Electrochemical behavior of [UO_2Cl_4]~(2-) in 1-ethyl-3-methylimidazolium based ionic liquids

In order to examine the chemical form of uranyl species in 1-ethyl-3-methylimidazolium(EMI) based ionic liquids,UV-visible absorption spectra of solutions prepared by dissolving [EMI] 2 [UO2Cl4] into a mixture of EMICl and EMIBF 4(50:50 mol%) were measured.As a result,it was confirmed that uranyl species in the mixture of EMICl and EMIBF 4 existed as [UO2Cl4]2-.Cyclic voltammograms(CVs) of [UO2Cl4]2-in the mixture were measured at 25 ℃ using a Pt working electrode,a Pt wire counter electrode,and an Ag/Ag + reference electrode(0.01 M AgNO 3,0.1 M tetrabutylammonium perchlorate in acetonitrile) in a glove box under an Ar atmosphere.Peaks corresponding to one redox couple were observed around-1.05 V(Epc) and-0.92 V(Epa) vs.ferrocene/ferrocenium ion(Fc/Fc +).The potential differences between two peaks(Ep) increased from 101 to 152 mV with an increase in the scan rate from 50 to 300 mV s-1,while the(Epc+Epa)/2 value was constant,-0.989 V vs.Fc/Fc + regardless of the scan rate.Furthermore,the diffusion coefficient of [UO2Cl4]2-and the standard rate constant were estimated to be 3.7 × 10-8 cm 2 s-1 and(2.7-2.8) × 10-4 cm s-1 at 25 oC.By using the diffusion coefficient and the standard rate constant,the simulation of CVs was performed based on the reaction,[UO2Cl4]2-+ e = [UO2Cl4]3-.The simulated CVs were found to be consistent with the experimental ones.From these results,it is concluded that [UO2Cl4]2-in the mixture of EMICl and EMIBF 4 is reduced to [UO2Cl4]3-quasi-reversibly at-0.989 V vs.Fc/Fc +.     

Oxidative heck-type reaction involving cleavage of a carbon-phosphorus bond of arylphosphonic acids

Cleavage of a carbon-phosphorus bond is achieved under palladium catalysis in an oxidative Heck-type reaction which exploits arylphosphonic acids. The reaction of arylphosphonic acids with alkenes provides arylation products in good yields in the presence of TBAF with trimethylamine oxide as an oxidant.     

Double bond cleavage reaction of silyl enol ethers using MoO2(acac)2-tBuOOH

The double bond of various silyl enol ethers is smoothly cleaved to give carbonyl compounds by an oxidizing reagent MoO₂(acac)₂-^tBuOOH.     

Radiation-induced postpolymerization of trioxane in the solid state. IV. Copolymerization of trioxane with dioxolane

The radiation-induced postpolymerization of trioxane with 1,3-dioxolane has been investigated. Trioxane and 1,3-dioxolane were carefully purified in a rigorously dry, high-vacuum system. In the present study it was found that trioxane can be easily copolymerized with 1,3-dioxolane to give a copolymer having high molecular weight and excellent thermal stability. Typically, the isothermal weight loss after heating for 60 minutes under nitrogen at 222°C was 3.5% for a copolymer of trioxane and 1.0 wt-%1,3-dioxolane preirradiated with a dose of 1.0 × 10⁵ Rad. The thermal stability of the copolymer was scarcely affected by the polymerization temperature and time, although it decreased slightly with increasing preirradiation dose. The dependences of the yield and inherent viscosity of the polymer on the preirradiation dosage, polymerization temperature and time were quite similar to those found for the homopolymerization of trioxane. The results were analyzed by using the kinetic scheme previously reported, and it was found that no chain transfer reaction occurs in this system. These results are discussed in comparison with those of homopolymerization reported previously.     

A single-strand conformation polymorphism method for the large-scale analysis of mutations/polymorphisms using capillary array electrophoresis

We present a high-throughput single-strand conformation polymorphism (SSCP) method, performed on a commercially available capillary array DNA sequencer. We tested various sieving matrices and electrophoretic conditions, using 51 DNA fragments which included 45 fragments carrying only one single nucleotide polymorphism (SNP), 4 fragments having two SNPs and 2 fragments with insertion or deletion. Resolution of alleles was improved by increasing concentrations of both sieving matrices and buffers, and all examined polymorphisms of DNA fragments were detected, most of them (45 fragments) as clearly split allele peaks in heterozygotes. Allele frequencies of SNPs can be estimated accurately by determining the relative amounts of alleles in pooled DNA. In this method, the turn-around time for the analysis of 96 samples is less than 3 h. These results demonstrate that capillary array-based SSCP is an efficient and accurate technique for the large-scale quantitative analysis of mutations/polymorphisms.     

Reaction of alpha,alpha-dibromo oxime ethers with Grignard reagents: alkylative annulation providing a pyrimidine core

A convergent synthesis of a pyrimidine core has been achieved. Treatment of alpha,alpha-dibromo oxime ethers, which are easily derived from the corresponding esters, with a variety of Grignard reagents provides trisubstituted pyrimidines in good yields. This new method offers an easy access to functionalized pyrimidines.     

Highly intense fluorescent diarylboron diketonate

Diarylboron diketonates were successfully prepared by the reaction of 1,3-diketone derivatives and arylboron compounds such as triphenylborane [BPh3] and fluorobis(pentafluorophenyl)borane diethyl etherate [(C6F5)2BF x OEt2]. The fluorescent emission of their complexes took place depending on the substituent of the arylboron moiety. In particular, a boron 1,3-bis(4-methoxyphenyl)-1,3-diketonate chelated by a strong electron-withdrawing C6F5 group exhibited the most intense fluorescence.     

Nanotransfer of the polythiophene molecular alignment onto the step-bunched vicinal Si(111) substrate

A poly(3-dodecylthiophene-2,5-diyl) film having in-plane anisotropic molecular arrangement was successfully fabricated by transferring its Langmuir-Blodgett film onto a step-bunched Si(111) substrate. Polarized near-edge X-ray absorption fine structure measurements revealed that the polythiophene main chains are preferentially orientated along periodic facet/terrace nanostructures on the step-bunched substrate, whereas less anisotropy was found on a flat substrate. The step-bunched Si substrate has been proved to be effective for controlling the in-plane molecular arrangement in the polymer thin film.