Silver(I)-Ion-Mediated Cytosine-Containing Base Pairs: Metal Ion Specificity for Duplex Stabilization and Susceptibility toward DNA Polymerases

Spectroscopic characterization of Ag^I-ion-mediated C-Ag^I-A and C-Ag^I-T base pairs found in primer extension reactions catalyzed by DNA polymerases was conducted. UV melting experiments revealed that C-A and C-T mismatched base pairs in oligodeoxynucleotide duplexes are specifically stabilized by Ag^I ions in 1:1 stoichiometry in the same manner as a C-C mismatched base pair. Although the stability of the mismatched base pairs in the absence of Ag^I ions is in the order C-A≈C-T>C-C, the stabilizing effect of Ag^I ions follows the order C-C>C-A≈C-T. However, the comparative susceptibility of dNTPs to Ag^I-mediated enzymatic incorporation into the site opposite templating C is dATP>dTTP≫dCTP, as reported. The net charge, as well as the size and/or shape complementarity of the metal-mediated base pairs, or the stabilities of mismatched base pairs in the absence of metal ions, would be more important than the stability of the metallo-base pairs in the replicating reaction catalyzed by DNA polymerases.     

Numerical Evaluation of Toughening by Crack-Face Grain Interlocking in Self-Reinforced Ceramics

Crack bridging associated with the pull-out process of interlocking grains in self-reinforced ceramic materials is studied through a micromechanical simulation. The pullout of a single inclined grain is modeled via the numerical solution of a general contact problem. The bridging-force versus crack-opening-distance curve indicates a nonlinear, springlike response for the pullout of interlocking grains. The sliding friction along the debonded interface, induced by highly localized contact stresses, dominates the total bridging force. The bridging force increases with grain inclination until eventual bridge failure. The pullout of misaligned grains mainly affects short-crack toughening, with a rising R -curve, whereas aligned grains contribute to long-crack toughening. The residual stresses of the thermal expansion anisotropy play a minor role in the pull-out process of grain interlocking and the resultant toughening. The proposed mechanism is operative in both single-phase and composite ceramics in which pullout of elongated grains/reinforcements occurs.     

Thermodynamic Regularities in Perovskite and K2NiF4 Compounds

It has been found that the enthalpy of formation of perovskite compounds, Δ_fH° (ABO₃, B = transition metais), from binary oxides can be well characterized in terms the tolerance factor, t≡(r_A+ r_o)√2 (r_B+ r_o), where r_A and r_B are the radii of A-site ions with 12-coordination and B-site ions with 6-coordination, respectively, and Δ_fH°=−168 + 270(1 − t) kJ·mol⁻¹ for A^IB^VO₃, Δ_fH°=−125 + 1000(1 − t) kJ·mol⁻¹ for A^IIB^IVO₃, and Δ_fH°=− 90 + 720(1 − t) kJ·mol⁻¹ for A^IIIB^IIIO₃. Although the thermodynamic data of K₂NiF₄ compounds are not extensive, a similar regularity can be found when use is made of the radii of A-site ions with 9-coordination for the K₂NiF₄ compounds. These correlations will be quite useful in predicting.     

Synthesis and Properties of Gemini-type Cationic Surfactants Containing Carbonate Linkages in the Linker Moiety Directed Toward Green and Sustainable Chemistry

Gemini-type cationic surfactants containing carbonate linkages as biodegradable and chemically recyclable segments, consisting of two long-chain alkyl groups, two quaternary ammonium groups and a linker moiety, were designed and synthesized as novel green and sustainable cationics with improved physicochemical and biological activities. The gemini-type cationics containing a carbonate linkage showed lower critical micelle concentration values compared to the corresponding single-type cationics. Also, the gemini-type cationics containing a carbonate linkage in the linker moiety showed strong antimicrobial activities. The biodegradability of the gemini-type cationics was significantly improved when a carbonate linkage was introduced into the linker moiety. The maximum biochemical oxygen demand-biodegradability of the gemini-type cationics containing a carbonate linkage in the linker moiety exceeded 70% after a 28-day incubation. Furthermore, the gemini-type cationics containing both a carbonate linkage and an n-dodecyl group showed a chemical recyclability using a lipase (E.C. 3.1.1.3).

Genotoxicity of nano/microparticles in in vitro micronuclei, in vivo comet and mutation assay systems

Background

Recently, manufactured nano/microparticles such as fullerenes (C₆₀), carbon black (CB) and ceramic fiber are being widely used because of their desirable properties in industrial, medical and cosmetic fields. However, there are few data on these particles in mammalian mutagenesis and carcinogenesis. To examine genotoxic effects by C₆₀, CB and kaolin, an in vitro micronuclei (MN) test was conducted with human lung cancer cell line, A549 cells. In addition, DNA damage and mutations were analyzed by in vivo assay systems using male C57BL/6J or gpt delta transgenic mice which were intratracheally instilled with single or multiple doses of 0.2 mg per animal of particles.

Results

In in vitro genotoxic analysis, increased MN frequencies were observed in A549 cells treated with C₆₀, CB and kaolin in a dose-dependent manner. These three nano/microparticles also induced DNA damage in the lungs of C57BL/6J mice measured by comet assay. Moreover, single or multiple instillations of C₆₀ and kaolin, increased either or both of gpt and Spi^- mutant frequencies in the lungs of gpt delta transgenic mice. Mutation spectra analysis showed transversions were predominant, and more than 60% of the base substitutions occurred at G:C base pairs in the gpt genes. The G:C to C:G transversion was commonly increased by these particle instillations.

Conclusion

Manufactured nano/microparticles, CB, C₆₀ and kaolin, were shown to be genotoxic in in vitro and in vivo assay systems.     

Development of a novel microstructure fabrication method with co-axial dual capillary solution flow type droplet cells and electrochemical deposition

A new method for maskless fabrication of metallic patterns or structures on metals is described. A solution flow type droplet cell, with co-axial dual capillaries was applied to form fine metal structures such as strips and rods. This type of droplet cell enables movement of the cell during formation. Nickel fine patterns with a width of about 200 μm were formed on a Cu substrate. The width of the formed pattern does not change with the scanning speed of the cell, but the thickness of the formed pattern changes with the speed. Two different deposition modes were examined to form metal rods, one is a mold free deposition mode and the other is a mold assisted deposition mode. Both modes enable the formation of Ni rods, however, reproducibility of mold free deposition mode was not good. The mold assisted deposition mode has far better the reproducibility, because of the use of the inside wall of the 100 μm diameter inner tube as the mold. It is possible to form nickel micro-rods, about 100 μm in diameter and 12 mm long with relatively smooth surfaces by the mold assisted deposition mode.     

Separation and determination of glycolipids from edible plant sources by high-performance liquid chromatography and evaporative light-scattering detection

Glycolipids from edible plant sources were accurately quantified by silica-based, normal-phase high-performance liquid chromatography using an evaporative light-scattering detector. Five major glycolipid classes (acylated steryl glucoside, steryl glucoside, ceramide monohexoside, monogalactosyldiacylglycerol, and digalactosyldiacylglycerol) were separated and determined with a binary gradient system consisting of chloroform and methanol/water (95∶5, vol/vol) without any interference from other lipid classes and pigments. The described method was applied to 48 edible plants available in Japan including cereals, legumes, vegetables, and fruits. Examined plant species contained glycolipids in wide concentration ranges, such as 5–645 mg/100 g tissue.     

Attractants for Rice Leaf Bug, <Emphasis Type="BoldItalic">Trigonotylus caelestialium</Emphasis> (Kirkaldy), are Emitted from Flowering Rice Panicles

Volatiles were extracted from rice plants of various growth stages with solid-phase microextraction (SPME) and analyzed by gas chromatography-mass spectrometry (GC-MS) to identify attractants that cause invasion of the rice leaf bug Trigonotylus caelestialium (Kirkaldy) into paddy fields. The composition of volatile blends produced by rice plants changed with rice development. In addition, volatile blend compositions differed between the panicles and the stems and leaves. The relative geranyl acetone content was high in all plant structures analyzed. In volatiles from whole plants in the fourth-leaf stage and panicles in the full-ripe stage, the relative content of green leaf volatiles (GLVs) was higher than that found in other rice plant structures. In contrast, relative terpene levels emitted from whole plants in the panicle-formation stage and by panicles and stems and leaves in the flowering stage were higher than those of other rice plant structures. However, the type of terpenes found differed between the panicles and the stems and leaves. Relative levels of β-caryophyllene in whole plants in the panicle-formation stage and panicles in the flowering stage were much higher than that in stems and leaves in the flowering stage. Our previous studies demonstrated that the odor from whole plants in the panicle-formation stage and panicles in the flowering stage is attractive to rice leaf bugs. Here, the attractiveness of β-caryophyllene to adult bugs was investigated in olfactometer assays. Adult females were attracted to β-caryophyllene at a concentration of 0.001%, which is approximately equivalent to the concentration produced by flowering rice panicles. However, β-caryophyllene also was present in the odor of whole plants in the fourth-leaf stage and in stems and leaves in the flowering stage. Furthermore, the amounts of this compound emitted from these structures were similar. Therefore, we suggest that the relative abundance of this compound in a volatile blend is important for attractance of the bugs.