A density functional theory investigation of the bromide oxidation mechanism by a vanadium bromoperoxidase model complex

Abstract  

Density functional theory has been used to study the mechanism of bromide oxidation by the oxo-peroxo complex K[VO(O₂)Hheida] (heida = N-(2-hydroxyethyl)iminodiacetic acid), which has the highest reported rate constant for bromide oxidation of any vanadium complex. Two possible mechanisms were explored, involving bromide attack on a protonated or unprotonated peroxo atom. The direct nucleophilic attack of bromide on a protonated peroxo begins the reaction, i.e. the protonated peroxo ligand is the active site of reaction. We examined five different transition states in the mechanism. Two transition states were found to have lower activation barriers. A reduction in the potential energy barriers, when calculated using the polarisable continuum model, indicates that with the involvement of acetonitrile as a solvent the transition states become more stable.     

Composition of essential oils in subterranean organs of three species of Valeriana L

Essential oils from the subterranean organs of three species of Valeriana L. from Iran (Valeriana sisymbriifolia Vahl, Valeriana alliariifolia Adams and Valeriana officinalis L.) belonging to Valerianaceae family have been obtained by hydrodistillation and analysed by gas chromatography-mass spectrometry in order to discern the differences and similarities between the volatile chemical compositions of these species. More than 100 components were identified in essential oils of the studied plants (Supplementary Table S1--online only). The principal common constituents of the three species of Valeriana were spathulenol, limonene, γ-terpinene, vulgarone B and p-cymene. The main essential oil ingredients were α-selinene (7.83%) in V. sisymbriifolia, limonene (3.53%) in V. alliariifolia and spathulenol (13.33%), α-campholenal (11.48%), vulgarone B (8.38%) and valerenal (8.32%) in V. officinalis plants. Ageratochromene (precocene II), a chromene substance with antibacterial, antifungal, insecticidal and antijuvenile hormonal activities, was found at high levels (35.59% and 36.58%) in the essential oils of V. sisymbriifolia plants.     

A comprehensive Monte Carlo simulation of styrene atom transfer radical polymerization

<正>An optimized and high-performance Monte Carlo simulation is developed to take thorough account of four different cases of termination in styrene ATRP.According to the simulation results,the bimolecular termination rate constant sharply drops throughout the polymerization when either chain-length dependency of termination rate constant,gel effect,or both together is applied to the simulation.In addition,as expected,the initiator is quickly decomposed at the early stages of the polymerization.The concentration of the catalyst in lower oxidation state decreases at first and then plateaus at higher conversion;furthermore,the steady concentration of M_t~nY/L in the polymerization is the highest when the chain-length-dependent diffusion-controlled termination rate constant is employed in the simulation.The rates of deactivation and chain end degradation reactions are also smaller in this case.Therefore,the fraction of dormant chains is higher throughout the reaction and consequently the portion of dead polymers decreases.Besides,molecular weight increases linearly with conversion;however,when neither gel effect nor chain-length dependency of termination rate constant is considered,the molecular weight deviates from linearity at the end of the reaction.The peak of chain length distribution shifts toward higher molecular weight too during the reaction.Finally,the molecular weight distribution broadens at higher conversion;however, the chain length distribution of polymers produced under conditions of applying chain-length-dependent diffusion-controlled termination rate constant is narrower.     

甲烷氧化偶联锂/氧化镁催化剂和纳米催化剂

采用初湿浸渍和溶胶凝胶法分别制备了Li/MgO催化剂和Li/MgO纳米催化剂. 比较两种Li/MgO催化剂对于甲烷氧化偶联反应的催化性能. 采用X射线衍射、BET吸附和透射电镜进行了表征.在973-1073 K和总压力为101 kPa下对催化剂进行了测试. 实验结果表明,Li/MgO纳米催化剂比普通催化剂对于甲烷氧化偶联反应表现为更高的甲烷转换率,较高选择性和较高的的主要产品(乙烷和乙烯)的产率.     

Efficient visible-light-induced photocatalytic degradation of MO on the Cr-nanocrystalline titania-S

In order to improve visible light photocatalytic activities of the nanometer TiO₂, a novel and efficient Cr,S-codoped TiO₂ (Cr-TiO₂-S) photocatalyst was prepared by precipitation-doping method. The crystalline structure, morphology, particle size, and chemical structure of Cr-TiO₂-S were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) techniques, respectively. Results indicate that the doping of Cr and S, cause absorption edge shifts to the visible light region (λ > 420 nm) compare to the pure TiO₂, reduces average size of the TiO₂ crystallites, enhances desired lattice distortion of Ti, promotes separation of photo-induced electron and hole pair, and thus improves pollutant decomposition under visible light irradiation. The photocatalytic activities of Cr-TiO₂-S nanoparticles were evaluated using the photodegradation of methyl orange (MO) as probe reaction under the irradiation of UV and visible light and it was observed that the Cr-TiO₂-S photocatalyst shows higher visible photocatalytic activity than the pure TiO₂. The optimal Cr-TiO₂-S concentration to obtain the highest photocatalytic activity was 5 mol% for both of Cr and S.     

Comment on “Delayed luminescence of biological systems in terms of coherent states” [Phys. Lett. A 293 (2002) 93]

Popp and Yan [F.A. Popp, Y. Yan, Phys. Lett. A 293 (2002) 93] proposed a model for delayed luminescence based on a single time-dependent coherent state. We show that the general solution of their model corresponds to a luminescence that is a linear function of time. Therefore, their model is not compatible with experimental delayed luminescence. Moreover, the functions that they use to describe the oscillatory behaviour of delayed luminescence are not solutions of the coupling equations to be solved.     

Varieties of Pragmatic Encroachment

According to a recent view, known as the 'pragmatic encroachment' thesis, an agent’s non-truth-related factors are relevant to the epistemic status of her beliefs. In particular, in addition to truth-related factors, practical factors are said to be relevant to the question whether or not true belief amounts to knowledge. Despite the intuitive appeal of the thesis, however, it is puzzling how practical factors can impact the truth-related factors that ground the epistemic status of one's beliefs. In this paper, I will distinguish between a strong and a weak sense of the way in which practical factors are said to be thus relevant. Their differences are explicated in terms of the nature and the extent to which practical factors are said to impact the epistemic status of one's beliefs. I begin by considering a strong version of the thesis that suggests principles according to which the practical rationality of one's actions is a necessary condition on knowledge and justification. Having noted an inadequacy in the formulation of such principles, the arguments in their support are subsequently stated and criticized. Finally, I identify two modest versions of the thesis of pragmatic encroachment and argue that they, too, fail to explain how practical factors can bear on the epistemic status of one's beliefs.     

Lattice Boltzmann simulation of non-Newtonian flows past confined cylinders

A second-order lattice Boltzmann algorithm is used for Power-Law non-Newtonian flow simulation. The shear dependent behavior of the fluid is implemented through calculating the shear locally from the lattice distribution functions. A step by step verification procedure is taken to ensure the accuracy and the physical correctness of the numerical simulation. The flow past a series of tandem arrangement of two cylinders is computed in a confined domain. The effects of Reynolds number, the Power-Law index, and the distance between two cylinders on both the flow field and the drag coefficients of the cylinders are examined in detail.     

Application of Monte Carlo simulation method to polymerization kinetics over Ziegler–Natta catalysts

In the current work, the Monte Carlo simulation method was applied to ethylene polymerization over Ziegler–Natta catalysts. As expected, polymerization over each center of a Ziegler–Natta catalyst leads to a polymer having a Schultz–Flory molecular weight distribution. Notwithstanding, the total molecular weight distribution obtained by all catalyst centers together is at least twice as broad as that of each center. As another interesting finding, the introduction of hydrogen to the reaction deactivates the catalyst active centers and thereby reduces the catalyst activity. Nevertheless, it does not mainly affect the polymerization kinetics. In addition, the polymer molecular weight falls as hydrogen is added to the reaction since it acts as a strong transfer agent. The same effect is seen when cocatalyst concentration increases. Hydrogen also widens the polymer molecular weight distribution. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 45–56, 2009