Polymerization of styrene with a simple rare earth metal initiator

The catalytic activity in the polymerization of styrene has been examined using commercially available simple rare earth metal compounds such as Sm(OiPr)₃, Sm(acac)₃, Sm(OCOMe)₃, SmI₂(THF)₂ or SmCl₃ coupled with Et₃Al or methylaluminoxane (MAO). Among these compounds, the Sm(OiPr)₃/AlEt₃ system shows the highest catalytic activity, especially in the presence of a minor amount of toluene at 60 °C. The random copolymerization of styrene with methyl methacrylate suggests that the present polymerization proceeds with a radical polymerization mechanism. (C₅Me₅)SmCl₃Na(THF) and (C₅Me₅)SmCl₃Li(THF) systems exhibit relatively low catalytic activity, even in the presence of AlEt₃. © 2001 Society of Chemical Industry     

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.     

125Te, 27Al, and 71Ga NMR Study of M2O3–TeO2 (M = Al and Ga) Glasses

The structures of M₂O₃–TeO₂ (M = Al and Ga) glasses have been investigated by means of ¹²⁵Te, ²⁷Al, and ⁷¹Ga NMR spectroscopies. The structural units of respective cations in M₂O₃–TeO₂ glasses were quantitatively analyzed. The fractions of TeO₄ trigonal bipyramid, AlO₆ and GaO₆ octahedra decreased and those of TeO₃ trigonal pyramid, AlO₄, AlO₅, and GaO₄ polyhedra increased with increasing M₂O₃ content. Based on the local structures around Te, Al, and Ga atoms, the structure models of M₂O₃–TeO₂ glasses were proposed.     

Pilot-Scale Operation of a Concrete Sludge Recycling Plant and Simultaneous Production of Calcium Carbonate

A pilot-scale plant to treat concrete sludge and produce calcium carbonate (CaCO₃) and an environmental purification agent (phosphorus adsorbent derived from concrete sludge, PAdeCS®) was designed, constructed, and operated. Concrete sludge from a concrete pile and pole production plant, boiler gas containing CO₂, and groundwater were used in the plant. The process involved calcium extraction from concrete sludge into water, followed by reaction of the calcium with CO₂ to produce crystalline CaCO₃. The pilot-scale plant was operated for 1 week, and the mass flows, conversion of CO₂ to CaCO₃, and net CO₂ emissions of the process were estimated. High-purity CaCO₃ (>97%) suitable for industrial use was obtained. Based on the power consumption of the process and the amount of CO₂ sequestered into CaCO₃, a net reduction in CO₂ emissions can be achieved using this process. The produced PAdeCS can be used as an inexpensive substitute for calcium series environmental purification agents.     

URINARY 2-HYDROXYFLUORENE AND 1-HYDROXYPYRENE LEVELS IN SMOKERS AND NONSMOKERS IN JAPAN AND THAILAND

2-Hydroxyfluorene (2-OHF) and 1-hydroxypyrene (1-OHP) in urine samples of smokers and nonsmokers were determined separately by using two high-performance liquid chromatography (HPLC) systems with fluorescence detection. Urine samples were collected from the subjects who lived in Japan and Thailand, and were not occupationally exposed to polycyclic aromatic hydrocarbons (PAHs). The mean concentrations of 2-OHF and 1-OHP of Thai smokers (0.75 and 3.03 μmol/mol creatinine) and nonsmokers (0.22 and 0.91 μmol/mol creatinine) were both higher than those of Japanese smokers (0.26 and 0.12 μmol/mol creatinine) and nonsmokers (0.04 and 0.06 μmol/mol creatinine), respectively. The difference between smokers and nonsmokers was more significant for 2-OHF than for 1-OHP, reflecting the higher intake of fluorene in the vapor phase by the smoking. Moreover, the higher urinary levels of both 2-OHF and 1-OHP were observed in Thai nonsmokers than those in Japanese nonsmokers, suggesting the higher background exposure to PAHs of Thai subjects.     

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.     

A Unique Approach to Characterization of Sol‐Gel‐Derived Rare‐Earth‐Doped Oxyfluoride Glass‐Ceramics

Using the sol‐gel route Nd³⁺‐doped oxyfluoride glass‐ceramics were prepared. LiYF₄ and YF₃ crystals were deposited in the glass‐ceramics and their size, distribution, and amount ratio were varied by changing the compositions and heating temperatures. The incorporation of Nd³⁺ ions into both the fluoride crystals was confirmed by the high‐resolution elemental mapping of the glass‐ceramics. The incorporated Nd³⁺ ions showed up and down conversion photoluminescence whose properties were obviously different among the samples. The preliminary site analysis for Nd³⁺ ions was carried out using a unique approach associated with the Prony series approximation. Finally, the approach was found to be useful for the analysis of materials that are structurally complicating.     

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.