Solvent extraction of uranium(VI) with benzyloctadecyldimethylammonium chloride (BODMAC) from highly concentrated chloride solution

The ²²²Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine the activity concentration of the ²²⁶Ra content, of which the ²²²Rn emanation fraction was calculated. The results showed that the ²²²Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of ²²⁶Ra. This revised version was published online in August 2006 with corrections to the Cover Date.     

Theoretical study of the local structure and Raman spectra of CaO-SiO2 binary melts

A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature.     

立体化学刚性的七配位环戊二烯基三(二苄基二硫代氨基甲酸)钛、锆、铪配合物的合成和性质

二烷基二硫代氨基甲酸基作为良好的双齿配体较易与过渡金属生成高配位的配合物,含有环戊二烯基的高配位钛、锆、铪配合物的研究相继出现^[1-5],这类七配位、18-电子构型的配合物是立体化学刚性,具有独特的光谱性质和结构行为。选择钛、锆和铪二茂二氯化物与三当量的二苄基二硫代氨基甲酸钠反应合成了五种未见报道的七配位配合物,讨论了产物的光谱性质和配位结构。     

The spin delocalization substituent parameter σ˙. 7. Meta-substituent effects on the cyclodimerization of trifluorostyrenes. A test for the σ˙JJ approach

Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σ_mb values derived from ¹⁹F NMR data the spin-delocalization substituent constant σ^˙_m values of these ten meta-substituents have been calculated. The averaged σ^˙_m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF₃, ?0.07; m-OMe, 0.10; m-NO₂, ?0.002; m-CN, 0.11 and m-CO₂Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σ^X and these σ^˙_m values support our belief that the σ_j?J approach is reliable and trustworthy.     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

蔗糖酯示波极谱分析法的研究

蔗糖酯分子在碱性条件下，加热水解为蔗糖和硬酯酸，在ｐＨ＞１０的ＮＨ＿３·Ｎ＿２Ｏ－（ＮＨ＿３）＿３Ｃ＿６Ｈ＿５Ｏ＿７体系中，于示波极谱仪上，峰电位─０．９１Ｖ处出现一灵敏度高和稳定性好的极谱图，其浓度从０．０２～０．２８ｍｇ／ｍＬ与峰电流呈线性关系，最低检出限为０．００４ｍｇ／ｍＬ，相对标准偏差为１．３％。     

Theoretical studies of dissociative phosphoryl transfer in interconversion of phosphoenolpyruvate to phosphonopyruvate: solvent effects, thio effects, and implications for enzymatic reactions

The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed.     

Curing and pyrolysis of epoxy resins containing 2-(6-oxido-6<Emphasis Type="Italic">H</Emphasis>-dibenz(<Emphasis Type="Italic">c</Emphasis>,<Emphasis Type="Italic">e</Emphasis>)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol or bisphenol S

This work examines the curing kinetics, thermal properties, and decomposition kinetics of diglycidyl ether of bisphenol A (DGEBA) epoxies with three different curing agents, 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol (ODOPN), bisphenol A (BPA), and bisphenol S (BPS). The differential scanning calorimetry curing study reveals that the curing kinetics of the DGEBA/ODOPN epoxy is first order, independent of the scan rate. The ODOPN-containing epoxy, unlike the conventional BPA one, includes a phosphorus-containing bulky pendant aromatic group and results in an increase in the glass-transition temperature of 83 K, the char yield increases by a factor of 3, and the limiting oxygen index values increase from 23 to 27. For the BPS system, the glass-transition temperature increased slightly, and both the char yield and the limiting oxygen index value increased insignificantly when the test was conducted in air. Finally, the thermogravimetric analysis decomposition study in N₂ from Ozawa's analysis demonstrates that the DGEBA/BPS epoxy has the highest activation energy, followed by the regular DGEBA/BPA system, and lastly the DGEBA/ODOPN has the lowest activation energy. The low activation energy for the ODOPN system is attributed to the initial decomposition of the phosphorus compound in the formation of an insulating layer.     

Microporous activated carbons prepared from palm shell by thermal activation and their application to sulfur dioxide adsorption

Textural characterization of activated carbons prepared from palm shell by thermal activation with carbon dioxide (CO(2)) gas is reported in this paper. Palm shell (endocarp) is an abundant agricultural solid waste from palm-oil processing mills in many tropical countries such as Malaysia, Indonesia, and Thailand. The effects of activation temperature on the textural properties of the palm-shell activated carbons, namely specific surface area (BET method), porosity, and microporosity, were investigated. The activated carbons prepared from palm shell possessed well-developed porosity, predominantly microporosity, leading to potential applications in gas-phase adsorption for air pollution control. Static and dynamic adsorption tests for sulfur dioxide (SO(2)), a common gaseous pollutant, were carried out in a thermogravimetric analyzer and a packed column configuration respectively. The effects of adsorption temperature, adsorbate inlet concentration, and adsorbate superficial velocity on the adsorptive performance of the prepared activated carbons were studied. The palm-shell activated carbon was found to have substantial capability for the adsorption of SO(2), comparable to those of some commercial products and an adsorbent derived from another biomass.     

Simultaneous hydrogen and peroxide production by photocatalytic water splitting

Photocatalytic oxidation of water is a promising method to realize large-scale H₂O₂ production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO₂(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H₂ and H₂O₂ production. Both H₂ and H₂O₂ are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^–1 h^–1 (first 1 h) for H₂ and H₂O₂, respectively, which is much higher than that of a commercial Pt/TiO₂(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H₂O₂, compared with the four-electron oxidation of water to O₂.