2,2''''-联吡啶和亚铁氰化钾对乙醛酸化学镀铜的影响

以乙醛酸作还原剂、Na2EDTA为络合剂、2,2'-联吡啶和亚铁氰化钾作为添加剂组成化学镀铜体系,研究了两种添加剂对化学镀铜速率、镀层表面形貌、组成和结构的影响.结果表明:添加适量的2,2'-联吡啶和亚铁氰化钾,不仅提高了镀液的稳定性,而且使沉积速率增加1倍.这两种添加剂的同时使用,使镀层颜色变亮,形貌发生变化.所得镀层是多晶铜,没有发现夹杂Cu20.     

Actinide heterobimetallic oxides (Th, U): reduction studies

In our laboratories we have been studying the synthesis and reactivity of binary actinide and lanthanide intermetallic compounds. In this work, the air-oxidation of ThCu₂ and AnNi₂ (An = Th, U) was followed by thermogravimetry (TG) and the products were characterized by X-ray powder diffraction (XRD). The heterobimetallic oxides obtained are described by the formulas 2MO·ThO₂ (M = Cu, Ni) and 2NiO·UO₃. The thermogravimetric analysis under hydrogen of these heterobimetallic oxides show one mass loss for 2MO·ThO₂ and two mass losses for 2NiO·UO₃ over a wide range of temperature (293–1273 K). The characterization by XRD shows that the reduction products are 2M·ThO₂ (M = Cu, Ni) and 2Ni·UO₂, with all the actinides in the 4+ oxidation state. The actinide heterobimetallic oxides were described as copper or nickel supported catalysts.     

Copper(II)–Ammonia Complexation Equilibria in Aqueous Solutions at Temperatures from 30 to 250°C by Visible Spectroscopy

The spectra of copper(II)–ammonia solutions in 2 mol-kg^–1 NH₄NO₃(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH₃)_n ²⁺, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH₄NO₃(aq). The formation constants of Cu(NH₃)_n ²⁺ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg^–1 CF₃SO₃H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH₃)₄ ²⁺ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu²⁺ and the Cu(NH₃)_n ²⁺ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes.     

一维链状配位聚合物[M(H2bpb)(H2O)4](SO4)2·6H2O[M=Zn(Ⅱ)，Cu(Ⅱ)]的合成及晶体结构表征

设计并合成了一个含吡啶基团的柔性配体：N，N′-Bis(3-pyridylmethyl)-1，4-benzenedimethylamine(bpb)。通过bpb与硫酸锌及硫酸铜反应得到了两个新型具有一维链状结构的配位聚合物：[M(H₂bpb)(H₂O)₄](SO₄)₂·6H₂O[M=Zn(Ⅱ) 1，Cu(Ⅱ) 2]。X-射线晶体结构测定表明，这两个     

Amino-Modified Silicate Xerogels Complexed with Cu(II) as Catalyst Precursors. Coordination State and Thermal Decomposition

The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN _n ]·N _5–n ·5xSiO_4/2 (n < 4) and [Cu(N–N)_n]·(N–N)_2–n ·2x SiO_4/2(n 2), where N = NH₂(CH₂)₃ SiO_3/2, N–N = NH₂(CH₂)₂NH·(CH₂)₃SiO_3/2 and x = [SiO_4/2]/[N] or [SiO_4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO_4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O₂ + 98% Ar stream coupled with quadrupole mass spectroscopy.     

催化动力学荧光光度法测定痕量铜

在氨性介质中，铜对H2O2氧化次甲基蓝褪色反应有强烈催化作用。研究发现，次甲基蓝的氧化产物在紫外线照射下发出强荧光，据此建立一种测定痕量铜的催化动力学荧光光度法。本法检出限达0．02ng／mL，铜的质量浓度在0～6ng／mL范围内与相对荧光强度（△F）有良好线性关系。     

Complexes self‐associate by hydrogen bonding and metallophilic attraction: Theoretical study

Hydrogen bonding and metallophilic attractions are studied in the model systems: [(AuNH₃Cl)₂], [(AuNH(CH₃)₂Cl)₂], [{Au₂(μ‐SH)(PH₂O)(PH₂OH)}₂], [(CuNH₃Cl)₂], and [{Cu(NH₃)Cl}₄] at the Hartree–Fock (HF) and second‐order Møller–Plesset (MP2) levels. The two interactions are found to be comparable and prevailing in the final structure. It is determined that the aurophilic contact has a same magnitude that the hydrogen bonding, and is stronger than the cuprophilic interaction. The presence of hydrogen bond directs the growth of the crystal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Chiral ditopic receptors. Application to palladium-catalyzed allylic alkylation

Chiral pyridinooxazoline, quinolinooxazoline, bis(oxazolino)pyridine (pybox), and bisoxazoline (box) derivatives containing crown ether residues were prepared. Some of the ligands were assessed in substrate binding studies and in palladium catalyzed allylic alkylations.     

2-巯基苯并咪唑保护的铜纳米团簇的制备及银离子检测

以2-巯基苯并咪唑为保护剂,聚乙烯吡咯烷酮为稳定剂,水合肼为还原剂,“一锅法”合成2-巯基苯并咪唑保护的,高稳定性、强荧光、大斯托克斯位移的铜纳米团簇(Cu NCs),并用于检测水样中的银离子含量。采用透射电子显微镜(TEM)和X射线光电子能谱(XPS)对铜纳米团簇的结构进行表征,通过荧光光谱和紫外可见光谱对其光学性能进行研究。研究表明:该铜纳米团簇的最大激发和发射波长分别为340和558 nm,在日光灯和紫外灯下分别为无色和橙色。Cu NCs具有较高的分散性,尺寸大小为2~3 nm。在最佳反应条件下,铜纳米团簇可以选择性地被银离子猝灭,且灵敏度高,线性范围为1~40μmol/L,检测限为0.5μmol/L。该方法用于检测实际水样(自来水、湖水)中银离子的浓度,结果令人满意,表明在环境监测中有非常高的应用价值。     

Properties of a genetic algorithm extended by a random self-learning operator and asymmetric mutations: A convergence study for a task of powder-pattern indexing

Genetic algorithms represent a powerful global-optimisation tool applicable in solving tasks of high complexity in science, technology, medicine, communication, etc. The usual genetic-algorithm calculation scheme is extended here by introduction of a quadratic self-learning operator, which performs a partial local search for randomly selected representatives of the population. This operator is aimed as a minor deterministic contribution to the (stochastic) genetic search. The population representing the trial solutions is split into two equal subpopulations allowed to exhibit different mutation rates (so called asymmetric mutation). The convergence is studied in detail exploiting a crystallographic-test example of indexing of powder diffraction data of orthorhombic lithium copper oxide, varying such parameters as mutation rates and the learning rate. It is shown through the averaged (over the subpopulation) fitness behaviour, how the genetic diversity in the population depends on the mutation rate of the given subpopulation. Conditions and algorithm parameter values favourable for convergence in the framework of proposed approach are discussed using the results for the mentioned example. Further data are studied with a somewhat modified algorithm using periodically varying mutation rates and a problem-specific operator. The chance of finding the global optimum and the convergence speed are observed to be strongly influenced by the effective mutation level and on the self-learning level. The optimal values of these two parameters are about 6 and 5%, respectively. The periodic changes of mutation rate are found to improve the explorative abilities of the algorithm. The results of the study confirm that the applied methodology leads to improvement of the classical genetic algorithm and, therefore, it is expected to be helpful in constructing of algorithms permitting to solve similar tasks of higher complexity.