Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

Irradiation-induced large bubble formation and grain growth in super nano-grained ceramic

In this work, 0.5TRPO•0.5Gd₂Zr₂O₇ ceramic with an average grain size of only ∼15 nm was prepared by a high pressure (5 GPa/520 °C) sintering method. Phase evolutions and microstructure changes of the as-fabricated super nano and micron-grained ceramics under a high-dose displacement damage induced by 300 keV Kr²⁺ ions were investigated. The results show that the super nano-grained ceramic has low degree of amorphization, obvious grain growth (2–3 times in grain size) and big Kr bubbles (10–68 nm) formation after irradiation. The micron-grained ceramic was severely amorphized after irradiation and many microcracks were formed parallel to its surface. The formation mechanism of Kr bubbles in the super nano-grained ceramic is on account of grain boundary diffusion and migration induced by the accumulation of the injecting Kr ions and irradiation defects. Nevertheless, microcracks formed in the micron-grained sample are caused by the accumulation of Kr atoms.     

Synthesis,Characterization, Speciation,and Biological Studies on Metal Chelates of Carbohydrates with Molecular Docking Investigation

The role of starch aerogel (St-AG) and carboxymethyl cellulose (CMC) as biolgical active compounds, when they subjected for complexation with metal ions, is assessed in this work. The complexation is carried out with palladium(II) and copper(II) ions, in solid state. Different tools of analysis are carried out to characterize and elucidate the structures of these complexes, namely: elemental analysis, IR, thermal analysis, magnetic measurement and molar conductance techniques. All synthesized complexes are formed with 1:2 (metal:ligand) stoichiometry except the case of aerogel starch 1:1 (Pd:starch). All isolated complexes show a satisfactory cytotoxic effect results against colon cancer cell lines HCT11. Additionally, these complexes are screened for their antibacterial activities against two types of Gram positive and negative bacteria. Molecular docking investigation confirmed the cytotoxicity and antibacterial results. Proton–ligands association constants and their complex formation constants with some bivalent metal ions, using potentiometric method show that the complexes formed in solution have a stoichiometry of 1:1 [metal:ligand]. The effects of metal ion, ionic radius, electronegativity and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3D transition metals followed the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺.     

Role of Metabolism in Bone Development and Homeostasis

Carbohydrates, fats, and proteins are the underlying energy sources for animals and are catabolized through specific biochemical cascades involving numerous enzymes. The catabolites and metabolites in these metabolic pathways are crucial for many cellular functions; therefore, an imbalance and/or dysregulation of these pathways causes cellular dysfunction, resulting in various metabolic diseases. Bone, a highly mineralized organ that serves as a skeleton of the body, undergoes continuous active turnover, which is required for the maintenance of healthy bony components through the deposition and resorption of bone matrix and minerals. This highly coordinated event is regulated throughout life by bone cells such as osteoblasts, osteoclasts, and osteocytes, and requires synchronized activities from different metabolic pathways. Here, we aim to provide a comprehensive review of the cellular metabolism involved in bone development and homeostasis, as revealed by mouse genetic studies.     

Morpholine As a Scaffold in Medicinal Chemistry: An Update on Synthetic Strategies

Morpholine is a frequently used heterocycle in medicinal chemistry and a privileged structural component of bioactive molecules. This is mainly due to its contribution to a plethora of biological activities as well as to an improved pharmacokinetic profile of such bioactive molecules. The synthesis of morpholines is a subject of much study due to their biological and pharmacological importance, with the last such review being published in 2013. Here, an overview of the main approaches toward morpholine synthesis or functionalization is presented, emphasizing on novel work which has not been reviewed so far. This review is an update on synthetic strategies leading to easily accessible libraries of bioactives which are of interest for drug discovery projects.     

阿尔泰南缘北塔山组火山岩锆石U-Pb定年及地质意义

新疆阿尔泰南缘北塔山组火山岩较为发育。本文对新疆阿尔泰南缘默色克奥依一带北塔山组火山岩进行地球化学分析和年代学研究。研究表明：U-Pb锆石年龄为（384.3±4.0Ma）Ma，为中泥盆世；该组火山岩属于钾质钙碱性系列，全碱（Na2O+K2O=2.07%-6.49%）和YiO2（0.24%-0.64%）含量较低，K2O含量（1.11%-4.04%）变化较大，稀土元素含量（∑REE）较低。稀土元素显示其轻稀土富集且分馏不明显；δEu值均大于1，为Eu富集型；δCe值均小于1，为Ce亏损型。该组火山岩微量元素P明显富集，K、Rb、Ba等大离子亲石元素（LILE）略富集，亏损Ta、Zr、Hf、Ti等高场强元素（HISF）。结合前人研究，本文认为默色克奥依一带北塔山组火山岩形成于岛弧及与俯冲过程有关的活动大陆边缘造山带环境，为泥盆纪古大洋俯冲消减过程中，俯冲板片脱水产生的流体交代上覆地幔楔部分熔融的产物。     

高泉背斜地层压力测井多参数综合解释与异常高压成因

目前国内外地层压力测井解释方法较多,但大多数方法基于欠压实沉积理论并局限于单一的地层岩性,尤其是针对盆地边缘山前深层构造,单一测井参数确定地层压力误差较大,且无法解释沉积压实机制以外的异常高压。为此,将多种异常高压机制相关的测井参数进行综合解释,建立适合山前复杂构造的地层压力测井多参数计算模型,评价准噶尔盆地南缘高泉背斜高探1井的地层压力剖面,其计算结果与钻井实测数据吻合,相对误差小于3.00%.同时,基于原始沉积加载—卸载过程力学原理,利用地层压力测井多参数分析判别出高泉背斜深层各层系异常高压的形成机制。     

厄瓜多尔Sacha油田砾石层安全钻进钻井液技术

厄瓜多尔Sacha油田TIYUYACU层存在上下2个砾石层,上砾石层厚度约为61 m,下砾石层厚度超过200 m。该地层研磨性强、渗透性强,对压力敏感,是钻井过程中出现复杂甚至事故的高发地层。本文通过分析Sacha 44MD井在砾石层出现的问题,从钻井液的角度找出问题出现的原因,提出优化方案。通过降低体系密度,加强封堵性等措施,实现了砾石层的安全快速钻进,自Sacha 44XD井以后,在砾石层钻进顺利,起下钻、下套管等也未出现遇阻等复杂情况,为解决砾石层钻进难题积累了宝贵的经验。     

汽油典型烃分子氧化生胶机理的分子模拟

为深入认识汽油在使用过程中氧化生胶的反应机理，选取汽油中相同碳数的典型烃分子作为模型化合物，采用基于密度泛函理论的量子化学从头计算方法，建立了不同结构的汽油分子通过氧化链式自由基反应生成相对分子质量较大、极性较高的沉积物分子的反应网络。通过对比不同反应路径的反应能垒大小，得出容易氧化生胶的汽油烃分子的结构特点以及贡献生成沉积物的关键控速步骤和关键中间体，从而为抑制该氧化生胶过程提出关键措施。结果表明，汽油分子结构中存在双键α位C-H、叔位C-H或苯基α位C-H时，容易引发链式自由基反应，但能否继续向沉积物的反应方向进行取决于相对分子质量增大后的产物中是否仍然存在双键α位C-H、叔位C-H、苯基α位C-H或者C=O这种使得相邻C-H键变弱的吸电子基团。另外，在氧化生胶反应过程中，氢过氧化物（ROOH）和过氧自由基（ROO·）是最关键的2个中间体，抑制氧化生胶反应的关键在于清除它们。