Layered ceramics based on InGaO3(ZnO)2: Preparation and experimental investigation of high-temperature heat capacity and thermal conductivity

This paper reports on a method for producing ceramics from a high-purity, submicron InGaO₃(ZnO)₂ powder synthesised using a PVA-assisted gel combustion method, as well as an experimental study of the thermophysical properties of the ceramic materials obtained. The platelet-like crystallites of the InGaO₃(ZnO)₂ obtained were several microns long and up to several hundred nanometres thick. Layered ceramics obtained by sintering compacted InGaO₃(ZnO)₂ powders at temperatures of 1373–1773 K had a bulk density that was 68–96 % of the theoretical density. The temperature dependence of heat capacity in the range 306–1346 K was studied experimentally for InGaO₃(ZnO)₂ using the DSC method. It was found that, in the range 323–1173 K, layered InGaO₃(ZnO)₂ ceramics had a low thermal conductivity, which decreased from 2.0–1.3 W/(m K. The results obtained make it possible to consider this material as a promising thermal barrier coating.     

Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF_2α and 1,15-PGF_2α lactones, many 1,15-lactones of E₂, E₃, F₂, F₃, A₂, and A₃ were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9β-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9β-PG analogs and future applications, are also discussed.     

Sol-gel auto-combustion synthesis of Ba–Sr hexaferrite ceramic powders

We report the mechanism involved in sol-gel auto-combustion synthesis of Ba–Sr-hexaferrite (Ba_1-xSr_xFe₁₂O₁₉; x = 0, 0.25, 0.5, 0.75 and 1, BSFO) ceramic powders through the analysis of the phases evolved during annealing of the as-synthesized powders, along with their structure and morphological studies. The XRD patterns of the as-synthesized samples indicate the formation of barium/strontium monoferrite ((Ba/Sr)Fe₂O₄) and maghemite (γ-Fe₂O₃) phases along with a minute amount of hematite (α-Fe₂O₃) phase. Annealing of these samples facilitates formation of BSFO phase through the solid state reaction between BaFe₂O₄ and γ-Fe₂O₃ phase. Interestingly, after annealing the samples with x = 0, 0.5 and 1, at 1000 °C for 2 h, we observed that phase pure Ba–Sr hexaferrite structure forms, but for samples with x = 0.25 and 0.75, high amount of hematite (α-Fe₂O₃) phase is observed, especially for x = 0.75. The reason associated with this could be the large difference between the ionic radii of Ba²⁺ and Sr²⁺ ions occupying the oxygen site. Furthermore, our study on annealing dependent phase evolution confirms that, this difference in ionic radii forbids the formation of a single phase Ba–Sr hexaferrite. The growth of clear hexagonal-shaped plate-like particles with varied particle sizes was observed for all the samples. The particle size variation may be due to the influence of the ionic radii difference on the sinterability of the samples. Our study provides a better understanding of synthesis mechanism of Ba–Sr hexaferrite samples.     

Sintering behavior of Ni–Zn ferrite powders prepared by molten-salt synthesis

Ni_0.5Zn_0.5Fe₂O₄ powders were prepared by a novel molten-salt synthesis method. The effects of calcination processes of the powders on their sintering behaviors were investigated. Compared with the synthesis by traditional solid-state reaction, the proposed molten-salt method can significantly reduce the synthesis temperature of Ni_0.5Zn_0.5Fe₂O₄ from 800 to 550°C below, and the prepared powders have relatively high sintering activity at low temperature, which can thus decrease the sintering temperature. However, the abnormal growth of grains is easy to occur during sintering, thus resulting in uneven grain size. In particular, during the molten-salt synthesis, the holding time for calcination is a dominant factor affecting the activity and crystallization degree of the resultant powders. From the point of view of increasing the density of sintered bodies, the optimal conditions for synthesizing Ni_0.5Zn_0.5Fe₂O₄ powder by the proposed molten-salt synthesis is 400°C for 6 h. In addition, the saturate magnetization of the finally obtained ferrite ceramics has nothing to do with the preparation processes, while their coercivity depends on their densification and grain size caused by their different processing routes.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

A review on direct synthesis of dimethoxymethane

Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles, which can be polymerize form the monomer of dimethoxymethane (DMM). The industrial synthesis of DMM is mainly involved two-step process: methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor. Due to huge energy consumption, this typical synthesis route of DMM needs to be upgraded and more green routes should be determined. In this review, four state-of-the-art one-step direct synthetic routes, including two upgrading routes (methanol direct oxidation and direct dehydrogenation) and two green routes (methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation), have been summarized and compared. Combination with the reaction mechanism and catalytic performance on the different catalysts, the challenges and opportunities for every synthetic route are proposed. The relationships between catalyst structure and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.     

Reconfigurable topology synthesis for application-specific NoC on partially dynamically reconfigurable systems

In this paper, a four-stage method for synthesizing reconfigurable ASNoC topology is proposed for partially dynamically reconfigurable systems, where the topology is reconfigured dynamically at run-time along with the application's execution. Firstly, a simulated annealing based topology-aware integrated optimization framework is proposed to generate the proper schedule and floorplan of task modules. Secondly, based on the schedule and floorplan of task modules, an Integer Linear Programming (ILP)-based method and a heuristic method, are proposed to partition the communication requirements of the application into $T$ time intervals. Thirdly, we explore the proper positions of switches in the floorplan for global communications. Finally, considering the reconfiguration costs between adjacent time intervals, the routing path allocation problem is solved for time intervals in an iterative procedure to generate fine-grained dynamically reconfigurable ASNoC topologies. Experimental results show that, compared to the random partition of communication requirements, the proposed heuristic method and ILP-based method can achieve 5.4% and 10.0% power consumption improvement, respectively. And, the reconfigurable ASNoC can achieve 31.6% power consumption improvement when compared with static ASNoC.     

面向二进制程序的导向性模糊测试方法

为了解决当前模糊测试技术中变异存在一定的盲目性以及变异生成的样本大多经过相同的高频路径的问题，提出并实现了一种基于轻量级程序分析技术的二进制程序模糊测试方法。首先对目标二进制程序进行静态分析来筛选在模糊测试过程中阻碍样本文件深入程序内部的比较指令；随后对目标文件进行插桩来获取比较指令中操作数的具体值，并根据该具体值为比较指令建立实时的比较进度信息，通过比较进度衡量样本的重要程度；然后基于模糊测试过程中实时的路径覆盖信息为经过稀有路径的样本增加其被挑选进行变异的概率；最后根据比较进度信息并结合启发式策略有针对性地对样本文件进行变异，通过变异引导提高模糊测试中生成能够绕过程序规约检查的有效样本的效率。实验结果表明，所提方法发现crash及发现新路径的能力均优于模糊测试工具AFL-Dyninst。     

Alteration of the Route to Menaquinone towards Isochorismate-Derived Metabolites

Chorismate and isochorismate constitute branch-point intermediates in the biosynthesis of many aromatic metabolites in microorganisms and plants. To obtain unnatural compounds, we modified the route to menaquinone in Escherichia coli. We propose a model for the binding of isochorismate to the active site of MenD ((1R,2S, 5S,6S)-2-succinyl-5-enolpyruvyl-6-hydroxycyclohex-3-ene-1-carboxylate (SEPHCHC) synthase) that explains the outcome of the native reaction with α-ketoglutarate. We have rationally designed variants of MenD for the conversion of several isochorismate analogues. The double-variant Asn117Arg–Leu478Thr preferentially converts (5S,6S)-5,6-dihydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHD), the hydrolysis product of isochorismate, with a >70-fold higher ratio than that for the wild type. The single-variant Arg107Ile uses (5S,6S)-6-amino-5-hydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHA) as substrate with >6-fold conversion compared to wild-type MenD. The novel compounds have been made accessible in vivo (up to 5.3 g L⁻¹). Unexpectedly, as the identified residues such as Arg107 are highly conserved (>94 %), some of the designed variations can be found in wild-type SEPHCHC synthases from other bacteria (Arg107Lys, 0.3 %). This raises the question for the possible natural occurrence of as yet unexplored branches of the shikimate pathway.