Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO₂ in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions.     

The effects of infusion of trieicosapentaenoyl-glycerol emulsion on extravascular lung water during myocardial ischemia and reperfusion in dogs

To test the effects of eicosapentaenoic acid (EPA) infusion on pulmonary edema induced by coronary ligation and reperfusion, extravascular lung water (EVLW) was measured in situ by the thermal-dye double indicator dilution method in dogs. In the control group of five dogs, 30 mL of a 10% soybean oil emulsion was infused through a leg vein. One hour after infusion, the left anterior descending coronary artery below the first diagonal branch was ligated for 15 min and then reperfused for 30 min. In the EPA group, six dogs were similarly treated with an emulsion of a 10% trieicosapentaenoyl-glycerol (90% pure). EVLW, pulmonary capillary wedge pressure, mean pulmonary artery pressure, mean blood pressure, and cardiac index were measured before and 15 min after coronary ligation, and 15 min and 30 min after coronary reperfusion. There were no significant differences in the hemodynamic indices between the two groups. EVLW significantly increased up to two times of baseline during coronary ligation in the control group (P< 0.05) and more during reperfusion (P<0.01), whereas EVLW did not increase in the EPA group. In conclusion, EPA inhibited EVLW accumulation and may be useful for ameliorating one of the ischemia-reperfusion-induced complications, pulmonary edema.     

The pharmacokinetics of water-in-oil-in-water-type multiple emulsion of a new tacrolimus formulation

We developed a water-in-oil-in-water (W/O/W)-type multiple emulsion of a new tacrolimus formulation. A potential approach to avoid the complications of systemic immunosuppression and simultaneously enhance immunosuppressive efficacy is to deliver immunosuppressive agents locally to the site of the target organs. The W/O/W emulsion is dispersed oil drops containing smaller water droplets that allow the delivery of drugs preferentially to the reticuloendothelial system (RES). Since the liver and the spleen are primary components of the RES, and the brain and the kidney have a poor RES, we hypothesized that a W/O/W emulsion of tacrolimus would prossess the pharmacokinetic benefits of local immunosuppression. We evaluated this hypothesis in a rat model. The tacrolimus levels of whole blood, the liver, spleen, brain, and kidney in rats given intravenous emulsions of tacrolimus (W/O/W group) were compared with a group administered tacrolimus alone (T group). There were no significant differences between the pharmacokinetic parameters of W/O/W group and T group based on whole blood data. However, the W/O/W group had significantly decreased tacrolimus levels in the brain and kidney, and significantly increased levels in the liver and spleen compared with the T group. These data suggest that the W/O/W emulsion is applicable as an intravenous drug carrier for local immunosuppression.     

The effect of salinity on nitrite accumulation in a down‐flow hanging sponge reactor

BACKGROUND: In this study, the inductive effect of salinity on nitrite accumulation in a down‐flow hanging sponge (DHS) reactor, developed as a novel and cost‐effective wastewater treatment process, was evaluated by conducting a long‐term continuous experiment lasting more than 1400 days. RESULTS: The influent salinity was controlled by adding NaCl at concentrations ranging from 0 to 25 g Cl^? L^?1. The effluent nitrite increased with increases in salinity, i.e. the fraction of nitrite to total nitrogen in the effluent increased from 1.6% at 0 g Cl^? L^?1 to 87.6% at 25 g Cl^? L^?1. Fluorescence in situ hybridization (FISH) analysis revealed that as salinity increased, the nitrifying bacterial community in the DHS changed markedly at the species level. In particular, the dominant nitrite‐oxidizing bacteria changed from Nitrospira‐sublineage I at 0 g Cl^? L^?1 to Nitrobacter spp. at 15 g Cl^? L^?1. At 25 g Cl^? L^?1, no nitrite‐oxidizing bacteria were detected. CONCLUSION: Our findings suggest that the DHS reactor is suitable for cost‐effective nitrite production processes and that salinity control using NaCl is an effective method for inducing nitrite accumulation. Copyright © 2012 Society of Chemical Industry     

Euphorbia tirucalli β-Amyrin Synthase: Critical Roles of Steric Sizes at Val483 and Met729 and the CH–π Interaction between Val483 and Trp534 for Catalytic Action

The functions of Val483, Trp534, and Met729 in Euphorbia tirucalli β-amyrin synthase were revealed by comparing the enzyme activities of site-directed mutants against that of the wild type. The Gly and Ala variants with a smaller bulk size at position 483 predominantly afforded monocyclic camelliol C, which suggested that the orientation of the (3S)-2,3-oxidosqualene substrate was not appropriately arranged in the reaction cavity as a result of the decreased bulk size, leading to failure of its normal folding into the chair–chair–chair–boat–boat conformation. The Ile variant, with a somewhat larger bulk, afforded β-amyrin as the dominant product. Intriguingly, various variants of Trp534 exhibited significantly decreased enzymatic activities and provided no aberrantly cyclized products, although the aromatic Phe and Tyr residues were incorporated and the steric sizes of the aliphatic residues were altered. Therefore, the Trp534 residue does not stabilize the transient cation through a cation–π interaction. Furthermore, the Trp residue, with the largest steric bulk among all natural amino acids, is essential for high enzymatic activity. Robust CH–π complexation between the Val483 and Trp534 residues is proposed herein. Altering the steric bulk at the Met729 position afforded the pentacyclic skeletons. Thus, Met729 is positioned at the E-ring formation site. More detailed insights into the functions of the Val483, Trp534, and Met729 residues are provided by homology modeling.     

Effect of BN nanoparticle content in SiC matrix on microstructure and mechanical properties of SiC/SiC composites

BN-nanoparticle-containing SiC-matrix-based composites comprising SiC fibers and lacking a fiber/matrix interface (SiC/BN + SiC composites) were fabricated by spark plasma sintering (SPS) at 1800°C for 10 min under 50 MPa in Ar. The content of added BN nanoparticles was varied from 0 to 50 vol.%. The mechanical properties of the SiC/BN + SiC composites were investigated thoroughly. The SiC/BN + SiC composites with a BN nanoparticle content of 50 vol.%, which had a bulk density of 2.73 g/cm³ and an open porosity of 5.8%, exhibited quasiductile fracture behavior, as indicated by a short nonlinear region and significantly shorter fiber pullouts owing to the relatively high modulus. The composites also exhibited high strength as well as bending, proportional limit stress, and ultimate tensile strength values of 496 ± 13, 251 ± 30, and 301 MPa ± 56 MPa, respectively, under ambient conditions. The SiC fibers with contents of BN nanoparticles above 30 vol.% were not severely damaged during SPS and adhered to the matrix to form a relatively weak fiber/matrix interface.     

Effects of dietary lipids on daunomycin-induced nephropathy in mice: comparison between cod liver oil and soybean oil

Although it is well known that dietary lipids affect the course of glomerulonephritis in rats and humans, the precise mechanisms involved have not been fully elucidated. The aim of this study was to investigate the effects of different types of dietary lipids (fish oil and vegetable oil) on daunomycin (DM)-induced nephropathy in mice fed on soybean oil (SO) or cod liver oil (CLO). Urinary protein excretion, serum albumin, creatinine, total cholesterol, and TG were measured, and glomerular histological changes were evaluated. Antioxidant enzymes were also measured, along with the levels of lipid peroxide, GSH, thromboxane (Tx) B_2′ and 6-keto prostaglandin F_1α in renal cortical tissue. Dietary CLO significantly reduced urinary albumin excretion and ameliorated the histological changes induced by DM. The increase of tissue lipid peroxide levels seen in SO-fed mice was suppressed in CLO-fed mice, whereas CLO-fed mice showed higher GSH levels than SO-fed mice throughout the experiment. In addition, renal tissue GSH peroxidase activity was significantly higher at 72 h after DM injection in CLO-DM mice than in SO-DM mice. Both renal cortical TxB₂ and 6-keto PGF_1α levels were significantly lower in CLO-DM mice than in SO-DM mice. These results suggest that inhibition of oxidative damage by dietary CLO played an important role in the prevention of DM nephropathy in this mouse model. The effect of CLO was closely associated with the inhibition of Tx synthesis.     

Crystal orientation of β-phase isotactic polypropylene induced by magnetic orientation of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide

Melt crystallization of isotactic polypropylene (iPP), containing crystallites of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide (DCNDCA) as a nucleating agent of the the β-phase iPP crystal, is carried out under a magnetic field (6 T) to obtain the alignment of the iPP crystal induced by magnetic alignment of DCNDCA. In a previous paper, DCNDCA was reported to undergo magnetic alignment in a liquid suspension. The obtained iPP sample exhibits alignment of the β-phase crystal with the c-axis aligned perpendicular to the magnetic field. The comparison of this alignment of iPP with the reported magnetic alignment of DCNDCA indicates that the β-phase crystal grows epitaxially on the DCNDCA crystal. The (330)_β plane of the iPP crystal lies on the bc-plane of the DCNDCA crystal in which the direction of the c-axis of the iPP coincides with the direction of the b-axis of the DCNDCA crystal.     

Decoupling between Enthalpy Relaxation and Viscous Flow and Its Structural Origin in Fragile Oxide Glass-Forming Liquids

The structural relaxation kinetics at the glass transition in tellurium oxide (TeO₂)-based glasses has been examined from viscosity and heat-capacity measurements to clarify the features of the structural relaxation in fragile oxide glass-forming liquids. A large decoupling between enthalpy relaxation and viscous flow, i.e., a large discrepancy between the activation energies for the enthalpy relaxation (recovery), Δ H , and viscous flow, E _η, has been demonstrated in TeO₂-based glasses. The values in x K₂O· x MgO·(100 − 2 x )TeO₂ glasses, for example, are ∼919–1051 kJ/mol for Δ H and ∼ 577–701 kJ/mol for E _η, given the ratio of Δ H/E _η≈ 1.44–1.59. Some viscosity and heat-capacity data (all data have been reported previously) obtained from similar experiments in Sb₂O₃–B₂O₃ glasses belonging to the category of strong glass-forming liquids have been reanalyzed in this paper for comparison; a strong coupling was found to exist between Δ H and E _η, i.e., Δ H/E _η≈ 0.98–1.18. An origin of decoupling between Δ H and E _η in fragile glass-forming systems such as TeO₂-based glasses has been discussed by considering the glass structure model for fragile glasses; strongly bonded correlated (highly constrained) regions are surrounded or connected by weakly bonded noncorrelated (unconstrained) parts.