顺式-二(乙二胺)二硝基合钴(Ⅲ)苹果酸盐的晶体结构及手性识别

合成了标题化合物，并用X-射线衍射法确定了该分子的晶体结构。化合物Δ（λλ），Λ（δδ）－cis－[Co（en）2（NO2）2]2d，l-C4H4O5，Co2C12N12O13H22，Mr=657．94．晶体属单斜晶系，空间群为P21/c，晶胞参数：a=13．969（4），b=6.440（1），c＝14．408（4）A，β=94.37（1）°，V=1292．3A3，Z=2，Dc=1．69g／cm3，μ=105.833cm－1，F（000）=668.最终偏离因子R=0.066，Rw=0．085。结构分析表明晶体存在无序现象，其阴离子C4H4O52-有两种排列方式。R-构型和S-构型的几率各为50％，手性识别是通过Δ构型的阳离子与阴离子R-构型C原子上羟基氧形成氢键相互作用；Λ构型的阳离子与阴离子S-构型C原子上羟基氧形成氢键相互作用而实现的。     

Construction of multiporphyrin arrays using ruthenium and rhodium coordination to phosphines

The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays.     

脑神经退行性疾病中的有机化学-朊病毒(疯牛病)中的蛋白物理有机化学和自由基化学

通过关于“普里昂”蛋白病毒疾病的已有临床、医学生理、免疫和化学等方面的现象，讨论了朊病毒当中的部分蛋白氧化损伤和蛋白自由基化学本质。     

乙醇-盐-水-5-Br-PADAP体系萃取分离测定钯

研究了在硫酸铵存在下 ,5 Br PADAP乙醇体系中Pd(Ⅱ )、Rh(Ⅲ )、Pt(Ⅳ )的萃取行为及乙醇溶液的分相条件 ,讨论了影响萃取率的各种因素 ,试验表明 ,室温下 ,一定 pH范围内 ,该体系中的Pd(Ⅱ )几乎可完全被乙醇相萃取 ,而Rh(Ⅲ )、Pt(Ⅳ )不被萃取或萃取率很低 ,从而可实现Pd(Ⅱ )、Rh(Ⅲ )、Pt(Ⅳ )混合离子的定量分离 ,同时建立了Pd(Ⅱ )的测定方法。乙醇相中Pd(Ⅱ ) 5 Br PADAP配合物表观摩尔吸光系数为 1.18× 10 5L·mol- 1·cm- 1,钯量在 0～ 9.6 0 μg/10ml范围内符合比耳定律 ,检出限为 0 .0 90 μg/10ml。用该法分离混合样和测定两种活性碳钯催化剂中钯 ,结果满意     

Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product

Ultraviolet photolysis of low concentrations of CH2I2 in methanol solution found that CH2I2 is converted into dimethoxymethane and some H+ and I- products. Picosecond time-resolved resonance Raman (ps-TR3) experiments observed that the isodiiodomethane (CH2I-I) photoproduct decayed faster as the concentration of methanol increases, suggesting that isodiiodomethane is reacting with methanol. Ab initio calculations indicate isodiiodomethane is able to react with methanol via an O-H insertion/HI elimination to form an iodoether (ICH2-O-CH3) and HI products. The iodoether can then further react via another O-H insertion/HI elimination reaction to form the dimethoxymethane (CH3-O-CH2-O-CH3) observed in the photochemistry experiments. A reaction mechanism consistent with these experimental and theoretical observations is proposed.     

Comparison of the dehalogenation of dihalomethanes (CH2XI, where X = Cl, Br, I) following ultraviolet photolysis in aqueous and NaCl saltwater environments

The ultraviolet photolysis of low concentrations of CH(2)XI (X = Cl, Br, I) were investigated in water and saltwater solutions by photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both kinds of solutions formed mostly CH(2)(OH)(2) and HI and HX products. However, photolysis of the CH(2)XI molecules in saltwater resulted in production of some CH(2)XCl products not observed in aqueous solutions without salt present. The appearance of these new products in saltwater solutions is accompanied by a decrease in the amount of CH(2)(OH)(2), HI, and HX products compared to photolysis in aqueous solutions without salt present. The possible implications for photolysis of CH(2)XI and other polyhalomethanes in seawater and other salt aqueous environments compared to nonsaltwater solvated environments is briefly discussed.     

Facile synthesis of 9-（N-amino-4-fluoromethyl-3-pyrrolidinyl）-2- fluoro-6-aminopurine from trans-4-hydroxy-L-proline

A novel and simple procedure for synthesis of azanucleoside by Mitsunobu reaction between N-(p-nitrobenzyloxycarbonyl)- trans-4-hydroxy-D-proline methyl ester obtained from trans-4-hydroxy-L-proline after six-step reaction and 2-fluoro-6-azidopurine is described,and azanucleoside is fluorinated by new fluridizer 2,2-difluoro-1,3-dimethylimidazolidine (DFI).All reactions could be carded out under mild condition.     

C9‐Iridoids from Scrophularia buergeriana

Four new iridoids, buergerinins B–E ( 1 – 4 ), along with three known iridoids, were isolated from the roots of Scrophularia buergeriana. Their structures were identified on the basis of spectroscopic analysis.     

Recent Advances in Rare‐Earth Polypnictides

The polypnictide complexes of rare earth cations have drawn the attention of the scientific community for their uncommon bonding modes and potential applications. Herein, we present a systematic and comprehensive summary on recent advances in the field of rare earth polypnictides, focusing on their synthesis, structures, and reactivities. The structural stabilizing effects imposed by the electropositive rare earth cations as well as the reducing capability of rare earth precursors in the synthesis of these polypnictide complexes are described in this review. We also disscuss in detail the bonding interactions and coordination modes between rare earth cations and polypnictide clusters as well as the similarities and the peculiarity of some structures.