Concentration fluctuation caused by reaction-diffusion coupling near catalytic active sites

The coupling of reaction and diffusion between neighboring active sites in the catalyst pore leads to the spatiotemporal fluctuation in component concentration, which is very important to catalyst performance and hence its optimal design. Molecular dynamics simulation with hard-sphere and pseudo-particle modeling has previously revealed the non-stochastic concentration fluctuation of the reactant/product near isolated active site due to such coupling, using a simple model reaction of A → B in 2D pores. The topic is further developed in this work by studying the concentration fluctuation due to such coupling between neighboring active sites in 3D pores. Two 3D pore models containing an isolated active site and two adjacent active sites were constructed, respectively. For the isolated site, the concentration fluctuation intensifies for larger pores, but the product yield decreases, and for a given pore size, the product yield reaches a peak at a certain reactant concentration. For two neighboring sites, their distance (d) is found to have little effect on the reaction, but significant to the diffusion. For the same reaction competing at both sites, larger d leads to more efficient diffusion and better overall performance. However, for sequential reactions at the two sites, higher overall performance presents at a smaller d. The results should be helpful to the catalyst design and reaction control in the relevant processes.     

Formation of Sn filled CNTs nanocomposite: Study of their magnetic,dielectric properties and enhanced microwave absorption performance at gigahertz frequencies

The Simplistic formation, advantageous configuration, non-colossal magnetoresistance and broadband absorption are important parameters for microwave absorbent materials. In this study, a core-shell nanocomposite comprising of Sn-filled carbon nanotubes (Sn/CNTs) was prepared by arc discharge method. The microstructure, morphology and surface composition of Sn/CNTs-based core-shell nanocomposites were characterized in detail. Sn/CNTs nanocomposite showed a magnetic signal due to the broken bonds and defects at interfaces in Sn/CNTs. The weak ferromagnetism was found to be helpful in improving magnetic permeability in the Sn/CNTs which confirms its role as a magnetic loss material under incident electromagnetic wave. Sn-filled CNTs revealed an appropriate value of dielectric constant, which plays an important role in impedance matching upon incident electromagnetic wave. The composite of Sn-CNTs and paraffin with a 50 wt % loading showed the lowest reflection loss (RL) of ?43.87 dB at 10 GHz, with a wide effective absorption band (RL ≤ ?10 dB) of 3 GHz in thickness of 2.3 mm. This enhanced performance is attributed to the combined effect of the conduction loss in one-dimensional core-shell architecture, the interfacial loss Sn-CNT interface, the magnetic loss due to defects-induced ferromagnetism in Sn shell, and in the carbon-containing atomic layers of CNTs.     

具有保护肠上皮细胞HT-29免受大肠杆菌和H2O2损伤潜力的植物乳杆菌的筛选

益生菌可在肠道定植从而发挥抗炎或抗氧化活性，有利于宿主肠道健康。本实验研究了从新疆传统发酵乳制品中分离得到的8?株植物乳杆菌对大肠杆菌侵袭和过氧化氢刺激肠上皮细胞HT-29的保护作用。结果表明：在8?株植物乳杆菌中，植物乳杆菌35具有最高的黏附能力。植物乳杆菌35可通过取代、竞争、排阻的方式抑制大肠杆菌对HT-29细胞的黏附，抑制率分别为42.60%、59.17%、60.19%。植物乳杆菌35及其多糖可抑制大肠杆菌刺激HT-29细胞产生白细胞介素-8；同时保护HT-29细胞免受过氧化氢的损伤，增加超氧化物歧化酶、谷胱甘肽过氧化物酶活力水平并降低丙二醛含量。结论：植物乳杆菌35及其粗胞外多糖具有抑制大肠杆菌O157诱导的炎症性肠病的潜力。     

四氢姜黄素经PI3K/Akt信号通路对人血小板活化和聚集的调控作用

目的：探讨姜黄素的主要肠道代谢物四氢姜黄素（tetrahydrocurcumin，THC）对血小板活化和聚集的影响及其可能的分子机制。方法：在体外实验中，用不同浓度的THC（0、0.5、1、10 μmol/L）提前与健康人纯化血小板共同孵育40 min，然后加入凝血酶激活血小板2 min，用流式细胞术测定血小板表面CD62P和CD63的表达量，用酶联免疫吸附法测定血小板释放血小板因子-4（platelet factor-4，PF4）和趋化因子配体-5（chemokine ligand 5，CCL5）水平，用血小板聚集仪检测血小板释放ATP水平和血小板最大聚集率，用Western blot蛋白免疫印迹法检测血小板磷酸肌醇-3-激酶（phosphoinositide 3-kinase，PI3K）和Akt蛋白的磷酸化水平。结果：与模型组（血小板悬液中加入0.05%二甲基亚砜）相比，THC能抑制凝血酶诱导的血小板表面CD62P和CD63的表达，抑制PF4、CCL5和ATP的释放，降低血小板最大聚集率，下调PI3K和Akt蛋白的磷酸化水平，且呈浓度依赖效应，其中10 μmol/L的浓度下作用效果显著（P＜0.01、P＜0.001）。PI3K的特异性激动剂740 Y-P可部分逆转THC对PF4和CCL5释放和血小板聚集的抑制作用（P＜0.05、P＜0.01）。结论：THC具有显著抑制血小板活化和聚集的作用，其机制可能是THC可下调PI3K/Akt介导的信号通路。     

Directional separation of hydrogen-containing gas mixture by hydrate-membrane coupling method

Recovery of hydrogen (H₂) from H₂-containing gas mixtures has great significance for energy conservation, cost reduction and benefit increase. However, the common separation methods have the ubiquitous problem due to phase equilibrium principle and results in the conflict between H₂ concentration and H₂ recovery rate in the product gas. Consequently, an innovative conception of hydrate-membrane coupling approach is proposed in this work. In the separation process, hydration and membrane permeation two separation driving forces coexist to achieve the aim of strengthening mass transfer kinetics. H₂ and non-H₂ components (hydrocarbons) are synchronously and directionally selected by membrane and hydrate to improve different phase compositions. Therefore, the gas in feed side could keep relatively high two separation driving forces (H₂ fugacity and hydrocarbons fugacity). The results show that the coupling method could synchronously increase both the concentration and the recovery rate of H₂ in the product gas. At the same time, the volume and concentration of the hydrocarbons in hydrate both increases effectively. It indicates that hydrate and membrane separation methods support each other in the separation process. The hydrate-membrane coupling method fundamentally solves the issue of the decreasing driving force resulting from single separation method and phase equilibrium relationship.     

Transition metal atoms anchored on nitrogen-doped α-arsenene as efficient electrocatalysts for nitrogen electroreduction reaction

Electrocatalytic reduction of N₂ to NH₃ under ambient conditions, inspired by biological nitrogen fixation, is a new approach to address the current energy shortage crisis. As a result, developing efficient and low-cost catalysts is critical. The catalytic activity, catalytic mechanism, and selectivity of α-arsenene (α-Ars) catalysts anchored with various transition metal atoms and doped with different numbers of N atom were investigated for N₂ reduction reaction (NRR) in this paper. Results reveal that compared with WN₃-α-Ars which is coordinated with three N atoms, asym-WN₂As-α-Ars that coordinated with two N atoms not only exhibits high catalytic activity (U_L = ?0.36 V), but can also successfully suppress the hydrogen evolution reaction (HER). It is manifested that reducing the number of coordination atoms can promote the selectivity of the transition metal (TM) loaded N-doped arsenene catalysts. Furthermore, activity origin analyses show both the charge on 1N–NH and φ form volcano-type relationship with the limiting potential. The active center of the catalyst, which acts as the charge transporter and has the moderate ability to retrieve charges, is the most efficient in NRR. Overall, this research creates high performance NRR catalysts by varying the number of coordinating N atoms, which provides a novel idea for the development of new NRR catalysts.     

高职模具类人才培养新模式的研究与实践

为了解决传统教学无法全面培养人才的问题,采用"课程融合+时空耦合+过程结合"的方式开展人才培养研究。以注射模设计与制造生产过程为导向,构建大项目牵引下的跨越课程、跨越学期的课程融合新模式,利用信息通信技术及互联网平台,将互联网与传统教学进行深度融合,创造新的教学生态,构建多元多维互动的时空耦合教学新关系,以全方位评价为引导,构建课程多元多维的评价新机制。以3个班级为对象开展不同模式下的教学,对试验班级成绩进行分析,研究结果表明:课程融合+时空耦合+过程结合新模式培养的学生更好地完成了综合项目,获得了较好的教学效果。     

Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction

Suzuki-Miyaura (S-M) is regarded the most powerful way for synthesis biaryls, triaryls, or incorporating of substituted aryl moieties in organic preparation by the cross-coupling of aryl boronic acid with aryl halides using the Pd catalyst. This work reports the combining of the hydrothermal and microwave-assisted protocol to convert the glucose to magnetic carbon spheres (Fe₃O₄-CSPs) decorated with Pd nanoparticles (NPs) as the catalyst for Suzuki-Miyaura cross-coupling reactions. The physicochemical properties in the produced composite were examined using FESEM, HRTEM, nitrogen isotherms, Raman spectroscopy, FTIR, XPS, and XRD. The as-fabricated composite Pd/Fe₃O₄-CSPs is mostly spherical with a core–shell structure and possesses a great surface area of 253.2 m²·g^-1. Its catalytic performance demonstrates that the composite has excellent stability and high tolerance Suzuki-Miyaura cross-coupling reactions in 30 min at 80 ℃. Both activated and deactivated aryl halides provided excellent yield. The as-fabricated catalyst was recycled for up to four catalytic cycles without a substantial decline in performance. Moreover, this research offers a facile roadmap for synthesizing Pd/Fe₃O₄-CSPs composites and promoting the practical implementation of Pd/Fe₃O₄-CSPs catalysts for organic transformation processes.     

Adaptation to Endoplasmic Reticulum Stress Enhances Resistance of Oral Cancer Cells to Cisplatin by Up-Regulating Polymerase η and Increasing DNA Repair Efficiency

Endoplasmic reticulum (ER) stress response is an adaptive program to cope with cellular stress that disturbs the function and homeostasis of ER, which commonly occurs during cancer progression to late stage. Late-stage cancers, mostly requiring chemotherapy, often develop treatment resistance. Chemoresistance has been linked to ER stress response; however, most of the evidence has come from studies that correlate the expression of stress markers with poor prognosis or demonstrate proapoptosis by the knockdown of stress-responsive genes. Since ER stress in cancers usually persists and is essentially not induced by genetic manipulations, we used low doses of ER stress inducers at levels that allowed cell adaptation to occur in order to investigate the effect of stress response on chemoresistance. We found that prolonged tolerable ER stress promotes mesenchymal–epithelial transition, slows cell-cycle progression, and delays the S-phase exit. Consequently, cisplatin-induced apoptosis was significantly decreased in stress-adapted cells, implying their acquisition of cisplatin resistance. Molecularly, we found that proliferating cell nuclear antigen (PCNA) ubiquitination and the expression of polymerase η, the main polymerase responsible for translesion synthesis across cisplatin-DNA damage, were up-regulated in ER stress-adaptive cells, and their enhanced cisplatin resistance was abrogated by the knockout of polymerase η. We also found that a fraction of p53 in stress-adapted cells was translocated to the nucleus, and that these cells exhibited a significant decline in the level of cisplatin-DNA damage. Consistently, we showed that the nuclear p53 coincided with strong positivity of glucose-related protein 78 (GRP78) on immunostaining of clinical biopsies, and the cisplatin-based chemotherapy was less effective for patients with high levels of ER stress. Taken together, this study uncovers that adaptation to ER stress enhances DNA repair and damage tolerance, with which stressed cells gain resistance to chemotherapeutics.     

Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions

Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO^•) play an important role, being the most aggressive towards biomolecules. The reactions of HO^• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO^• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO^•, and by CB triplets allowed for assigning transient species to the pathways of products formation.