Development and performance evaluation of a GC-FPD method for quantification of ethephon in feeds

An analytical method of ethephon in feeds by GC-FPD was developed. Ethephon was extracted with ethyl acetate-hydrochloric acid (100 : 1) from feed samples. The extract was treated with added trimethylsilyldiazomethane in acetone-acetic acid (99 : 1) and this methylation procedure was repeated three times. Methylated ethephon was cleaned up on a graphitized carbon mini-column and a silicagel mini-column, and determined by GC-FPD. A method performance study in 7 laboratories was conducted with three kinds of samples spiked with ethephon at 10 mg/kg, 1 mg/kg and 0.5 mg/kg. The recovery of ethephon ranged from 81.8% to 90.8% (the reproducibility standard deviation (RSDr) were within 11%) and HorRat values were 0.58 to 0.94. The limit of detection (S/N≧3) and the limit of quantitation (S/N≧10) of ethephon in samples except hay were 0.02 mg/kg and 0.05 mg/kg, respectively. In the case of hay, the corresponding values were 0.2 mg/kg and 0.5 mg/kg, respectively.     

Ceramide Metabolism Regulated by Sphingomyelin Synthase 2 Is Associated with Acquisition of Chemoresistance via Exosomes in Human Leukemia Cells

Ceramide levels controlled by the sphingomyelin (SM) cycle have essential roles in cancer cell fate through the regulation of cell proliferation, death, metastasis, and drug resistance. Recent studies suggest that exosomes confer cancer malignancy. However, the relationship between ceramide metabolism and exosome-mediated cancer malignancy is unclear. In this study, we elucidated the role of ceramide metabolism via the SM cycle in exosomes and drug resistance in human leukemia HL-60 and adriamycin-resistant HL-60/ADR cells. HL-60/ADR cells showed significantly increased exosome production and release compared with parental chemosensitive HL-60 cells. In HL-60/ADR cells, increased SM synthase (SMS) activity reduced ceramide levels, although released exosomes exhibited a high ceramide ratio in both HL-60- and HL-60/ADR-derived exosomes. Overexpression of SMS2 but not SMS1 suppressed intracellular ceramide levels and accelerated exosome production and release in HL-60 cells. Notably, HL-60/ADR exosomes conferred cell proliferation and doxorubicin resistance properties to HL-60 cells. Finally, microRNA analysis in HL-60 and HL-60/ADR cells and exosomes showed that miR-484 elevation in HL-60/ADR cells and exosomes was associated with exosome-mediated cell proliferation. This suggests that intracellular ceramide metabolism by SMS2 regulates exosome production and release, leading to acquisition of drug resistance and enhanced cell proliferation in leukemia cells.     

Anammox Bacterial S-Adenosyl-l-Methionine Dependent Methyltransferase Crystal Structure and Its Interaction with Acyl Carrier Proteins

Ladderane lipids (found in the membranes of anaerobic ammonium-oxidizing [anammox] bacteria) have unique ladder-like hydrophobic groups, and their highly strained exotic structure has attracted the attention of scientists. Although enzymes encoded in type II fatty acid biosynthesis (FASII) gene clusters in anammox bacteria, such as S-adenosyl-l-methionine (SAM)-dependent enzymes, have been proposed to construct a ladder-like structure using a substrate connected to acyl carrier protein from anammox bacteria (AmxACP), no experimental evidence to support this hypothesis was reported to date. Here, we report the crystal structure of a SAM-dependent methyltransferase from anammox bacteria (AmxMT1) that has a substrate and active site pocket between a class I SAM methyltransferase-like core domain and an additional α-helix inserted into the core domain. Structural comparisons with homologous SAM-dependent C-methyltransferases in polyketide synthase, AmxACP pull-down assays, AmxACP/AmxMT1 complex structure predictions by AlphaFold, and a substrate docking simulation suggested that a small compound connected to AmxACP could be inserted into the pocket of AmxMT1, and then the enzyme transfers a methyl group from SAM to the substrate to produce branched lipids. Although the enzymes responsible for constructing the ladder-like structure remain unknown, our study, for the first time, supports the hypothesis that biosynthetic intermediates connected to AmxACP are processed by SAM-dependent enzymes, which are not typically involved in the FASII system, to produce the ladder-like structure of ladderane lipids in anammox bacteria.     

Contrasting Lubrication Properties of Imidazolium-Based Ionic Liquids Affected by the Nature of the Surface Under High Vacuum

The lubrication performance of imidazolium-based ionic liquids was evaluated under high vacuum using a ball-on-disk tribometer. A ball and a flat disk made of SUS440C stainless steel were used as specimens. A surface of the as-received flat disk specimen was covered with a thick oxide layer (>40 nm). For an examination of the effect of the surface oxide layer on the tribological performance of the ionic liquids under high vacuum, another specimen with a thin oxide layer (approx. 4 nm thick) was prepared. The ionic liquids with the TFSA anion showed better lubrication performance with the thicker oxide layer specimen, whereas the ionic liquids with the BF4 anion showed superior performance with the thinner oxide layer specimen. These results are discussed based on the HSAB principle. It is shown that the mechanism of the opposite tribological characteristics can be reasonably explained in terms of the chemical hardness by the HSAB principle.     

Shape optimization of steady‐state heat‐conduction fields considering temperature dependency of thermal conductivity coefficient

This paper presents a numerical analysis method for shape optimization of domains with steady‐state heat‐conduction fields considering the temperature dependence of the thermal conductivity coefficient. In this paper, we formulate two shape optimization problems, namely, maximization of thermal dissipation on heat transfer boundaries and minimization of heat‐conduction fields. The shape gradient functions for these shape optimization problems are derived theoretically using the Lagrange multiplier method and formulae of the material derivative. Reshaping is accomplished using the traction method proposed as a solution to the shape optimization problems. The proposed method is validated from the results of two‐dimensional numerical analysis. © 2011 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20374     

Optogalvanic spectroscopy using 389 nm coherent light source accurately tuned to resonance frequency of 2S->3P of He

An efficient 389 nm coherent light source, made possible through the single-pass second-harmonic generation of a picosecond Ti:sapphire laser with a periodically poled lithium niobate waveguide, was developed for the metastability exchange optical pumping of hyperpolarized ³He gas, which is applicable to imaging with nuclear magnetic resonance. The second-harmonic light provided such a broad spectrum that some split sub-levels of its metastable state under an applied magnetic field could be pumped efficiently and simultaneously. Optogalvanic spectroscopy using the light source indicated that the spectral width of ³He was much less than 70 GHz, which was similar to the spectral width of the light source.     

Phase and Formation/Dissolution of Precipitates in Biomedical Co-Cr-Mo Alloys with Nitrogen Addition

The precipitates in as-cast and heat-treated biomedical Co-28Cr-6Mo-(0 to 0.35)C-(0.15 to 0.25)N alloys (mass pct) were investigated. Heat treatment was carried out at temperatures of 1473?K to 1573?K (1200???C to 1300???C) for holding periods of 0 to 43.2?ks. In the as-cast and heat-treated Co-Cr-Mo-N alloys, no precipitates were detected; nitrogen effectively inhibited the formation of the ??-phase and stabilized the face-centered cubic (fcc) metallic ??-phase. The precipitates observed in the as-cast and heat-treated Co-Cr-Mo-C-N alloys were of the M₂₃X₆ type, M₂X type, ??-phase (M₂T₃X type with a ??-Mn structure), and ??-phase (M₆X-M₁₂X type). Complete precipitate dissolution was detected in the alloys with carbon contents of less than 0.3 mass pct regardless of the nitrogen content. The main precipitates were of the M₂X and M₂₃X₆ types after heat treatment for 1.8 to 43.2?ks. The ??-phase precipitate was detected in the early stage of heat treatment at high temperatures. The formation of the M₂X-type precipitate was enhanced by the addition of nitrogen, although the constitution of the precipitates depended on the balance between the nitrogen and carbon contents and the heat-treatment conditions.