Stereoselective synthesis of 3,3-diarylacrylonitriles as tubulin polymerization inhibitors

A series of 3,3-diarylacrylonitriles were synthesized stereoselectively as tubulin polymerization inhibitors for potential use in cancer chemotherapy. This synthetic route features stannylcupration and palladium-catalyzed Stille cross-coupling chemistry, allowing both E and Z isomers of 3,3-diarylacrylonitriles to be prepared in a very short sequence of reactions.     

Selectively light scattering spectrometric detection of copper (II) based on a new synthesized oxamide ligand

Light scattering (LS) signals have been applied for analytical detections, but the selectivity is poor. In order to improve the selectivity, pre-separation or new machines are generally considered. Differing from these methods, we synthesized a highly selective oxamide ligand, N′,N′-bis (2-aminophenyl) oxamide (NAPO). It was found that the LS signals of NAPO, measured with a common spectrofluorometer, could be selectively enhanced by copper ion in neutral medium. Thus, a new highly selective detection method for copper ion could be developed over the range of 0.9-31.0 μM with the limit of determination of 97.6 nM (3σ). Foreign ions including Cd(II), Al(III) could be allowed even if present at the level of 7-fold more than that of Cu²⁺, avoiding pre-separation procedures from complicated samples such as real wastewater samples. Mechanism studies showed that the reaction between NAPO and copper ion could form some kinds of clusters and induce the enhanced LS signals.     

Photopolymerization of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester and properties of the cured films

A series of novel waterborne hyperbranched polyurethane acrylates for aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were investigated and used as UV curable oligomers. The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine. The photopolymerization kinetics of these WHPUDs was studied with respect to polymerization rates and unsaturation conversions in the presence of a photoinitiator using differential scanning calorimetry. The polymerization rates of the resins under UV irradiation and the gel contents in the cured films showed an increasing trend with higher concentration of acrylate functionality, which is in favor of the theory of radical chain polymerization. The mechanical and thermal behaviors of UV cured films of aqueous dispersions were evaluated by tensile testing and dynamic mechanical thermal analysis (DMTA). The results of DMTA investigations indicated that the glass transition temperature shifted to higher temperature as the content of the hard segment consisting of IPDI-HEA increased. Moreover, the storage modulus and pendulum hardness also increased with increasing the hard segment content. As the degree of neutralization increased, the T_g and tensile strength decreased, whereas, the elongation at break increased.     

Migration behavior and enantioseparation of hydrobenzoin and structurally related compounds in capillary zone electrophoresis with a dual cyclodextrin system consisting of heptakis-(2,3-dihydroxy-6-O-sulfo)-beta-cyclodextrin and beta-cyclodextrin

Migration behavior and enantioseparation of racemic hydrobenzoin and structurally related compounds, including benzoin and benzoin methyl ether, in CZE with a dual CD system consisting of heptakis-(2,3-dihydroxy-6-O-sulfo)-beta-CD (SI-S-beta-CD) and beta-CD as chiral selectors in the presence and absence of borate complexation at pH 9.0 were investigated. The results indicate that enantioseparation of hydrobenzoin is mainly governed by CD complexation of hydrobenzoin-borate complexes with SI-S-beta-CD when SI-S-beta-CD concentration is relatively high. Whereas CD complexation of hydrobenzoin-borate complexes with beta-CD plays a significant role in enantioseparation when SI-S-beta-CD concentration is comparatively low. The (S,S)-enantiomer of the hydrobenzoin-borate complex was found to interact more strongly than the corresponding (R,R)-enantiomer with both SI-S-beta-CD and beta-CD. These two types of CD show the same chiral recognition pattern, but they exhibit opposite effects on the mobility of the enantiomers of hydrobenzoin-borate complexes. Enantiomer migration reversal of hydrobenzoin occurred in the presence of borate complexation when varying the concentration of beta-CD, while keeping SI-S-beta-CD at a relatively low concentration. Binding constants of the enantiomers of benzoin-related compounds to beta-CD and those of hydrobenzoin-borate complexes to SI-beta-CD were evaluated; the mobility contributions of all complex species to the effective mobility of the enantiomers of hydrobenzoin as a function of beta-CD concentration in a borate buffer were analyzed. In addition, comparative studies on the enantioseparation of benzoin-related compounds with SI-S-beta-CD and with randomly sulfate-substituted beta-CD were made.     

Selective dye-labeling of newly synthesized proteins in bacterial cells

We describe fluorescence labeling of newly synthesized proteins in Escherichia coli cells by means of Cu(I)-catalyzed cycloaddition between alkynyl amino acid side chains and the fluorogenic dye 3-azido-7-hydroxycoumarin. The method involves co-translational labeling of proteins by the non-natural amino acids homopropargylglycine (Hpg) or ethynylphenylalanine (Eth) followed by treatment with the dye. As a demonstration, the model protein barstar was expressed and treated overnight with Cu(I) and 3-azido-7-hydroxycoumarin. Examination of treated cells by confocal microscopy revealed that strong fluorescence enhancement was observed only for alkynyl-barstar treated with Cu(I) and the reactive dye. The cellular fluorescence was punctate, and gel electrophoresis confirmed that labeled barstar was localized in inclusion bodies. Other proteins showed little fluorescence. Examination of treated cells by fluorimetry demonstrated that cultures supplemented with Eth or Hpg showed an 8- to 14-fold enhancement in fluorescence intensity after labeling. Addition of a protein synthesis inhibitor reduced the emission intensity to levels slightly above background, confirming selective labeling of newly synthesized proteins in the bacterial cell.     

高表面电荷密度单分散苯乙烯磺酸钠纳米微球的制备

利用无皂乳液聚合 ,在苯乙烯 (St)的反应体系中引入适量的苯乙烯磺酸钠 (NaSS)参加共聚合 ,在聚合过程中分两阶段加料 ,第一阶段中NaSS浓度是决定乳胶粒粒径及单分散性的关键因素。当反应达到较高转化率 ( >90 % )时加入第二阶段单体混合物 ,此阶段中NaSS与St的比例决定了最终胶粒的表面电荷密度。利用上述两阶段无皂乳液聚合法成功地制备了粒径小于 10 0nm、单分散性指数小于 1.0 5以及表面电荷密度大于 3 0 μC·cm-2 的一系列乳胶粒     

发动机润滑油老化及检测方法

发动机润滑油老化后会增加发动机磨损 ,缩短发动机使用寿命。检测机油品质时可用理化性能指标检测法及经验判断法。而经验判断对运输企业及维修企业更实用     

Experimental study on crack curving propagation in bending beams under impulsive load

Dynamic fracture behaviour of crack curving in bent beams has been investigated. In order to understand the propagation mechanism of such cracks under impact, an experimental method is used that combines dynamic photoelasticity with dynamic caustics to study the interaction of the flexural waves and the crack. From the state change of the transient stresses in polymer specimen, the curving fracture in the impulsively loaded beams is analyzed. The dynamic responses of crack tips are evaluated by the stress intensity factors for the cracks running in varying curvature paths under bending stress wave. The project supported by the National Natural Science Foundation of China and the Scientific Commission of Yunnan Province of China     

Sn60Pb40钎料合金的具有蠕变和塑性边界的粘塑性本构方程

采用具有蠕变和塑性边界的粘塑性本构方程对Sn-Pb共晶合金的基本力学行为进行了模拟和预测。结果表明：在较宽的外部变量范围（应变率为10^-5-10^-2S^-1,温度为－55－125℃）内,模拟结果与实验结果吻合良好。证明了该方程用于描述Sn-Pb共晶合金的力学行为具有良好的预测能力。     

Analysis of electric boundary condition effects on crack propagation in piezoelectric ceramics

There are three types of cracks: impermeable crack, permeable crack and conducting crack, with different electric boundary conditions on faces of cracks in piezoelectric ceramics, which poses difficulties in the analysis of piezoelectric fracture problems. In this paper, in contrast to our previous FEM formulation, the numerical analysis is based on the used of exact electric boundary conditions at the crack faces, thus the common assumption of electric impermeability in the FEM analysis is avoided. The crack behavior and elasto-electric fields near a crack tip in a PZT-5 piezoelectric ceramic under mechanical, electrical and coupled mechanical-electrical loads with different electric boundary conditions on crack faces are investigated. It is found that the dielectric medium between the crack faces will reduce the singularity of stress and electric displacement. Furthermore, when the permittivity of the dielectric medium in the crack gap is of the same order as that of the piezoelectric ceramic, the crack becomes a conducting crack, the applied electric field has no effect on the crack propagation. The project supported by the National Natural Science Foundation of China (19672026, 19891180)