High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Frequency dependence of ionic conductivity and dielectric relaxation studies in Na3H(SO4)2 single crystal

Electrical impedance measurements of Na₃H(SO₄)₂ were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO₄ tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ω^s. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition.     

甚高频等离子体增强化学气相沉积法沉积μc-Si∶H薄膜中氧污染的初步研究

对不同的本底真空条件下,采用甚高频等离子体增强化学气相沉积技术沉积的氢化微晶硅（μc_Si∶H）薄膜中的氧污染问题进行了比较研究.对不同氧污染条件下制备的薄膜样品的x射线光电子能谱与傅里叶变换红外吸收光谱测量结果表明：μc_Si∶H薄膜中,氧以Si—O，O—O和O—H三种不同的键合模式存在,不同的键合模式源自不同的物理机理.μc_Si∶H薄膜的Raman光谱、电导率与激活能的测量结果进一步显示：沉积过程中氧污染程度的不同,对μc_Si∶H薄膜的结构特性与电学特性产生显著影响；而不同氧污染对μc_Si∶H薄膜电学特性的影响不同于氢化非晶硅（a_Si:H）薄膜. 关键词： 氢化微晶硅薄膜 甚高频等离子体增强化学气相沉积 氧污染     

Optical spectroscopy of Yb/Er codoped NaY(WO4)2 crystal

Erbium and ytterbium codoped double tungstates NaY(WO₄)₂ crystals were prepared by using Czochralski (CZ) pulling method. The absorption spectra in the region 290-2000 nm have been recorded at room temperature. The Judd-Ofelt theory was applied to the measured values of absorption line strengths to evaluate the spontaneous emission probabilities and stimulated emission cross sections of Er³⁺ ions in NaY(WO₄)₂ crystals. Intensive green and red lights were measured when the sample were pumped by a 974 nm laser diode (LD), especially, the intensities of green upconversion luminescence are very strong. The mechanism of energy transfer from Yb³⁺ to Er³⁺ ions was analyzed. Energy transfer and nonradiative relaxation played an important role in the upconversion process. Photoexcited luminescence experiments are also fulfilled to help analyzing the transit processes of the energy levels.     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Pressure-induced polymorphism in enstatite (MgSiO3) at room temperature: clinoenstatite and orthoenstatite

The phase transition of a synthetic clinoenstatite in a diamond-anvil cell has been studied by using Raman spectroscopy at various pressures and room temperature. The phenomena observed in clinoenstatite have been compared with that observed in orthoenstatite. It is found that the pressure-induced phase transitions in the two enstatites are reversible, but with different transition pressures and transition behavior. An analysis of Raman spectra has revealed that the two enstatites have different high-pressure polymorphs. This result suggests that the space group of the high-pressure polymorph of orthoenstatite is not of C2/c, and that orthoenstatite and orthoferrosilite have different transition routes at room temperature and high pressure. The compressional behavior of the high-PC2/c enstatite is also discussed according to the pressure dependences of Raman frequencies.     

Electroanalytical and chromatographic determination of pentachlorophenol and related molecules in a contaminated soil: a real case example

Electroanalytical and chromatographic methodologies have been applied for the determination of pentachlorophenol (PCP) and some of its derivatives in real soil samples contaminated by industrial discharge. The analytes were extracted with hexane from soil samples collected at different points of the site and mixed to produce a representative sample. Square wave voltammetry (SWV) experiments were carried out on either a boron-doped diamond (BDD) electrode or a gold ultramicroelectrode (Au-UME) in an analyte composed by the Britton-Robinson (B-R) buffer at pH 5.5 with the direct addition of proper amounts of the extract. The voltammetric responses revealed an irreversible anodic peak at approximately 0.80 V vs. Ag/AgCl with a peak current showing a linear dependence on PCP concentration. This linear relationship yielded a detection limit (DL) of 2×10⁻⁸ mol l⁻¹ (or 5.5 μg l⁻¹) for the BDD electrode and 6.9×10⁻⁸ mol l⁻¹ (18.4 μg l⁻¹) for the Au-UME, while the independently measured HPLC detection limit was 1.1×10⁻⁸ mol l⁻¹ (3.0 μg l⁻¹). The application of electroanalytical and chromatographic methodologies in the analysis of soil extracts revealed, besides the PCP responses, signals for some related molecules such as o-tetrachlorobenzoquinone (o-chloranil), hexachlorobenzene and tetrachlorophenol. Recovering experiments for PCP showed a concentration of 27.5 mg kg⁻¹ for the electroanalytical determinations and 26.8 mg kg⁻¹ for the HPLC analysis, values exceedingly high if considering that the maximum residue limit established for natural waters by the Brazilian Environmental Agency is 10 μg l⁻¹.     

Determination of anions in rainwater by capillary electrophoresis with conductivity detection

A routine method for the determination of chloride, nitrate and sulfate anions in rainwater by capillary electrophoresis was developed. The system uses an end-column non-suppressed conductivity detector. Linear calibration plots were generated from 0.050 to 20 mg/l, which is the range generally found in wet depositions. Accuracy and precision were evaluated by analyzing certified standards of simulated rainwater and environmental samples, or by comparing CE results with those obtained by IC, the reference technique for anion analysis in wet deposition. The reproducibility of the method was satisfactory except at the lower and upper limits of the analytical range. Sensitivity lay in the range of few μg/l.     

无机螺旋体超分子配合物的组装、应用和结构转化研究进展

简述了近年来报道的具有新颖结构和性能的无机螺旋体超分子配合物的组装、应用和结构转化方面的最新进展,并展望了无机螺旋体的发展前景及其开发应用潜力。