Two Supramolecular Nickel(II) Complexes: Syntheses,Crystal Structures and Solvent Effects

Two nickel(II) complexes, namely {[NiL(MeOH)(μ‐OAc)]₂Ni} · 2CH₂Cl₂ · 2MeOH ( 1 ) and {[NiL(EtOH)(μ‐OAc)]₂Ni} · 2EtOH ( 2 ) {H₂L = 5, 5′‐dimethoxy‐2, 2′‐[(ethylene)dioxybis(nitrilomethylidyne)]diphenol}, were synthesized and structurally characterized. Two trinuclear Ni^II complexes are both hexacoordinate around the central Ni^II atoms, showing octahedral coordination arrangements, and each complex comprises three divalent Ni^II atoms, two deprotonated L^2– ligands, in which four μ‐phenoxo oxygen atoms forming two [NiL(X)] (X = MeOH or EtOH) units, and coordinated and non‐coordinated solvent molecules. Complex 1 exhibits a 2D supramolecular network through intermolecular O–H ··· O, C–H ··· O and C–H ··· π interactions, whereas complex 2 forms an infinite 1D chain by intermolecular C–H ··· O hydrogen bonding interactions.     

Preparation and performance of a novel polyimide foam

A new type of polyimide foam (PIF) was prepared and characterized based on a one‐pot process by the reaction of a first solution with different ratios of a second solution. The first solution was comprised of pyromellitic dianhydride (PMDA), N, N‐dimethyl formamide (DMF), methanol, water, surfactant, and catalysts, while the second solution contained polyaryl polymethylene isocyanate (PAPI). In the present study, the relationships among compositions, structures, and properties of PIFs were investigated. The results indicated that with the increase in the weight ratio of PAPI/(first solution), the foaming degrees of PIFs increased from 10.14 to 10.52 times and the apparent densities before postcure decreased from 15.96 to 14.51 kg/m³. The open cell contents, average sound absorption coefficients, and average cellular diameters of PIFs after postcure increased with increase in the weight ratio of PAPI/(first solution). The glass transition temperatures (T_g) of PIFs after postcure first increased from 287 to 299°C, then decreased to 292°C, and the 5% weight loss temperatures and 10% weight loss temperatures presented the same trend as well. The compressive and flatwise tensile properties scaled very well with the relative densities of the foams after postcure, with the highest compressive strength of 0.03 MPa and the highest flatwise tensile strength of 0.15 MPa. Copyright © 2011 John Wiley & Sons, Ltd.     

离子液体催化CO2与环氧化物合成环状碳酸酯

综述了离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展。目前报道的离子液体主要包括咪唑盐、季铵盐、季鏻盐等。对比了传统离子液体与功能化离子液体对CO2环加成反应的催化活性、选择性以及催化作用机制。与传统的离子液体相比,功能化离子液体的羟基或羧基等官能团与卤素离子等Lewis碱之间存在协同效应,使得其对CO2与环氧化物的环加成反应具有更好的催化活性;将功能化离子液体固载于无机材料(SiO2,SBA-15,MCM-41等)或聚合物所得的多相催化剂不仅保持了官能团与阴离子之间的协同效应,而且载体与离子液体活性组分之间也显示出协同效应,使得该类催化剂具有很好的催化活性,稳定性好,可以多次重复使用,具有较好的工业化前景,是值得深入研发的一类催化材料。此外,离子液体对于手性环状碳酸酯的合成也具有较好的催化活性和立体选择性。     

Synthesis and antitumor and antibacterial evaluation of fluoroquinolone derivatives(Ⅲ):Mono- and bis-Schiff-bases

To further explore an efficient modified route for the shift from an antibacterial fluoroquinolone to an antitumor one,mono-Schiff bases 6a-6h related to ciprofloxacin C3 carbonylhydrazone and bis-Schiff bases 4a-4h corresponding to C3/C7 carbonylhydrazone/hydrazone attached on a skeleton of ciprofloquinolone were designed and synthesized,and their in vitro antitumor activity against CHO,HL60,L1210 cells and antibacterial activity against Staphylococcus aureus and Escherichia coli were also reported.     

An efficient and facile synthesis of novel substituted pyrimidine derivatives: 4-amino-5-carbonitrile-2-nitroaminopyrimidine

One-pot, multicomponent reaction for the synthesis of novel substituted pyrimidine derivatives: 4-amino-5-carbonitrile-2-nitroaminopyrimidine from aromatic aldehydes, 1-nitroguanidine, and malononitrile under ethanol is described. Because of containing many active functional groups, such as amino, cyan and nitro, these products are important intermediate of organic synthesis. The advantages of this procedure include the short reaction time, mild reaction conditions, and excellent yields.     

双甘氨肽分子印迹聚合物微球的吸附性能研究

以双甘氨肽(Gly-Gly)为印迹分子,丙烯酰胺(AM)、二甲基丙烯酸乙二醇酯(EDMA)分别作为功能单体和交联剂,在低温条件下采用乳液聚合于水相中制备了双甘氨肽分子印迹聚合物微球(Gly-Gly-MIPMs)。通过静态、动态平衡吸附和薄层色谱(TLC)分离实验,研究了Gly-Gly-MIPMs的选择吸附性能,并进行了Scatchard模型分析。结果表明,Gly-Gly-MIPMs对Gly-Gly分子具有较好的特异性吸附,最大单位饱和吸附量0.428mmol/g,印迹因子2.19。     

Ni-Cu/Al_2O_3催化剂上顺酐液相选择加氢制丁二酸酐反应性能

以Al2O3为载体,采用等体积浸渍法制备了一系列Ni-Cu/Al2O3催化剂,用于顺酐液相加氢反应,并结合低温N2物理吸-脱附、H2程序升温还原、H2程序升温脱附、X射线衍射、CO程序升温表面反应等表征结果,详细考察了催化剂中Cu含量对其催化性能的影响.结果表明,Cu的引入提高了活性组分Ni的分散度,促进了催化剂上C=C的加氢活性;同时,由于Ni-Cu双金属间的相互作用,明显抑制了催化剂表面C=O的加氢.当Cu含量为7%时,催化剂上顺酐加氢定向合成丁二酸酐的活性最高.在210oC,H2压力5.0MPa的条件下反应40min时,顺酐转化率与丁二酸酐选择性均达100%.     

C–H⋯F,C–H⋯O interactions in the crystal structure of 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane and 2-pentafluorophenyl-3-phenyl-1-(p-tosyl)-aziridine

Existence and nature of C–H?F, C–H?O interactions in 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane (1) and 2-pentafluorophenyl-3-phenyl-1-(p-tosyl)-aziridine (2) are discussed. In compound 1 with a linear molecule, C–H?F, C–H?O hydrogen bonds assemble adjacent molecules into the two-dimensional layers, F?F, O?F interactions connect adjacent layers into three-dimensional supramolecular networks. Owing to the inductive effect of nitro group, the C–H acidity of nitrophenyl increases and the numbers of C–H?F, C–H?O hydrogen bonds also increase, C–H?F, C–H?O interactions become stronger and more important. 1D ribbons of compound 2 are stabilized by C–H?F, C–H?O intermolecular interactions. Nonplanar tritopic molecule would demand the formation of a π?π packing interactions between benzene rings and pentafluorobenzene rings in 2.     

A new two‐dimensional cadmium coordination polymer with 1H‐imidazole‐4‐carboxylate and oxalate

The title compound, poly[aqua(μ₂‐1H‐imidazole‐4‐carboxylato‐κ³N³,O:O′)hemi(μ₂‐oxalato‐κ⁴O¹,O²:O^1′,O^2′)cadmium(II)], [Cd(C₄H₃N₂O₂)(C₂O₄)_0.5(H₂O)]_n, exhibits a two‐dimensional network. The Cd^II cation is coordinated to one N atom and two carboxylate O atoms from two 1H‐imidazole‐4‐carboxylate (Himc) ligands, two carboxylate O atoms from the bridging oxalate anion and one ligated water molecule; these six donor atoms form a distorted octahedral configuration. The oxalate anion lies on a centre of inversion. The Himc ligands connect the Cd^II cations to form –Cd–Himc–Cd–Himc–Cd– zigzag chains, with a Cd...Cd separation of 5.8206 (6) Å along the b direction, which are further linked by tetradentate oxalate anions to generate a two‐dimensional herringbone architecture in the ab plane. These layers are extended to form a three‐dimensional supramolecular framework via O—H...O and N—H...O hydrogen bonds and π–π stacking interactions. The solid‐state photoluminscent behaviour of the title compound has been investigated at room temperature.