Preparation of dibromopyridines having -(CH2)m-SO3Na groups as monomers for new polypyridines

Dibromopyridines or dibromopyridone with -(CH₂)_m-SO₃Na group(s) has been prepared via the reactions of the corresponding dibromopyridines with -OH and -NH₂ groups with sultone. These compounds were converted into polymers with the -(CH₂)_m-SO₃H groups via organometallic polycondensation. The polymer showed proton conducting properties and high stability toward oxidation.     

Effect of the Conformation of Polymer Chain on the Reduction Rate of Polyacrylatopentaamminecobalt(III) by Polymer-Bound Ferrous Chelates and the Excited State of Tris(Bipyridine)Ruthenium(Ii)

Electron transfer reactions of Co(NH₃)₅PAA (PAA = polyacrylic acid) with either the polyanionic polymer-bound ferrous chelate, Fe¹¹P-SS (P-SS = vinylbenzylaminediacetate-co-styrenesulfonate) or the uncharged polymer-bound ferrous chelate, Fe¹¹P-VPRo (P-VPRo = vinylbenzylaminediacetate-co-vinylpyrrolidone), and the Ru(bpy)²⁺ ₃ photosensitized reduction of Co(NH₃)₅PAA have been investigated in aqueous solutions at pH 5.4, I = 0.06 (I is ionic strength), and 25°C. For the ferrous chelate reductions, the second-order rate constants for Fe¹¹-PSS and Fe¹¹P-VPRo were almost equal to that for the corresponding nonpolymer-bound ferrous chelate, Fe¹¹BDA (BDA = benzylaminediacetate). The results indicate that there is no appreciable steric hindrance due to the polymer chains of the polymer-bound ferrous chelates and that the effect of columbic repulsion force between the polyanion chains can be ignored for the reaction of Co(NH₃)₅PAA with Fe¹¹P-SS. The results also suggest that there are two kinds of the pendant Co(III) species, “reactive” and “inert.” The inert Co(III) species are shielded by the polymer chains from attack of the Fe(II) chelates that are present in the bulk solutions. A similar reaction behavior was observed in the Ru(bpy)²⁺ ₃ photosensitized reduction of Co(NH₃)₅PAA at pH 5.4. For the Co(III) complex having an extremely few Co(III) complex moieties on the polymer chain, almost all of the Co(III) groups were hardly reduced by the excited state of Ru(bpy)²⁺ ₃, and reverse quenching occurred due to binding of the Ru(bpy)²⁺ ₃ to the polyacrylic acid chain of the polymer complex. On the other hand, for Co(NH₃)₅PAA with a relatively large number of the Co(III) moieties on the polymer chain, lifetime measurements at a higher concentration of the Ru(bpy)²⁺ ₃ showed a double-exponential fit, which suggests that there are two parallel decay processes. The fast and slow components mainly correspond to the decays: Ru(bpy)²⁺ ₃ quenched by Co(III) and reverse quenching due to binding of Ru(bpy)²⁺ ₃ into the compact polymer chains.     

The Mukaiyama Aldol Reaction: 40 Years of Continuous Development

A directed cross‐aldol reaction of silyl enol ethers with carbonyl compounds, such as aldehydes and ketones, promoted by a Lewis acid, a reaction which is now widely known as the Mukaiyama aldol reaction. It was first reported in 1973, and this year marks the 40th anniversary. The directed cross‐aldol reactions mediated by boron enolates and tin(II) enolates also emerged from the Mukaiyama laboratory. These directed cross‐aldol reactions have become invaluable tools for the construction of stereochemically complex molecules from two carbonyl compounds. This Minireview provides a succinct historical overview of their discoveries and the early stages of their development.     

Regioselective Alkylation of Thiazolylsulfonamides: Direct and Efficient Synthesis of 3‐Alkylthiazolidene Derivatives

Various N‐3‐alkylated thiazolidenesulfonamide derivatives were efficiently prepared by the direct endo‐selective alkylation of thiazolylsulfonamides. The effects of different bases and solvents were investigated, and the NaH–THF combination was found to be the most effective at conferring high yields and endo‐selectivity.     

Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones.     

A novel condition for capillary electrophoretic analysis of reductively aminated saccharides without removal of excess reagents

We have identified novel CE conditions for the separation of 7‐amino‐4‐methylcoumarin‐labeled monosaccharides and oligosaccharides from glycoproteins. Using a neutrally coated capillary and alkaline borate buffer containing hydroxypropylcellulose and ACN, saccharide derivatives form anionic borate complexes, which move from the cathode to the anode in an electric field and are detected near the anodic end. Excess labeling reagents and other fluorescent products remain at the cathodic end. Fluorimetric detection using an LED as a light source enables determination of monosaccharide derivatives with good linearity between at least 0.4 and 400 μM, may correspond to 140 amol to 140 fmol. The lower LOD (S/N = 5) is only 80 nM in the sample solution (ca. 28 amol). The results were comparable to reported values using fluorometric detection LC. The method was also applied to the analysis of oligosaccharides that were enzymatically released from glycoproteins. Fine resolution enables profiling of glycans in glycoproteins. The applicability of the method was examined by applying it to other derivatives labeled with nonacidic tags such as ethyl p‐aminobenzoate‐ and 2‐aminoacridone‐labeled saccharides.     

Investigation of radon and thoron concentrations in a landmark skyscraper in Tokyo

The temporal variation of the radon concentration, and the radon and thoron concentrations every 3 months for a year were measured using two types of devices in a landmark skyscraper, the Tokyo Metropolitan Government Daiichi Building. In the measurement of temporal variation of the radon concentration using a pulse type ionization chamber, the average radon concentration was 21 ± 13 Bq m^?3 (2–68 Bq m^?3). The measured indoor radon concentration had a strong relationship with the operation of the mechanical ventilation system and the activities of the office workers. The radon concentration also increased together with temperature. Other environmental parameters, such as air pressure and relative humidity, were not related to the radon concentration. In the long-term measurements using a passive radon and thoron discriminative monitor, no seasonal variation was observed. The annual average concentrations of radon and thoron were 16 ± 8 and 16 ± 7 Bq m^?3, respectively. There was also no relationship between the two concentrations. The annual average effective dose for office workers in this skyscraper was estimated to be 0.08 mSv y^?1 for 2000 working hours per year. When considering the indoor radon exposure received from their residential dwellings using the annual mean radon concentration indoors in Japan (15.5 Bq m^?3), the annual average effective dose was estimated to be 0.37 mSv y^?1. This value was 31 % of the worldwide average annual effective dose.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines (6) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6: Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^?2, applied voltage 20 V, at 70°C) in the smectic B phase.     

Synthesis and properties of polyfluoro(silyl)acetylene nanoparticles by reaction of fluoro(silyl)acetylenes with triethylamine

Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side.