The synthetic pyrethroid isomers I. Preparation

Abstract

Enantiomers and racemic mixtures of selected benzilic esters using resolved and raceme permethrinic or chrysanthemic acids of high purity were synthesised via improved methods based on conventional steps. Nine basic structures of selected derivatives having hydrogen, bromo or phenoxy group at meta position were prepared including the well known insecticides of phenothrin, permethrin and cypermethrin. The optical purity of these compounds were determined via an NMR method applying chiral shift reagents. The configuration of the isomers of new a‐cyano‐benzyl esters were assigned via a rule realized by comparing the characteristic 1H NMR shifts of the dimethyl groups attached to the cyclopropane ring.     

有机磷酸酯类阻燃剂毒性效应研究进展

有机磷酸酯类阻燃剂(organophosphate flame retardants,OPFRs)作为多溴联苯醚等溴代阻燃剂(brominated flame retardants,BFRs)的替代品被广泛应用,由此带来的环境影响广受关注。目前针对OPFRs的生物毒性研究仍相对有限,需要更全面调查其在多环境介质中的暴露状况、环境归趋、生物毒性效应等研究成果,在此基础上才能综合评价其可能引起的生态风险。因此,综述了OPFRs对水生生物、哺乳动物和人类等多种生物体的急性毒性、生殖与发育毒性、神经毒性、脏器毒性、基因毒性与致突变性和内分泌干扰性。OPFRs的多种生物毒性已得到证实,但相关致毒机制研究尚不完整深入。最后对OPFRs的进一步研究存在的问题进行分析,提出了研究展望,以期促进开展OPFRs的环境风险和人体健康风险研究。     

城市污泥中邻苯二甲酸酯的好氧降解规律研究

为评价邻苯二甲酸酯类环境激素在环境中的滞留情况,妥善解决城市污泥的处理处置问题,对城市污泥中6种邻苯二甲酸酯的好氧生物降解规律进行了研究。结果表明,邻苯二甲酸酯的好氧生物降解性随烷基链含碳数的增加而降低;其好氧降解过程可用一级动力学模型描述;其好氧生物降解速率常数与烷基链含碳数、降解半衰期与烷基链含碳数、降解速率常数与正辛醇—水分配系数之间存在良好的相关性。     

Preparation of starch esters

A review of starch esters prepared from either aqueous or solvent-based reactions leading to high (3.0)- and/or low (<0.2)-degree of substitution (DS) derivatives are discussed. A novel process for making intermediate-DS (0.5–1.8) starch esters from aqueous media is compared to traditional methods.     

Chemistry of preen gland secretions of passerines: different pathways to same goal? why?

Summary. Passeriformes is the largest order of birds and includes one third of the bird species of the world, living in very diverse habitats. We investigated the chemistry of preen gland secretions of some groups of passerines from temperate regions found in diverse microhabitats. Some of the common components were mixtures of homologous monoesters made up of long chain acids and alcohols. Individual species had characteristic distribution of esters and was unique to a given species, although there were some individual variations. We compared the composition of acids and alcohols that formed same molecular weight esters in different species and we found that the combination of acids and alcohols to arrive at same molecular compositions varied distinctly between species. To compare compositions of over all acids and alcohols that formed the esters, the representative samples of secretions from the individual species were transesterfied the produce methyl esters and alcohols. We found that there were distinct differences in number of acids and alcohols that produced the combination of homologous mixtures of esters. Also they differed both qualitatively and quantitatively. There were also seasonal differences in the secretion components. Thus though the intact mixtures of esters in individual species had some similarities, they were very complex mixtures and differed characteristically for individual species. Here we discuss possible causes for evolution of these variations. We suggest that the evolution in variation of preen gland secretion is probably due to selective pressures caused by ectosymbionts such as feather-mites and feather-chewing lice that live on feathers and probably feed on the secretions and surrounding environments     

邻苯二甲酸酯类环境激素降解研究

概括介绍了邻苯二甲酸酯类化合物的理化性质、毒性和致癌作用，以及其对环境生态系统的影响，论述了近年来在邻苯二甲酸酯类化合物的降解方面所取得的进展，重点讨论了邻苯二甲酸酯的光催化降解。     

Biotechnology to develop innovative syntheses using CO2

We present an overview of possible biotechnological applications for using carbon dioxide for the synthesis of chemicals. These approaches are very appealing as they contribute to the implementation of new synthetic methodologies that reduce waste and make a better use of carbon and energy. Several synthetic approaches will be considered including both the incorporation of the whole COO moiety or its reduction to other C₁ molecules. Each option will be discussed making a comparison between the natural and artificial process in order to highlight the possibility to learn from Nature and develop useful mimetic or enzymatic systems.     

环境中的邻苯二甲酸酯

本文较为系统地评述了邻苯二甲酸酯的环境行为、生态效应、环境归趋、数学模型和处理技术。指出邻苯二甲酸酯是生产量大和应用面广的人工合成有机化学品,是目前世界上全球性的一类环境有机污染物。这类化合物的低水溶度和低挥发性导致了它们的高吸附亲和性,从而使得该类化合物在固体颗粒物表面的行为对于研究它们在环境中各种过程具有十分重要的作用。     

UV／TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜，研究了UV-Vis／TiO2以及UV／TiO2／H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明，TiO2在暗处对酞酸酯没有降解作用；UV／TiO2体系能有效光降解DBP和DEHP，TiO2具有明显的光催化作用，增强因子分别为，fDBP=2．06，fDEHP=1．53；在一定浓度范围内DBP在UV／TiO2体系中的降解速率与其初始浓度成负一级动力学关系；UV／TiO2／H2O2体系对DBP的光降解能力远大于UV／TiO2和UV／H2O2体系，H2O2能显著提高TiO2的光催化活性。     

水环境中邻苯二甲酸酯的迁移转化研究

邻苯二甲酸酯(PAEs)是一类普遍使用的化学工业品,并广泛存在于环境中.已有研究表明,PAEs环境内分泌干扰物,对人类和自然环境有非常大的危害.总结了PAEs在地表水中的分布和在水体中迁移转化的主要途径,如水解、光降解、与颗粒物(沉积物或悬浮颗粒物)的作用以及生物转化作用,并指出对它们进一步研究的重要性和今后主要的研究方向.