Catalytic combustion of methane over a highly active and stable NiO/CeO2 catalyst

In the last decades, many reports dealing with technology for the catalytic combustion of methane (CH₄) have been published. Recently, attention has increasingly focused on the synthesis and catalytic activity of nickel oxides. In this paper, a NiO/CeO₂ catalyst with high catalytic performance in methane combustion was synthesized via a facile impregnation method, and its catalytic activity, stability, and water-resistance during CH₄ combustion were investigated. X-ray diffraction, low-temperature N₂ adsorption, thermogravimetric analysis, Fourier transform infrared spectroscopy, hydrogen temperature programmed reduction, methane temperature programmed surface reaction, Raman spectroscopy, electron paramagnetic resonance, and transmission electron microscope characterization of the catalyst were conducted to determine the origin of its high catalytic activity and stability in detail. The incorporation of NiO was found to enhance the concentration of oxygen vacancies, as well as the activity and amount of surface oxygen. As a result, the mobility of bulk oxygen in CeO₂ was increased. The presence of CeO₂ prevented the aggregation of NiO, enhanced reduction by NiO, and provided more oxygen species for the combustion of CH₄. The results of a kinetics study indicated that the reaction order was about 1.07 for CH₄ and about 0.10 for O₂ over the NiO/CeO₂ catalyst.     

Involvement of GPx-3 in the Reciprocal Control of Redox Metabolism in the Leukemic Niche

The bone marrow (BM) microenvironment plays a crucial role in the development and progression of leukemia (AML). Intracellular reactive oxygen species (ROS) are involved in the regulation of the biology of leukemia-initiating cells, where the antioxidant enzyme GPx-3 could be involved as a determinant of cellular self-renewal. Little is known however about the role of the microenvironment in the control of the oxidative metabolism of AML cells. In the present study, a coculture model of BM mesenchymal stromal cells (MSCs) and AML cells (KG1a cell-line and primary BM blasts) was used to explore this metabolic pathway. MSC-contact, rather than culture with MSC-conditioned medium, decreases ROS levels and inhibits the Nrf-2 pathway through overexpression of GPx3 in AML cells. The decrease of ROS levels also inactivates p38MAPK and reduces the proliferation of AML cells. Conversely, contact with AML cells modifies MSCs in that they display an increased oxidative stress and Nrf-2 activation, together with a concomitant lowered expression of GPx-3. Altogether, these experiments suggest that a reciprocal control of oxidative metabolism is initiated by direct cell–cell contact between MSCs and AML cells. GPx-3 expression appears to play a crucial role in this cross-talk and could be involved in the regulation of leukemogenesis.     

膨胀机主轴缝隙腐蚀的电化学分析

为探究膨胀机主轴的缝隙腐蚀行为,搭建了模拟缝隙腐蚀实验装置。通过电化学测试,确定了不同缝隙位置处的自腐蚀电位随时间的变化规律,并揭示了缝隙内腐蚀反应的发展过程。结果表明:缝隙内腐蚀反应经历双电层形成-氧浓差电池形成-金属水解三个反应过程。在富氧条件下,腐蚀产物的主要成分为Fe(OH)2。随着氧气的耗尽,氧浓差电池形成,腐蚀产物逐渐向FeOOH和Fe3O4转变。     

有机激发三重态参与的光化学反应研究进展

光化学反应包括直接光解和间接氧化反应，其中间接氧化反应主要通过活性氧化性物种（reactive oxygen species, ROS）包括单线态氧（¹O₂）、过氧自由基（{\mathrm{O}}_{\mathrm{2}}^{-}）和羟基自由基（·OH）等进行。近年来，有机激发三重态（³C^*）作为一种特殊的氧化剂参与光化学反应引起了广泛关注。本文主要综述了有机三重态光敏剂的形成和光化学反应机制、³C^*参与的环境光化学反应、³C^*自由基寿命、反应速率及稳态浓度测定和激发三重态的应用5个方面，并对未来有机分子激发三重态的研究方向进行了展望，指出³C^*是很多挥发性有机化合物（VOCs）或半/中等挥发性有机化合物（S/IVOCs）在大气中重要的汇，自然水体中溶解性有机质（dissolved organic matter，DOM）的激发三重态（³DOM^*）是污染物降解的主要氧化剂。今后应扩大³C^*与有机物反应的研究范畴，测定不同体系中³C^*的稳态浓度、产生速率（量子产率）等，为污染物治理提供理论依据。     

基于涡动相关法的沉积物-水界面氧通量与水动力条件响应关系

沉积物-水界面是物质参与环境地球化学循环和生物耦合的"热区",水动力条件是沉积物-水界面物质交换的关键影响因素。溶解氧作为常用的水质评价指标,对调节生物化学进程有重要作用,因此本文采用涡动相关法这种非侵入式通量测量技术开展室内试验研究,探究沉积物-水界面氧通量与水动力条件的响应关系。结果表明:随着水体紊动增加(采用Batchelor尺度表征),扩散边界层厚度减小,氧通量增大。分析室内试验和相关研究中水动力条件、扩散边界层厚度及氧通量的关系,发现扩散边界层厚度与Batchelor尺度呈正相关关系,拟合结果表明可以用Batchelor尺度近似表示扩散边界层厚度;氧通量与扩散边界层厚度呈负相关关系,且当扩散边界层厚度小于0.5 mm时,扩散边界层厚度变化对氧通量影响更强烈,当厚度大于0.5 mm后,氧通量基本保持稳定。     

Contribution of the Internal and External Oxygen to the Oxidation of Microencapsulated Fish Oil

Microencapsulation aims to protect polyunsaturated fatty acids against oxidation by embedding oil droplets in a solid matrix. In such a system the internal (dissolved and entrapped) and external (in the environment) oxygen can be differentiated. The study aims to quantify the impact of both oxygen sources on the oxidation of microencapsulated fish oil. The impact of the solubilized oxygen in bulk fish oil is investigated by saturating the oil with nitrogen, synthetic air, and pure oxygen. Even though more dissolved oxygen results in more oxidation products, the difference between the oxidation of the nitrogen and air saturated oil is significant but low. For encapsulated fish oil powders, the internal oxygen is modified by preparing oil‐in‐water emulsions under atmospheric and inert conditions. The feed is atomized and spray dried with either nitrogen or air. Powders are stored under vacuum and in vials and the hydroperoxides and anisidine value are determined in the total‐ and encapsulated oil. The internal oxygen has a minor impact, whereas the external oxygen is the main determinant for autoxidation. Apart from oxidizing the non‐encapsulated oil, the external O₂ penetrates into the particle and reacts with the encapsulated oil. Practical Applications: Comparing the contribution of the internal and external oxygen to the oxidative stability shows that the internal O₂ plays a minor role and can be neglected. This means that the emulsion preparation as well as the spray drying process can be conducted under ambient conditions. An inert production is not extending the shelf life significantly as long as the external O₂ determines oxidation. The focus should be on optimizing the diffusion barrier properties of the wall matrix to reduce the penetration of the external oxygen into the particle system. Alternatively, packaging solution reducing the external O₂ will extend the shelf life of the microencapsulated oil.     

微电解Fenton法处理有机废水可行性研究

采用微电解Fenton法处理硫铵酯-苯甲羟肟酸-苯胺黑有机废水。考察了初始pH值、铁屑及活性炭投入量、曝气量、H₂O₂用量、催化剂MnO₂加入量和反应时间对废水COD、NH₃-N和色度去除率的影响。最佳条件为:初始pH=3、铁屑用量70 g/L、活性炭用量80 g/L、H₂O₂用量7 mg/L、MnO₂用量8.0 g/L、曝气量500 mL/(min·L)、反应时间20 min,此时废水COD、NH₃-N和色度的去除率达88.21%、93.57%和98.68%。通过多因素正交实验确定了影响COD、NH₃-N和色度去除率的因素强弱顺序为:铁屑投入量=活性炭投入量>H₂O₂用量>pH值>MnO₂用量。     

Properties of polyamide 6,10/poly(vinyl alcohol) blends and impact on oxygen barrier performance

The oxygen transmission rate, average volume of free‐volume cavities (V_f) and fractional free volume (F_v) of polyamide 6,10 (PA610)/poly(vinyl alcohol) (PVA) (i.e. PA610_xPVA⁰⁵_y, PA610_xPVA⁰⁸_y and PA610_xPVA¹⁴_y) blend films reduced to minimum values when their PVA contents reached corresponding optimal values. Oxygen transmission rate, V_f and F_v values obtained for optimal PA610_xPVA^z_y blown films were reduced considerably with decreasing PVA degrees of polymerization. The oxygen transmission rate of the optimal bio‐based PA610₈₀PVA⁰⁵₂₀ blown film was only 2.4 cm³ (m²·day·atm)^?1, which is about the same as that of the most often used high‐barrier polymer, ethylene–vinyl alcohol copolymer. Experimental findings from dynamic mechanical analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction and Fourier transform infrared spectroscopy of the PA610_xPVA^z_y blends indicate that PA610 and PVA in the blends are miscible to some extent at the molecular level when the PVA contents are less than or equal to the corresponding optimal values. The considerably enhanced oxygen barrier properties of the PA610_xPVA^z_y blend films with optimized compositions are attributed to the significantly reduced local free‐volume characteristics. © 2017 Society of Chemical Industry