Synthesis of nonracemic allylic hydroxy phosphonates via alkene cross metathesis

Allylic hydroxy phosphonates and their derivatives can be interconverted by using cross metathesis with second generation Grubbs catalyst. The absolute stereochemistry of the starting phosphonate is conserved in the product. Cross metathesis reaction of the acrolein-derived phosphonate 2a yields a series of functionalized allylic hydroxy phosphonates. However, the cross metathesis reaction is often accompanied by competing dimerization and alkene migration reactions leading to a reduction in yield. The cinnamaldehyde- and crotonaldehyde-derived phosphonates 2b and 2c were also examined. In general, the metathesis reactions of phosphonates 2b and 2c are considerably slower than those for phosphonate 2a leading to mixtures. Several hydroxyl-protected derivatives of the phosphonate 2a (methyl carbonate 3a, acetate 4a, N-tosyl carbamate 5a, TBDMS 6a, and acetoacetate 7a) undergo metathesis without competing side reactions to give substituted allylic phosphonates in good to excellent yield.     

严格反馈非线性系统中参数收敛的系统化方法

研究严格反馈非线性系统中参数的收敛性.在适当的持续激励条件下,通过构造一个显式、全局的强Lyapunov函数,给出了系统参数估计收敛于真值的充分条件,且闭环信号全局一致有界,跟踪误差渐近收敛于零.仿真算例验证了设计方案的可行性和有效性.     

Wear Performance and Mechanisms of Polyphenylene Sulfide/Polytetrafluoroethylene Wax Composite Coatings Reinforced by Graphene

Polyphenylene sulfide (PPS) composite coatings reinforced by graphene were prepared through a spraying method. Wear performance of the composite coatings were evaluated using a block-on-ring test rig, and the results showed that the wear life of the composite coatings were over seven times higher than that of a pure PPS coating. Wear mechanisms of PPS composite coatings reinforced by graphene are discussed. It was concluded that adhesive wear was the major wear mechanism of the pure PPS coating but the wear form of the composite coatings was dominated by abrasive wear due to the graphene filler that has high mechanical strength. In addition, fatigue wear appeared for composite coatings with higher content of graphene. The formation of a uniform thin transfer film on the counterpart ring and fine wear debris for the composites coatings during abrasion were consistent with the improvement of wear performance. The 3D morphology of the surface of the counterpart ring was also used to discuss the wear mechanism of PPS composite coatings.     

Non‐Isothermal Crystallization Kinetics of PA6/Attapulgite Composites Prepared by Melt Compounding

The non‐isothermal crystallization behaviors of neat polyamide 6 (PA6) and PA6/attapulgite (ATB) composites were examined using differential scanning calorimetry. The results show that ATB acts as a nucleator for PA6 matrix, accelerating the crystallization, and simultaneously obstructs the crystallization especially for the composites with higher ATB content. The analysis results using the Jeziorny and Liu equations verify the dual actions of the nucleation and the obstruction of crystallization of the ATB in the PA6 matrix. Kissinger's method is employed to obtain the activation energy of the crystallization processes; the results further indicate that the addition of ATB may also cause the above actions. It is speculated that there is a very complicated crystallization mechanism in the PA6/ATB composites based on the analysis of Avrami exponents obtained by the Jeziorny model.     

生态风险评价理论和方法

生态风险评价从最初单物种毒性测试数据为基础、从急性毒性数据外推获得慢性毒性数据的简单模型方法,逐步过渡到以多物种测试为基础和通过微、中宇宙生态系统模拟法获取数据、建立模型,以及以生态毒理模型为基础的生态风险评价方法.本文讨论生态风险评价方法的发展过程及不同阶段存在的问题,阐述以个体、种群和生态系统为基础的生态风险评价方法的特点和相互之间的区别,指出生态风险评价正在从个体走向群落的发展趋势.本文同时对风险表征方法、数据选择和常用统计方法作了评述,并对生态风险评价的发展趋势进行了预测.     

Synthesis and incorporation into cyclic peptides of tolan amino acids and their hydrogenated congeners: construction of an array of A-B-loop mimetics of the Cε3 domain of human IgE

The disruption of the human immunolobulin E-high affinity receptor I (IgE-FcεRI) protein-protein interaction (PPI) is a validated strategy for the development of anti asthma therapeutics. Here, we describe the synthesis of an array of conformationally constrained cyclic peptides based on an epitope of the A-B loop within the Cε3 domain of IgE. The peptides contain various tolan (i.e., 1,2-biarylethyne) amino acids and their fully and partially hydrogenated congeners as conformational constraints. Modest antagonist activity (IC(50) ～660 μM) is displayed by the peptide containing a 2,2'-tolan, which is the one predicted by molecular modeling to best mimic the conformation of the native A-B loop epitope in IgE.     

Fabrication of micro-sized-copper column array through localized electrochemical deposition using 20-μm-diameter micro-anode

Journal of Solid State Electrochemistry - Local electrochemical deposition (LECD) is an economical and efficient three-dimensional (3D) microstructure fabrication method. In this study, we...     

不同孔结构两亲性沸石的制备及其对相界面反应的催化性能

 通过三甲基氯硅烷(TMS)对沸石表面进行修饰,制得了两亲性沸石样品TMS-Hβ, TMS-HY和TMS-HZSM-5,并采用X射线衍射、红外光谱、水饱和吸附量测定和酸碱滴定等手段对改性样品进行了表征. TMS对这三种母体沸石的改性结果有所不同: 对于HZSM-5沸石, TMS仅在外表面修饰; 对于Hβ沸石,少量TMS进入沸石孔道; 而对于HY沸石, TMS则导致沸石结构部分坍塌. 两亲性TMS-HZSM-5和TMS-Hβ沸石在乙酸异戊酯相界面水解反应中表现出明显优于各自母体沸石的催化性能. 两亲性沸石表面硅烷基的稳定性对其催化性能有一定的影响. 相对于TMS-HZSM-5沸石, TMS-Hβ沸石表面硅烷基的稳定性较强; 在较高的相界面反应温度下, TMS-Hβ样品仍能维持两亲性能,表现出较高的催化活性.     

复合结构壳体蠕变变形有限元研究

基于蠕变理论，采用有限元数值计算方法，用ANSYS作为计算平台，建立了壳体结构的蠕变变形计算模型．对由耐火材料是镁碳砖炉衬和炉壳组成的复合结构转炉，由于高导热率的镁碳砖广泛使用，引起转炉炉壳的温度升高，导致转炉不同程度地出现了炉壳蠕变变形，致使炉壳使用寿命缩短．研究转炉炉壳蠕变变形的状态及分布规律，可为控制炉壳蠕变变形、延长炉壳使用寿命提供依据．运用所述的有限元计算模型，对复合结构的转炉炉壳的蠕变变形行为进行模拟，模拟结果与现场测量值基本吻合．