食品药品来源的CFTR氯离子通道抑制剂的研究进展

CFTR氯离子通道是目前国际上新兴的治疗分泌型腹泻的分子药靶,CFTR抑制剂通过阻断离子通道的过度分泌来治疗腹泻症状。由于其抑制剂极为稀少,因此CFTR抑制剂的筛选工作是相关领域中最基础、最关键的环节。天然产物兼具结构和生物活性的多样性,在新药和先导化合物的发现中起着重要作用,是药物开发的主要来源,而食品药品来源的天然产物更因为对人体安全无毒副作用而倍受青睐。食品药品来源的CFTR氯离子通道抑制剂对于CFTR相关的腹泻等疾病的机理研究和治疗具有重要价值,同时也为天然产物资源用于现代药物发现提供了依据。     

冷轧带钢切边圆盘剪装置的优化与改进

针对冷轧带钢切边后产生的边部梗压印缺陷,结合切边圆盘剪的剪切原理,设计了一种圆盘剪复合衬套,其采用100Cr钢质内圈和MC尼龙外圈复合结构组成,取代原纯钢质衬套,使圆盘剪在剪切带钢过程中由钢性接触转变为弹性接触,从而避免了带钢边部梗压印缺陷的产生,提高了切边质量与剪切里程数,降低了圆盘剪备件成本,提高了生产效率。     

Chemical-Shift Perturbations Reflect Bile Acid Binding to Norovirus Coat Protein: Recognition Comes in Different Flavors

Bile acids have been reported as important cofactors promoting human and murine norovirus (NoV) infections in cell culture. The underlying mechanisms are not resolved. Through the use of chemical shift perturbation (CSP) NMR experiments, we identified a low-affinity bile acid binding site of a human GII.4 NoV strain. Long-timescale MD simulations reveal the formation of a ligand-accessible binding pocket of flexible shape, allowing the formation of stable viral coat protein–bile acid complexes in agreement with experimental CSP data. CSP NMR experiments also show that this mode of bile acid binding has a minor influence on the binding of histo-blood group antigens and vice versa. STD NMR experiments probing the binding of bile acids to virus-like particles of seven different strains suggest that low-affinity bile acid binding is a common feature of human NoV and should therefore be important for understanding the role of bile acids as cofactors in NoV infection.     

芳烃与烯烃烷基化反应的催化机理进展

芳烃与烯烃的反应在有机合成中应用广泛。随着环保要求的提高，用于芳烃烷基化反应的传统催化剂逐渐被新型绿色催化剂所替代。近年来研究发现离子液体和分子筛对该反应具有高效催化作用且环境友好。本文探讨了离子液体和分子筛的酸性，总结了相应的的催化机理，对有关实验和理论研究工作进行了分析。同时揭示了离子液体和分子筛的结构对其催化性能的影响，为烷基化反应进一步研究奠定了基础。分析表明离子液体既能作为B酸，也能作为L酸起催化作用；分子筛主要作为B酸起催化作用，同时其催化性能与孔道结构、孔径大小及反应物尺寸密切相关。离子液体的稳定性较差、成本较高，而分子筛失活较快，未来需围绕提高离子液体稳定性、改进其制备方法以降低成本及改善分子筛结构以延长使用周期等方面展开研究。     

Dependence of zeolite topology on alkane diffusion inside diverse channels

Zeolites have been widely used for the processes of adsorption, separation, and catalysis, which are strongly correlated with molecular diffusion. However, the correlation between pore dimension and diffusion properties has not been systematically investigated so far. In this work, the diffusion properties of alkanes in six zeolites with similar pore sizes but different pore dimension have been examined. It is found that the diffusion coefficients of alkanes in zeolites are 2–5 orders of magnitude smaller than that in gas phase. Moreover, the diffusion of alkanes inside zeolites is sensitive to the pore dimension, and can be differentiated by 1-D straight, 1-D tortuous, and 3-D intersecting channels, based on the derived quantitative correlation between the diffusion behavior and pore dimension. Our work may not only provide deep insights into the effects of pore dimension on diffusion, but also benefits for the future design and practical applications of zeolite catalysts.     

Modeling of sequence length distribution for olefin copolymerization with vanadium-based catalyst

Some thermodynamic and mechanical properties of a polyolefin, such as the melting temperature and the rigidity, are dependent on the nature of its sequence distribution. Accurate modeling of sequence length distribution (SLD) is important in precisely tuning and optimizing the properties of polymers produced. In this article, we proposed a model to predict the molecular weight distribution (MWD) and SLD for olefin copolymerization with vanadium-based catalyst. Due to the 2,1-insertion of α-olefin with vanadium-based catalyst, the SLD is expressed by uninterrupted methylene sequence distribution instead of conventional triad sequence distribution. To obtain a reliable model, parameter estimation with experimental data is first conducted. The SLD model along with the estimated kinetic parameters can be used to predict unmeasurable sequence length fraction. For the experimental conditions studied, the average methylene sequence length is predicted to change from 10 to 4 units as the propylene/ethylene mole feed ratio increases from 1.1 to 3.4.     

A molecular model for ion dehydration in confined water

Although ion dehydration in confined water is ubiquitous in many important processes concerning ion adsorption, transport and separation, and so forth, few theoretical models have been developed to unravel the mechanism of dehydration in confined space. Herein, a molecular model is proposed by weighing the molecular orientation of surrounding water within the first hydration shell, and then this model is applied to predict the hydration numbers and hydrated radii of simple ions with the help of molecular density functional theory. The predictions are rationalized not only with parallel simulations but also with relevant experimental measurements. We find that the ion hydration in confined water is depressed owing to the confinement, and thus the multilayer hydration shell is disturbed, which results in the decline of hydration number and hydrated radius, favoring the ion dehydration. This work provides an insightful route toward the quantitative understanding and prediction of ion dehydration in confined water.     

单晶/多晶镍轴向拉伸力学性能的分子动力学模拟

为提高航空发动机推重比采用整体叶盘新技术却带来了盘叶连接区域高风险失效问题。本文采用分子动力学对连接区单晶/多晶镍(SPSNi)的力学性能进行模拟,首先通过对比了不同晶态镍拉伸原子图。发现,由于单晶/多晶界面的存在使得拉伸后界面处的非晶化程度加剧,易于孔洞萌生,加剧了SPSNi突然断裂的风险。最后重点研究了单晶/多晶镍的应变率效应与温度效应。当应变率大于1í10_⁸s_^-1小于2í10_¹⁰s_^-1时,SPSNi对加载应变率几乎不敏感,屈服强度小幅上升。超过2í10_¹⁰s_^-1之后,其屈服强度随着应变率的增加而迅速下降。这是因为在高应变率下,SPSNi的FCC原子大规模迅速转变为无序的非晶结构,导致了晶体镍承载能力迅速下降。可以将应变率2í10_¹⁰s_^-1作为SPSNi拉伸变形的阈值。不同温度下,SPSNi屈服强度随温度的增大而线性下降。这是由于在温度的影响下,位错网络的初始镶嵌结构逐渐变得不规则,初始失配应力随着温度的升高而下降。     

High-temperature degradation of butadiene-based model elastomers by reactive molecular dynamics simulation

Thermal degradation of butadiene-based model elastomers was analyzed via a novel reactive molecular dynamics simulation (ReaxFF) method. The molecular simulation was carried out on 40 monomer units connected together. Degradation pathways of both homopolymer and copolymer of butadiene-based model elastomers such as polybutadiene (BR) and poly (styrene-co-butadiene) (SBR) were studied. The evolution of different fragmented products was examined as a function of time and heating rate. The formation mechanisms of different degraded fragments were visualized via the simulation method. The major decomposition products obtained from these model compounds were the monomers and comonomers. Pyrolysis gas chromatography–mass spectrometry (py-GC–MS) analysis was performed on the commercial samples of BR and SBR to verify the simulation results. The results obtained from the reactive simulation were very consistent with the experimental results. The activation energy required for the thermal decomposition of butadiene-based model elastomers were calculated both from the ReaxFF simulation and thermogravimetric analysis (TGA). The results were also in good agreement. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48592.     

NDQ催化剂在400 kt/a Spheripol聚丙烯工业装置上的应用

以三乙基铝为助催化剂,环已基甲基二甲氧基硅烷为外给电子体,使用NDQ催化剂在400 kt/a的Spheripol聚丙烯工业装置上试生产了注塑专用聚丙烯HA8012和HP-M12。结果表明:试生产期间,装置运行平稳,聚合工艺参数可控可调,聚丙稀细粉含量低;采用NDQ催化剂生产的HA8012和HP-M12具有较宽的相对分子质量分布(6.0~6.5)、较低的二甲苯可溶物含量(质量分数为1.5%~2.0%)、较高的拉伸强度(大于38 MPa)和弯曲模量(1.8~2.2 GPa)。