Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Br?nsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.     

Aqueous electrochemistry of poly(vinylanthraquinone) for anode-active materials in high-density and rechargeable polymer/air batteries

A layer of poly(2-vinylanthraquinone) on current collectors underwent reversible electrode reaction at -0.82 V vs Ag/AgCl in an aqueous electrolyte. A repeatable charging/discharging cycles with a redox capacity comparable to the formula weight-based theoretical density at the negative potential suggested that all of the anthraquinone pendants in the layer was redox-active, that electroneutralization by an electrolyte cation was accomplished throughout the polymer layer, and that the layer stayed on the current collector without exfoliation or dissolution into the electrolyte during the electrolysis. The charging/discharging behavior of the polymer layer in the aqueous electrolyte revealed the capability of undergoing electrochemistry even in the nonsolvent of the pendant group, which offered insight into the nature of the anthraquinone pendants populated on the aliphatic chain. Charging/discharging capability of air batteries was accomplished by using the polymer layer as an organic anode-active material. A test cell fabricated using the conventional MnO(2)/C cathode catalyst exhibited a discharging voltage at 0.63 V corresponding to their potential gap and a charging/discharging cycle of more than 500 cycles without loss of the capacity.     

New Synthesis of Poly(Phenylenesulfide)S Through an Electron Transfer

Poly(p-phenylenesulfide) (PPS) is efficiently and conveniently produced by a cationic and oxidative polymerization. Diphenyldisulfide is polymerized to PPS through one electron transfer at room temperature. The polymer is isolated as a white powder whose 1,4-structure is confirmed by IR. Phenylbis(phenylthio)sulfonium ion acts as an active species which is formed by oxidation of the S-S bond of diphenyldisulfide, and electrophilically substitutes on the phenyl ring. This polymerization is applicable to the polymerization of alkyl-substituted diphenyldisulfides to give PPSs, such as poly(2-methylphenylenesulfide) and poly(3,5-dimethylphenylene-sulfide).     

Polyhydroxybutyrate production from carbon dioxide by cyanobacteria

Genetic characterization and enhancement of polyhydroxybutyrate (PHB) accumulation in cyanobacteria were investigated for efficient PHB production from CO₂. The genome DNAs in the PHB-accumulating strains Synechococcus sp. MA19 and Spirulina platensis NIES46 retained the highly homologous region to phaC of Synechocystis PCC6803, whereas low homology was detected in the nonaccumulating strains Synechococcus sp. PCC7942 and Anabaenacylindrica NIES19. Synechococcus sp. MA19, which accumulates PHB up to 30% of dry cell weight from CO₂ as the sole carbon source, was mutated by insertion of transposon Tn5 to enhance the PHB accumulation. Genetic and physiological analysis of the mutant indicated that decreased phosphotransacetylase activity could trigger an increase of acetyl coenzyme A leading to enhancement of PHB accumulation. PHB synthase in Synechococcus sp. MA19 was probably attached to thylakoid membrane since PHB granules were associated with pigments. A genetically engineered cyanobacteria retaining soluble PHB synthase from Ralstonia eutropha accumulated pigment-free PHB granules, which is an advantage for the purification of PHB.     

Temperature programmed desorption of F-doped SnO<Subscript>2</Subscript> films deposited by inverted pyrosol technique

Fluorine-doped tin dioxide (FTO) films were deposited on silicon wafers by inverted pyrosol technique using solutions with different doping concentration (F/Sn=0.00, 0.12, 0.75 and 2.50). The physical and electrical properties of the deposited films were analyzed by SEM, XRF, resistivity measurement by four-point-probe method and Hall coefficient measurement by van der Pauw method. The electrical properties showed that the FTO film deposited using the solution with F/Sn=0.75 gave a lowest resistivity of 3.2·10^–4 ohm cm. The FTO films were analyzed by temperature programmed desorption (TPD). Evolved gases from the heated specimens were detected using a quadruple mass analyzer for mass fragments m/z, 1(H⁺), 2(H₂ ⁺), 12(C⁺), 14(N⁺), 15(CH₃ ⁺), 16(O⁺), 17(OH⁺ or NH₃ ⁺), 18(H₂O⁺ or NH₄ ⁺), 19(F⁺), 20(HF⁺), 28(CO⁺ or N₂ ⁺), 32(O₂ ⁺), 37(NH₄F⁺), 44(CO₂ ⁺), 120(Sn⁺), 136(SnO⁺) and 152(SnO₂ ⁺). The majority of evolved gases from all FTO films were water vapor, carbon monoxide and carbon dioxide. Fluorine (m/z 19) was detected only in doped films and its intensity was very strong for highly-doped films at temperature above 400°C.     

Mössbauer study of Lu2Fe3O7: A two-dimensional antiferromagnet on a triangular lattice

Mössbauer studies reveal that there are two kinds of Fe³⁺ spins with completely different characteristics in Lu₂Fe₃O₇: one is an Ising-like property and the other is a Heisenberg-like property in a two-dimensional antiferromagnet on a triangular lattice. The former spin orders ferrimagnetically along thec-axis at around 220 K. The latter spin is lying in thec-plane and a corresponding hyperfine magnetic field is observed at temperatures below 50 K. At very low temperatures, however, the latter spin has a component parallel to thec-axis and couples with the former spin. This finding is consistent with the modulated profile of the magnetic scattering in neutron diffraction and the result of a magnetization measurement.     

On perfect one-factorization of the complete graphK 2p

Anderson [1, 2] and Nakamura [4] have constructed perfect 1-factorizations ofK _2p independently, wherep is an odd prime. In this paper, we show that these two 1-factorizations are isomorphic.