Immobilization of copper in organic-inorganic hybrid materials: a highly efficient and reusable catalyst for the Ullmann diaryl etherification

The immobilization of copper in organic-inorganic hybrid materials catalyzing the Ullmann reaction has been described. Phenols reacted with aryl iodides, aryl bromides and aryl chlorides smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper catalyst. The protocol involved the use of DMSO as the solvent, and potassium fluoride as the base. The reactions generated the corresponding cross-coupling products in good to excellent yields. Furthermore, the silica-supported copper could be recovered and recycled by a simple filtration of the reaction solution and used for 10 consecutive trials without loss of its reactivity.     

New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms

The reaction of Mn(2)(CO)(7)(mu-S2) (1) with [CpMo(CO)(3)](2) (Cp = C(5)H(5)) and [Cp*Mo(CO)(3)](2) (Cp* = C(5)(CH(3))(5)) yielded the new mixed-metal disulfide complexes CpMoMn(CO)(5)(mu-S2) (2) and Cp*MoMn(CO)(5)(mu-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) A and S-S = 2.042(2) and 1.9973(10) A for 2 and 3, respectively. A tetranuclear metal side product CpMoMn(3)(CO)(13)(mu3-S)(mu4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)(3)](2). Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn(CO)(5)[mu-SC(=O)S] (5) and Cp*MoMn(CO)(5)[mu-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)(5)[mu-S(C=NBu(t))S] (7) and Cp*MoMn(CO)(5)[mu-S(C=NBu(t))S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn(CO)(5)(mu-SCH(2)CH(2)S) (9), Cp*MoMn(CO)(5)(mu-SCH(2)CH(2)S) (10), CpMoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (11), and Cp*MoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)(5)[mu-SCH(2)C(=CH(2))S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.     

基于改进断裂点理论的机场吸引范围界定

合理界定机场吸引范围,是构建坚固民航运输网络的关键环节。现有的机场吸引范围界定方法,很少考虑与其衔接的地面交通网络,以及旅客出行偏好的影响。为提高机场吸引范围的实用性,本文以城市断裂点理论为基础,对其中的重要参数予以改进。首先,以综合交通运输为背景,指出发达的公路和铁路运输网络对民用机场具有很大的竞争与促进作用,并提出以地面交通出行时间为量化标准的吸引范围界定方法。然后,为分析旅客出行偏好的行为机理,针对于与机场衔接的地面交通网络来建立离散选择模型。其次,将研究区域的机场所在城市看作是一个整体,运用专家评价法和熵权法综合确定机场的吸引规模,并通过机场吞吐量与城市对外出行总量针对机场规模进行修正。最后,通过算例验证改进模型的实际可操作性,为确定多机场系统吸引范围界定提供新的思路和方法。     

震区中小跨径桥梁墩柱配筋率取值范围

为研究配筋率对钢筋混凝土桥梁延性抗震性能的影响,并在不同设防烈度对主筋配筋率的合理取值进行细分。以钢筋混凝土桥梁为研究对象,通过拟静力模型试验与有限元数值分析的方法,研究竖向钢筋(主筋)配筋率对桥墩延性的影响,提出典型桥墩的多级性能水平量化指标;并探究在氯离子侵蚀的恶劣环境下,不同配筋率对桥梁抗震性能所带来的影响,从而对氯离子侵蚀环境下的震区中小跨径桥梁墩柱配筋率取值范围提供参考建议。结果表明：考虑氯离子侵蚀作用下的恢复力模型能够较好地反映刚度的退化特性,墩柱的最佳配筋率取值范围为1.11%～2.72%;当加速度为0.3g(g为重力加速度)时,仅从配筋率的角度已无法满足墩柱的损伤指标,建议采用减隔震体系进行抗震设计,如采用延性体系时配筋率不得小于2.64%。研究结果可为中小跨径连续桥梁抗震设计提供参考。     

睡莲科植物酯酶同功酶的数量分类研究

采用垂直平板聚丙烯酰胺凝胶盘状电泳技术,对国内睡莲科植物（包括６个属的６个代表种及３个品种）的叶片进行了酯酶同功酶的测定,初步结果表明被测植物均有各自稳定的酯酶酶谱．运用数量分类学方法对被测植物进行聚类,其中白睡莲与其派生的红睡莲和黄睡莲２品种聚为一类,南芡与北芡亦聚为一类,而此２类与萍蓬草、莲、莼菜和王莲的亲缘关系较远,且后４种植物之间亲缘关系亦远．该结果与由过氧化物同功酶酶谱的分析结果基本相似．