Influence of phosphate species on green rust I transformation and local structure and morphology of γ-FeOOH

To clarify the role of phosphate in the formation of corrosion products, the transformation of GRI(Cl⁻) with the addition of phosphate was characterized through XRD, TEM, and solution analysis. Electrochemical analysis showed that the transformation of GRI(Cl⁻) was delayed and the size of the final products, i.e., γ-FeOOH was reduced in the phosphate added case. X-ray absorption spectroscopy indicated that the neighboring Fe–Fe coordination number of FeO₆ octahedral unit in γ-FeOOH was decreased. These effects of phosphate are attributed to its adsorption on GRI(Cl⁻) and nucleated γ-FeOOH that prevented particle growth during oxidation process.     

Functional binders for reversible lithium intercalation into graphite in propylene carbonate and ionic liquid media

Poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), and poly(vinyl alcohol) (PVA), which have oxygen species as functional groups, were utilized as a binder for graphite electrodes, and the electrochemical reversibility of lithium intercalation was examined in PC medium and ionic liquid electrolyte, lithium bis(trifluoromethanesulfonyl)amide dissolved in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (BMP-TFSA). Columbic efficiency of 75–80% with more than 300 mAh g^?1 was achieved upon first reduction/oxidation cycle in both electrolytes using these binding polymers, which were significantly improved in comparison to a conventional PVdF binder (less than 45% of columbic efficiency for the first cycle). For the graphite-PVdF electrode, co-intercalation and/or decomposition of PC molecules solvating to Li ions were observed by the electrochemical reduction, resulting in the cracking of graphite particles. In contrast, the co-intercalation and decomposition of PC molecules and BMP cations for the first reduction process were completely suppressed for the graphite electrodes prepared with the polymers containing oxygen atoms. It was proposed that the selective permeability of lithium ions was attained by the uniform coating of the graphite particles with PAA, PMA, and PVA polymers, because the electrostatic interaction between the positively charged lithium ions and negatively charged oxygen atom in the polymer should modulate the desolvation process of lithium ions during the lithium intercalation into graphite, showing the similar functions like artificial solid-electrolyte interphase.     

Methacrylate-based ionic liquid: radical polymerization/copolymerization with methyl methacrylate and evaluation of molecular weight of the obtained homopolymers

Azobisisobutyronitlite (AIBN)-induced free radical polymerization of a methacrylate-based ionic liquid monomer, 1-(2-methacryloxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Met-IL) was carried out in a common organic solvent, N,N-dimethylformamide (DMF), and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI). The molecular weight of the obtained poly(Met-IL) was evaluated by transforming it to non-ionic poly(methyl methacrylate) with hydrolysis of the imidazolium-salt-substituted pendant ester groups and methyl esterification. Radical copolymerization with methyl methacrylate (MMA) was also carried out in both DMF and EMImTFSI. Analysis of copolymer composition revealed that the reactivity of Met-IL was lower than that of MMA in both DMF and EMImTFSI solutions.     

Elevation of plasma levels of L-dopa in transdermal administration of L-dopa-butylester in rats

To increase delivery of L-dopa in its transdermal absorption, a new lipophilic derivative of L-dopa, L-dopa-butylester, was synthesized. An in-vitro study employing two-chamber diffusion cells, in which the excised rat abdominal skin was mounted, revealed that, in the presence of L-menthol and ethanol, L-dopa-butylester penetrated in its original form more effectively than L-dopa. L-Dopa-butylester sheets were made by immersing wiper sheets in methanol containing the compound, and then evaporating the methanol. An extraction study of the compound from the sheets revealed that its stability was maintained for at least 12 weeks. In an in-vivo cutaneous absorption study, an L-dopa-butylester sheet was attached to the shaved rat abdominal skin. A hydrogel containing L-menthol and ethanol was spread on vinyl tape, and this sheet was placed over it. In plasma, the L-dopa level rose linearly between 30 and 180 min after the cutaneous application; L-dopa-butylester was not detected. The L-dopa level was higher than that in which L-dopa was applied. These findings indicated that the lipophilic nature of L-dopa-butylester further increased its penetration through the skin, and that L-dopa-butylester that was taken up into the general circulation system was rapidly converted to L-dopa by hydrolysis in the body.     

Production of lepidimoide by an endophytic fungus from polysaccharide extracted from Abelmoschus sp.: identification of the product and the organism producing it

A highly potent allelopathic factor, lepidimoide, was initially extracted from mucilage of germinated cress seeds. Polysaccharide extracted from okra (Abelmoschus esculentum Moench) is considered to have a similar structure to lepidimoide as its repeating unit. We therefore initiated the screening of enzymes capable of degrading okra polysaccharide into lepidimoide from endophytes. We discovered an endophytic fungal strain AHU9748 isolated from Coleus galeatus, which produced an oligosaccharide having similar properties to lepidimoide on thin layer chromatography. The physico-chemical data from ESI-MS, NMR spectra and other analyses also showed the purified product to be identical to lepidimoide. The strain AHU9748 was identified as a fungus belonging to the coelomycetes, closely related to the genus Colletotrichum, based on morphological characteristics and sequence analysis of the 18S rDNA and ITS region.     

Synchronized fresh cell bioreactor system for continuous L-(+)-lactic acid production using Lactococcus lactis IO-1 in hydrolysed sago starch

An efficient bioreactor, termed a 'synchronized fresh cell bioreactor', was developed and consisted of a pH-dependent substrate feed system coupled with cross flow filtration and turbidity control. The effect of high dilution rate and high cell density coupled with high cell viability on the production of l-lactic acid in continuous culture by Lactococcus lactis IO-1 in enzyme-hydrolysed sago starch medium was investigated. For all changes in dilution rate, cells responded in a synchronized way to the addition of glucose by increasing the rate of biomass formation. Consequently, a glucose-free feed solution was required to maintain the cell concentration at a particular pre-set value. This set-up facilitated the maintenance of the cells in a permanent log phase. At a cell concentration of 15 gl(-1) and a feed glucose concentration of 53 gl(-1), volumetric LA productivities of 8.2, 19.3 and 33.1 gl(-1)h(-1) were obtained at dilution rates of 0.21, 0.50 and 1.1 h(-1), respectively. The respective residual glucose concentrations in the spent medium were 1.90, 0.24 and 3.80 gl(-1). By increasing the cell density, the volumetric productivity increased proportionally. At high cell density, higher dilution rates resulted in lower lactate concentrations in the culture medium resulting in higher productivity. This reactor facilitated efficient operation with high cell viability by maintaining the cells in continuous growth phase for long-term fermentation. Therefore, the growth rate (mu) was calculated according to the Monod equation. Using this system, high specific productivities can be obtained which guarantees high commercial productivity at economical cost with only a small investment for setting up the sago industry.     

Human buprenorphine N-dealkylation is catalyzed by cytochrome P450 3A4

Buprenorphine (BN) is a thebaine derivative with analgesic properties. To identify and characterize the cytochrome P450 (CYP) enzyme(s) involved in BN N-dealkylation, in vitro studies using human liver microsomes and recombinant human CYP enzymes were performed. Norbuprenorphine formation from BN was measured by a simple HPLC-UV assay method, without extraction. The BN N-dealkylation activities in 10 human liver microsomal preparations were strongly correlated with microsomal CYP3A-specific metabolic reactions, i.e. triazolam 1'-hydroxylation (r = 0.954), midazolam 1'-hydroxylation (r = 0.928), and testosterone 6beta-hydroxylation (r = 0.897). Among the eight recombinant CYP enzymes studied (CYP1A2, CYP2A6, CYP2B6, CYP2C9, CYP2C19, CYP2D6, CYP2E1, and CYP3A4), only CYP3A4 could catalyze BN N-dealkylation. The apparent KM value for recombinant CYP3A4 was similar to that for human liver microsomes (23.7 vs. 39.3 +/- 9.2 microM). The demonstration of BN N-dealkylation by recombinant CYP3A4 and the agreement in the affinities (apparent KM values) of human liver microsomes and recombinant CYP3A4 provide the most supportive evidence for BN N-dealkylation being catalyzed by CYP3A4.     

Stress disturbance due to broken fibres in metal matrix composites with non-uniform fibre spacing

Premature fracture of weaker fibres causes stress disturbances in composites. These disturbances are affected by non-uniformity of fibre spacing. In order to evaluate quantitatively how the disturbances in metal matrix composites are affected by the extent of non-uniformity of fibre spacing, a method of calculation is presented on the basis of two-dimensional shear lag analysis. Static tensile stress concentrations in the intact fibres to broken fibres, tensile stress distribution along the fibre axis in the broken and intact fibres and shear stresses between broken and intact fibres were calculated by the method presented, using some examples. It is shown quantitatively that the spacing between broken and intact fibres and that between intact and next fibres has a significant influence on tensile stress concentrations in intact fibres and also on the shear stresses between broken and intact fibres: the narrower the former spacing and the wider the latter spacing, the higher become both tensile and shear stress concentrations. This tendency is enhanced when the number of broken fibres is large and when the strain hardening of the matrix is high.