纳米Y2O3/钴基合金激光熔覆层的组织

利用5 kW CO2激光器,在Ni基高温合金表面,熔覆纳米稀土氧化物(Y2O3)/钴基合金复合材料,制备了涂层.利用光学显微镜、扫描电镜及透射电镜分析了熔覆层的组织结构.结果表明: 熔覆层的主要相组成为γ-Co,ε-Co,Cr23C6和Y2O3;加入纳米Y2O3,凝固组织由细长的柱状树枝晶转变为较短的树枝晶;纳米Y2O3含量增大至1%时整个断面获得等轴晶组织;纳米Y2O3作为异质形核的核心,细化了组织;纳米Y2O3在熔覆层中分布不均匀,促进了γ-Co向ε-Co的转变;熔覆层的亚结构为堆跺层错.对熔覆层等轴组织形成机制进行了分析.     

Three-dimensional configurations of organic/inorganic hybrid nanostructural blocks (I). A quantum mechanical investigation for ladder-like structure of vinylsilsesquioxane

Silsesquioxanes (SSO) or polyhedral oligomericsilsesquioxanes (POSS) are generally prepared frommolecular precursors using the hydrolytic condensa-tion of trialkoxysilane, RSi(OR')3. They are organic/inorganic hybrid nanostructural blocks with theircomplete general formula Tn(T = RSiO1.5, n = 1,2, …), and the incomplete generic formula is Tn-(OH)x(OR')y[x, y = 0, 1, 2, …, T= RSiO1.5 ?(x+y)/2n][1,2].Each VSSO, possessing a certain structural formulaand molecular weight, may h…     

希土季铵盐配合物的研究——Ⅴ.[(n-C4H9)4N]3Nd(NCS)6的晶体结构研究

合成了硫氰酸合希土酸四丁基季铵盐配合物,测定了它们的远红外光谱及部分配合物的中红外光谱,结果表明,配合物中的NCS^-是以氮原子与Ln³⁺配位。用X射线单晶衍射法测定了[(n-C₄H₉)₄N]₃Nd(NCS)₆晶体的结构,结果表明,该晶体属单斜晶系,C_c空间群,晶胞参数为:a=25.188(8)Å,b=13.320(6)Å,c=25.322(8)Å,β=121.30(2)°,晶胞体积V=7258.9ų,每一晶胞中有四个配合物分子,中心离子Nd³⁺与六个来自NCS^-的氮原子配位,这六个氮位于配位正八面体的六个顶角上,构成配阴离子Nd(NCS)₆^3-,它与三个[(n-C₄H₉)₄N]⁺以静电引力结合成中心分子,所以晶体为离子型晶体。     

The molecular structure of chlorothiomethoxymethyl-bis(triphenylphosphine)palladium(II) methylenechloride solvate at −160°C

The precise molecular structure of [PdCl(CH₂SCH₃)(PPh₃)₂] has been determined from three-dimensional X-ray diffraction data collected at ?160°C. The CH₂Cl₂ solvated crystal ([PdCl(CH₂SCH₃)(PPh₃)₂ · CH₂Cl₂]) belongs to the monoclinic system, space group P2₁/n, with four formula units in a cell of dimensions: a 14.973(3), b 15.333(3), c 17.377(3) Å and β 115.77(1)° at ?160°C. The structure was solved by the conventional heavy atom method and refined by the least-squares procedure to R = 0.035 for observed reflections. The geometry around the palladium atom is square-planar. The phosphorus atoms of the two triphenylphosphine ligands are mutually trans. The CH₂SCH₃ group is bonded to the palladium atom only through the PdC σ-bond and the sulfur atom is not bonded to the metal atom (PdC(1) 2.061(3), SC(1) 1.796(3), SC(2) 1.817(5), Pd?S 2.973(1) Å, PdC(1)S 100.64(14)° and C(1)SC(2) 101.28(18)°). The structure is in contrast to that of [PdCl(CH₂SCH₃)(PPh₃)], in which both the carbon and sulfur atoms of the CH₂SCH₃ group are bonded to the palladium atom.     

Molecular weight distribution studies. I. Radiation-induced polymerization of liquid α-methylstyrene

The concentration of water in purified and BaO-dried α-methylstyrene was found to be 1.1 × 10^?4M. The radiation-induced bulk polymerization of the α-methylstyrene thus prepared was studied in the temperature range of ?20°C to 35°C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polymerization of α-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer k_f changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. k_f and k_p at 20°C were found to be 0.95 × 10⁴ l./mole-sec and 0.99 × 10⁶ l./mole-sec, respectively.     

On-line post-column fluorescence detection for N-terminal tyrosine-containing peptides in high-performance liquid chromatography

A detection system based on on-line post-column fluorescence derivatization is described for the determination of N-terminal tyrosine-containing peptides by reversed-phase high-performance liquid chromatography. The peptides are automatically converted into fluorescent derivatives by reaction with hydroxylamine, cobalt (II) and borate after peptide separation on a reversed-phase column (TSKgel ODS-120T) followed by passage through an ultraviolet absorbance detector. The reaction system permits the fluorescence detection at 435 nm (emission) with excitation at 335 nm for N-terminal tyrosine-containing synthetic peptides in as little as picomole amounts. The facile fluorescence detection of N-terminal tyrosine-containing fragments produced from methionine-enkephalin by enzymatic degradation using a rat brain homogenate was achieved by comparison with the ultraviolet absorption detection at 215 nm.     

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO<Subscript>2</Subscript> photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry

An online UV photolysis and UV/TiO₂ photocatalysis reduction device (UV–UV/TiO₂ PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 L dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV–UV/TiO₂ PCRD–KBH₄–acid interface. The detection limits obtained for seleno-DL-cystine (SeCys), selenite (Se^IV), seleno-DL-methionine (SeMet), and selenate (Se^VI) were 2.1, 2.9, 4.3, and 3.5 ng mL^–1, respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV–UV/TiO₂ PCRD–ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH₄.     

Trace lead measurement and on-line removal of matrix interference in seawater by isotope dilution coupled with flow injection and ICP-MS

Isotope dilution analysis method coupled with flow injection and inductively coupled plasma mass spectrometry (ID-FI-ICP-MS), enabled trace lead concentration in seawater to be determined and the high salt concentration in the matrix, such as Na⁺, Ca²⁺ and Mg²⁺, to be removed on-line. The operational parameters of the FI system including pH for the chelating reaction, concentration of 8-hydroxyquinoline-5-sulfonic acid (8-HQS), sample loading time and injection speed, washing time and speed, eluting acid concentration and eluting speed, and instrumental parameters for ICP-MS were optimized and selected. Accurate results could be achieved because the isotope ratios required can be precisely measured in the range of the eluting peak by means of ID-FI-ICP-MS. The 3σ detection limit was 0.204 ng ml⁻¹. The trace lead concentration of seawater in south Xiamen, China was 0.988 ± 0.039 ng ml⁻¹. The recoveries of spiked Pb standard in seawater and standard reference water (GBW 08607) were 97.9 and 101.0%, respectively, with a relative standard deviation of 0.98%. This method can be used to determine trace lead concentration in high salt matrix samples, and is especially useful when the eluting peaks do not have a Gaussian-distribution.     

掺硼多晶金刚石膜的电化学性能研究

采用EACVD(Electron Assisted Chemical Vapor Deposition)方法制备了掺硼金刚石膜, 并用扫描电镜、拉曼光谱及霍尔效应等测试方法对其表面形貌、生长特性、载流子浓度以及导电性能进行了分析. 测试结果表明, 掺硼金刚石膜是由微米级晶粒组成的多晶膜, 其载流子浓度为4.88×1020 cm-3, 电阻率为0.03 Ω·cm, 是高品质金刚石膜. 用该金刚石膜制作电化学电极, 利用循环伏安法分别测量了金刚石膜电极在氯化钾空白底液、亚铁氰化钾溶液和左旋半胱氨酸溶液中的循环伏安曲线, 发现该金刚石膜电极在水溶液中具有宽的电化学窗口(约为3.7 V)和接近零的背景电流, 在生物制剂的检测中具有很高的灵敏度和良好的稳定性, 是一种理想的电化学电极材料.     

TixNy团簇结构的密度泛函研究

采用杂化密度泛函方法(B3LYP)和有效核势基组预测了Ti_xN_y (x≤3, y≤2)团簇的结构及稳定性, 并分析了可能存在构型的电子结构. 结果表明Ti₂N中体系的自旋多重度由Ti原子决定. Ti₃N中随着N的配位数增加, N的负电荷增加, 平均每个Ti向N提供约0.3个电子. 从Ti₂N₂可能稳定构型分析, 成键数目越多, 能量上越有利, 且Ti—N键的数目的增加, 将削弱N—N间的成键.