Mechanism of the fast exchange between bound and free guests in cucurbit[7]uril-guest systems

The fast exchange is found to be due to the mismatch between the hydrophobic interaction inside the CB[7] cavity and the ion-dipole/hydrogen-bonding interactions in the port region of the CB[7]. This mismatch also induces the multi-step separation process between guest and CB[7] molecules, as elucidated by molecular dynamics simulation.     

金属络合物的相转移催化分析与分离

以可简单分离回收、可反复使用为目标，详细介绍了相转移催化的变化发展过 程．通过对溶剂的选择，使得催化剂选择性地溶解在某一液相中，而使产物溶解在 另一液相中，如水-有机两相催化体系；通过温度的变化，简单地实现了在较高温 度下反应为均相体系以提高催化剂的活性，而在较低温度下实现了催化剂与产物不 相溶使得催化剂得以简单分离，如温控型水-有机两相催化体系、氟-有机两相催化 体系、温控型含氟催化剂、温控型有机金属催化剂等．     

One-pot oxidation of sulfides to sulfones by reusable heterogeneous ruthenium catalyst in the presence of molecular oxygen

A reusable solid catalyst, MnFe_1.8Cu_0.15Ru_0.05O₄, has been developed as an effective catalyst for the aerobic oxidation of sulfides and sulfoxides to sulfones. The ruthenium modified spinel catalyst is the first example reported for such reaction under mild condition with molecular oxygen as the only oxidant. The oxidation reaction proceeded via an electrophilic attack of the oxygen atom of the catalyst on the electron-rich sulfur atom of the substrate.     

硫化CoMo/Al2O3催化剂上H2同时催化还原SO2和NO(Ⅱ)——催化反应活性相及机理探讨

主要通过XPS表征、热力学计算以及一系列设计的评价实验等方法,对硫化CoMo/Al2O3催化剂上H2同时催化还原SO2和NO反应的活性相、吸附活性位以及反应机理进行了研究.结果表明,金属硫化物相是SO,和NO转化的主要活性相,并与载体Al2O3共同承担H2S转化为单质硫的作用.此外,反应过程中产生的品格空位也对NO转化起着重要作用.催化剂表面的阴离子空位是SO2和NO共同的吸附活性位,SO2对NO的吸附有抑制作用,而催化剂表面的L碱佗也是SO2的吸附活性位,NO可促进SO2的氧化吸附.最后,本文从反应分子的吸附与活化、NO的转化及品格硫的流失、SO2还原到H2S、H2S的转化、晶格硫的补充等5个方面提出了反应机理.     

载体模板效应对氧化钯的热化学行为及其甲烷燃烧稳定性的影响

通过对PdO活性组分在单斜与四方型氧化锆载体上的热化学性质和催化活性进行比较性的研究显示, 单斜型ZrO₂的表面原子能够满足与PdO的结构适应性匹配条件, 它可以通过界面原子的取向附生作用对表面PdO物种聚集形态进行调控, 从而促进PdO组分在单位载体表面上的分散. 此外, 升降温循环过程的DTG分析还表明, 单斜载体模板在反复的氧化还原循环中逐渐将结晶型PdO加工成取向附生型PdO, 不断改善PdO物种的氧迁移性质, 促进了热还原钯物种在高温区的氧化再生. 这两种载体效应有效地抑制了甲烷燃烧反应在高温区的活性振荡, 增加了燃烧的稳定性与催化剂的反应耐受性. 四方ZrO₂晶相在载体内的掺杂将导致上述的载体效应受到明显抑制.     

甲烷在Ni/TiO2催化剂表面的活化

考察了Ni/TiO2催化剂甲烷部分氧化和二氧化碳重整制合成气的反应活性,实验表明,以TiO2为载体的镍系催化剂对于甲烷部分氧化制合成气反应具有较好的活性,尤其对H2的选择性较高,对二氧化碳重整制合成气反应具有较好的低温反应活性.采用脉冲-质谱在线分析等技术,在无气相氧条件下向Ni/TiO2催化剂脉冲CH4,发现甲烷在催化剂表面的活化（转化）及其氧化产物的选择性与金属催化剂表面氧的浓度密切相关.CH4与Ni/TiO2催化剂作用过程中存在明显的氢溢流和氧溢流现象,可能是这种溢流效应使得Ni/TiO2催化剂具有良好的反应活性和抗积碳性能.     

水滑石型固体碱碱性位的内标CO2-TPD-MS表征

通过共沉淀法制备了一系列不同镁铝比的水滑石样品,依据物相分析与热失重实验结果确认了合成的样品具有水滑石结构。以方解石型CaCO₃为内标,对水滑石样品碱性位的CO₂-TPD定量表征进行校正,并比较了不同实验参数对方法精密度的影响。经过各测试参数的敏感性分析证实,用CaCO₃脱附峰面积校正后,水滑石碱密度测量结果的RSD分别由9.7%、12.3%下降为4.3%、7.3%,而汇总分析的RSD可从29.6％下降至6.6%。CO₂-TPD定量分析精密度明显提高,证实了内标法的优势及其应用于固体碱定量表征的可行性。将内标法所得结果与固体碱催化酯交换反应的性能关联,结果发现,水滑石催化性能受到活性相的碱强度与碱密度双重指标的调控,碱强度和碱密度越大,酯交换催化效率越高。     

新型铁锰复合氧化物催化低温脱除NOx

采用溶胶-凝胶法合成了一系列铁锰复合氧化物催化剂,利用X射线衍射(XRD)对催化剂的活性相态进行研究,并考察了铁锰摩尔比及焙烧温度对催化性能的影响.结果表明,该催化剂体系征低温(80-220℃)下选择性催化氨还原NOx反应中显示出优异的活性.其中Fe(0.4)-MnOx(500)(即摩尔比n(Fe)/(n(Fe)+n(Mn))=0.4,焙烧温度500℃)催化剂具有最佳低温催化活性,在空速30000 h-1,温度80℃的条件下,NOx转化效率达到90.6%,N2 选择性达100%.Fe-MnOx复合氧化物催化剂中形成的Fe3Mn3O8晶相有利于促进NO氧化成NO2,从而提高低温选择性催化还原的活性.     

Design,synthesis and biological evaluation of LpxC inhibitors with novel hydrophilic terminus

In order to develop novel LpxC inhibitors with good activities and metabolic stability, two series of compounds with hydrophilic terminus have been synthesized and their in vitro antibacterial activities against Escherichial coli and Pseudomonas aeruginosa were evaluated. Especially, compounds 22b and c exhibited comparable antibacterial activities to CHIR-090 and better metabolic stability than CHIR-090 and LPC-011 in liver microsomes (rat andmouse), which indicated the terminal methylsulfone may be a preferred structure in the design of LpxC inhibitors and worthy of further investigations.     

Structural,stereochemical, and bioactive studies of cembranoids from Chinese soft coral Sarcophyton trocheliophorum

A series of highly oxidative new cembranoids with diverse structural features such as a dienoate moiety (sarcophytonolides S – U, 1–3) or an α,β-unsaturated ε-lactone (sartrolides H – J, 4–6) were obtained from Hainan soft coral Sarcophyton trocheliophorum, along with known related analogues 7–13. It is an extremely challenging work to determine the absolute configurations of these metabolites. For compounds 1, 3 and 4, solution TDDFT calculation of ECD and specific rotation were applied in combination with conformational analysis and NMR data to determine their relative and absolute configurations, leading to the revision of relative configuration of 14. The absolute configurations of compounds 8–10 were determined by the solid-state TDDFT-ECD approach, and that of 8 was further confirmed by single-crystal X-ray diffraction experiment with Cu Kα radiation. In the bioassays, compound 8 exhibited not only moderate protein tyrosine phosphatase 1B (PTP1B) inhibitory activity (IC₅₀?=?15.4?μM) but also moderate antibacterial activity against Staphylococcus aureus Newman strain (MIC₅₀?=?250?μM).