CRYSTAL AND MOLECULAR STRUCTURE OF A NOVEL Au Ag SUPRACLUSTER COMPOUND [Au_13Ag_12(μ-Br)_4(μ_3-Br)_2(Ph_3P)_10-

<正> [Au13Ag12(μ-Br)1(μ3-Br)2 (Ph3P)10Br2] Br, monoclinic. space group C2/m, a = 36. 496(17). b=16. 878(7), c-=19. 772(9) A , β=99. 87(5)°, V=11998. 9 A3.Z=2. The final R(Rw) is 0. 097(0. 109) for 3779 reflections with I>3σ(I). The structure can he considered as two icosahedral cluster units (AurAg6) sharing one vertex and linked hy six bromine atoms. The Au - Au, Au - Ag. and Ag-Ag distances fall in the ranges of 2. 69-2. 96. 2. 84-3. 02. and 2. 92-3. 26 A, respectively.     

钴（Ⅱ）与2,2’-联吡啶-1,1’-二氧化物的多核配合物的合成和性质

以无水CoCl2和2,2’-联吡啶-1,1’-二氧化物为原料,在DMF溶剂中合成了一种多核配合物.经元素分析、紫外光谱、红外光谱和摩尔电导等方法测得它的组成为[Co3(bipyO2)4Cl4]Cl2,并对该配合物的气敏特性进行了研究. 结果表明, 该配合物对氨气有良好的敏感性和选择性.由它制作的传感器可望用于涉氨化工生产中氨浓度的自动测量和控制.     

Bestimmung von Gleichgewichtskonstanten für Ligandenaustauschreaktionen von [TcNX4]− (X = Cl,Br) mit Hilfe der EPR

Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe₃(CO)₁₁^2? and Fe₄(CO)₁₃^2? were reacted with compounds EX₃ and with organic derivatives REX₂ and R₂EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)₄Fe? AsMe₂? Fe(CO)₄]^?, [HFe₃(CO)₉(mu;₃-SbBu^t)]^?, [Fe₃(CO)₁₀ (mu;₃-Sb)]^?, and [Fe₃(CO)₁₀(mu;₃-Bi)]^? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra.     

Elution of organic solutes from different polarity sorbents using subcritical water

The intermolecular interactions between organic solutes and sorbent matrices under subcritical water conditions have been investigated at a pressure of 50 bar and temperatures ranging from 50 to 250°C. Both polar and nonpolar organics (chlorophenols, amines, n-alkanes, and polycyclic aromatic hydrocarbons) and five different sorbent matrices (glass beads, alumina, Florisil, silica-bonded C₁₈, and polymeric XAD-4 resins) were used. From the same matrix, the polar solutes always eluted at lower temperatures, while the moderately polar and nonpolar solutes only eluted at higher temperatures. Similar to matrix effects previously observed using supercritical carbon dioxide, the sorbent type greatly influenced the elution efficiency under subcritical water conditions. Lower temperatures are sufficient to elute a particular solute from glass beads, alumina, and Florisil, but higher temperatures (less polar water) are needed to elute the same solute from silica-bonded C₁₈. The highest temperatures were required to elute aromatic organics from XAD-4. These matrix effects demonstrate that, while low temperature water can break inert or dipole interactions between solutes and glass beads, alumina, and Florisil, higher temperature water is required to interrupt the van der Waals attractions between solutes and silica-bonded C₁₈, and even higher temperatures needed to overcome the π-electron interactions between aromatic solutes and XAD-4.     

Fluorescence study of the solubilization of benzo[a]pyrene: application to its detection in coal washing waters

The solubilization of benzo[a]pyrene by organic solvents (dioxane, toluene and dichloromethane) and a surfactant (Triton X-100) was investigated. These media were successfully used for the determination of benzo[a]pyrene using fluorescence detection, with excellent limits of detection and large linear analytical ranges. Benzo[a]pyrene was detected in coal washing waters using liquid chromatography with fluorescence detection. The stability of this compound in dioxane was also examined.     

Comparison of gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry for the determination of fatty and resin acids in paper mill process waters

A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking.     

Electron capture detector response to low electron affinity aromatic hydrocarbons using positive ion stabilization and alkyl chloride sensitization

The electron capture detector (ECD) response to numerous aromatic hydrocarbons of low electron affinity (EA) is shown to be detrimentally affected by two processes which compete with and typically overwhelm the electron capture reactions of these molecules. It is shown that the effects of these two undesired reactions can be eliminated by the permanent addition of trimethylamine and one of several alkyl monochlorides to the detector make-up gas. These modifications of the detector gas result in greatly increased sensitivity, increased linearity, and increased reproducibility of response. A kinetic model for the ECD responses of low EA resonance capture molecules is developed which appears to explain these improvements.     

Application of particles as pseudo-stationary phases in electrokinetic chromatography

Since the introduction of micelles by Terabe et al. (1984), many different species have been employed as carriers for electrokinetic chromatography. As it is not possible to separate uncharged solutes or ions with equal mobility in capillary electrophoresis, these phases are added to introduce or improve selectivity.

This review surveys the application of particles as pseudo-stationary phases. Up to now only very few applications exist based either on polymer particles for the separation of catechols and primary amines or silica-based material. With these particles separations are shown for phenols, polycyclic aromatic hydrocarbons and naphthalene derivatives. The characteristic properties of particles as pseudo-stationary phases and their benefits as well as their limitations are discussed.     

Coupling of thermal desorption in modified closeable sampling columns with wide-bore capillary gas chromatography and mass spectrometric detection

In contrast to usability of Curie-point pyrolysis at 700°C directly attached to gas chromatography-mass spectrometry (GC-MS) for determination of organic wood preservatives in waste wood samples the investigation method reported here consists of thermal desorption at temperatures about 260°C in connection with GC-MS for peak identification or GC with flame ionization detection for quantitative analyses. So-called “modified closeable sampling columns” are used as batch-reactor in thermal desorption experiments. Desorbed vapours can be introduced on capillary columns without sample discrimination and without a disturbing lost of resolution. In this manner a lot of individual polycyclic aromatic hydrocarbons were determinated in waste wood samples, especially in railway sleepers.     

钪—铋—三溴偶氮胂混合多核络合物显色反应及其在钪光度分析中应用研究

本文研究了钪-铋-三溴偶氮胂络合物的共显色反应。实验表明,共显色反应是由于形成混合多核络合物所致。钪络合物最大吸收峰在635nm,表观摩尔吸光系数为7.1×10~4L·mol~(-1)·cm~(-1)。钪在0～5μg/25ml遵守比尔定律。