Synthesis, resolution and racemisation studies of new tridentate ligands for asymmetric catalysis

A method for the high-yielding preparation of two tridentate, isoquinoline-derived ligands, involving successive Suzuki cross-coupling reactions, is described. The first ligand could be resolved via molecular complexation with N-benzylcinchonidinium chloride, while the second was resolved by chromatographic separation of its epimeric camphorsulfonates. The barrier to rotation about the central biaryl axis was evaluated via racemisation studies, and the absolute configuration assigned by X-ray crystallography.     

Glass capillary gas chromatography of amino acid enantiomers

Glass capillaries coated with Chirasil-Val, a chirally functionalised polysiloxane, are capable in principle of resolving all protein amino-acid enantiomers in a single run and within a short analysis time, thus allowing for example the quantitative amino acid determination by enantiomer labelling. The elution characteristics of the individual amino acids however are also dependent upon the chemical nature of the capillary wall surface, and a surface pretreatment is found to be necessary if all protein amino acids are to be analysed. Of the various methods of pretreatment tested, etching of borosilicate glass with gaseous HCl followed by deposition of colloidal silicic acid is considered to be the most suitable.     

Improved operator comfort and off-road capability through pendulum arm technology

The Nordic forest industry requires just-in-time wood deliveries. Operations must continue regardless of season, weather and terrain. Soil compaction and deep ruts must be avoided while providing high performance and a reasonable working environment for operators.The Xt28 pendulum arm forwarder is a full-size concept forwarder with six hydrostatic propelled wheels on pendulum arms built on a three-piece frame connected with two articulation joints. The Xt28 concept machine was tested according to Skogforsk standard machine tests. Rut depth test focused on soil interaction where rut depth was measured related to number of passes. Machine dynamics were measured using standardized test track with focus on operator comfort.The project proved the potential of pendulum arm technology in off-road transportation. Automatic pendulum arm levelling, equalized ground pressure between wheels and improved operator comfort through reducing adverse vibrations and roll angles, simultaneously reducing dynamic forces transferred to the forest floor. Pendulum arm technology improves travel speed in adverse terrain, providing unparalleled side slope capability and enhanced productivity.     

有机物添加剂对碱性锌电极的影响

通过腐蚀实验,测量了锌在碱性溶液中的腐蚀速度,比较了几种有机物添加剂的缓蚀效果 用恒电位极化的方法研究了锌的沉积电流随时间的变化企图用该方法考查一些有机物添加剂对二次碱性锌电极枝晶生长的抑制作用 测量了多孔锌电极在含有各种有机物添加剂的碱液中的阴,阳极极化曲线结果发现,季胺盐型有机表面活性剂 Ｃ Ｔ Ｍ Ｂ在碱性溶液中对锌具有一定的缓蚀作用还可以抑制二次锌电极上枝晶的生长 又不会严重影响锌电极的阳极放电行为为碱性电池中锌电极代汞缓蚀剂的研究提供了一种新的途径     

Water-catalyzed racemisation of lactide

The reactions of lactide racemisation, hydrolysis, or alcoholysis in the presence of water or anhydrous alcohol have been investigated separately. A small amount of water leads to lactide racemisation, hydrolysis, or both. Water acts as a catalyst for the racemisation of lactide. The racemisation mechanism has been studied by substituting D₂O instead of H₂O and measuring the substituent by gas chromatography-mass spectrometry (GC-MS). The experimental results show that the hydrogen atom on a chiral carbon of lactide is substituted by a ²H atom of D₂O. The reaction of lactide with water is in good agreement with the mechanism of addition-elimination. The addition of water to the carbonyl group produces an intermediate with a pair of hydroxyls connected to a carbon atom. If a hydroxyl hydrogen atom is transferred to the ester bond (CO-O), the hydrolysis of lactide generally occurs. Any of these hydroxyls could also be dehydrated with the close methine, thus producing an enolate, and the transfer of hydrogen from the enolic hydroxyl group results in lactide racemisation. The conversion of d- or l-lactide into meso-lactide is a reversible and endothermic reaction when catalyzed by water. When lactide reacts with alcohol, its alcoholysis occurs more readily than its racemisation.     

被测体材质对电涡流位移传感器特性的影响

本文通过对电涡流传感器的位移特性实验分析不同被测体材料对于传感器输出特性的影响     

Nucleophile-assisted racemisations of halosilanes — kinetic studies

Kinetic studies have been carried out on the nucleophile-induced racemisation of PhMeCHSiMe₂X, 2, X = triflate, Br or Cl. Thirteen nucleophiles were studied. The results are interpreted in terms of two competing mechanisms for racemisation: (a) nucleophile attack on a silane-nucleophile complex formed by displacement of the halide by the nucleophile, and (b) halide-halosilane exchange, with inversion of configuration. Solvent effects were examined, and kinetic orders in the nucleophile and in one case for the halosilane were determined. The order in added nucleophile varied between one and two, with strong nucleophiles in polar media. Anomalously high orders in nucleophile were observed in non-polar media and are ascribed to aggregation of the nucleophile. A kinetic analysis of the competing mechanisms was attempted, and was consistent with the experimental findings. In this particular series of reactions involving compounds with good leaving groups and relatively powerful nucleophiles there was no evidence for intermediates involving extracoordinate silicon.