Finding of remarkable synergistic effect on the aroxyl-radical-scavenging rates under the coexistence of α-tocopherol and catechins

Measurements of aroxyl radical (ArO^•)-scavenging rate constants () of antioxidants (AOHs) (α-tocopherol (α-TocH) and three catechins (CatHs) (ie, epicatechin (EC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) were performed in ethanol solution, using stopped-flow spectrophotometry. values were measured not only for each AOH, but also for the mixtures of two AOHs (α-TocH and CatH). A notable synergistic effect that the value of α-TocH increases 1.29, 1.84, and 1.65 times under the coexistence of constant concentrations of EC, EGC, and EGCG, respectively, was observed for the solutions including α-TocH and CatH. Similarly, values of CatHs (EC, EGC, and EGCG) increased 1.72, 2.25, and 2.34 times under the coexistence of constant concentrations of α-TocH, respectively. UV-Vis absorption of α-tocopheroxyl radical (α-Toc^•) (λ_max = 428 nm), which had been produced by reaction of α-TocH with ArO^•, decreased remarkably under the coexistence of α-TocH and CatHs due to the fast α-TocH-regeneration reaction by CatHs. The result suggests that the prooxidant reaction due to α-Toc^• is suppressed by the coexistence of CatHs. By analyzing the formation and decay curves of α-Toc^•, it has been ascertained that one molecule of EGCG having three OH groups at B-ring may rapidly regenerate three molecules of α-Toc^• to α-TocH.     

Radiation-induced polymerization at high dose rate. II. α-Methylstyrene in bulk

Bulk polymerization of α-methylstyrene was carried out in a wide dose rate range, 7.6–256 rad/sec by γ rays and 8.5 × 10³–2.1 × 10⁵ rad/sec by electron beams. At high dose rate by electron beams, cationic polymerization took place along with formation of oligomeric product of DP _n = ～4. At low dose rate by γ rays, radical polymerization was found to occur in water-saturated monomer. The cationic polymerization at high dose rate proceeds with essentially the same mechanism as was already known in γ-ray polymerization of dry monomers. Relatively low reaction rate of the cationic polymerization compared with that of styrene is explained with the fact that the propagation of α-methylstyrene is much more easily inhibited by a slight amount of water.     

Numerical study on combustion of H2—O2 in a supersonic reactive expansion in a nozzle

A study on expansion flow inside a nozzle considering full mechanism chemistry of hydrogen and oxygen was carried out. In this study, a full implicit scheme for turbulent reactive flow was obtained by combining the second order TVD scheme of Yee and Harten (1987, Implicit TVD schemes for hyperbolic conservation laws in curvilinear coordinates. American Institute of Aeronautics and Astronautics Journal, 25(2), 266–274) with the efficient implicit lower-upper scheme of Shuen and Yoon (1989, Numerical study of chemically reacting flows using a lower-upper symmetric successive overrelaxation scheme. American Institute of Aeronautics and Astronautics Journal, 27(12), 1752–1756). The species equations, Navier–Stokes equations and turbulence model were implemented in the numerical scheme and solved in conjunction with full detailed finite rate chemistry. The numerical scheme is verified by comparison with experimental results of a converging–diverging nozzle. Effects of inlet pressure, temperature and fuel-oxidant mass ratio on nozzle flow field were studied. Variation of chemical species under different conditions was investigated by considering a chemical mechanism. Results show that increasing inlet pressure increases the rate of reactions due to increasing the concentration of reactants. For lower inlet pressure the radical H increases slightly in the diverging part of the nozzle, while for higher pressures it decreases along the nozzle. Inlet fuel–oxidant mass ratio affects the variation of all species with a greater effect for a near stoichiometric ratio. It was also shown that a higher inlet temperature provides a more enhanced reaction zone in the diverging part of the nozzle.     

Novel lactonization of ethenetricarboxylate derivatives: intermolecular trapping of alkenes

A novel cyclization of 1,1-diethyl 2-tert-butyl ethenetricarboxylate (1a) in the presence of a Lewis acid afforded a 5,5-dimethyl-gamma-lactone derivative 2a. The reaction process has been shown to arise from formation by trapping of isobutylene generated in situ. Lewis acid-promoted intermolecular reactions of 1,1-diethyl 2-hydrogen ethenetricarboxylate (5) and various alkenes to afford highly functionalized gamma-lactones were also developed. [reaction: see text]     

Irreversible temperature‐responsive formation of high‐strength hydrogel from an enantiomeric mixture of starburst triblock copolymers consisting of 8‐arm PEG and PLLA or PDLA

Starburst triblock copolymers consisting of 8‐arm poly(ethylene glycol) (8‐arm PEG) and biodegradable poly(L ‐lactide) (PLLA) or its enantiomer poly(D ‐lactide) (PDLA), 8‐arm PEG‐b‐PLLA‐b‐PEG ( Stri‐L ), and 8‐arm PEG‐b‐PDLA‐b‐PEG ( Stri‐D ) were synthesized. An aqueous solution of a 1:1 mixture ( Stri‐Mix ) of Stri‐L and Stri‐D assumed a sol state at room temperature, but instantaneously formed a physically crosslinked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high‐storage modulus (9.8 kPa) at 37 °C. Interestingly, once formed at the transition temperature, the hydrogel was stable even after cooling below the transition temperature. The hydrogel formation process was irreversible because of the formation of stable stereocomplexes. In aqueous solution, gradual hydrolytic erosion was observed because of degradation of the hydrogel. The combination of rapid temperature‐triggered irreversible hydrogel formation, high‐mechanical strength, and degradation behavior render this polymer mixture system suitable for use in injectable biomedical materials, for example, as a drug delivery system for bioactive reagents or a biodegradable scaffold for tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6317–6332, 2008     

Persistence of Si(111)7 × 7 surface structure under air exposure

Changes in Si(111) 7 × 7 pattern with air exposure are studied by RHEED. The relation between exposure time and air-oxidized film thickness is obtained using an ellipsometer. As a result, it is found that the 7 × 7 surface after air exposure (760 Torr, 20 h) still exhibits several 7 × 7 spots near normal ones in the RHEED pattern. The air-oxidized film thickness corresponding to this exposure is about 13 Å. The fact that the 7 × 7 spots do not disappear with HF etching of the oxide film indicates that the superstructure remains not at the oxide surface but at the substrate selvedge. The 7 × 7 spots gradually disappear after longer exposure time and no 7 × 7 spots can be observed after 40 h (about 15 Å in oxide thickness). For a sample exposed longer than 40 h, no 7 × 7 spots reappear, even if the oxide is removed by HF. Therefore, it is concluded that the structure of the substrate selvedge changes with exposure time.     

Chemo- and stereoselective six-membered oxonium ylide formation–[2,3]-sigmatropic rearrangement of 2-diazo-3-ketoesters with dirhodium(II) catalyst and its application to the synthesis of (+)-tanikolide

Dirhodium(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement of 6-allyloxy-2-diazo-3-ketoesters possessing a C-6 substituent is described. The reaction of 6-alkyl- or 6-aryl-substituted 6-allyloxy-2-diazo-3-ketoesters with a catalytic amount of Rh₂(S-PTTL)₄ proceeded in a chemoselective and stereoselective manner to provide 6-substituted 2-allyl-3-oxotetrahydropyran-2-carboxylates in good yields and with high diastereoselectivities. To demonstrate the utility of this sequential reaction, we conducted the total synthesis of (+)-tanikolide, in which the construction of the δ-lactone skeleton was achieved by employing a 2-iodobenzamide-catalyzed oxidative cleavage of tetrahydropyran-2-methanol.