Automated chemical resonance generation and structure filtration for kinetic modeling

This work discusses efficient and automated methods for constructing a set of representative resonance structures for arbitrary chemical species, including radicals and biradicals, consisting of the elements H, C, O, N, and S. Determining the representative reactive structures of chemical species is crucial for identification of reactive sites and consequently applying the correct reaction templates to generate the set of important reactions during automated chemical kinetic model generation. We describe a fundamental set of resonance pathway types, accounting for simple resonating structures, as well as global approaches for polycyclic aromatic species. Automatically discovering potential localized structures along with filtration to identify the representative structures was shown to be robust and relatively fast. The algorithms discussed here were recently implemented in the Reaction Mechanism Generator (RMG) software. The final structures proposed by this method were found to be in reasonable agreement with quantum chemical computation results of localized structure contributions to the resonance hybrid.     

Influence of the pH Value on the Hydrothermal Degradation of Fructose

The hydrothermal treatment of sugars features a promising technology for the production of fine and platform chemicals from renewable resources. In this work the hydrothermal decomposition of fructose was studied in a buffered medium at a pH range between 2.2 and 8.0. It is demonstrated that at lower pH values mainly 5-hydroxymethylfurfural (HMF), levulinic acid and humin are generated, while lactic acid and acetic acid are produced at higher pH values. The work shows that the use of moderate acidic conditions may have advantages for the hydrothermal HMF production over the use of strongly acidic conditions, as especially the degradation into levulinic acid is suppressed. Besides, this study deals with a rather complex reaction network, hence limitations and need for adaption of the kinetic model are discussed.     

Mathematical modeling of a slurry reactor for DME direct synthesis from syngas

In this paper,an axial dispersion mathematical model is developed to simulate a three-phase slurry bubble column reactor for direct synthesis of dimethyl ether(DME) from syngas.This large-scale reactor is modeled using mass and energy balances,catalyst sedimentation andsingle-bubble as well as two-bubbles class flow hydrodynamics.A comparison between the two hydrodynamic models through pilot plantexperimental data from the literature shows that heterogeneous two-bubbles flow model is in better agreement with the experimental data thanhomogeneous single-bubble gas flow model.Also,by investigating the heterogeneous gas flow and axial dispersion model for small bubblesas well as the large bubbles and slurry(i.e.including paraffins and the catalyst) phase,the temperature profile along the reactor is obtained.Acomparison between isothermal and non-isothermal reactors reveals no obvious performance difference between them.The optimum values ofreactor diameter and height were obtained at 7 m and 50 m,respectively.The effects of operating variables on the axial catalyst distribution,DME productivity and CO conversion are also investigated in this research.     

地球化学模拟在高放废物地质处置中的应用与发展

随着核能事业的发展,高放废物的处理和处置问题日益突出.其中,研究高放废物在环境介质中的吸附、扩散和迁移行为是获取放射性核素对周围环境和人群健康影响的基础参数的最重要和最直接的途径.近年来,人们利用已有的实验数据及核素的基础热力学和动力学数据,附以相应的数学模型,建立了一些地球化学模拟软件,用于分析核素在地质介质中可能发生的连续性和长期性变化.目前,国内外常用的地球化学模拟软件有十多种.本文从热力学平衡计算原理、种态分布计算方法和表面配位模型假设等几个方面对地球化学模拟软件进行了简要介绍,对近年来地球化学模拟软件在核素种态分布计算和表面配位模型模拟两方面的应用进行了举例分析,并以Ca-U-CO3配合物为例,说明完备的热力学数据对地球化学模拟软件发展的重要性,以期促进我国地球化学模型的应用和发展.     

Evaluating impacts of fish stock enhancement and biodiversity conservation actions on the livelihoods of small‐scale fishers on the Beijiang River,China

Inappropriate development and overexploitation have seriously degraded aquatic resources in China. Stakeholders identified three fish stock enhancement and biodiversity conservation scenarios for the Beijiang River: S1, increased fish restocking; S2, no fishing season and habitat conservation; and S3, strict pollution control. Potential impacts of these actions on the livelihoods of fishers were evaluated using applied economic modeling. Baseline costs and benefits came from logbooks from 30 fishers and a survey of 90 households in three villages. The financial net benefit for a household was US$1583 (￥11,160) annually, representing a 142% and 387% return on capital and operating costs, respectively. Larger catches associated with S1 and S2 generated a net benefit of US$1651 and US$1822, respectively. Strict pollution control resulting in higher catches (+20%) and lower operating costs (?20%) would increase the net benefit by 15.9% to US$1835 annually. Pollution control would benefit other resource users and is a prerequisite for ecological restoration. Recommendations for Resource Managers

• Stringent pollution control measures are essential to conserve aquatic biodiversity and enhance the livelihoods of fishers but will require considerable public and private sector investment.
• Enhanced fish stocks in the Beijiang River could benefit poor livelihoods but may not be sufficient to lift households out of poverty, aged fishers require government assistance to diversify their livelihoods, access alternative urban employment, and survive with dignity.
• Adopting the economic modeling approach presented here could enable responsible authorities to simultaneously evaluate fish stock enhancement and biodiversity conservation options.
• Broader application of the approach presented here could help ensure small‐scale inland fisheries are managed sustainably and aquatic ecosystems are restored and protected by 2020, in line with Target 6 of the United Nations’ Convention on Biological Diversity Strategic Plan for Biodiversity.

     

Kinetics Study of the Thermal Decomposition of Post-consumer Poly(Ethylene Terephthalate) in an Argon Atmosphere

The thermal decomposition of post-consumer samples of a carbonated water bottle made of poly(ethylene terephthalate), PC-PET, was examined by linear temperature programing under an argon atmosphere to determine its mass loss kinetics. A simple kinetic model, called the first order pseudo single-component model, was used. The total weight-loss of each sample assumed to be in two periods, with each period corresponding to a one step decomposition of the PC-PET to volatiles. Three methods for determining the kinetic parameters by thermal gravimetric analysis were examined: differential analysis at a constant heating rate (differential), temperatures of a given conversion at a number of heating rates (isoconversional), and the maximum rate at multiple heating rates (peak temperature). The latter two multiple heating rates methods results were comparable to each other but they were not in agreement with the results from the differential method. The results of the differential method were insensitive to the heating rate and consistent with kinetics data reported in the literature for PET.     

Modeling,stability and the activity assessment of glutathione reductase from Streptococcus Thermophilus; Insights from the in-silico simulation study

Antioxidant enzymes (AEs) are the main parts of the natural barriers of the body which deactivate the oxidant factors. To discover and understand their structures and function will deserve a deeper investigation. Accordingly, as an AE of probiotic strains, glutathione reductase of Streptococcus thermophilus (GRst), is characterized and modeled by in-silico methods. The investigation indicated the physicochemical properties of the enzyme and estimated its half-life of being more than 10 h. The analysis revealed that the enzyme is composed of 86 strands, 123 helices, and 241 random coils. Homology modeling of the GRst led to the construction of the enzyme’s 3D model that 62% of which is analogous to the glutathione reductase of Escherichia Coli (GRec), and which is qualitatively high in terms of Molpdf, ERRAT, Verify-3D and Ramachandran scores. Moreover, the structural stability of the model was substantiated within 10 and 20 ns at 400 and 300 K, respectively. Interestingly, these data showed that the enzyme is more stable than GRec at 400 K. In other words, the active cavity of the constructed model is characteristic of 38 amino acid residues within 4 Å around the NADPH and GSSG as corresponding ligands of GRst. Noteworthy, herein is the fact that, CYS40 and CYS45 are specified as the active site residues of this enzyme. Furthermore, the interaction assays of the model support its antioxidant capability which is even more than that of GRec.In general, these data provide a new model of AEs being inclusive of high antioxidant capacity and thermostability.     

Neural network modeling of hydrological systems: A review of implementation techniques

This paper presents a review of procedural steps and implementation techniques used in the development of artificial intelligence models, generally referred to as artificial neural networks (ANNs), within the water resources domain. It focusses on identifying different areas wherein ANNs have found application thereby elucidating its advantages and disadvantages as well as various challenges encountered in its use. Results from this review provide useful insights into how the performance of ANNs can be improved and potential areas of application that are yet to be explored in hydrological modeling. Recommendations for Resource Managers

• Development of integrated and hybrid artificial intelligent tools is critical to achieving improved forecasts in hydrological modeling studies.

• Further research into comprehending the internal mechanisms of neural networks is required to obtain a practical meaning of each network component deployed to solve real‐world problems.

• More robust optimization techniques and tools like differential evolution, particle swarm optimization and deep neural nets, are yet to be fully explored in the water resources analysis, and should be given more attention to enhance neural networks aptitude for modeling complex and nonlinear hydrological processes.

     

Charge-Transfer versus Charge-Separated Triplet Excited States of [ReI(dmp)(CO)3(His124)(Trp122)]+ in Water and in Modified Pseudomonas aeruginosa Azurin Protein

A computational investigation of the triplet excited states of a rhenium complex electronically coupled with a tryptophan side chain and bound to an azurin protein is presented. In particular, by using high-level molecular modeling, evidence is provided for how the electronic properties of the excited-state manifolds strongly depend on coupling with the environment. Indeed, only upon explicitly taking into account the protein environment can two stable triplet states of metal-to-ligand charge transfer or charge-separated nature be recovered. In addition, it is also demonstrated how the rhenium complex plus tryptophan system in an aqueous environment experiences too much flexibility, which prevents the two chromophores from being electronically coupled. This occurrence disables the formation of a charge-separated state. The successful strategy requires a multiscale approach of combining molecular dynamics and quantum chemistry. In this context, the strategy used to parameterize the force fields for the electronic triplet states of the metal complex is also presented.