α-单取代环十二酮肟及缩氨基硫脲的合成及晶体结构

单晶X射线衍射分析表明, α-单取代环十二酮与氨衍生物羟胺和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α-单取代环十二酮肟或缩氨基硫脲. 利用底物的“角位羰基参与反应”原理, “记忆效应”及进攻试剂与底物是否形成氢键解释了这一实验结果. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α-角反取代环十二酮肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α-边外取代环十二酮肟或缩氨基硫脲.     

Aculeoside I, a novel 18,19-seco-ursane saponin isolated from Ilex aculeolata

A novel 18,19-seco-ursane saponin, aculeoside I (1), in addition to four known saponins were isolated from the leaves of Ilex aculeolata Nakai and identified by using spectroscopic and chemical methods. The structure of the new saponin was established as 3,19-dihydroxyl-16,21-epoxy-18,19-seco-13(18)-urs-ene-28-oic-acid-19-O-alpha-L-rhamnopyranosyl-(1 --> 2)-alpha-L-arabinopyranoside.     

2A12-T6铝合金表面双-(γ-三乙氧基硅丙基)四硫化物薄膜的特性

采用傅立叶变换红外光谱分析了2A12-T6铝合金表面自组装双-(!-三乙氧基硅丙基)四硫化物硅烷偶联剂(SCA)薄膜结构特征,并采用电化学极化曲线评价了薄膜的耐蚀性能.结果表明,铝材表面自然晾干,SCA薄膜分子之间主要通过氢键连接,腐蚀电流密度减小1个数量级以上.120℃的加热处理促进铝板表面通过SiOSi链接而形成SCA网状薄膜结构,并通过在界面上形成SiOAl界面相结构而与铝板表面牢固连接,腐蚀电流密度降低2个数量级以上.SCA乙醇溶液浸泡处理10min比浸泡2s～1min的铝板表面SCA薄膜内氢键缔合羟基要多.     

α-单取代环十二酮构象的研究

利用分子力学计算，单晶X射线分析和~1H NMR技术研究了α-单取代环十二酮 的构象。结果表明，它们的优势构象的环骨架仍是[3333]构象，而羰基则在2-C位 置上。在晶体中，它们的优势构象为α－角顺取代[3333]-2-酮构象，而在溶液中 则取α－角顺取代和α－边外取代[3333]-2-酮两种构象，且两种构象处于动力学 平衡之中，以α－边外取代[3333]-2-酮构象占优势。     

Secondary succession and its effects on soil moisture and nutrition in abandoned old-fields of hilly region of Loess Plateau, China

Floristic composition, community structure and soil moisture and nutrient contents in abandoned fields of different ages were analyzed to clarify the regenerative aspects of succession as a tool for vegetation restoration. The results indicated that secondary succession in this region can be interpreted as an auto-succession: there are main changes in species-relative abundance and species turnover. Annual or biennial species (e.g. Artemisia scoparia), acted as pioneers and strongly dominated the early stages. Then, they underwent a progressive decline, while forbs (e.g. Artemisia sacrorum) and grasses (e.g. Xanthium sibiricum) had their peak abundance at intermediate stages. Dwarf shrubs (e.g. Lespedeza dahurica) and short rhizome grass (e.g. Bothriochloa ischaemum) appeared at mid-succession stage and gradually increased in abundance during succession, becoming dominant at late stages. The first axis of detrended correspondence canonical analysis arranged the sites according to their fallow time, indicating a successional sere. The second axis, associated with diverging pathways of regeneration, correlated with topographic factors and soil moisture and nutrition. Structural divergence between plots increased as succession went on, attained the highest at the mid-succession stage, decreased at the late stage.

Soil moisture and available phosphorus content decreased steadily with field age after their abandonment, whereas pools of organic matter, total and available nitrogen, potassium and total phosphorus increased with field age. The pace and direction of recovery of native vegetation and natural soil properties in these abandoned fields resembled classic old-field succession, which is a form of secondary succession that often serves as a template for guiding restoration efforts. Interface between the abandoned field soil and plant system was crucial to the above process. Our current study supported the generally accepted hypothesis in the succession literature.     

南蛇藤昆虫拒食倍半萜成分的研究(Ⅱ)

南蛇藤昆虫拒食倍半萜成分的研究（Ⅱ）王明安,陈馥衡（北京农业大学应用化学系,北京,１０００９４）关键词南蛇藤,倍半萜,结构分析卫矛科植物含多种类型β－二氢沉香呋喃倍半萜多醇酯衍生物和生物碱［１］,有些化合物显示了良好的昆虫拒食和抗肿瘤活性［２～４］．...     

炔丙型硫Ylide环丙烷化反应及其立体选择性

炔丙型硫Ylide与丙烯酸酯的反应是一个多反应竞争的复杂反应, 通常环丙烷化产物收率很低. 本文通过对反应底物的优化, 成功获得了高收率、高选择性的反式环丙烷化产物. 同时利用Gaussian 03程序, 选择密度泛函BHHLYP方法, 6-31G**基组对反应路径及过渡态模型进行了计算, 进而采用密度泛函理论中的B3LYP方法, 选择6-31G**基组, 对顺、反式产物的热稳定性进行了分析, 明确了该反应的高非对映选择性是由过渡态的能量差异和产物的热稳定性两个因素共同决定的, 而过渡态的能量差异可以归于分子内弱的立体电子效应的不同.     

线叶紫菀中一个单萜酸的化学结构

线叶紫菀中一个单萜酸的化学结构王明安，陈耀祖（北京农业大学应用化学系，北京，１０００９４）（兰州大学化学系）关键词线叶紫菀，单萜，结构分析线叶紫菀（ＡｓｔｅｒｆａｒｒｅｒｉＷ．Ｗ．ＳｍｉｔｈｅｔＪ．Ｆ．Ｊｅｆｆｅｒｙ）系菊科紫菀属多年生草本植物，用于...     

PP/PP-g-MAH与铝板粘接界面相的XPS研究

用X射线光电子能谱(XPS)研究铝板/聚丙烯层状复合材料的粘接界面相，提出了粘接界面的化学反应机制.研究发现,聚丙烯(PP)中加入马来酸酐接枝聚丙烯(PP-g-MAH)时，铝板面上Al 2p、O 1s谱线明显向高结合能端移动，表明PP-g-MAH与铝板表面发生了化学反应，形成Al－O－C配位键.配位键的形成使界面粘接强度明显提高. PP中不含PP-g-MAH时，铝板面上Al 2p、O 1s谱线处于低结合能端，聚丙烯未与铝板表面形成化学配位作用.