Organometallic Syntheses with Diazoalkanes

In recent years, aliphatic diazo compounds have proved to be more and more versatile as reagents in the preparative chemistry of organometallic complexes. As readily accessible compounds, they are not only suitable for the synthesis of known kinds of metal complexes but also open fresh routes to novel complex systems. The comparatively new field of diazoalkane complex chemistry exhibits numerous unexpected and novel reactions, and introduces interesting and promising aspects into the chemistry of carbonylmetal compounds.     

Effect of ionic additives on the elution of sodium aryl sulfonates in supercritical fluid chromatography

Addition of a small amount of polar solvent (i.e., modifier) to CO2 in packed column supercritical fluid chromatography (SFC) has shown major improvements in both polar analyte solubility and interaction of the polar analyte with the stationary phase. Recently, the addition of an ionic component (i.e., additive) to the primary modifier by one of us has been shown to extend even further the application of SFC to polar analytes. In this work, the effect of various ionic additives on the elution of ionic compounds, such as sodium 4-dodecylbenzene sulfonate and sodium 4-octylbenene sulfonate, has been studied. The additives were lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride dissolved in methanol. Three stationary phases with different degrees of deactivation were considered: conventional cyanopropyl, deltabond cyanopropyl, and bare silica. The effect of additive concentration and additive functionality on analyte retention was investigated. Sodium 4-dodecylbenzene sulfonate was successfully eluted using all the additives with good peak shape under isocratic/isobaric/isothermal conditions. Different additives, however, yielded different retention times and in some cases different peak shapes.     

催化燃烧去除VOCs污染物的最新进展

催化燃烧是目前最有效的处理挥发性有机物(VOCs)技术之一. 本文从催化剂活性组分、催化剂载体、有效组分颗粒大小、水蒸汽的影响及催化燃烧反应中的积碳等几个方面, 对近年来催化燃烧处理VOCs的研究进行了总结. 分析表明: 贵金属催化剂的研究主要着重于选择有效的载体和双组分贵金属催化剂; 非贵金属催化剂的研究主要集中在高活性的过渡金属复合氧化物、钙钛矿和尖晶石型等催化剂的研制, 还有这些活性组分粒径大小及载体对催化燃烧VOCs反应活性的影响;此外, 在实际应用中,水蒸汽和催化剂积碳失活等问题对催化燃烧VOCs的反应也有很大影响. 本文的评述将为选择合适的催化燃烧技术处理VOCs污染物提供一定参考.     

Use of allyl, 2-tetrahydrofuryl, and 2-tetrahydropyranyl ethers as useful C3-, C4-, and C5-carbon sources: palladium-catalyzed allylation of aldehydes

Palladium-diethylzinc or palladium-triethylborane catalytically promotes self-allylation of 2-(allyloxy)tetrahydrofurans, 2-(allyloxy)tetrahydropyrans, and their hydroxy derivatives on the rings (ribose, glucose, mannose, deoxyribose, deoxyglucose). All the reactions proceed at room temperature and provide polyhydroxyl products, sharing a structural motif of a homoallyl alcohol, in good to excellent yields with high levels of stereoselectivity. Useful C3-unit elongation, which makes the best use of an allyl ether as a protecting group and a nucleophilic allylation agent, is demonstrated. Mechanisms for the umpolung reaction (of an allyl ether into an allylic anion) and stereoselectivity associated with allylation of aldehydes are discussed.     

The Chemistry of Simple Phosphorus-Carbon Compounds

With the aid of selected examples an overview is given of the development trends in phosphoruscarbon chemistry over the past few years. An attempt is made to demonstrate the relationships between various parameters and properties such as constitution, basicity, substitution by functional groups, reaction behavior etc. of the compounds. In the case of basis compounds containing methylphosphorus groups the state of development of industrially interesting processes is also outlined. In addition, the synthesis of a few bifunctional phosphorus-carbon compounds which can be employed as comonomers in the production of polymers is described.     

Retention characteristics of volatile compounds on tenax TA

The chromatographic separation properties of long, thin adsorption tubes enable substance-specific quantitative enrichment and reduction to be achieved when sampling and thermal desorption are carried out in the same flow direction. The specific retention volumes, and also the breakthrough and peak end volumes, of 69 compounds in the boiling range between-164 and 126°C and of a relative molecular mass between 16 and 119 were determined at temperatures between 30 and 130°C: normal alkanes, isoalkanes, cycloalkanes, alkenes, polyenes, alkynes, aromatics, ethers, alcohols, aldehydes, ketones, carboxylic acids and their esters, nitroalkanes, O-heterocycles, S-heterocycles, chloroalkanes, water, nitrogen monoxide, nitrogen dioxide, carbon dioxide, and sulfur dioxide. The correlation between adsorbent temperature and specific retention volume of these components, presented in the form of diagrams, permits the required quantity of adsorbent to be determined for a given sample volume. Contrary to literature sources, even extremely volatile compounds such as propane, propene, methanol, formaldehyde, formic acid, and chloromethane can be quantitatively retained on Tenax provided the operating conditions are appropriately selected.     

Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.     

Synthesis of calixarene-cyclodextrin coupling products

The coupling of two or four mono-6-amino β-cyclodextrin (amino-CD) units, (unprotected or permethylated hydroxyls), to diisopropoxycalix[4]arene crown-6 (CAL) was realised using the N,N′-succinyldiamide linker. The resulting molecules in two series were characterised with the help of mass and NMR spectroscopies. The yields of all coupling products were improved for permethylated sugar series compared to the hydroxylated CD series or to our previous studies. The two β-cyclodextrin (β-CD) residues coupled to disubstituted CAL were orientated from the same side of the crown ether.     

肉桂酸类分子非线性光学效应的理论研究

计算了一系列肉桂酸（苯基丙烯酸）类化合物的二阶非线性光学系数，系统地研究了取代基的电子性质和取代位置对其非线性光学性质的影响，并且探讨了该类化合物的饱和取代效应．研究表明，该类化合物的非线性光学性质与其分子结构有着密切的关系．