Modification of cyanate ester resin by soluble polyimides

Soluble polyimides (PIs) were prepared as random or multiblock types with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA) as acid dianhydride components and 4,4′‐bis(m‐aminophenoxy) diphenyl sulfone (m‐BAPS) as a diamine component by a one‐pot process and used to improve the brittleness of the cyanate ester resin. Random‐type PIs were more effective as modifiers than multiblock‐type PIs. The morphologies of the modified resins depended on PI structure, molecular weight, and concentration. The most effective modification of the cyanate ester resin was attained because of a heterogeneous phase structure composed of a flat matrix phase and phase‐inverted structures of the modified resin; a 15 wt % inclusion of a random PI (weight‐average molecular weight = 63,400) composed of 6FDA, s‐BPDA, and m‐BAPS (0.5/0.5/1.0 molar ratio) led to a 65% increase in the fracture toughness for the modified resin with a slight loss of flexural strength and a retention of flexural modulus and glass‐transition temperature, compared with the values for the unmodified resin. Water absorptivity of the modified resin was comparable to that of the unmodified resin up to 400 h, and then, water absorption of the modified resins increased considerably. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1–11, 2003     

Electromigration of sodium ions and electro-osmotic flow in water-saturated, compacted Na-montmorillonite

Sodium ions spiked with ²²Na as a tracer were migrated by electromigration and electro-osmosis in the water-saturated compacted Na-montmorillonite at dry densities 1.0×10³ kg m⁻³, under an electric potential gradient. Dissolved helium was also migrated by electro-osmosis in the montmorillonite. After migration, concentration profiles of the sodium ions and helium were obtained by γ-spectrometry and mass-spectrometric methods, respectively. From the profiles of both chemical species, not only migration due to electrokinetic phenomena but also mechanical dispersion was observed in the montmorillonite. The dispersion coefficients, D_i, and apparent migration rates, U_i^a, of ²²Na and helium were found in the compacted Na-montmorillonite at 1.0×10³ kg m⁻³. The migration of helium in the montmorillonite under an electric potential gradient reflects that of water because helium migrates as an electrically neutral species. The parameters D_He^m, U_He^a, and α_He correspond to those of water. The mechanical dispersion coefficients, D_Na^m, of ²²Na⁺ ions are much smaller than those of water obtained by helium. The dispersivity parameters, α_Na, for ²²Na⁺ obtained from these D_Na and U_Na^a values are 10⁻⁵ m and those for water (α_He) are 10⁻³ m. This indicates that ²²Na⁺ ions migrate in different spaces than water in the compacted montmorillonite under a potential gradient. This finding suggests that the migration of Na⁺ ions occurs in the interlayer and/or on the outer surfaces of the montmorillonite; whereas dissolved helium migrates in the pore water.     

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.     

A Single Mutation at the Ferredoxin Binding Site of P450 Vdh Enables Efficient Biocatalytic Production of 25‐Hydroxyvitamin D3

Vitamin D₃ hydroxylase (Vdh) from Pseudonocardia autotrophica is a cytochrome P450 monooxygenase that catalyzes the two‐step hydroxylation of vitamin D₃ (VD₃) to produce 25‐hydroxyvitamin D₃ (25(OH)VD₃) and 1α,25‐dihydroxyvitamin D₃ (1α,25(OH)₂VD₃). These hydroxylated forms of VD₃ are useful as pharmaceuticals for the treatment of conditions associated with VD₃ deficiency and VD₃ metabolic disorder. Herein, we describe the creation of a highly active T107A mutant of Vdh by engineering the putative ferredoxin‐binding site. Crystallographic and kinetic analyses indicate that the T107A mutation results in conformational change from an open to a closed state, thereby increasing the binding affinity with ferredoxin. We also report the efficient biocatalytic synthesis of 25(OH)VD₃, a promising intermediate for the synthesis of various hydroxylated VD₃ derivatives, by using nisin‐treated Rhodococcus erythropolis cells containing Vdh_T107A. The gene‐expression cassette encoding Bacillus megaterium glucose dehydrogenase‐IV was inserted into the R. erythropolis chromosome and expressed to avoid exhaustion of NADH in a cytoplasm during bioconversion. As a result, approximately 573 μg mL^?1 25(OH)VD₃ was successfully produced by a 2 h bioconversion.     

Influence of water content in sub-flooring materials using adhesive on chemical compounds emission

Indoor air pollution is caused predominantly by emission of primary pollutants from building materials or finishing materials. Recently, there has been increasing interest in the new secondary pollutants caused by chemical reaction of the primary pollutants. In this study, the pollutants emitted from poly(vinyl chloride) (PVC) flooring material were measured, and 2-ethyl-1-hexanol (2E1H) and volatile organic compounds (VOCs) emitted from composite building materials made of PVC flooring material used as a self-leveling flooring were measured to identify the mechanism of emission of 2E1H. The moisture sorption isotherm was measured with a Magnetic Suspension Balance to examine the moisture content of the self-leveling flooring material and its effect on emission of 2E1H. 2E1H was emitted from the PVC flooring material through hydrolysis or oxidation of di-2-ethylhexyl phthalate (DEHP). The composite building material including the self-leveling flooring material emitted more 2E1H through hydrolysis over time. It was determined that liquid prevails in the self-leveling flooring material when the water content is higher than 4% and vapor prevails when the water content is lower than 4%. The prevailing liquid in the flooring material contributes to the increased emission of 2E1H and the prevailing vapor in the material did not cause increase in emission of 2E1H. It is considered that control of water in the self-leveling flooring material or concrete slab is very important in order to inhibit emission of 2E1H through hydrolysis of DEHP on the floor.     

Synthetic Molecular Gear Based on Double-Decker Porphyrin Complexes

New rotary molecular machines (1 and 2) were synthetically constructed from two distinct porphyrin-based rotors, a cerium(IV) bis(porphyrinate)s double-decker (CeDD) and a porphyrinatorhodium(III)-based rotor. These rotors are adjacently mounted on rotational axes aligned to near vertical as resembling the bevel-gear-shaped structure. Structural study using NMR analysis reveals that these distinct rotors are connected through a coordination bond between rhodium(III) and a pyridyl group. At temperature from 193 to 393 K, each rotor represents rotational motion driven by heat fluctuation without decomposition into the corresponding precursors in dichloromethane-d ₂ and tetrachloroethane-d ₄. Importantly, the mechanical interaction between the teeth of these rotors is strongly dependent on the central metal atom in a DD rotor and the teeth structure in a porphyrinatorhodium(III)-based rotor. Understanding such relationship between the chemical structures and mechanical interaction is of importance for generating cooperative motion in the hybrid machinery system.     

Hydrogen-bond-assisted isotactic-specific radical polymerization of N-isopropylacrylamide with pyridine N-oxide

Radical polymerization of N-isopropylacrylamide (NIPAAm) in CHCl₃ at low temperatures in the presence of pyridine N-oxide (PNO) was investigated. An isotactic poly(NIPAAm) with meso diad content of 61% was successfully prepared at −60 °C in the presence of a two-fold amount of PNO. Thermodynamic analysis suggested that the isotactic-specificity was entropically induced, probably due to conformational fixation near the propagating chain-end through coordination by PNO.     

Correlations of Hepatic Hemodynamics,Liver Function,and Fibrosis Markers in Nonalcoholic Fatty Liver Disease: Comparison with Chronic Hepatitis Related to Hepatitis C Virus

The progression of chronic liver disease differs by etiology. The aim of this study was to elucidate the difference in disease progression between chronic hepatitis C (CHC) and nonalcoholic fatty liver disease (NAFLD) by means of fibrosis markers, liver function, and hepatic tissue blood flow (TBF). Xenon computed tomography (Xe-CT) was performed in 139 patients with NAFLD and 152 patients with CHC (including liver cirrhosis (LC)). The cutoff values for fibrosis markers were compared between NAFLD and CHC, and correlations between hepatic TBF and liver function tests were examined at each fibrosis stage. The cutoff values for detection of the advanced fibrosis stage were lower in NAFLD than in CHC. Although portal venous TBF (PVTBF) correlated with liver function tests, PVTBF in initial LC caused by nonalcoholic steatohepatitis (NASH-LC) was significantly lower than that in hepatitis C virus (C-LC) (p = 0.014). Conversely, the liver function tests in NASH-LC were higher than those in C-LC (p < 0.05). It is important to recognize the difference between NAFLD and CHC. We concluded that changes in hepatic blood flow occurred during the earliest stage of hepatic fibrosis in patients with NAFLD; therefore, patients with NAFLD need to be followed carefully.     

Metastatic Voyage of Ovarian Cancer Cells in Ascites with the Assistance of Various Cellular Components

Epithelial ovarian cancer (EOC) is the most lethal gynecologic malignancy and has a unique metastatic route using ascites, known as the transcoelomic root. However, studies on ascites and contained cellular components have not yet been sufficiently clarified. In this review, we focus on the significance of accumulating ascites, contained EOC cells in the form of spheroids, and interaction with non-malignant host cells. To become resistant against anoikis, EOC cells form spheroids in ascites, where epithelial-to-mesenchymal transition stimulated by transforming growth factor-β can be a key pathway. As spheroids form, EOC cells are also gaining the ability to attach and invade the peritoneum to induce intraperitoneal metastasis, as well as resistance to conventional chemotherapy. Recently, accumulating evidence suggests that EOC spheroids in ascites are composed of not only cancer cells, but also non-malignant cells existing with higher abundance than EOC cells in ascites, including macrophages, mesothelial cells, and lymphocytes. Moreover, hetero-cellular spheroids are demonstrated to form more aggregated spheroids and have higher adhesion ability for the mesothelial layer. To improve the poor prognosis, we need to elucidate the mechanisms of spheroid formation and interactions with non-malignant cells in ascites that are a unique tumor microenvironment for EOC.     

Lipid analog with 2-nitrophenol trigger designed for liposome fusion at physiological pH

A novel lipid analog with two long alkyl (C₁₆) chains, an aspartate skeleton, a connecting alkyl (C₈) chain, and 2-nitrophenol trigger group is synthesized by an efficient synthetic route, which can induce liposome fusion at physiological pH.