氮杂冠醚研究Ⅶ、双仲胺型氮杂冠醚对过渡金属离子的选择性萃取作用

合成了五种新型双仲胺型氦杂冠醚，研究了它们对过渡金属离子进行液—液萃取，并用原子吸收法测定其浓度。实验结果表明：这类冠醚对Ａｇ￣＋、Ｐｄ￣（２＋）、和Ｐｔ￣（４＋）等贵金属离子有较强的选择配位性能，对选择性分离这些金属离子有重要的意义。     

Redox Polymerization of Methyl Methacrylate in the Fluorous Triphasic System

Fluorous-phase chemistry is currently a topic of considerable interest1-6. Since fluoroustriphasic reactions were first described by the Curran and co-workers7, this triphasicsystem has been widely used for detagging7,8 and phase-vanishing reactions9-11. …     

Syntheses and Crystal Structures of 4,4‘—Diformyl—diphenoxyethane and 4,4’,4‘’—Triformyl—triphenoxytriethylamine

Two title compounds, 4,4'-diformyl-diphenoxyethane (compound 1, C16H14O4)and 4,4',4'-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris2-chloroethylamine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ', = 105.823(6)o, V = 675.7(2)'3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, (MoK = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ', = 99.505(1)°, V = 2383.5(3) '3, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, (MoK = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 dialdehyde is located at the crystallographic inversion center nearby the midpoint of C8-C8A single bond. The three chains in the molecule of compound 2 trialdehyde are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.     

Novel Gel—like Process for Synthesizing Submicron LiaNi0.8Co0.2O2 Powders Used in Lithium Ion Batteries

A novel gel-like process has been developed for synthesizing LiaNi0.8Co0.2O2 powders,using citric acid as a chelating agent. This process improves the homogeneity of constituent cation and enhances their reactivity in the obtained precursor. The results of electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. Its initial capacity reached 181.6 mAh/g and reversible efficiency at the first cycle is about 88.6%.     

A new two‐dimensional CdII coordination polymer constructed by pyrazine‐2,3‐dicarboxyl­ate

In the title compound, poly[μ₅‐pyrazine‐2,3‐dicarboxyl­ato‐cadmium(II)], [Cd(C₆H₂N₂O₄)]_n or [Cd(pdc)]_n, where pdc is the pyrazine‐2,3‐dicarboxyl­ate anion, the Cd^II atom is six‐coordinated by five carboxyl­ate O atoms and one N atom from five different pdc ligands in a distorted octa­hedral CdO₅N coordination geometry. Two Cd^II atoms are bridged by carboxyl­ate groups of the pdc ligands to create a dimeric unit. The dimeric units are further connected by the pdc ligands to generate an inter­esting two‐dimensional structure.     

Determination of Utratrace Silver Using Surfactant As Sensitizer by Catalytic Near Field Laser Thermal Lens Spectrometry

Thermal lens spectrometry (TLS) is an excellent tool for trace analysis1. TLS allows the detection of absorbances of 10-7～10-8, concentration of ≈ 10-11 mol稬-1 and the analysis of 10-15 L volumes with ≈10-2 absorbing molecules2. Kinetic analysis is playing an increasingly important part in modern analytical chemistry. Therefore, TLS shows much promise in combination with kinetic analysis. However, there are few data on TLS applications in kinetic analysis method so far3～4. A ne…     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.     

Influence of the water molecule on cation-pi interaction: ab initio second order Møller-Plesset perturbation theory (MP2) calculations

The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions.     

Large-scale synthesis and microstructure of SnO2 nanowires coated with quantum-sized ZnO nanocrystals on a mesh substrate

Large-quantity single-crystal SnO(2) nanowires coated with quantum-sized ZnO nanocrystals (nc-ZnO/SnO(2) nanowires) were directly synthesized by thermal evaporation of SnO powder and a mixture of basic ZnCO(3) and graphite powders. A common stainless steel mesh was used to collect the products. The microstructure and possible growth mechanism of the nc-ZnO/SnO(2) nanowires were investigated. Results showed that tetragonal structured SnO(2) nanowires were obtained, whose surfaces were coated with single-layer ZnO nanocrystals with an average diameter of less than 5 nm. The nanowires had cross-rectangle section with width-to-thickness aspect ratio ranging from 2:1 to 5:1. The lengths of the nanowires were several tens of micrometers. ZnO nanocrystals were single crystalline wurtzite structures, which coated the whole nanowires and distributed uniformly. The possible growth mechanism of the composite nanowires may be enucleated that Zn atoms in the source vapor will replace the Sn atoms on the surface of the formed SnO(2) nanowires due to the higher reducibility of Zn than Sn. Two strong Raman scattering peaks at 626 and 656 cm(-1) appeared in the micro-Raman spectrum of nc-ZnO/SnO(2) nanowires. The origins of the peaks were discussed. Most importantly, the method can be extended to other composite oxide nanowires that are synthesized by oxidizing two kinds of metals, such as high reducibility elements Mg, Al, Zn, and Ti, and low reducibility elements In, Ge, Ga, etc.     

116例冠心病患者血清中钙镁镉铅铍含量的探讨

测定了１１６例冠心病患者血清中钙、镁、镉、铅、铍的含量并与正常对照组比较。结果显示，常量元素钙、镁与微量元素镉、铅含量降低，而铍的含量升高。它们之间的差异有显著性或高度显著性，Ｐ〈０．０５或Ｐ〈０．０１。