Dicobalt octacarbonyl-catalyzed tandem

Novel 5-5-6 tricyclic compounds containing cyclopentenone have been constructed by the dicobalt octacarbonyl catalyzed tandem [2 + 2 + 1] and [2 + 2 + 2] cycloaddition reaction between a diyne and two phenylacethylene under CO pressure.     

接枝改性碳酸钙及其在聚合物中的应用研究

介绍了近年来碳酸钙表面接枝改性的研究进展,讨论了自由基接枝聚合、辐照接枝聚合和力化学表面接枝聚合及偶联剂预处理与辐照并用接枝聚合改性方法。其中重点讨论了最新研究的偶联剂预处理与辐照并用接枝改性纳米碳酸钙的方法。用此方法制备的聚合物/纳米碳酸钙纳米复合材料在其他力学性能基本不变的情况下,大幅度提高了其缺口冲击强度和断裂伸长率。指出了碳酸钙表面接枝改性应向着提高接枝单体量和采用弹性体单体方面发展。     

SCF discrete-variational Xα calculations of the NH4Cl Auger spectrum

Formalism for calculations of the singlet and triplet Auger energies within the Xα model is presented. Using this method the KVV Auger spectrum of NH₄Cl is calculated and the theoretical intensities are determined within a one-center approximation. The calculated spectrum reproduces quite well all the main features observed for solid NH₄Cl. A new interpretation of the spectrum is suggested.     

Migration of radiocesium in a zeolite-solution system

Some properties of natural zeolite from Zaloka gorica, Slovenia, Yugoslavia were investigated to establish its applicability in solidification and for storage purposes of radioactive waste. It was found that this material is a rather good sorber for cesium, with a capacity of about 0.6 meq g^–1. The migration rate of Cs⁺ in a system ion exchanger-aqueous solution was investigated and correlated with the sorption behaviour of cesium in a system. The leaching rate of cesium from concrete containing zeolite was measured.     

The stability constant ratios of tri-N-octyl amine hydrochloride and bisulphate

The equilibria between the solution of TOA in toluene and mixtures of sulphuric and hydrochloric acid been studied. They were characterized by ratios of stability constants of amine salts formed in the organic phase.     

Thermal degradation behavior of poly(4-hydroxybutyric acid)

Thermal degradation behavior of poly(4-hydroxybutyric acid) (P(4HB)) was investigated by thermogravimetric and pyrolysis-gas chromatography mass spectrometric analyses under both isothermal and non-isothermal conditions. Based on the thermogravimetric analysis, it was found that two distinct processes occurred at temperatures below and above 350 °C during the non-isothermal degradation of P(4HB) samples depending on both the molecular weight and the heating rate. From ¹H NMR analysis of the residual P(4HB) molecules after isothermal degradations at different temperatures, it was confirmed that the ω-hydroxyl chain-end was remained unchanged in the residual P(4HB) molecules at temperatures below 300 °C, while the ω-chain-end of P(4HB) molecules was converted to 3-butenoyl units at temperatures above 300 °C. In contrast, the majority of the volatile products evolved during thermal degradation of P(4HB) was γ-butyrolactone regardless of the degradation temperature. From these results, it is concluded that during the thermal degradation of P(4HB), the selective formation of γ-butyrolactone via unzipping reaction from the ω-hydroxyl chain-end predominantly occurs at temperatures below 300 °C. At temperatures above 300 °C, both the cis-elimination reaction of 4HB unit and the formation of cyclic macromolecules of P(4HB) via intramolecular transesterification take place in addition to unzipping reaction from the ω-hydroxyl chain-end. Finally, the primary reaction of thermal degradation of P(4HB) at temperatures above 350 °C progresses by the cyclic rupture via intramolecular transesterification of P(4HB) molecules with a release of γ-butyrolactone as volatile product. Moreover, we carried out the thermal degradation tests for copolymer of 93 mol% of 4HB with 7 mol% of 3-hydroxybutyric acid (3HB) to examine the effect of 3HB units on thermal stability of P(4HB).     

Ratiometric chemosensing of Mg ions by a calix[4]arene diamide derivative

A new chemosensor with a phenanthroimidazole subunit based upon calix[4]arene-diamide has been synthesized, and its Mg²⁺-selective fluoroionophoric properties were investigated in an aqueous DMSO solution. The compound exhibited a pronounced Mg²⁺-selective fluoroionophoric behavior over other physiologically relevant metal ions. A significant red shift in fluorescence emission (Δλ = 86 nm) provided the ratiometric determination as well as naked-eye detection of Mg²⁺ ions.     

Synthesis and Structure of MnCl2(HDpyF) (HDpyF = N,N′‐di(2‐pyridyl)formamidine): New Crystallographic Disorder and Bonding Mode of the HDpyF Ligand

The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl₂‐4H₂O afforded the complex MnCl₂(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation.     

Substituent effects on heats of formation, group interactions, and detonation properties of polyazidocubanes

We have calculated the heats of formation (HOFs) for a series of polyazidocubanes by using the density functional theory (DFT), Hartree-Fock, and MP2 methods with 6-31G* basis set as well as semiempirical methods. The cubane skeleton was chosen for a reference compound, that is, the cubane skeleton was not broken in the process of designing isodesmic reactions. There exists group additivity for the HOF with respect to the azido group. The semiempirical AM1 method also produced reliable results for the HOFs of the title compounds, but the semiempirical MINDO3 did not. The relationship between HOFs and molecular structures was discussed. It was found that the HOF increases 330-360 kJ/mol for each additional number of the azido group being added to the cubane skeleton. The distance between azido groups slightly influences the values of HOFs. The interacting energies of neighbor azido groups in polyazidocubanes are in the range of 2.3 approximately 6.6 kJ/mol, which are so small and less related to the substituent numbers. The average interaction energy between nearest neighbor --N3 groups in the most stable conformer of octaazidocubane is 2.29 kJ/mol at the B3LYP/6-31G* level. The relative stability related to the number of azido groups of the title compounds was assessed based on the calculated HOFs, the energy gaps between the frontier orbitals, and the bond orders of the C--N3 and C--C bonds. The predicted detonation velocity of hepta- and octa-derivatives is over 9 km/s, and the detonation pressure of them is ca. 40 GPa or over.     

β微管蛋白中紫杉醇(Taxol)结合腔的性质分析

采用多拷贝同时搜寻法(MCSS), 并结合现有微管抑制剂的SAR及3D-QSAR对β微管蛋白中Taxol(紫杉醇)结合腔的性质进行了分析. 结构研究结果表明, Taxol结合腔以疏水性质为主, 并指出官能团分布的具体位置: 在Phe270上方(Leu361-Pro272-Leu273-Leu228之间)的弧形区域、Asp26羧基下方及其与Glu22羧基之间、M-loop的中部, 以及Asp224内侧且靠近Arg276的胍基的位置. 而Asp224的内侧又是新提出的结合位点. 研究结果符合现有微管抑制剂的SAR, 为现有抗肿瘤药物的结构改造以及小分子微管抑制剂设计提供了理论依据.