Reactivity and mechanism of stable heterocyclic silylenes with carbon tetrachloride

The potential energy surfaces for the reactions of stable silylenes with carbon tetrachloride have been characterized in detail using density functional theory [B3LYP/6-311G(d)], including zero-point corrections. Five stable silylene species (1-5) have been chosen in this work as model reactants. The activation barriers and enthalpies of the reactions are compared to determine the relative reactivity of the stable silylenes on the reaction potential energy surface. Our theoretical findings suggest that stable silylene 5, which has two carbon atoms bonded to the silicon center and does not contain a resonance structure, is relatively unstable with respect to the reaction with haloalkanes, in comparison with the other stable silylenes (1-4). Of the three possible reaction paths, Cl abstraction (path 1), CCl3 abstraction (path 2), and CCl4 insertion (path 3), path 1 is found to be most favorable, with a very low activation energy and a large exothermicity. In short, electronic as well as steric factors play a dominant role in determining the chemical reactivity of the stable silylene species kinetically as well as thermodynamically. Furthermore, a configuration mixing model based on the work of Pross and Shaik is used to rationalize the computational results. The results obtained allow a number of predictions to be made.     

DiffServ‐based bandwidth‐constrained anycast routing in a mobile IPv6 network

This paper proposes a differentiated service (DiffServ)‐based bandwidth‐constrained network layer anycast routing for a mobile IPv6 network. The proposed algorithm comprises three steps: (1) When moving into a new foreign network, the mobile node (MN) chooses a feasible path to easily locate the nearest server that can serve it. To perform path selection, a multi‐level list structure (MLLS) is defined and used to store the available bandwidth and hop count of a path. (2) An ingress extended edge router (E‐ER) uses the multi‐level list algorithm (MLLA) to examine the MLLS for selecting the feasible path with the smallest number of hops that satisfies the MN bandwidth request. (3) The E‐ER uses a condition of path change (CPC) variable to determine whether it should optimize the route between itself and the server. Simulation results indicate that the proposed algorithm offers better performance than the existing related approaches in terms of the average running time, request blocking rate, and reducing the control overhead of the simulated network. Copyright © 2010 John Wiley & Sons, Ltd.     

Modified particle swarm optimization algorithm with simulated annealing behavior and its numerical verification

The hybrid algorithm that combined particle swarm optimization with simulated annealing behavior (SA-PSO) is proposed in this paper. The SA-PSO algorithm takes both of the advantages of good solution quality in simulated annealing and fast searching ability in particle swarm optimization. As stochastic optimization algorithms are sensitive to their parameters, proper procedure for parameters selection is introduced in this paper to improve solution quality. To verify the usability and effectiveness of the proposed algorithm, simulations are performed using 20 different mathematical optimization functions with different dimensions. The comparative works have also been conducted among different algorithms under the criteria of quality of the solution, the efficiency of searching for the solution and the convergence characteristics. According to the results, the SA-PSO could have higher efficiency, better quality and faster convergence speed than compared algorithms.     

Antioxidant activities of extracts and metabolites isolated from the fungus Antrodia cinnamomea

Three different solvent partitions (n-hexane, ethyl acetate [EtOAc] and n-BuOH) of the culture broth from Antrodia cinnamomea were assayed with two different radical scavenging methods: 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging and superoxide radical scavenging (SOD) assay. The EtOAc layer exhibited the best antioxidant activity. Two major antioxidant metabolites were isolated from the active EtOAc layer. The antioxidant activities of compounds 1-6 were further evaluated by DPPH, SOD and trolox equivalent antioxidant capacity (TEAC) assays. Compounds 3 and 5 showed stronger free radical scavenging than the reference BHA, ED???=?1.36 and 34.24 μM. Compound 5 displayed moderate SOD activity (ED???=?310.0?μM), and its antioxidant capacity of TEAC value was 2.2 mM trolox equivalency.     

Reconstruction for a class of the inverse transmission eigenvalue problem

The authors present a constructive algorithm for the numerical solution to a class of the inverse transmission eigenvalue problem. The numerical experiments are provided to demonstrate the efficiency of our algorithms by a numerical example.     

Pressure-induced valence anomaly in TmTe probed by resonant inelastic X-ray scattering

The pressure-induced valence transition in TmTe was investigated by resonant inelastic x-ray scattering at the Tm L3 edge, a powerful probe of the rare-earth valent state. The data are analyzed within the Anderson impurity model which yields key parameters such as the Tm 4f-5d hybridization. In addition to the general tendency of the f electrons towards delocalization, we find a plateau in both the Tm valence and hybridization pressure dependences between 4.3 and 6.5 GPa which is interpreted in terms of an n-channel Kondo (NCK) screening process. This behavior is at odds with the usually continuous, single-channel Kondo-like f delocalization while being supported by the seminal calculations of the NCK temperature in Tm ion by Saso et al. Our study raises the interesting possibility that an NCK effect realized in a compressed mixed-valent f system could impede the concomitant electron delocalization.     

Adlay Seed (Coix lacryma-jobi L. var. Ma-yuen Stapf.) Ethanolic Extract Fractions and Subfractions Induce Cell Cycle Arrest and Apoptosis in Human Breast and Cervical Cancer Cell Lines

The antitumor effects of Coix lacryma-jobi L. var. ma-yuen Stapf. (adlay seed) ethanolic extract have been increasingly shown. This study aimed to investigate the beneficial effects of both the fractions and subfractions of adlay seed ethanolic extract on the human breast (MCF-7) and cervical (HeLa) cancer cell lines, as well as exploring their possible mechanisms of action. The ethanolic extracts were obtained from different parts of adlay seed, including AHE (adlay hull extract), ATE (adlay testa extract), ABE (adlay bran extract) and PAE (polished adlay extract). The results of a 3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyl- tetrazolium bromide (MTT) assay showed that AHE-Ea and ATE-Ea showed significant growth inhibitory effects in a dose-dependent manner. The results also showed that the AHE-Ea-K, AHE-Ea-L, ATE-Ea-E and ATE-Ea-F subfractions inhibited cell proliferation, induced cell cycle arrest in the G0/G1 phase and decreased CDK4/Cyclin D1 protein expression. Finally, the extract activated caspase-3 activity and PARP protein expression, which induced MCF-7 and HeLa cell apoptosis. We then used liquid chromatography–mass spectrometry (LC/MS) to identify the potential active components., Quercetin showed an anticancer capacity. In conclusion, the AHE-Ea-K, AHE-Ea-L, ATE-Ea-E and ATE-Ea-F subfractions showed antitumor effects through the inhibition of MCF-7 and HeLa cell line viability, as well as inducing apoptosis and cell cycle arrest.     

Selenium-Based Catalytic Scavengers for Concurrent Scavenging of H2S and Reactive Oxygen Species

Hydrogen sulfide (H₂S) is an endogenous gasotransmitter that plays important roles in redox signaling. H₂S overproduction has been linked to a variety of disease states and therefore, H₂S-depleting agents, such as scavengers, are needed to understand the significance of H₂S-based therapy. It is known that elevated H₂S can induce oxidative stress with elevated reactive oxygen species (ROS) formation, such as in H₂S acute intoxication. We explored the possibility of developing catalytic scavengers to simultaneously remove H₂S and ROS. Herein, we studied a series of selenium-based molecules as catalytic H₂S/H₂O₂ scavengers. Inspired by the high reactivity of selenoxide compounds towards H₂S, 14 diselenide/monoselenide compounds were tested. Several promising candidates such as S6 were identified. Their activities in buffers, as well as in plasma- and cell lysate-containing solutions were evaluated. We also studied the reaction mechanism of this scavenging process. Finally, the combination of the diselenide catalyst and photosensitizers was used to achieve light-induced H₂S removal. These Se-based scavengers can be useful tools for understanding H₂S/ROS regulations.     

Polar Metabolites from the Actinobacterium Isoptericola chiayiensis Isolated from Mangrove Soil

Chemistry of Natural Compounds -