Functional Characterization of 3-Aminobenzoic Acid Adenylation Enzyme PctU and UDP-N-Acetyl-d-Glucosamine: 3-Aminobenzoyl-ACP Glycosyltransferase PctL in Pactamycin Biosynthesis

Pactamycin is an antibiotic produced by Streptomyces pactum with antitumor and antimalarial properties. Pactamycin has a unique aminocyclitol core that is decorated with 3-aminoacetophenone, 6-methylsaliciate, and an N,N-dimethylcarbamoyl group. Herein, we show that the adenylation enzyme PctU activates 3-aminobenzoic acid (3ABA) with adenosine triphosphate and ligates it to the holo form of the discrete acyl carrier protein PctK to yield 3ABA-PctK. Then, 3ABA-PctK is N-glycosylated with uridine diphosphate-N-acetyl-d -glucosamine (UDP-GlcNAc) by the glycosyltransferase PctL to yield GlcNAc-3ABA-PctK. Because 3ABA is known to be a precursor of the 3-aminoacetophenone moiety, PctU appears to be a gatekeeper that selects the appropriate 3-aminobenzoate starter unit. Overall, we propose that acyl carrier protein-bound glycosylated 3ABA derivatives are biosynthetic intermediates of pactamycin biosynthesis.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Geometry Dependence of Magnetization Reversal in Nanocomposite Alloys

The geometrical optimization of aligned hard-soft permanent-magnet nanocomposites is investigated by model calculations. Considered criteria are the shapes of the soft and c-axis-aligned hard phases, the packing fraction of the soft phase, and magnetostatic interactions. Taking into account that the energy product is enhanced via the volume fraction of the soft phase, subject to maintaining coercivity, we find that the best structures are soft-magnetic cubes as well as long rods with a square cross section. Comparing embedded soft cubes with embedded soft spheres of the same size, our nucleation-field analysis shows that the volume fraction of the soft phase is enhanced by 91%, with a coercivity reduction of only 25%. Magnetostatic interactions often but not always deteriorate the permanent-magnet performance, as exemplified by the example of MnBi:FeCo bilayers and multilayers.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

Development of anchored oligothiophenes on substrates for the application to the tunable transparent conductive films

Bis(triethoxysilyl)-substituted oligothiophene with a moderate π-conjugation length was newly synthesized and polymerized to give a polysilsesquioxane network having oligothiophene units dispersed homogeneously without phase separation. The polymer was fixed on glass or ITO substrate by spin-coating and annealing. The resulting film exhibited a high mechanical strength due to the covalent bonding with the substrates, and was electrochemically stable even after 300 redox cycles in electrolyte solution. Chemical oxidation of the polymer films yielded electrically conductive and almost transparent films.     

Effect of Lipase Activity and Specificity on the DAG Content of Olive Oil from the Shodoshima-Produced Olive Fruits

Olive oils have a higher relative diacylglycerol (DAG) content than other plant oils. The lipase in olive fruits is involved in DAG production and is directly related to the acidity of the olive oil. However, the lipase activity and positional selectivity have not been clarified. To investigate the properties of olive fruit lipase, olive fruits of the Mission variety harvested during mid-December of 2005 on Shodoshima Island (Japan) were stored at 20, 30 or 40 °C for 4 weeks. Changes in the acidity and acylglycerol content of the oils extracted from the stored fruits were analyzed. The acidity and DAG content of the olive oils increased due to triacylglycerol (TAG) hydrolysis during storage. sn-1,2-DAGs preferentially increased during the early stages of storage, indicating that the olive fruit lipase is enantioselective for the sn-3 position, while non-enzymatic isomerization of sn-1,2-DAGs was observed throughout the entire duration of storage. Kinetic analysis revealed that the enantioselectivity of olive fruit lipase for the sn-3 position was approximately four times greater than for the sn-1 position. The lipase was gradually inactivated at temperatures of 30 °C or higher, and the ratios of the rate constant for inactivation to TAG hydrolysis at the sn-3 position was 0.2, 13, and 23 at 20, 30, and 40 °C, respectively.     

Direct synthesis of H2O2 acid solutions on carbon cathode prepared from activated carbon and vapor-growing-carbon-fiber by a H2/O2 fuel cell

Direct synthesis of H₂O₂ acid solutions was studied using a gas-diffusion cathode prepared from activated carbon (AC), vapor-growing-carbon-fiber (VGCF) and poly-tetra-fluoro-ethylene (PTFE) powders, with a new H₂/O₂ fuel cell reactor. O₂ reduction to H₂O₂ was remarkably enhanced at the three-phase boundary (O₂(g)-electrode(s)-acid(l)) at the [AC + VGCF] cathode. Fast diffusion processes of O₂ to the active surface and of H₂O₂ to the bulk acid solutions were essential for H₂O₂ accumulation. Synergy of AC and VGCF was observed for the H₂O₂ formation. RRDE and cyclic voltammetry studies indicated that the surface of AC functioned as the active phase for O₂ reduction to HO₂, and VGCF functioned as an electron conductor and a promoter to convert HO₂ to H₂O₂. A maximum H₂O₂ concentration of 353 mM (1.2 wt%) was accomplished under short-circuit conditions (current density 12.7 mA cm⁻², current efficiency 40.1%, geometric area of cathode 1.3 cm², reaction time 6 h).     

Photocatalytic H2 evolution under visible light irradiation on Zn1-x Cu x S solid solution

The H₂ evolution reaction from an aqueous Na₂SO₃ solution proceeded with 3.7% quantum yield under visible light irradiation (λ > 420 nm) on a Zn_0.957Cu_0.043S solid solution photocatalyst without co‐catalysts such as Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nanoparticle formation in H2O/N2 and H2O/Ar mixtures under irradiation by 20 MeV protons and positive corona discharge

To investigate the contribution of ions to gas nucleation, we have performed experiments on the formation of water droplets in H₂O/N₂ and H₂O/Ar gas mixtures by irradiation with a 20 MeV proton beam and by positive corona discharge. The size of the formed nanoparticles was measured using a differential mobility analyzer equipped with a Faraday cup electrometer. Using the proton beam, droplets around 10 nm in diameter were observed for both positively and negatively charged particles, but none were found when the corona discharge was used. This implies the importance of the presence of both positive and negative ions for the formation of nanosize droplets, which attract each other by Coulomb interactions, enhancing the collision frequency and leading to the formation of the 10 nm droplets.