Hydraulic reactivity and cement formation of baghdadite

In this study, the hydraulic reactivity and cement formation of baghdadite (Ca₃ZrSi₂O₉) was investigated. The material was synthesized by sintering a mixture of CaCO₃, SiO₂, and ZrO₂ and then mechanically activated using a planetary mill. This leads to a decrease in particle and crystallite size and a partial amorphization of baghdadite as shown by X-ray powder diffraction (XRD) and laser diffraction measurements. Baghdadite cements were formed by the addition of water at a powder to liquid ratio of 2.0 g/ml. Maximum compressive strengths were found to be ~2 MPa after 3-day setting for a 24-h ground material. Inductively coupled plasma mass spectrometry (ICP-MS) measurements showed an incongruent dissolution profile of set cements with a preferred dissolution of calcium and only marginal release of zirconium ions. Cement formation occurs under alkaline conditions, whereas the unground raw powder leads to a pH of 11.9 during setting, while prolonged grinding increased pH values to approximately 12.3.     

Role of Polyinosinic:Polycytidylic Acid-Induced Maternal Immune Activation and Subsequent Immune Challenge in the Behaviour and Microglial Cell Trajectory in Adult Offspring: A Study of the Neurodevelopmental Model of Schizophrenia

Multiple lines of evidence support the pathogenic role of maternal immune activation (MIA) in the occurrence of the schizophrenia-like disturbances in offspring. While in the brain the homeostatic role of neuron-microglia protein systems is well documented, the participation of the CX3CL1-CX3CR1 and CD200-CD200R dyads in the adverse impact of MIA often goes under-recognized. Therefore, in the present study, we examined the effect of MIA induced by polyinosinic:polycytidylic acid (Poly I:C) on the CX3CL1-CX3CR1 and CD200-CD200R axes, microglial trajectory (MhcII, Cd40, iNos, Il-1β, Tnf-α, Il-6, Arg1, Igf-1, Tgf-β and Il-4), and schizophrenia-like behaviour in adult male offspring of Sprague-Dawley rats. Additionally, according to the “two-hit” hypothesis of schizophrenia, we evaluated the influence of acute challenge with Poly I:C in adult prenatally MIA-exposed animals on the above parameters. In the present study, MIA evoked by Poly I:C injection in the late period of gestation led to the appearance of schizophrenia-like disturbances in adult offspring. Our results revealed the deficits manifested as a diminished number of aggressive interactions, presence of depressive-like episodes, and increase of exploratory activity, as well as a dichotomy in the sensorimotor gating in the prepulse inhibition (PPI) test expressed as two behavioural phenotypes (MIA_PPI-low and MIA_PPI-high). Furthermore, in the offspring rats subjected to a prenatal challenge (i.e., MIA) we noticed the lack of modulation of behavioural changes after the additional acute immune stimulus (Poly I:C) in adulthood. The important finding reported in this article is that MIA affects the expression and levels of the neuron-microglia proteins in the frontal cortex and hippocampus of adult offspring. We found that the changes in the CX3CL1-CX3CR1 axis could affect microglial trajectory, including decreased hippocampal mRNA level of MhcII and elevated cortical expression of Igf-1 in the MIA_PPI-high animals and/or could cause the up-regulation of an inflammatory response (Il-6, Tnf-α, iNos) after the “second hit” in both examined brain regions and, at least in part, might differentiate behavioural disturbances in adult offspring. Consequently, the future effort to identify the biological background of these interactions in the Poly I:C-induced MIA model in Sprague-Dawley rats is desirable to unequivocally clarify this issue.     

A comparative study on pyrolysis reactivity and gas release characteristics of biomass and coal using TG-MS analysis

Pyrolysis reactivity and gas release characteristics of biomass and coals were comparatively investigated using TG-MS. In addition, chemical compositions and structures of tested samples were determined to correlate pyrolysis gas release characteristic. It was found that pyrolysis reactivity and gaseous product release were hardly varied with pyrolysis heating rate. Furthermore, pyrolysis rates of two biomass samples were greater than those of coals, which were mainly attributed to the chemical compositions and the gaseous product evolution process. The result also showed that gaseous product release during pyrolysis process was related to the presence of different functional groups in samples.     

酯交换法合成碳酸甲乙酯催化剂的研究进展

碳酸甲乙酯（EMC）是一种环境友好型的不对称碳酸酯，因其独特的结构性质被广泛用作溶剂或有机合成中间体，特别是随着锂离子电池的迅猛发展，其作为电池电解液主要成分市场需求量急增。文中简单介绍了光气法、氧化羰化法和酯交换法合成碳酸甲乙酯的研究进展。重点针对最具发展前景的酯交换法合成EMC工艺路线中所用催化剂进行了综述；讨论和分析了该路线所用催化剂的类型、结构、性质及性能，并对当前研究中存在的问题进行了归纳和分析总结。最后本文分析并展望了酯交换法合成EMC催化剂的研究方向及新型合成工艺发展趋势，提出研发经济、高效、稳定且制备工艺简单的非均相催化剂，并与反应精馏技术耦合是今后的主要发展趋势，期望为EMC的高效合成提供参考和借鉴。     

Physicochemical structure characteristics and intrinsic reactivity of demineralized coal char rapidly pyrolyzed at elevated pressure

This study aims to investigate the effect of pyrolysis pressure on the physical and chemical structure characteristics and reactivity of subbituminous demineralized coal char. The pyrolysis experiments were studied under different pressures using a pressurized drop tube reactor (PDTR). Structural properties of coal chars were investigated by the application of scanning electron microscopy (SEM), nitrogen adsorption analyzer, automatic mercury porosimeter, and Raman spectroscopy, respectively. The Random Pore Model was used to determine kinetic parameters and intrinsic reactivity of chars. The specific pore volume of chars pyrolyzed at 900–1000 °C increased first and then decreased with pyrolysis pressure increasing, and the maximum value of the specific pore volume of chars occurred at 1.0 MPa. The degree of graphitization of chars deepened with the increase of temperature or pressure. Intrinsic activation energy of char-O₂ was within the range of 126–134 kJ/mol. The intrinsic reactivity of char-O₂ reaction showed strong correlation the Raman parameters with the change of pyrolysis conditions, and it suggested that the intrinsic reactivity of char-O₂ reaction was mainly affected by aromatic ring structures rather than pore structures.     

Effects of typical soybean meal type on the properties of soybean-based adhesive

In order to effectively apply soybean meal for the preparation of water-resistant soybean-based adhesives for plywood, the effects of three typical soybean meal products, namely, low-temperature soybean meal (LM), high-temperature soybean meal (HM), and physical soybean meal (PM), on the properties of soybean-based adhesive were investigated. The results indicated that the number of reactive groups in the three soybean meals followed the order LM > HM > PM, which in turn led to various crosslinking densities when these soybean meals were crosslinked by epichlorohydrin-modified polyamide (EMPA) during the curing process. The LM soybean adhesive had 6.6% higher soaking bond strength and 16.5% higher boiling-dry-boiling bond strength than the HM soybean adhesive, and 19% higher soaking bond strength and 33% higher boiling-dry-boiling bond strength than the PM soybean adhesive, respectively. These three soybean meals could be used to prepare soybean adhesives for interior-use plywood because all plywood panels bonded with their adhesives passed a water-soaking test at 63 °C for 3 h, but only the LM soybean adhesive achieved the desired water resistance for floor-base plywood. Among the three evaluated soybean meals, LM was the most promising raw material for the preparation of soybean-based adhesive because of a greater number of reactive groups, higher crosslinking density, and superior bond strength. Plywood panel bonded with HM soybean adhesive had a water resistance lower than, but very close to, the standard required value (>0.8 MPa) for floor-base plywood.     

Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

Chemical Bonding by the Chemical Orthogonal Space of Reactivity

The fashionable Parr–Pearson (PP) atoms-in-molecule/bonding (AIM/AIB) approach for determining the exchanged charge necessary for acquiring an equalized electronegativity within a chemical bond is refined and generalized here by introducing the concepts of chemical power within the chemical orthogonal space (COS) in terms of electronegativity and chemical hardness. Electronegativity and chemical hardness are conceptually orthogonal, since there are opposite tendencies in bonding, i.e., reactivity vs. stability or the HOMO-LUMO middy level vs. the HOMO-LUMO interval (gap). Thus, atoms-in-molecule/bond electronegativity and chemical hardness are provided for in orthogonal space (COS), along with a generalized analytical expression of the exchanged electrons in bonding. Moreover, the present formalism surpasses the earlier Parr–Pearson limitation to the context of hetero-bonding molecules so as to also include the important case of covalent homo-bonding. The connections of the present COS analysis with PP formalism is analytically revealed, while a numerical illustration regarding the patterning and fragmentation of chemical benchmarking bondings is also presented and fundamental open questions are critically discussed.     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

高炉喷吹煤粉燃烧性与反应性的研究与应用

为了研究高炉喷吹煤粉的冶金性能，采用热重分析法对6种无烟煤和1种烟煤进行燃烧性与反应性研究。结果表明，与无烟煤相比，烟煤在不同温度下的燃烧性和反应性均明显高于无烟煤。混煤的燃烧率实测值大于加权值，使用混煤可以发挥无烟煤和烟煤各自的优点，加快燃烧过程，提高混煤燃烧率。随着混煤中粒度小于74 μm煤粉所占比例的增加，燃烧率增大。在高煤比喷吹条件下，混煤煤粉粒度小于74 μm的比例控制在75%左右。结合无烟煤的燃烧性和反应性试验结果，建议喷吹煤粉采购中应尽可能多地采购无烟煤C资源，同时控制无烟煤E的采购量；高炉提煤比操作中应将无烟煤C确定为喷吹用无烟煤的首选煤种，以提升混煤燃烧率和发挥未燃煤粉保护焦炭的作用。