amyloid deposition in the stomach, small intestine, and large intestine, and increased α1-antitrypsin fecal concentration. However, the plasma FITC-dextran was unchanged between the dermatitis models and wild-type littermates. The over-produced serum amyloid A1 in the liver was detected in the plasma in the dermatitis model. Antibodies against TNF-α and IL-α/β showed partial effects on amyloid deposition; however, JAK inhibitors improved gastrointestinal amyloidosis with the improvement of skin symptoms. Chronic dermatitis is closely related to secondary amyloidosis in the gastrointestinal tract, resulting in hypoalbuminemia. Therefore, active control of skin inflammation is essential for preventing gastrointestinal complications.     

Photoinduced cooperative reorientation in polymer blend films with hydrogen-bonded mesogenic side groups

Thermally enhanced photoinduced cooperative reorientation in hydrogen (H)-bonded polymer blend films was investigated. The films consisted of two kinds polymethacrylates with hexamethylene spacer groups terminated with 4-oxycinnamic acid (P6CA), 4-oxybenzoic acid (P6BA) or 4-(4′-oxyphenyl)benzoic acid (P6PBA) in the side chains. The films were subjected to linearly polarized ultraviolet (LPUV) light and subsequent annealing. Sufficient cooperative in-plane molecular reorientation in P6CA–P6BA blend films was achieved for the first time. In P6CA–P6PBA blend films, however, reorientation was not observed. The molecular weight, as well as the thermal properties of the homopolymers and the degree of photoreaction all played an important role in the cooperative reorientation behavior of the blend films. Finally, uniform alignment control of low-molecular-weight liquid crystals (LCs) on the molecularly reoriented polymer blend films perpendicular to the polarization E of LPUV light was obtained.     

The modification of porous chromato-gel surface for liquid chromatography by poly(4-vinylpyridine) microgels

A porous chromato-gel for liquid chromatography was modified by fixing poly(4-vinylpyridine) (P4VP) microgels of homogeneous size on its surface, and the microgels were further quarternized by using iodomethane or bromoacetic acid, in order to vary the chromatographic characters of the original chromato-gel. The character of the porous chromato-gel before and after modification was investigated by the retention volume (Ve) of dextran and pullulan standards with various molecular weights (MW: 2 × 10–2 × 10⁶ g/mol). It was found that a single layer of microgels had been fixed compactly on the surface of the chromato-gel, and the retention volume (Ve) and the limit exclusion molecular weight (LEMW) [the molecular weight where the d(Ve)/d(MW) became maximum] were affected remarkably by the sizes and chemical characters of the fixed microgels. The retention volume and LEMW decreased when the pore size formed by microgels was smaller than the hole size of the chromato-gel, while the reverse result was obtained when the pore size formed by the microgels became larger than the hole size of the chromato-gel. After the microgels were quarternized, the retention volume decreased further. Furthermore, the chromato-gel quarternized by bromoacetic acid showed excellent chromatographic character. This study provided an advantage in that the chromatographic characters of the chromato-gel can be varied and improved easily. © 1993 John Wiley & Sons, Inc.