衬钽管石墨炉中小量氢气的影响及稀土基质激光晶体中铕的测定

通过纯氩中加入小量氢气,研究了保护气体对衬鉏管石墨炉分析性能的影响,结果表明,采用5％H_2-Ar作保护气体,可以显著提离衬鉏管的成品率,明显延长衬鉏管的使用寿命,使衬钽管的测定重现性得到改善,而对测定灵敏度没有明显影响。干扰试验表明,本方法可直接用于稀土基质激光晶体中铕的测定,分析结果与计算值基本一致。     

Rh complexes of 1-(2,4,6-triisopropylphenyl-)3-methyl-1H-phosphole: preparation and use as catalysts in the hydroformylation of styrene

In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations. Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)₂ + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%.     

轻稀土B-15-C-5联吡啶三元配合物

合成了稀土(Ln=La—Eu)硝酸盐与苯并-15-冠-5和2,2’-联吡啶的三元配合物,并培养出La-配合物的单晶,测定了的分子结构和晶体结构。经元素分析确定其化学组成为Ln(NO_3)_3·bipy·2H_2O·B-15-C-5。晶体属单斜晶系,空间群为P2_1/n。晶胞参数:a=11.951(6),b=18.181(7),c=14.754(5);β=96.19(3)°;V=3187.0,Z=4,D_c=1.637g/cm~3。最后偏离因子R=0.035。     

Achieving ‘Desirable and Feasible’ Change: An Application of Soft Systems Methodology

Rational intervention in human affairs, if it is to constitute not only action but also research, so that future interventions may be made more effective, needs a well-defined methodological framework. Soft systems methodology (S.S.M.) provides one such framework. S.S.M. is doubly systemic: it is itself a learning system, and within that system it uses systems models, models of human activity systems. It accepts that such models are not models of parts of the real world, only models of ways of perceiving the real world, that is to say, models relevant to debate about ‘reality’ (one man's ‘terrorism’ is another's ‘freedom fighting’).S.S.M. is here illustrated by means of an account of a systems study of change in the information function of a sophisticated science-based company. The study is described from the point of view of a professional analyst who was helping a team of three managers carry out the study. The course of the study is described, and a separate commentary relates its activity to the seven stages of S.S.M. The study involved three cycles round stages 2–3–4–5 of S.S.M., the stages in which models of relevant human activity systems are built and compared with the real world in order to construct a rich debate about changes whose introduction in the problem situation world be both (systemically) desirable and (culturally) feasible.     

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.     

The anion sequence in the phase transformation of mesostructures templated by non-ionic block copolymers

A p6m to Ia3d mesophase evolution is achieved by simply adjusting the acidity and/or anion species in the presence of block copolymers; the unusual anion sequence that affects the phase behavior of block copolymer templated mesostructured solids is revealed to be SO(4)(2-)(HSO(4)(-)) > NO(3)(-) > Br(-) > Cl(-).     

苯基重氮盐-冠醚分子嵌合物的FAB-MS及其准分子离子生成机理的研究

Fast atom bombardment mass spectra of a series of arenediazonium salts with various substituents complexed with 18-crown-6 and dibenzo-24-crown-8 ethers were examined. The correlation between quasi-molecular ion abundance of various complexes and the properties, coordination ability of donor-acceptor linkages in the complexes were studied. By using molecular orbital calculation we have successfully demonstrated that the correlation cited is related to the electron cloud densities on the heteroatoms α-N and β-N of arenediazonium salts.     

Determination of iron(II) with chemically-modified carbon-paste electrodes

The utility of carbon-paste electrodes modified with 2,2'-bipyridyl and Nafion for the differential pulse voltammetric determination of iron(II) in aqueous medium is demonstrated. The method is based on formation of the 2,2'-bipyridyl complex of iron(II) and its accumulation by the Nafion. The differential pulse voltammetric response of the accumulated complex is used as the analytical signal. The response was evaluated with respect to carbon-paste composition, preconcentration time, pH, iron(II) concentration and other variables. A 3-min accumulation period permits measurement of iron(II) down to 10(-8)M, and a relative standard deviation of 3.8% for 2 x 10(-6)M iron(II). Rapid and convenient chemical renewal allows use of a single modified carbon-paste electrode in multiple analytical measurements over several days. The proposed procedure was applied to the determination of iron in certified standard reference materials and trace iron in natural waters.     

Influence of shell strength on shape transformation of micron-sized,monodisperse, hollow polymer particles

Micron-sized, monodisperse, non-spherical polymer particles with "rugby ball" and "red blood corpuscle"-like shapes were produced by seeded polymerization of the dispersion of (divinylbenzene/vinylbiphenyl/xylene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method which the authors proposed in 1991. Their non-spherical shapes were based on buckling of the shell of the resultant hollow particles. In this article, the reversible shape transformation of the hollow composite polymer particle between spherical and such non-spherical shapes was studied in detail by controlling the shell strength. A part of the shell was buckled by external pressure which was caused by evaporation of xylene from the hollow when the shell had the tensile modulus below the critical value calculated from the pressure-buckling relationship of a spherical shell proposed by Uemura. The plasticization of the shell by a good solvent was one of key factors for the shape transformation.