Hydrometallation of 1-alkyl-3-trifluoromethyl propargyl alcohols

The hydrometallation of trifluoromethylated propargyl alcohol derivatives with metal hydride reagents proceeds smoothly to give cis- and trans-olefins on H₂O quenching. The halodemetallation of intermediate formed in the reaction process was also examined.     

Synthesis of cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives by use of the [2 + 8] cycloaddition reaction of indolizines and dimethyl acetylenedicarboxylate

The reaction of 1-ethoxycarbonylmethylpyridinium bromides 5a-k with nitro ketene dithioacetal, 1,1-bis-(methylthio)-2-nitroethylene ( 2 ), in the presence of triethylamine in ethanol gave the desired ethyl 2-methyl-thioindolizine-3-carboxylates 3a-k in good yields, along with ethyl 2-methylthio-1-nitroindolizine-3-carboxyl-ates 4a-d . Deesterification of 3 using sodium hydroxide in methanol followed by treatment with polyphosphoric acid gave the corresponding 2-methylthioindolizines 5a-d in good yields. The desulfurization of 5 with Raney-nickel in ethanol occurs smoothly to give the 1,2,3-unsubstituted indolizines 6a-c (a , parent indolizine; b , 8-methylindolzine; c , 6,8-dimethylindolizine). Similarly, pyrrolo[2,1-a]isoquinoline ( 19 ) was also synthesized. These indolizine and pyrrolo[1,2-a]isoquinoline derivatives were allowed to react with dimethyl acetylene to give the corresponding cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives in good results.     

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.     

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.     

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.