Target-selective fluorescent "switch-on" protein labeling by 6π-azaelectrocyclization

Application of azaelectrocyclization and FRET techniques to lysine groups enabled the selective and sensitive detection of a target protein from a mixture, with high fluorescence contrast.     

Effect of co-adsorbed CO and reaction temperature on the dynamics of N2 desorption under steady-state N2O-CO reaction on Rh(110)

We have investigated the effect of co-absorbed CO and reaction temperature on the angular distribution of N(2) desorption by N(2)O decomposition under the steady state of N(2)O-CO reaction on Rh(110). Spatial distributions of desorbing product N(2) emission have been measured at various surface temperatures and CO coverages. The decomposed N(2) collimates at 48°-61° off normal in the parallel plane to [001] and [110] directions, indicating that adsorbed N(2)O just before the decomposition is oriented along the [001] direction. Although the inclined and collimated N(2) desorption is always observed at any steady-state CO coverage and reaction temperature, the shape of the collimated N(2) distribution varied dependent on the co-adsorbed CO coverage. The distribution becomes sharp and shifts toward the surface normal direction with increasing CO coverage. These effects of adsorbed CO on the angular distribution of N(2) are interpreted by the collision of desorbed N(2) with co-adsorbed CO.     

Incipient structural and vibrational relaxation process of photolyzed carbonmonoxy myoglobin: statistical analysis by perturbation ensemble molecular dynamics method

The incipient structural and vibrational energy relaxation process of photolyzed carbonmonoxy myoglobin was analyzed by the perturbation ensemble molecular dynamics (PEMD) method, in which many pairs of perturbed and unperturbed MD simulations are executed for ensemble-averaging to obtain statistically significant results by canceling out thermal fluctuations. First, we have shown that the experimentally reported anisotropic expansion can be detected within a picosecond after photolysis. The good agreement between the experimental and computational results indicates that the PEMD method can predict legitimately those changes driven by perturbations even if the changes might be subtle and smaller than thermal fluctuations. Second, the structural relaxation including the ??clamshell rotation?? in E and F helices was successfully analyzed. The high time resolution analysis has clarified the incipient structural dynamics on a subpicosecond timescale: the clamshell rotation starts at His64, Val68, and His93 following both the heme doming and the dissociated CO ligand collision. Third, the vibrational energy relaxation from the heme to the globin matrix is elucidated not only temporally but also spatially. This is the first ??thorough?? report of the spacetime-resolved excess kinetic energy redistribution of photolyzed MbCO in the globin matrix with a statistically significant precision, ±1?K. The incipient anisotropic vibrational relaxation occurs clearly within a picosecond in the direction perpendicular to the heme plane by the ??through-bond?? and ??through-projectile?? pathways, and the isotropic relaxation then follows by the ??through-space?? pathway. Finally, it is concluded that the PEMD method is a powerful tool to understand the incipient relaxation process driven by the perturbation.     

The Inequality 8pg < μ for Hypersurface Two-dimensional Isolated Double Points

The Milnor number μ and the geometric genus p_g of normal 2-dimensional double points are studied by using Zariski's canonical resolution. By using formulas due to E. HORIKAWA and H. LAUFER, we represent μ ? 8p_g in terms of the number of blowing-ups along ?¹ and the number l of ?even”? components in the resolution process. A key point of our arguments is the fact that if l is small then the resolution process is restricted very much. For rational double points and double points with p_a = 1, each classes are characterized by numerical invariants appearing in this resolution process. For the case p_a = 1, we can make our inequality sharper and can prove 12 · p_g ? 3 ≤ μ. This is an another proof of Xu-Yau's inequality for the singularity with p_a = 1 in our situation.     

Electrochemical and thermal properties of hyperbranched polymer electrolytes for batteries

Terminal-acetylated hyperbranched poly(ethylene glycol) derivatives containing diethylene, triethylene, and hexaethylene and 3,5-dioxybenzoate branching units (poly-Ac1a, poly-Ac1b, and poly-Ac1c) were synthesized. Electrochemical and thermal properties of the hyperbranched polymer electrolytes with lithium salts such as LiCF₃SO₃ and LiN(CF₃SO₂)₂, the composite hyperbranched polymer electrolytes with LiN(CF₃SO₂)₂ containing α-LiAlO₂ and γ-LiAlO₂ fillers, and the hyperbranched polymer blended poly(ethylene oxide) electrolytes with LiN(CF₃SO₂)₂ were investigated and discussed. Paper presented at the 8th EuroConference on Ionics, Carvoeire, Algarve, Portugal, Sept. 16–22, 2001.     

Polymer electrolytes plasticized with hyperbranched polymer for lithium polymer batteries

Hyperbranched polymers (HBPs) with different terminal groups and different ethylene oxide (EO) chain lengths were prepared, and the influence of the HBP structures including molecular weights and molecular weight distribution on the ionic conductivity and the mechanical property of the composite polymer electrolytes composed of poly (ethylene oxide) (PEO), HBP, BaTiO₃ as a ceramic filler, and LiN(CF₃SO₂)₂ as a lithium salt were investigated. It was found that the molecular weights of the HBP do not affect significantly the ionic conductivity, but the molecular weight distribution might affect it, and also further branching at the terminals of the HBP led to a decrease in the ionic conductivity. The HBP with longer EO chain length was effective for enhancement of the ionic conductivity in comparison with the HBP with shorter one. The increase in cross-linkable groups (acryloyl group) at the terminals of the HBP improved the tensile strength, but caused the ionic conductivity to decrease. Loosely cross-linked composite polymer electrolyte showed higher ionic conductivity and higher tensile strength than no cross-linked one. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

On-line liquid chromatography and circular dichroism detection of stereo-isomers of alpha-tocopherol derivatives generated by an electrochemical reaction

The electrochemical oxidation of (+/-)-alpha-tocopherol on a porous graphite electrode was performed in the presence of methanol, and successive separation and detection of the products were performed by an on-line liquid chromatography/mass spectrometry system. Three products were identified, one of which was determined to be alpha-tocopheryl quinone, because its m/z was 469 [M+Na](+). The other two products showed identical mass and UV spectra, and were suspected to be diastereomers of 9-methoxy-alpha-tocopheron, because their molecular weights were m/z 483 [M+Na](+), and also because it is known that the chemical oxidation of alpha-tocopherol by benzoyl peroxide or N-bromosuccinimide in the presence of methanol should provide 9-methoxy-alpha-tocopheron. To confirm that these two compounds were diastereomers, a circular dichroism detector was used. The signs of both peaks detected by the circular dichroism detector at 230 nm were opposite. In addition to observations of identical mass and ultraviolet spectra, these results indicated that the two products were diastereomers of 9-methoxy-alpha-tocopheron, whose stereochemistry is different at the newly generated chiral center of the 9-position. The on-line use of a circular dichroism detector with an electrochemical cell/liquid chromatography system may expand the utility of the system to study the metabolism of a chiral drug.     

Synthesis of n-alkyl-n-(1-hydroxyperoxyalkyl)nitrosamines by oxygenation of lithiated dialkylnitrosamines

N-Alkyl-N(1-hydroperoxyalkyl)nitrosamines were synthesized from N,N-dialkylnitrosamines by lithiation with lithium diisopropylamide, followed by oxygenation with oxygen in good yields.