Possibilities of the Formation of Enol-Ethers in Lignin by Soda Pulping

In the alkaline decomposition of a β-O-4 type lignin model compound (erythro-guaiacylglycerol-β-guaiacyl ether, compound 1), an isomeric pair of C₆C₂ enol-ether (2-methoxy-4-[2-(2-methoxyphenoxy)-vinyl]-phenol, compound 2) was detected as the main decomposition product with no trace of C₆C₃ enol-ether (4-[3-hydroxy-1-(2-methoxyphenoxy)-propenyl]-2-methoxy-phenol, compound 3) or other dimers. In contrast, compound 2 was not detected in the alkaline decomposition products of compound 3. Under alkaline conditions, the γ-hydroxymethyl group of compound 3 was reduced to form 2-methoxy-4-[1-(2-methoxyphenoxy)-propenyl]-phenol (compound 4). In the HSQC analysis of soda lignin, the formation of substructures of C₆C₂ type enol-ether (related to compound 2) was confirmed. However, no substructures related to compound 4, which could be formed if a substructure of C₆C₃ type enol-ether was formed under alkaline conditions, were detected. Therefore, it could be concluded that C₆C₃ type enol-ethers could not be intermediates of alkaline decomposition products of lignin.     

Hydrostatic Pressure Influences HIF-2 Alpha Expression in Chondrocytes

Hypoxia-inducible factor (HIF)-2α is considered to play a major role in the progression of osteoarthritis. Recently, it was reported that pressure amplitude influences HIF-2α expression in murine endothelial cells. We examined whether hydrostatic pressure is involved in expression of HIF-2α in articular chondrocytes. Chondrocytes were cultured and stimulated by inflammation or hydrostatic pressure of 0, 5, 10, or 50 MPa. After stimulation, heat shock protein (HSP) 70, HIF-2α, nuclear factor kappa B (NF-κB), matrix metalloproteinase (MMP)-13, MMP-3, and vascular endothelial growth factor (VEGF) gene expression were evaluated. The levels of all gene expression were increased by inflammatory stress. When chondrocytes were exposed to a hydrostatic pressure of 5 MPa, HIF-2α, MMP-13, and MMP-3 gene expression increased significantly although those of HSP70 and NF-κB were not significantly different from the control group. In contrast, HIF-2α gene expression did not increase under a hydrostatic pressure of 50 MPa although HSP70 and NF-κB expression increased significantly compared to control. We considered that hydrostatic pressure of 5 MPa could regulate HIF-2α independent of NF-κB, because the level of HIF-2α gene expression increased significantly without upregulation of NF-κB expression at 5 MPa. Hydrostatic pressure may influence cartilage degeneration, inducing MMP-13 and MMP-3 expression through HIF-2α.     

Proton-conducting electrolyte membranes based on hyperbranched polymer with a sulfonic acid group for high-temperature fuel cells

The hyperbranched polymers (HBP-SA-Acs) with both a sulfonic acid group as a functional group and an acryloyl group as a cross-linker at terminals in different ratios of sulfonic acid group/acryloyl group (SO₃H/Ac) were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked hyperbranched polymer electrolyte membranes (CL-HBP-SAs) were prepared by thermal polymerizations of the HBP-SA-Acs using benzoyl peroxide, and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the CL-HBP-SAs were found to be in the range of 2.2 × 10⁻⁴ to 3.3 × 10⁻⁶ S/cm, depending upon the SO₃H unit contents, at 150 °C under dry condition, and showed the Vogel-Tamman-Fulcher (VTF) type temperature dependence, indicating that proton transfer is cooperated by local polymer chain motion. All CL-HBP-SAs were thermally stable up to 260 °C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurement using a single membrane electrode assembly cell with a cross-linked electrolyte membrane was successfully performed under non-humidified condition. It was demonstrated that applying the concept of dry polymer system to proton conduction is one possible approach toward high-temperature fuel cells.     

Growth Inhibition of Bacteria by Salsa Mexicana

ABSTRACT: Antimicrobial activity of salsa mexicana against Escherichia coli, Klebsiella pneumoniae, Bacillus subtilis, Bacillus cereus, Staphylococcus aureus , and Saccharomyces cerevisiae was studied. The pressed salsa juice suppressed completely the growth of E. coli, B. subtilis , and S. aureus. K. pneumoniae and B. cereus were suppressed partly but Saccharomyces cerevisiae was not suppressed at all by the juice. Three types of microbicidal or microbiostatic components have been found: (1) H⁺, (2) volatile compounds, and (3) non-ionized carboxylic acids or analogous compounds. It is proposed that the supplementation of stink bugs in the salsa seen widely in the south of Mexico is used to intensify the herbal odor of the salsa.     

Effect of gene disruption of succinate dehydrogenase on succinate production in a sake yeast strain

Succinate dehydrogenase (SDH) of Saccharomyces cerevisiae consists of four subunits encoded by the SDH1, SDH2, SDH3, and SDH4 genes. We determined the effect of SDH deficiency on the productivity of organic acids in a sake yeast strain Kyokai no. 9. The SDH activity of single disruptants was retained at 30-90% of that of the wild-type strain, but the activity disappeared in double disruptants of the SDH1 and SDH2 or SDH1b (the SDH1 homologue) genes. Two double disruptants showed no growth on a medium containing glycerol as the sole carbon source, while the single disruptants could utilize glycerol. These results indicate that double disruption of the SDH1 and SDH2 or SDH1b genes is required for complete loss of SDH activity and that the SDH1b gene compensates for the function of the SDH1 gene. The sdh1 sdh1b disruptant showed a marked increase in succinate productivity of up to 1.9-fold along with a decrease in malate productivity relative to the wild-type strains under shaking conditions. Under both static and sake brewing conditions, the productivity of these organic acids in the disruptants was virtually unchanged from that in the wild-type strain. Furthermore, SDH activity was undetectable in the wild-type and the disrupted strains under static conditions. These results suggest that SDH activity contributes to succinate production under shaking conditions, but not under static and sake brewing conditions.     

Corrosion resistance of structural materials in high-temperature aqueous sulfuric acids in thermochemical water-splitting iodine–sulfur process

Very harsh environments exist in the iodine–sulfur process for hydrogen production. Structural materials for sulfuric acid vaporizers and concentrators are exposed to high-temperature corrosive environments. Immersion tests were carried out to evaluate the corrosion resistance of ceramics and to evaluate corrosion-resistant metals exposed to environments of aqueous sulfuric acids at temperatures of 320, 380, and 460 °C, and pressure of 2 MPa. The aqueous sulfuric acid concentrations for the temperatures were 75, 85, and 95 wt%, respectively. Ceramic specimens of silicon carbides (SiC), silicon-impregnated silicon carbides (Si–SiC), and silicon nitrides (Si₃N₄) showed excellent corrosion resistance from weight loss measurements after exposure to 75, 85, and 95 wt% sulfuric acid. High-silicon irons with silicon content of 20 wt% showed a fair measure of corrosion resistance. However, evidence of crack formation was detected via microscopy. Silicon enriched steels severely suffered from uniform corrosion with a corrosion rate in 95 wt% sulfuric acid of approximately 1 g m⁻² h⁻¹. Among the tested materials, the ceramics SiC, Si–SiC, and Si₃N₄ were found to be suitable candidates for structural materials in direct contact with the considered environments.     

Cooperative localization by using knowledge of self-organized regularity

In this article, a new localization approach for a team of robots that use the emergent properties of their formation is proposed. Synchronized behavior sometimes generates spin-off effects that include geometric patterns. The question then arises as to whether it is possible to use these patterns for something important for robots. In this article, Takayama’s control strategy, which is a target enclosure formation, is discussed. A simple and useful expansion of Monte Carlo localization by the emergent pattern is proposed. The proposed algorithms are confirmed through a series of computer simulations.     

Preparation of Cu2ZnSnS4 thin films by sulfurizing electroplated precursors

Cu₂ZnSnS₄ (CZTS) thin films were prepared by sulfurizing precursors deposited by electroplating. The precursors (Cu/Sn/Zn stacked layers) were deposited by electroplating sequentially onto Mo-coated glass substrates. Aqueous solutions containing copper sulfate for Cu plating, tin sulfate for Sn plating and zinc sulfate for Zn plating were used as the electrolytes. The precursors were sulfurized by annealing with sulfur at temperatures of 300, 400, 500 and 600 °C in an N₂ gas atmosphere. The X-ray diffraction peaks attributable to CZTS were detected in thin films sulfurized at temperatures above 400 °C. A photovoltaic cell using a CZTS thin film produced by sulfurizing an electroplated Sn-rich precursor at 600 °C exhibited an open-circuit voltage of 262 mV, a short-circuit current of 9.85 mA/cm² and an efficiency of 0.98%.     

Intragenic Tsc2 somatic mutations as Knudson''s second hit in spontaneous and chemically induced renal carcinomas in the Eker rat model

Membrane conductances during hypoosmotic swelling were characterized in rat astrocytes in primary tissue culture. Using whole cell patch clamp techniques, mean +/- SEM cell conductance in isoosmotic phosphate-buffered saline (PBS) was 55.6 +/- 5.8 pS/pF. Cell conductance (mean +/- SEM) increased from this initial value to 187 +/- 46%, 561 +/- 188%, and 1216 +/- 376% within 9 min of exposure to 220 mOsm, 190 mOsm, and 145 mOsm PBS, respectively. With each of these hypoosmotic exposures, no change occurred in membrane capacitance. When CsCl replaced KCl in the microelectrode solution, a similar conductance increase was obtained at each osmolality. However, when gluconate salts were used in place of chloride salts in the electrode solution, no significant conductance increase was observed with 190 mOsm PBS. With a KCl microelectrode solution, all conductance increase which occurred in 190 mOsm PBS was inhibited by 200 microM niflumic acid, but not by 5 mM BaCl(2). Both niflumic acid and BaCl(2) inhibited 60-80% of the conductance increase of cells in 145 mOsm PBS. Using a microelectrode solution containing taurine as the major anion, membrane conductance increased 5-fold when cells were placed in 250 mOsm medium. This conductance increase was completely inhibited by 200 microM niflumic acid. Thus, independent chloride and potassium conductances are activated by hypoosmotic swelling of cultured astrocytes while plasma membrane area is unaltered. The chloride conductance pathway is activated at a significantly lower degree of hypoosmotic exposure than that which activates the potassium pathway and may be permeable to anionic taurine. These conductance pathways may mediate diffusive loss of potassium, chloride, and taurine from these cells during volume regulation following hypoosmotic swelling.     

3-FG as substrate for investigating flux through the polyol pathway in dog lens by 19F-NMR spectroscopy

PURPOSE: To investigate flux through the polyol pathway in the dog lens by 19F-nuclear magnetic resonance (19F-NMR) spectroscopy, using 3-fluoro-3-deoxy-D-glucose (3-FG) as a substrate. METHODS: 3-FG metabolism was monitored by 19F-NMR analysis. Dog lenses were incubated in Dulbecco's modified Eagle's medium containing 10 mM 3-FG. Enzymatic reductase and dehydrogenase activities were spectrophotometrically determined, whereas the analyses of 3-FG metabolites were conducted by 19F-NMR analysis. Aldose reductase (AR) was immunohistochemically localized in dog lens with antibodies raised against dog kidney AR. RESULTS: 19F-NMR spectra indicate that incubation of purified dog lenses AR with 3-FG results in the formation of 3-fluoro-3-deoxy-D-sorbitol (3-FS) and that incubation of dog liver sorbitol dehydrogenase (SDH) with 3-FS results in the formation of 3-fluoro-3-deoxy-D-fructose (3-FF). This confirms that 3-FG is metabolized to 3-FF by the polyol pathway enzymes. The affinity (Km) of AR for 3-FG is approximately 20-fold better than that for D-glucose, whereas the Km of SDH for 3-FS was fourfold less than for D-sorbitol. 3-FG in cultured dog lenses is metabolized primarily to 3-FS; however, small amounts of 3-FF and 3-fluoro-3-deoxy-D-gluconic acid (3-FGA) are also formed. 3-FS formation was reduced by the AR inhibitor AL 1576, and 3-FF formation was eliminated by the SDH inhibitor CP-166,572. In dog lens epithelial cells cultured with 3-FG, only 3-FS is formed. Similarly, only 3-FS is formed when lens capsule containing primarily epithelial lens contaminated with superficial epithelial cells was incubated in 3-FG. Similar incubation of the remaining cortex resulted primarily in the formation of 3-FS and 3-FGA. This enzymatic distribution was confirmed by spectrophotometric activity analysis and the immunohistochemical localization of AR. CONCLUSIONS: The data confirm that flux through the polyol pathway primarily results in sorbitol accumulation. The absence of fructose and gluconic acid from cultured lens epithelium suggests that the epithelial cells primarily contain AR, whereas differentiated fiber cells also contain SDH and glucose dehydrogenase.