Enhancement of the electrocatalytic O2 reduction on Pt–Fe alloys

The design of high performance cathode electrocatalysts is essential for polymer–electrolyte fuel cells, which are now attracting enormous interest as a primary power source for zero-emission electric vehicles. We have discovered a significant enhancement of electrocatalytic activity of Pt by alloying with Fe, and found a maximum activity at ca. 50% Fe content, which results in 25 times higher activity than pure Pt activity. It was confirmed experimentally at Pt–Fe bulk alloys that the alloy catalyst surface consists of a pure Pt skin-layer (<1 nm in thickness) that is modified in the electronic structure by that of the bulk alloy. The enhancement could be well explained by the 5d-vacancy of the surface, but not by Pt interatomic distance or roughening of the surfaces.     

Molecule-Based Artificial Photosynthesis

Guidelines for the design of molecules with a long lifetime of the charge-separated state and for the formation of a self-assembled monolayer were studied by preparing various model compounds linking donor and acceptor with chemical bonds. Based on the obtained results we designed and prepared the SAMs of C₆₀-(porphyrin)-(ferrocene)-(CH₂)₁₁SH on a gold surface and observed a photocurrent with high efficiency (25% quantum yield). In addition, a well-defined, rigid-sheet-structured oligoporphyrin with 21 porphyrin chromophores was prepared as a model for antenna chlorophylls.     

Nonlinear Normal Modes of a Parametrically Excited Cantilever Beam

We investigate theoretically thenonlinear normal modes of a vertical cantilever beam excited by aprincipal parametric resonance. We apply directly the method ofmultiple scales to the governing nonlinear nonautonomousintegral-partial-differential equation and associated boundary conditions.In the absence of damping, it is shown that the system has nonlinear normal modes, as defined by Rosenberg, even in the presence of the parametric excitation.We calculate the spatial correction to the linear mode shapedue to the effects of the inertia and curvature nonlinearities andthe parametric excitation. We compare the result obtained withthe direct approach with that obtained using a single-mode Galerkindiscretization.The deviation between the two predictions increases as the oscillationamplitude increases.     

Predicted radiolysis yield in a Fricke solution irradiated with various heavy ions

Experimental data on the spatial distribution of the energy deposited around an energetic heavy ion, from 1 MeV proton to 5.9 MeV/n uranium ion, which have been reported in the literature were documented to obtain a scaled radial dose distribution; (β/Z*)² D(Z*, β,t)=200 (for t=0–1), 200/t² (for t=1t_c), and 200 t_c/t³ (for t>t_c) where Z* and β are the effective charge and velocity relative to c, the velocity of light, of the incident ion, respectively, D the dose in unit of Gy, t the radial distance in unit of nm, t_c the critical distance empirically determined.

Then, if we know the yield of any chemical reaction as a function of dose from the results of experiments using γ-radiations or fast electrons or theoretical calculations, we can calculate the probability for the yield of the chemical reaction in the system bombarded with a heavy ion of the effective charge Z* and velocity β. The results of the present calculation of the LET-values and of G(Fe³⁺) in the ferrous sulfate acidic solution are presented and compared with reported experimental results.     

197Au and125Te Mössbauer spectroscopic study on the low temperature phases of Ag3AuX2 (X=S,Se, and Te)

¹⁹⁷Au and¹²⁵Te Mössbauer spectroscopy has been applied for the low-temperature β-phases of Ag₃AuX₂ (X=S, Se, and Te). The values of I. S. and Q. S. for¹⁹⁷Au suggest that the gold atoms, linearly coordinated by two chalcogen atoms in these phases, exist as monovalent cations. The¹²⁵Te Mössbauer spectra suggest that the tellurium atoms are substantially ionic for both Ag₂Te and Ag₃AuTe₂. The nature of X-Au-X bonds is discussed on the basis of the Mössbauer data and the bond distances.     

Polycatenar mesogens with a perfluorinated moiety showing a variety of liquid crystalline polymorphism

Polycatenar materials composed of a four-aromatic-ring core, with either a bulky or end-branched perfluorinated moiety attached at one end through a methylene spacer group, and three peripheral alkoxy chains of varying length (the carbon number n = 4, 6, 8, 10, 12, 14, 16) on the other end-ring, were synthesized to investigate the roles of the chemical structure of the compositional segments in relation to liquid crystalline phase formation. It was found that a homologous series of polycatenar materials exhibited a variety of liquid crystalline phases strongly dependent on the length of the peripheral alkyl chains. Moreover it was shown that changes in the spacer group and in the structure of the perfluorinated segment had a significant influence on mesophase formation.     

Novel observation of a circular dichroism band originating from amyloid fibril.

A peptide fragment of a non-amyloid-beta component (NAC(1-13)) was studied by CD and electron microscopy. Typical amyloid fibrils were observed by EM in a solution of NAC(1-13). In addition to the beta-structural CD band in the far-UV region, a novel CD band near 285 nm was observed in a peptide solution of NAC(1-13). Taking the NAC(1-13) to contain neither an aromatic amino acid residue nor cystine into account, the CD band can be attributed to amyloid fibrils of NAC(1-13).     

Ion-channel sensors based on ETH 1001 ionophore embedded in charged-alkanethiol self-assembled monolayers on gold electrode surfaces.

An ion-channel sensor was demonstrated by immobilizing ETH 1001, an ionophore for ion-selective electrodes, on a gold electrode surface. The approach for preparing the sensor was to incorporate the ionophore into a mixed self-assembled monolayer of 10-mercaptodecanesulfonate and 11-hydroxy-1-undecanethiol formed on the surface. The voltammetric responses for the thus prepared sensor to the primary cation Ca(2+) were observed by using [Fe(CN)(6)](3-/4-) as an electroactive marker. The ionophore was stably immobilized on the electrode surface with the hydrophobic interaction between its alkyl chains and those of the alkanethiol. The introduction of a proper charge density to the electrode surface improved the sensor sensitivity with retaining the selective response to Ca(2+) against Mg(2+) with concentrations above 10(-4) M.