Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

A novel technique for detecting single nucleotide polymorphisms by analyzing consumed allele-specific primers

We present a simple and rapid polymerase chain reaction (PCR)-based technique, termed consumed allele-specific primer analysis (CASPA), as a new strategy for single nucleotide polymorphism (SNP) analysis. The method involves the use of labeled allele-specific primers, differing in length, with several noncomplementary nucleotides added in the 5'-terminal region. After PCR amplification, the amounts of the remaining primers not incorporated into the PCR products are determined. Thus, nucleotide substitutions are identified by measuring the consumption of primers. In this study, the CASPA method was successfully applied to ABO genotyping. In the present method, the allele-specific primer only anneals with the target polymorphic site on the DNA, so it is not necessary to analyze the PCR products. Therefore, this method is only little affected by modification of the PCR products. The CASPA method is expected to be a useful tool for typing of SNPs.     

Evaluation of the evaporation behavior of Pd, Mo, Te, and Sb in simulated low level radioactive liquid waste

To sophisticate the nuclear fuel recycling processes, the transfer percentages for Pd, Mo, Te, and Sb should be determined. Each element solution containing NaNO₃ or HNO₃ was fed consistently into the thin film evaporator regulated in vac and at 50 °C. The analyte percentages in the inside of the lid, in the condenser, and in the distillate were 10^-1%/m², 10^-3%/m², and 10^-3% (DF = 10⁵), respectively. The Mo percentage in the condenser was lower by a factor of 10 than those of other elements investigated. The NO₃ ^- percentages were nearly constant despite increasing HNO₃ concentrations, however, the ratios decreased with increasing NaNO₃ concentrations.     

Reactions of hydropolysilanes with alcohols catalysed by tris(triphenylphosphine)chlororhodium

[RhCl(PPh₃)₃] is a very effective catalyst for the cleavage of Si-Si bonds by alcohols.     

Formation of non-racemic E- and Z-olefins based on discrimination of enantiotopic carbonyl groups in α-diketones by a chiral phosphonate reagent

A chiral HWE reagent reacted with an alternative carbonyl group of meso-α-diketones of bicyclo[2.2.1] system to give non-racemic (Z)- and (E)-olefins, respectively.     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

Oxovanadium(V)-catalyzed enantioselective Meerwein-Ponndorf-Verley cyanation of aldehydes using acetone cyanohydrin

Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect.