Raman microscopy of selected tungstate minerals

A series of tungstate bearing minerals including scheelite, stolzite, ferberite, hübnerite, wolframite, russellite, tungstenian wulfenite and cuprotungstite have been analyzed by Raman microscopy. The results of the Raman spectroscopic analysis are compared with published data. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the pargenetic relationships between the minerals. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra. The nu1(Ag) band is observed at 909 cm(-1) and although the corresponding nu1(Bu) vibration should be inactive a minor band is observed around 894 cm(-1). The bands at 790 and 881 cm(-1) are associated with the antisymmetric and symmetric Ag modes of terminal WO2. The band at 695 cm(-1) is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The nu4(Eg) band was absent for scheelite. The bands at 353 and 401 cm(-1) are assigned as either deformation modes or as r(Bg) and delta(Ag) modes of terminal WO2. The band at 462 cm(-1) has an equivalent band in the infrared at 455 cm(-1) assigned as delta(as)(Au) of the (W2O4)n chain. The band at 508 cm(-1) is assigned as nu(sym)(Bg) of the (W2O4)n chain.     

Simultaneous determination of lead(II) and cadmium(II) at a diacetyldioxime modified carbon paste electrode by differential pulse stripping voltammetry

A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb²⁺ and Cd²⁺ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd²⁺) and −0.91 V (Pb²⁺) demonstrates the possibility of simultaneous determination of Pb²⁺ and Cd²⁺. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10⁻⁷-1.5×10⁻⁵ mol l⁻¹ (Pb²⁺) and 2.5×10⁻⁷-2.5×10⁻⁵ mol l⁻¹ (Cd²⁺), respectively. For 5 min preconcentration, detection limits of 1×10⁻⁸ mol l⁻¹ (Pb²⁺) and 4×10⁻⁸ mol l⁻¹ (Cd²⁺) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10⁻⁷ mol l⁻¹ Pb²⁺ and Cd²⁺ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb²⁺) and 3.2% (Cd²⁺), respectively. Interferences by some metals were investigated. Only Ni²⁺ and Hg²⁺ apparently affected the peak currents of Pb²⁺ and Cd²⁺. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb²⁺ and Cd²⁺ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb²⁺ and Cd²⁺.     

聚苯胺/二氧化钛复合薄膜的制备及其气敏性能

室温条件下, 运用静电力自组装和原位化学氧化聚合相结合的方法制备了聚苯胺/纳米二氧化钛(PANI/TiO2)复合薄膜和聚苯胺(PANI)薄膜, 并通过XPS和SEM对薄膜进行了分析表征. 采用平面叉指电极式器件制备了PANI/TiO2复合薄膜和PANI薄膜气体传感器, 研究了其在常温下对有毒气体NH3和CO 的敏感性能. 结果表明, PANI/TiO2复合薄膜较PANI薄膜具有更优的灵敏度和响应恢复特性.     

Fe–Hg Interactions and P Chemical Shifts in [Fe(CO)3 (PPh2R)2(HgCl2)] (R=pym, fur, py, thi)

In order to study the effects of R group on Fe–Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)₃(PPh₂R)₂ (R=pym:1, fur: 2, py: 3,thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)₃(PPh₂R)₂(HgCl₂)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyses were also performed to explain the nature of the Fe–Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atoms there are, the higher is the stabilility of the complex. (2) The Fe–Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, thereisa σ-bond between Fe and Hg atoms. However, in 7 and 8, the Fe–Hg interactions act as σ_P–Fe→n_Hg and σ_C–Fe→n_Hg delocalization. (3) Through Fe→Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction.     

Larvicidal and structural studies of some triphenyl- and tricyclohexyltin para-substituted benzoates

Several new triphenyl- and tricyclohexyltin para-substituted benzoates were synthesized. Their structures were characterized by IR and Mössbauer spectroscopies. The structures were determined to be four-coordinated monomers. Larvicidal activities of the new compounds as well as other benzoates were evaluated against the 2nd larval instar of the Anopheles stephensi and Aedes aegypti mosquitoes. Results from the screening studies indicated that the triphenyltin benzoates were more toxic towards the Ae. aegypti larvae. A quantitative-structure activity relationship was also developed for the An. stephensi larvae.     

双氮桥联1,10-菲咯啉大环化合物分子构型的从头算研究

应用规范不变原子轨道法(GIAO)在RHF/6-31G**和B3LYP/6-31G**水平上计算了质子化双氮桥联1,10-菲咯啉大环化合物(H4HAPP2+)C2h和C2h构型的1HNMR,并用TDDFT法计算了H4HAPP2+电子光谱.结果表明,B3LYP/6-31G*优化的C2h构型为较优构型,经谐振频率验证无虚频,C2h构型是H4HAPP2+合理的对称性构型.     

CBS法合成光学活性二茂铁基醇

以非天然氨基酸合成的手性β-氨基醇(4a～4c)为催化剂，用于不对称硼烷还原反应来合成光学活性的二茂铁基醇(1a～1e)，对映体过量值高达96%。     

A nickel(0) catalyzed cycloaddition of alkynes and isocyanates that affords pyrimidine-diones

A Ni/N-heterocyclic carbene catalyzed cycloaddition of one alkyne and two isocyanates that affords pyrimidine-dione is described. The key to the success of this protocol is the use of unsymmetrically substituted alkynes that favors the formation of pyrimidine-diones over pyridones. A variety of pyrimidine-diones were prepared. A one-pot cycloaddition and Stille coupling were reported for tributyl(1-propynyl)tin. Competition studies also provide insights into the mechanism of the cycloaddition.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLVI. Polarographisches Verhalten von Dibenzyl- und Diphenyltitan in aprotischen Lösungsmitteln

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLVI. Polarographic Properties of Dibenzyl and Diphenyl Titanium in Aprotic Solvents The polarographic properties of dibenzyl and diphenyl titanium were investigated using acetonitrile (AN), dimethylformamide (DMF), and dimethylsulfoxide (DMSO) as solvents. Both compounds are reduced irreversibly at very negative potentials in a two-electron step with formation of titanium. The half-wave potentials depend on the donor strength of the solvents. With increasing donor number the half-wave potentials are shifted to more negative values. The fact that the limiting currents turned out to be diffusion controlled suggests a monomeric structure of the titanium diorganyls in AN, DMF, and DMSO.     

Metal-free synthesis of 2-mercaptobenzothiazoles and 6-(4-substituted-1H-1,2,3-triazol-1-yl)-2-mercaptobenzothiazoles via microwave-assisted synthesis pathway

Abstract

A simple, efficient, and metal-free methodology for the preparation of 2-mercaptobenzothiazole and derivatives in excellent yields via microwave-assisted pathway is reported. Our condition provides a convenient protocol for the synthesis of a diverse collection of 2-mercaptobenzothiazoles and 6-(4-substituted-1H-1,2,3-triazol-1-yl)-2-mercaptobenzothiazoles with a very simple purification process. This report provides an alternative protocol for fast access to the wide range of compounds for sequence synthesis and biological studies.