双（1,2—丙二胺）合铜的TCNQ盐的合成与光谱研究

合成了导电性ＴＣＮＱ盐Ｃｕ（ｐｎ）２（ＴＣＮＱ）ｎ（ｎ＝２和３，ｐｎ＝１，２－丙二胺，ＴＣＮＱ＝７，７，８，８－四氰基对苯二醌二甲烷）。红外光谱、电子光谱和Ｘ－光电子能谱研究表明ＴＣＮＱ盐中存在ＴＣＮＱ°和ＴＣＮＱ－，ＴＣＮＱ°与ＴＣＮＱ－之间发生了部分电子转移，致使铜呈混合价态。它们的粉末室温电导率为１．１×１０－５～２．４×１０－６ｏｈｍ－１ｃｍ－１。     

Carbonyl and hydridocarbonyl complexes of ruthenium (II) and osmium (II) with tertiary arsines

Ruthenium halides (Cl and Br) react with monotertiary arsines-Ph₂RAs (R=Me, Et, Pr ⁿ ) in methoxyethanol, in the presence of aq. formaldehyde to give monocarbonyl complexes of ruthenium(II) of the type RuX₂(CO) (Ph₂RAs)₃. Carbonylation of an ethanolic solution containing ruthenium trichloride and the arsine at room temperature yieldtrans dicarbonyl compounds of the formula RuCl₂(CO)₂ (Ph₂RAs)₂. The osmium monocarbonyls OsX₂(CO) (Ph₂RAs)₃ (X=Cl, Br; R=Me, Et) react with NaBH₄ in methanol to yield complexes of the composition OsHX(CO) (Ph₂RAs)₃. The ruthenium analogues RuHCl(CO) (Ph₂RAs)₃ have also been made. Structures have been assigned to all these compounds on the basis of IR and NMR spectral results.     

Tetramethyldisilan-1,2-diyl-verbrückte Dicyclopentadienyl-und Diindenylmetalldichloride der 4. Gruppe – Kristallstruktur von

Tetramethyldisilane-1,2-diyl bridged Dicyclopentadienyl and Diindenyl Metal Dichlorides of the Group 4 Metals – Crystal Structure of Dicyclopentadienyl and diindenyl metal dichlorides of the type Cp′? SiMe₂SiMe₂? Cp′MCl₂ (Cp′ = C₅H₄, M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ); Cp′ = C₉H₇, M = Zr ( 4 ), Hf ( 5 )) were synthesized and characterized by means of their ¹H, ¹³C, ²⁹Si-n.m.r., MS, and IR spectra. The crystal structure of 2 was determined.     

纳米氧化铝负载双硫腙分离富集-原子吸收法测定地质样品中的金、铂、钯的研究

金、铂、钯在地质样品中的含量甚微,国内外常采用ICP-AES,ICP-MS和ETAAS直接测定。FAAS法由于仪器便宜、操作方便,也广泛应用于预富集后的痕量贵金属的分析。目前,在测定贵金属的分析方法中,常采用固相萃取法富集分离样品,主要的固相萃取剂有:无机吸附剂,交联树脂[1],螯合树脂[     

pH值对聚四氨基酞菁钴膜电化学和紫外光谱性质的影响

用循环伏安法在导电玻璃(ITO)和玻碳电极(GC)上制备了聚氨基酞菁钴(CoTAPc)修饰电极(CoTAPc/GC)。探讨了pH值对CoTAPc膜的光谱和电化学性质的影响，发现其氧化还原电位与pH值有线性关系，电催化活性也随酸度的增加而增加。CoTAPc膜的紫外吸收带变化与溶液pH值及在溶液中浸泡时间有关。     

Direct and simultaneous voltammetric analysis of heavy metals in tap water samples at Assiut city: an approach to improve the analysis time for nickel and cobalt determination at mercury film electrode

Tap water samples (Assiut city, lie in the middle north of upper Egypt, approx. 370 km from Cairo, January-March, 2002) were taken from the eight sampling sites of different locations at Assiut city. The samples are analyzed to determine the total content of cadmium, copper, lead and zinc by differential pulse anodic stripping voltammetry (DPASV) while nickel and cobalt are determined by a new simple differential pulse adsorptive stripping voltammetry (DPAdSV), using dimethylglyoxime (DMG) as the complexing agent. This method uses sodium sulfite as the supporting electrolyte, which facilitates the removal of oxygen interference without the traditional necessity of purging with inert gas. The effect of various parameters was studied using DPASV (for Cd, Pb, Cu and Zn) and AdSV (for Ni and Co) methods. Subsequently, under the so found experimental conditions, the stability of calibration curves and the detection limits (μg/l) have been determined. The data achieved (for all metals utility) are comparable to those measured by the graphite furnace atomic absorption spectrophotometric (GF-AAS) method. The effects of the interferences between these metal ions have been investigated. Moreover, the effect of storage was discussed and the obtained results were compared favorably with standard official methods. Statistical analysis of the database exhibits applicability and the accuracy of the techniques. The results obtained from the two techniques (Voltammetry and GF-AAS) are in very good agreements in the most tap water samples.     

Tetrakis(thiadiazolo)porphyrazines. 3. Acid-base Properties and Stability of Tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine in Sulfuric Acid Solutions

AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H₂{[SN₂)₄PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF₃CO₂H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF₃CO₂H-H₂SO₄. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–287, February, 2005.     

Determination of dipole moment in the ground and excited state by experimental and theoretical methods of N-nonyl acridine orange

The absorption and fluorescence spectra of N-nonyl acridine orange are determined at room temperature (298 K) in cyclohexane, benzene, carbon tetrachloride, chloroform, chlorobenzene and dichloromethane. The ground state of dipole moment was obtained by impedance measurements using Guggenheim-Debeye's method. The experimental excited state dipole moment of N-nonyl acridine orange was determined using Bakhshiev's and Kawski-Chamma-Viallet's formulae and solvent polarity parameter proposed by Reichardt. These experimental results were completed with theoretical results using quantum chemical methods. The experimental (muexp=10.76 D) and theoretical (mucal=9.9 D) dipole moments in the ground and excited state (muexp*=14.56 D) were compared.     

Group 6 tetracarbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene: Spectral characterization,electrochemistry, solvatochromism and photophysical studies

A new series of group 6 carbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene (α/β-NaiPy) are described in this work. The complexes are formulated as cis-[M(CO)₄(α/β-NaiPy)] by elemental, mass and other spectroscopic data. The complexes show emission spectra at room temperature and their quantum yield lies between 0.4 and 0.5. All the complexes exhibit negative solvatochromism. Cyclic voltammetry shows metal centred oxidation and ligand reductions.     

Determination of copper in medicinal plants used as dietary supplements by atomic absorption spectrometry with direct flame solid analysis

An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g⁻¹ if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS.