Temperature dependence of CO insertion on S-, Ag-, and Cu-promoted Rh/SiO2 catalysts

The addition of sulfur and silver to Rh/SiO₂ inhibits hydrogenation of C₂H₄, but promotes CO insertion and extends the linearity of Arrhenius curves for CO insertion above 543 K.

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Rh/SiO₂ C₂H₄, CO CO 543 .

     

Immunochemical determination of dioxins in sediment and serum samples

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are considered highly toxic contaminants and the environmental and biological monitoring of these compounds is of great concern. Immunoassays may be used as screening methods to satisfy the growing demand for rapid and low cost analysis. In this work, we describe the application of an immunoassay that uses 2,3,7-trichloro-8-methyldibenzo-p-dioxin (TMDD) as a surrogate standard for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to sediment and human serum samples. Sample extraction and preparation methods were developed with the aim to establish the simplest, cost-effective and efficient removal of the matrix interferences in the enzyme-linked immunosorbent assay (ELISA). The overall method for sediments is based on a hexane extraction; clean up by a multilayered silica gel column and an activated carbon column; an organic solvent exchange with DMSO–Triton X-100 and ELISA measurement. The gas chromatography–high resolution mass spectrometry (GC–HRMS) validation studies (n = 13) revealed that the method is suitable for the toxic equivalents (TEQ) screening of dioxin in sediments with a method detection limit of about 100 pg g⁻¹ dry sediment with a precision of 13–33% R.S.D. The analysis of a large number of samples originating from different sources would be required to establish more precisely the screening level, as well as the number of false positives and negatives of dioxin TEQ by the immunoassay for sediments. The immunoassay method for sediment analysis offers improvement in speed, sample throughput, and cost in comparison to GC–HRMS. Dioxins were determined in serum samples after a simple liquid–liquid extraction and solvent exchange into DMSO–Triton X-100 without further dilution. The current method (approximate method LOQ of 200 pg ml⁻¹ serum) is not sufficiently sensitive for the determination of dioxins in serum to measure acceptable exposure limit.     

The Studies of Free Radical Cyclization Reactions Mediated by Sulfonyl Chloride (II)

A study on the free radical cyclization reaction of substituted 1,6-dienes mediated by p-toluenesulfonyl chloride is described.     

CO disproportionation on Ni-based catalysts

Ni/SiO₂ exhibits higher activity for CO dissociation than coprecipitated Na–Mn–Ni, which is a higher oxygenate synthesis catalyst at 303 K, while Na–Mn–Ni exhibited higher CO dissociation activities at 673 K.     

Free Radical Reaction between 1,6-Dienes and P-Toluenesulfonyl Cyanlde

A sulfonyl-radical-induced addition-cyclization reaction of 1,6-dienes with p-toluenesulfonyl cyanide giving functionalized cyclopentane systems is described.     

Furostanol saponins with inhibitory action against COX-2 production from Tupistra chinensis rhizomes

Two furostanol saponins were obtained from the n-butanol fraction of methanol extract from Tupistra chinensis rhizomes,a folk medicine of Shennongjia Forest District of Hubei Province.Their structures were determined as (25S)-26-O-(β-D-glucopyranosyl)- furost-1β,3β,22α,26-tetrol-3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside (1) and (25R)- 26-O-(β-D-glucopyranosyl)-furost-1β,3β22α,26-tetrol 3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glu- copyranoside (2),on basis of chemical and spectroscopic evidences.1 and 2 displayed marked inhibitory action towards COX-2 production in macrophages of the rat abdomen induced by LPS at 20μg/mL.     

肽核酸骨架分子键联卟啉的合成及结构表征

以5,10,15-三苯基-20-(4-羧基苯基)卟啉和5,10,15-三苯基-20-(4-羟基苯基)卟啉为原料, 分别与N-(Boc-氨乙基)甘氨酸乙酯(3)及其衍生物4作用, 得到了两种肽核酸骨架分子键联卟啉化合物6和8. 中间体和目标化合物均由紫外-可见光谱、红外光谱、核磁共振光谱、质谱及元素分析所确证. 目标化合物的荧光光谱测试结果表明, 肽核酸单元分子的链接对卟啉分子的荧光波长和强度影响不大.     

Synthesis of laterally substituted bistolane liquid crystals

Methods for synthesizing bistolane liquid crystal materials with lateral methyl and ethyl substituents are presented. Some of the bistolanes are nematic at room temperature. These highly conjugated mesogens exhibit wide nematic ranges, small enthalpies of fusion, high birefringence and modest viscosity. Their potential applications for flat panel displays employing light scattering or Bragg reflection and for infrared optically phased arrays are foreseeable.     

Indium-mediated allenylation of arylacyl bromides in a route for the synthesis of substituted furans

A three-step, single purification procedure has been developed for the concise synthesis of substituted furans from arylacyl bromides.