Mathematical modeling of photoinitiated coating degradation: Effects of coating glass transition temperature and light stabilizers

A mathematical model, describing coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature, was extended to simulate the behavior of a coating with a low glass transition temperature. The effects of adding light stabilizers (a UV absorber and a radical scavenger) to the coating were also explored. The extended model includes photoinitiated oxidation reactions, intrafilm oxygen permeability, water absorption and diffusion, reduction of crosslink density, absorption of ultraviolet radiation, a radical scavenger reaction, and simulates the transient development of an oxidation zone. Simulations are in good agreement with experimental data for a fast degrading epoxy-amine coating with a glass transition temperature of −50 °C. It was found that the degradation rate of the non-stabilized coating was influenced significantly by the diffusion rate of oxygen in the oxidation zone, whereas light absorption by the photoproducts formed was only a secondary effect. On the other hand, the degradation rate of the stabilized coating was mainly influenced by the light absorption capability of the coating and in this case there was no oxygen diffusion resistance. Finally, simulations showed that the rate constants of the photoinitiating and oxidation reactions, taking place within the epoxy-amine family of coatings, are strong functions of the specific crosslinker used and must be estimated, in each case, by calibration of the model against adequate experimental data series.     

Importance of a Conserved Lys/Arg Residue for Ligand/PDZ Domain Interactions as Examined by Protein Semisynthesis

PDZ domains are ubiquitous small protein domains that are mediators of numerous protein–protein interactions, and play a pivotal role in protein trafficking, synaptic transmission, and the assembly of signaling‐transduction complexes. In recent years, PDZ domains have emerged as novel and exciting drug targets for diseases (in the brain in particular), so understanding the molecular details of PDZ domain interactions is of fundamental importance. PDZ domains bind to a protein partner at either a C‐terminal peptide or internal peptide motifs. Here, we examined the importance of a conserved Lys/Arg residue in the ligand‐binding site of the second PDZ domain of PSD‐95, by employing a semisynthetic approach. We generated six semisynthetic PDZ domains comprising different proteogenic and nonproteogenic amino acids representing subtle changes of the conserved Lys/Arg residue. These were tested with four peptide interaction partners, representing the two different binding modes. The results highlight the role of a positively charged amino acid in the β1–β2 loop of PDZ domains, and show subtle differences for canonical and noncanonical interaction partners, thus providing additional insight into the mechanism of PDZ/ligand interaction.     

The Discovery and Structure-Activity Evaluation of (+)-Floyocidin B and Synthetic Analogs

Tuberculosis represents one of the ten most common courses of death worldwide and the emergence of multidrug-resistant M. tuberculosis makes the discovery of novel anti-tuberculosis active structures an urgent priority. Here, we show that (+)-floyocidin B representing the first example of a novel dihydroisoquinoline class of fungus-derived natural products, displays promising antitubercular hit properties. (+)-Floyocidin B was identified by activity-guided extract screening and its structure was unambiguously determined by total synthesis. The absolute configuration was deduced from a key synthesis intermediate by single crystal X-ray diffraction analysis. A hit series was generated by the isolation of further natural congeners and the synthesis of analogs of (+)-floyocidin B. Extensive biological and physicochemical profiling of this series revealed first structure-activity relationships and set the basis for further optimization and development of this novel antitubercular scaffold.     

燃气管线动态泄漏扩散的危险性分析

通过对燃气管线动态泄漏过程的分析,建立了动态泄漏率计算模型。以湍流扩散微分方程为基础,根据动态泄漏率不定常的特点,建立了燃气管线动态泄漏扩散模型。讨论分析了火灾爆炸的可能性危险范围和伤害性危险范围的参考标准和计算方法。在实际应用的基础上,对各种危险范围给予了讨论和分析,并对给定条件下的伤害及破坏范围给予了计算。这将为设立和制订高压长输管线和城市主要输运管道附近的重要建筑物(学校等)的修建安全距离提供安全标准和参考,同时也为降低事故可能造成的危害程度提供保障。     

Interaction of titanium diboride/boron nitride evaporation boats with aluminium

Hexagonal boron nitride/titanium diboride composites are widely used as evaporation boats for aluminium deposition to produce functional and decorative layers on different target materials. The lifetime of such a material is limited mainly by the interaction of the metal with the ceramic substrate, but the corrosion mechanism has still not yet been thoroughly investigated and understood. In this article the corrosion mechanism for the evaporation boats used was investigated using thermodynamic calculations, FESEM, EDX and XRD phase analysis. The analysis showed that hexagonal boron nitride (hBN), which is thermodynamically less stable than TiB₂, is passivated during the application process through the formation of AlN surface layers, whereas the thermodynamically more stable TiB₂ phase dissolves and Ti-rich components precipitate in cooler regions of the evaporation boats.     

喷射电沉积块体纳米晶Co-Ni合金工艺的研究

利用扫描电子显微镜（SEM），能谱仪（EDS）及X射线衍射（XRD）等分析方法研究了工艺参数对电解液喷射电沉积法制备块体纳米晶Co-Ni合金沉积层成分及结构的影响。结果表明；在本实验条件下，随电解液喷射速度的增加，沉积层中钴含量增加，而晶粒尺寸减小；随电解液温度的升高，沉积层中钴含量减小到一定值后增大，晶粒尺寸呈相反的趋势。沉积层的表面形貌为胞状结构。     

Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

Abstract  

Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDA), a possible plastics precursor. The novel catalyst systems were characterized by nitrogen physisorption, XRPD, TEM and EDS analysis, and applied for the oxidation with no added base at moderate to high pressures of dioxygen and elevated temperatures. The effects of support, temperature and oxidant pressure were studied and optimized to allow a quantitative yield of FDA to be obtained.     

球罐开罐检验分析及球罐的安全质量控制

通过对兴平化肥厂 6 0 0m3 液氨球罐历次全面定期检验中发现的缺陷分析 ,指出了球罐主要缺陷及其产生的条件和机理 ,从制造工艺控制、运行中介质有害物质的控制及水压试验等几方面 ,论述了球罐质量控制的问题 ,提出了预防主要危害缺陷的方法