Aromaticity on the fly: cyclic transition state stabilization at finite temperature.

We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.

Accurate screened exchange band structures for the transition metal monoxides MnO, FeO, CoO and NiO.

We report calculations of the band structures and density of states of the four transition metal monoxides MnO, FeO, CoO and NiO using the hybrid density functional sX-LDA ('screened exchange local density approximation'). Late transition metal oxides are prototypical examples of strongly correlated materials, which pose challenges for electronic structure methods. We compare our results with available experimental data and show that our calculations generally yield accurate predictions for the fundamental band gaps and valence bands, in favourable agreement with previously reported theoretical studies. For MnO, the band gaps are still underestimated, suggesting additional many-body effects that are not captured by our screened hybrid functional approach.

A fast detailed-chemistry modelling approach for simulating the SI-HCCI transition

An established Stochastic Reactor Model (SRM) is used to simulate the transition from Spark Ignition (SI) to Homogeneous Charge Compression Ignition (HCCI) combustion mode in a four cylinder in-line four-stroke naturally aspirated direct injection SI engine with cam profile switching. The SRM is coupled with GT-Power, a one-dimensional engine simulation tool used for modelling engine breathing during the open valve portion of the engine cycle, enabling multi-cycle simulations. The mode change is achieved by switching the cam profiles and phasing, resulting in a Negative Valve Overlap (NVO), opening the throttle, advancing the spark timing and reducing the fuel mass as well as using a pilot injection. A proven technique for tabulating the model is used to create look-up tables in both SI and HCCI modes. In HCCI mode several tables are required, including tables for the first NVO, transient valve timing NVO, transient valve timing HCCI and steady valve timing HCCI and NVO. This results in the ability to simulate the transition with detailed chemistry in very short computation times. The tables are then used to optimise the transition with the goal of reducing NO x emissions and fluctuations in IMEP. Copyright © 2010 SAE International.

A detailed chemistry simulation of the SI-HCCI transition

A Stochastic Reactor Model (SRM) has been used to simulate the transition from Spark Ignition (SI) mode to Homogeneous Charge Compression Ignition (HCCI) mode in a four cylinder in-line four-stroke naturally aspirated direct injection SI engine with cam profile switching. The SRM is coupled with GT-Power, a one-dimensional engine simulation tool used for modelling engine breathing during the open valve portion of the engine cycle, enabling multi-cycle simulations. The model is initially calibrated in both modes using steady state data from SI and HCCI operation. The mode change is achieved by switching the cam profiles and phasing, resulting in a Negative Valve Overlap (NVO), opening the throttle, advancing the spark timing and reducing the fuel mass as well as utilising a pilot injection. Experimental data is presented along with the simulation results. The model is used to investigate key control parameters and their effects on parameters that are difficult to measure experimentally. The effect of the spark in the first HCCI cycles is found to have a major impact on the stability of the transition. Copyright © 2010 SAE International.

Water, salt water, and alkaline solution uptake in epoxy thin films

As a means of characterizing the diffusion parameters of fiber reinforced polymer (FRP) composites within a relatively short time frame, the potential use of short term tests on epoxy films to predict the long-term behavior is investigated. Reference is made to the literature to assess the effectiveness of Fickian and anomalous diffusion models to describe solution uptake in epoxies. The influence of differing exposure conditions on the diffusion in epoxies, in particular the effect of solution type and temperature, are explored. Experimental results, where the solution uptake in desiccated (D) or undesiccated (U) thin films of a commercially available epoxy matrix subjected to water (W), salt water (SW), or alkali concrete pore solution (CPS) at either 20 or 60°C, are also presented. It was found that the type of solution did not significantly influence the diffusion behavior at 20°C and that the mass uptake profile was anomalous. Exposure to 60°C accelerated the initial diffusion behavior and appeared to raise the level of saturation. In spite of the accelerated approach, conclusive values of uptake at saturation remained elusive even at an exposure period of 5 years. This finding questions the viability of using short-term thin film results to predict the long-term mechanical performance of FRP materials. © 2013 Wiley Periodicals, Inc.

FLUCTUATION OF SIZE-FRACTIONATED ALKALINE PHOSPHATASE AFTER BLOOM DISAPPEARANCE IN TWO SHALLOW PONDS

The temporal and vertical fluctuations of size fractionated alkaline phosphatase activity (APA) and kinetics parameters as well as orthophosphate (o-P) and chlorophyll concentrations were investigated after bloom disappearance in two shallow ponds A and B from 27 October 2001 to 15 April 2002. Pond A (Microcystis) bloomed seriously but pond B did not. The data of o-P and chlorophyll suggested that phosphorus was the principal limiting nutrimental element and its vertical flux should be regarded as an important driving factor for algal growth. In pond A, the accumulation of algae-derived detritus after bloom disappearance in overlying water stimulated excretion of algal fraction APA, mainly produced by attached bacteria responsible for detritus decomposition, whereas bacterial fraction APA preferred to function in surface water. Interestingly, completely contrary phenomena were observed in pond B. In season, even though no obvious difference for size-fractionated APA in both ponds, the total APA in pond A peaked earlier showing higher activity and efficiency (low K-m and high V-max values) as a result of algal-derived detritus input. In summary, it is suggested that the excretion of alkaline phosphatase with strongly catalyzing efficiency and high activity should be taken as important contributor to algal-derived detritus decomposition, further fueling nutrient recycle and accelerating algal development next year. Furthermore, some inhibitors and surfactants were testified to be good tools to identify the origin of dissolved alkaline phosphatase.

Microcystin-RR induced apoptosis in tobacco BY-2 suspension cells is mediated by reactive oxygen species and mitochondrial permeability transition pore status

When tobacco BY-2 cells were treated with 60 mu g/mL MC-RR for 5 d, time-dependent effects of MC-RR on the cells were observed. Morphological changes such as abnormal elongation, evident chromatin condensation and margination, fragmentation of nucleus and formation of apoptotic-like bodies suggest that 60 mu g/mL MC-RR induced rapid apoptosis in tobacco BY-2 cells. Moreover, there was a significant and rapid increase of ROS level before the loss of mitochondrial membrane potential (Delta Psi(m)) and the onset of cell apoptosis. Ascorbic acid (AsA), a major primary antioxidant, prevented the increase of ROS generation, blocked the decrease in Delta Psi(m) and subsequent cell apoptosis, indicating a critical role of ROS in serving as an important signaling molecule by causing a reduction of Delta Psi(m) and MC-RR-induced tobacco BY-2 cell apoptosis. In addition, a specific mitochondrial permeability transition pores (PTP) inhibitor, cyclosporin A (CsA), significantly blocked the MC-RR-induced ROS formation, loss of Delta Psi(m), as well as cell apoptosis when the cells were MC-RR stressed for 3 d, suggesting that PTP is involved in 60 mu g/mL MC-RR-induced tobacco cell apoptosis signalling process. Thus, we concluded that the mechanism of MC-RR-induced apoptosis signalling pathways in tobacco BY-2 cells involves not only the excess generation of ROS and oxidative stress, but also the opening of PTP inducing loss of mitochondrial membrane potential. (C) 2007 Published by Elsevier Ltd.