添加钛、铌、锰、硫及镁对亚共晶灰铸铁初生奥氏体形核及生长的影响

共晶铸铁在共晶凝固时,熔体中碳的状态,即“C的微小集合体”已经被深入研究.然而时于与初生奥氏体密切相关的铁原子的状态,即“铁的微小集合体”却缺乏研究.本文作者提出,在亚共晶灰铸铁熔体中,初晶γ的形核受“Fe的富集部”的影响,而“Fe的富集部”的形成及消失与“C的微小集合体”有关.研究表明,初生奥氏体的形核过冷度、形核数和晶核生长形貌随工艺条件如过热度、保温时间和冷却速率而变化.本文讨论了在熔体的过热度、保温时间和冷却速率固定的条件下,钛、铌、锰、硫和镁这五种添加元素对亚共晶灰铸铁初晶γ的凝固过程的影响.     

The Association of Cholesterol Uptake and Synthesis with Histology and Genotype in Cortisol-Producing Adenoma (CPA)

Cortisol-producing adenoma (CPA) is composed of clear and compact cells. Clear cells are lipid abundant, and compact ones lipid poor but associated with higher production of steroid hormones. PRKACA mutation (PRKACA mt) in CPA patients was reported to be associated with more pronounced clinical manifestation of Cushing’s syndrome. In this study, we examined the association of histological features and genotypes with cholesterol uptake receptors and synthetic enzymes in 40 CPA cases, and with the quantitative results obtained by gas chromatography-mass spectrometry (GC-MS) analysis in 33 cases to explore their biological and clinical significance. Both cholesterol uptake receptors and synthetic enzymes were more abundant in compact cells. GC-MS analysis demonstrated that the percentage of compact cells was inversely correlated with the concentrations of cholesterol and cholesterol esters, and positively with the activity of cholesterol biosynthesis from cholesterol esters. In addition, hormone-sensitive lipase (HSL), which catalyzes cholesterol biosynthesis from cholesterol esters, tended to be more abundant in compact cells of PRKACA mt CPAs. These results demonstrated that both cholesterol uptake and biosynthesis were more pronounced in compact cells in CPA. In addition, more pronounced HSL expression in compact cells of PRKACA mt CPA could contribute to their more pronounced clinical manifestation.     

Characterization and hydrogen sorption behaviors of FeNiCr-carbon composites derived from Fe,Ni and Cr-containing polyacrylonitrile fibers prepared by electrospinning method

In order to enhance hydrogen storage capacity of carbonaceous materials through metal modification, FeNiCr-carbon composites were prepared by calcination of Fe, Ni and Cr-containing polyacrylonitrile (PAN) fibers fabricated by electrospinning method. Fe (III), Ni (II) and Cr (III) acetylacetonates (M (acac)_n) were selected as metal sources. Increase of specific surface area and formation of micropores were observed on heat decomposition of M (acac)_n particularly through introduction of steam. Maximal hydrogen content, 1.62 mass%, was obtained at 77 K under 0.8 MPa of hydrogen for a FeNiCr-carbon composite, which contained about 15.5 mass% of metals and had specific surface area of 501 m² g^?1. The hydrogen content exceeded the hydrogen physisorption limit, 2.34 mass% per 1000 m² g^?1, which was calculated on the basis of the commensurate–incommensurate transition with an enhancing factor ρ of 1.126. After hydrogenation at 653 K, no hydrogen desorption peaks were observed for FeNiCr powders derived from M (acac)_n, and one peak at 828 K for a carbonaceous sample prepared from unmodified PAN fibers. From the most promising FeNiCr-carbon composite, another peak was recorded at 752 K in addition to the peak at 828 K. The former would be originated from hydrogen on novel sorption sites additionally created on the composite formation.     

Ionization probability of secondary ions sputtered from Si(1 1 1) and Ge(1 1 1) surfaces

We have measured the energy distributions of the secondary ions sputtered from the Si(1 1 1) and Ge(1 1 1) surfaces and investigated the ionization probabilities of sputtered Si⁺ and Ge⁺ ions for clarifying their ionization mechanisms. The observed ionization probabilities depend on the velocity of Si⁺ and Ge⁺ ions. This velocity dependence can be successfully analyzed by a theoretical expression, which was proposed originally for the metal surfaces. This implies that the ionization mechanism of Si⁺ and Ge⁺ ions is the same as ions sputtered from the metal surface, i.e., the resonant electron transfer in the high velocity regime and the thermal excitation process in the low velocity regime. The difference in the ionization probability between Si⁺ and Ge⁺ ions is well explained by the difference in the band gap energy.     

Evaluation of the Anti-Proliferative Activity of Rare Aldohexoses against MOLT-4F and DU-145 Human Cancer Cell Line and Structure-Activity Relationship of D-Idose

D-Allose (D-All), a C-3 epimer of D-glucose (D-Glc), is a naturally rare monosaccharide, which shows anti-proliferative activity against several human cancer cell lines. Unlike conventional anticancer drugs, D-All targets glucose metabolism and is non-toxic to normal cells. Therefore, it has attracted attention as a unique “seed” compound for anticancer agents. However, the anti-proliferative activities of the other rare aldohexoses have not been examined yet. In this study, we evaluated the anti-proliferative activity of rare aldohexoses against human leukemia MOLT-4F and human prostate cancer DU-145 cell lines. We found that D-All and D-idose (D-Ido) at 5 mM inhibited cell proliferation of MOLT-4F cells by 46 % and 60 %, respectively. On the other hand, the rare aldohexoses at 5 mM did not show specific anti-proliferative activity against DU-145 cells. To explore the structure–activity relationship of D-Ido, we evaluated the anti-proliferative activity of D-sorbose (D-Sor), 6-deoxy-D-Ido, and L-xylose (L-Xyl) against MOLT-4F cells and found that D-Sor, 6-deoxy-D-Ido, and L-Xyl showed no inhibitory activity at 5 mM, suggesting that the aldose structure and the C-6 hydroxy group of D-Ido are important for its activity. Cellular glucose uptake assay and western blotting analysis of thioredoxin-interacting protein (TXNIP) expression suggested that the anti-proliferative activity of D-Ido is induced by inhibition of glucose uptake via TXNIP-independent pathway.     

Analysis of imazalil and its major metabolite in citrus fruits by GC-FTD

A simplified simultaneous analytical method of imazalil (IZ) and its major metabolite, alpha-(2,4-dichlorophenyl)-1H-imidazole-1-ethanol (IZM), in citrus fruits was developed, and commodities samples were investigated. A homogenate of citrus fruits was extracted with ethyl acetate under basic conditions. The crude extract was partitioned between 0.025 mol/L of sulfuric acid and ethyl acetate. The analytes were extracted from the aqueous fraction under basic conditions with ethyl acetate. The extract solution was purified with an ENVI-Carb cartridge, and then analyzed by GC-FTD and GC/MS. Recoveries of IZ and IZM added to grapefruit at the level of 0.05 microgram/g were 90.0 and 108.7%, and those in the case of lemon were 100.4 and 93.0%, respectively. The detection limits were 0.01 microgram/g in samples. By this method, IZ and IZM were analyzed in 46 citrus fruits on the market and were detected simultaneously in some samples.     

Oxidation of Fe (II) in sulfuric acid solutions with dissolved molecular oxygen

The oxidation of Fe(II) with dissolved molecular oxygen was studied in sulfuric acid solutions containing 0.2 mol . dm^-3 FeSO₄ at temperatures ranging from 343 to 363 K. In solutions of sulfuric acid above 0.4 mol . dm^-3, the oxidation of Fe (II) was found to proceed through two parallel paths. In one path the reaction rate was proportional to both [Fe²⁺]² and po₂, exhibiting an activation energy of 51.6 . kJ mol^-1. In another path the reaction rate was proportional to [Fe²⁺]², [SO_4-], and po₂ with an activation energy of 144.6 kJ . mol^-1. A reaction mechanism in which the SO_4- ions play an important role was proposed for the oxidation of Fe(II). In dilute solutions of sulfuric acid below 0.4 mol . dm^-3, the rate of the oxidation reaction was found to be proportional to both [Fe(II)]² and Po₂, and was also affected by [H⁺] and [SO_2- ⁴]. The decrease in [H⁺] resulted in the increase of reaction rate. The discussion was further extended to the effect of Fe (III) on the oxidation reaction of Fe (II).     

L-Ergothioneine scavenges superoxide and singlet oxygen and suppresses TNF-α and MMP-1 expression in UV-irradiated human dermal fibroblasts

The hair lipid composition collected from 44 Japanese females between 1 and 81 years of age was examined for eight lipids including hydrocarbons (HCs), squalene (SQ), wax esters (WEs), triglycerides (TGs), fatty acids (FAs), cholesterol (CH), ceramides (CERs), and 18-methyl eicosanoic acid (MEA). In this study, the 5-cm length from the proximal root end of hair fibers, which had never been exposed to any chemical treatment, was used after 5-min incubation with hexane following shampooing. Hair lipids were extracted with solvent and subsequent alkali-solvent and were then analyzed by a combination of chromatography. Although the average contents of the lipids showed great fluctuations among individuals, there were significant correlations between the levels of each lipid, which allowed for the classification of the hair lipids into four groups: group A: SQ, WEs, TGs, and FAs (designated as endogenous lipids based upon their sebum origin); group B: CH and CERs (designated as endogenous lipids); group C: HC (unknown origin); and group D: MEA (the other endogenous lipid). A principal component analysis for eight lipids revealed that the hair lipid composition was characterized by a predominant negative correlation between each lipid for groups A and B. This negative correlation suggests that the endogenous lipids in group B serve as a barrier against the penetration of predominantly sebum-derived exogenous lipids (group A). Endogenous lipids consisting of CH and CERs (group B) and MEA (group D) should be designated as intrinsic internal lipids of human hair.     

Reaction mechanism of fluoroacetate dehalogenase from Moraxella sp. B

Fluoroacetate dehalogenase (EC 3.8.1.3) catalyzes the dehalogenation of fluoroacetate and other haloacetates. The amino acid sequence of fluoroacetate dehalogenase from Moraxella sp. B is similar to that of haloalkane dehalogenase (EC 3.8.1.5) from Xanthobacter autotrophicus GJ10 in the regions around Asp-105 and His-272, which correspond to the active site nucleophile Asp-124 and the base catalyst His-289 of the haloalkane dehalogenase, respectively (Krooshof, G. H., Kwant, E. M., Damborsky, J., Koca, J., and Janssen, D. B. (1997) Biochemistry 36, 9571-9580). After multiple turnovers of the fluoroacetate dehalogenase reaction in H218O, the enzyme was digested with trypsin, and the molecular masses of the peptide fragments formed were measured by ion-spray mass spectrometry. Two 18O atoms were shown to be incorporated into the octapeptide, Phe-99-Arg-106. Tandem mass spectrometric analysis of this peptide revealed that Asp-105 was labeled with two 18O atoms. These results indicate that Asp-105 acts as a nucleophile to attack the alpha-carbon of the substrate, leading to the formation of an ester intermediate, which is subsequently hydrolyzed by the nucleophilic attack of a water molecule on the carbonyl carbon atom. A His-272 --> Asn mutant (H272N) showed no activity with either fluoroacetate or chloroacetate. However, ion-spray mass spectrometry revealed that the H272N mutant enzyme was covalently alkylated with the substrate. The reaction of the H272N mutant enzyme with [14C]chloroacetate also showed the incorporation of radioactivity into the enzyme. These results suggest that His-272 probably acts as a base catalyst for the hydrolysis of the covalent ester intermediate.