Ring opening reaction of gem-difluorocyclopropyl ketones with nucleophiles

Syntheses of gem-difluorocyclopropyl ketones (3a–d) and their reactions with nucleophiles are described. Ring opening reactions of 3a,c and d with a methanolate and a thiolate anion took entirely different courses of bond scission of the cyclopropane ring.     

O(3P)原子和硅烷化学反应动力学研究

本文报道了用流动放电-化学发光技术测定O(~3P)和硅烷化学反应速率常数.在293—413K范围内, 结果为k=(1.05±0.36)×10~(-10)exp[(-3.06±0.10) kcal·mol~(-1) /RT] cm~3·molecule~(-1)·s~(-1)并用过渡态理论将上述实验结果外推到200—2000 K范围内. 计算结果以三参数公式表示为: k=7.67×10~(-19) T~(2.59) exp(-720 cal·mol~(-1)/RT) cm~3·molecule~(-1)·s~(-1).     

Elementary Reactions of Metal Alkyl in Anionic Polymerization. III. Reaction Mode of n-Butylmagnesium Bromide with α,β-Unsaturated Carbonyl Compounds∗

Reaction modes of n-butylmagnesium bromide with α,β-unsaturated esters, ketones, and nitriles were investigated in ether under anionic polymerization conditions. n-Butane and conjugate addition products observed were with all the monomers examined, but carbonyl addition products were not detected except with the unsaturated esters. Product distribution depends mainly upon reaction temperature and the concentration of the Grignard reagent, not upon the concentration of the unsaturated compounds. n-Butyl-magnesium bromide etherate in toluene gave similar results.     

Fluorine in Shark Teeth: Its Direct Atomic‐Resolution Imaging and Strengthening Function

Atomic‐resolution imaging of beam‐sensitive biominerals is extremely challenging, owing to their fairly complex structures and the damage caused by electron irradiation. Herein, we overcome these difficulties by performing aberration‐corrected electron microscopy with low‐dose imaging techniques, and report the successful direct atomic‐resolution imaging of every individual atomic column in the complex fluorapatite structure of shark tooth enameloid, which can be of paramount importance for teeth in general. We demonstrate that every individual atomic column in shark tooth enameloid can be spatially resolved, and has a complex fluorapatite structure. Furthermore, ab initio calculations show that fluorine atoms can be covalently bound to the surrounding calcium atoms, which improves understanding of their caries‐reducing effects in shark teeth.     

NMR‐based analysis of the chemical composition of Japanese persimmon aqueous extracts

Japanese persimmon (Diospyros kaki L.) is recognized as an outstanding source of biologically active compounds relating to many health benefits. In the present study, NMR spectroscopy provided a comprehensive metabolic overview of Japanese persimmon juice. Detailed signal assignments of Japanese persimmon juice were carried out using various 2D NMR techniques incorporated with broadband water suppression enhanced through T₁ effects (BB‐WET) or WET sequences, and 26 components, including minor components, were identified. In addition, most components were quantitatively evaluated by the integration of signals using conventional ¹H NMR and BB‐WET NMR. This is the first detailed analysis combined with quantitative characterization of chemical components using NMR for Japanese persimmon. Copyright © 2015 John Wiley & Sons, Ltd.     

Experimental detection of proteolytic activity in a signal peptide peptidase of Arabidopsis thaliana

Background

The ubiquitin ligase COP1, COnstitutively Photomorphogenic 1, functions in many biological responses in mammalian cells, but its downstream pathway remains unclear.

Results

Here, we identified FIP200, a key regulator of mammalian autophagy, as a novel COP1-interacting protein by yeast two-hybrid screening. The interaction was confirmed by a GST-pulldown assay. Split-GFP analysis revealed that interaction between COP1 and FIP200 predominantly occurred in the cytoplasm and was enhanced in cells treated with UV irradiation. Different forms of FIP200 protein were expressed in cultured mammalian cells, and ectopic expression of COP1 reduced one of such forms.

Conclusions

These data suggest that COP1 modulates FIP200-associated activities, which may contribute to a variety of cellular functions that COP1 is involved in.     

The novel approach to indole alkaloids by using Pd(II)-catalyzed cyclization

The synthesis of indole skeleton by using Pd(II)-catalyzed cyclization of the urethane has been achieved. The urethanes with allylic alcohol were converted into vinyl indolines in good yield. The vinyl indoline was transformed into some intermediates of indole alkaloids.     

Duplex dual-labeled fluorescence probe-based melting curve and endpoint genotyping assays for genotyping of rs2000999 and haptoglobin gene deletion

Haptoglobin (Hp) is a hemoglobin-binding serum glycoprotein. Some variations in the Hp gene (HP) or Hp-related gene (HPR), including a single-nucleotide polymorphism in intron 2 of HRP, rs2000999, and a complete deletion of the HP gene (HP^del), one of the rare variants of HP, have been reported to correlate with the serum cholesterol concentration as well as the serum Hp concentration. In this study, we developed a duplex dual-labeled fluorescence probe-based method to simultaneously determine the rs2000999 G > A polymorphism by melting curve genotyping and the zygosity of HP^del by endpoint genotyping. This method was then validated by using the genomic DNA from 94 Japanese subjects for whom genotypes of rs2000999 and HP^del zygosity had already been determined. The results obtained with this method were in perfect agreement with the previous ones. Thus, the present method enables us to estimate these two polymorphisms in relatively large-scale groups of subjects, especially in Asian populations where the HP^del is distributed.     

Study of the beam loading effect in the CSNS/RCS

The China Spallation Neutron Source/Rapid Cycling Synchrotron (CSNS/RCS) accelerates a high-intensity proton beam from 80 MeV to 1.6 GeV. Since the beam current and beam power is high, the beam loading is a severe problem for the stability of the circulating beam in the RCS. To study the beam loading effect in the CSNS/RCS theoretically, the RLC circuit model of the rf cavity, the method of Fast Fourier Transform and the method of Laplace transform have been employed to obtain the impedance of the rf system, the beam spectrum and the beam-induced voltage, respectively. Based on these physical models, the beam dynamics equations have been revised and a beam loading model has been constructed in the simulation code ORIENT. By using the code, the beam loading effect on the rf system of the CSNS/RCS has been investigated. Some simulation results have been obtained and conclusions have been drawn.     

New mu-opioid receptor agonists with phenoxyacetic acid moiety

New muq-opioid receptor (MOR) agonists containing 4-hydroxypiperidine, piperidine and piperazine moieties were synthesized and evaluated to find a peripheral opioid analgesic. Among the synthesized compounds, 12-[1-[3-(N,N-dimethylcarbamoyl)-3,3-diphenylpropyl]-4-hydroxypiperidin-4-yl]phenoxy]acetic acid (8: SS620) having phenoxyacetic acid and 4-hydroxypiperidine moieties showed the highest agonist potency on the MOR in an isolated guinea-pig ileum preparation, and it also had selectivity to the human MOR expressed in Chinese hamster ovary (CHO)-K1 cells compared with the same types of delta- and kappa-opioid receptors (DOR and KOR). In addition, compound 8 showed a 10 times more potent MOR agonist activity than loperamide. Furthermore, compound 8 showed a peripheral analgesic activity in vivo screening on rat.