几个石松类生物碱的质谱分析

采用电子轰击电离高分辨质谱及B/E联动扫描(LinkedScan)法,研究了HuperzineE,F,G三个lycopodine类新生物碱的质谱行为。并应用这些结果确定了另一个新生物碱HuperzineO的结构。     

超分子体系中的光物理和光化学过程

总结了我们组近几年来对超分子体系中的光物理和光化学过程所做的工作,包括三个部分：(1)微反应器控制的有机光化学反应的选择性,(2)疏水、疏脂作用对光物理和光化学过程的影响,(3)超分子体系中的电子转移、能量传递和光化学转换。     

孔结构梯度分布SiO2膜的仿生合成

以正硅酸乙酯为硅源,十六烷基三甲基溴化铵大分子的组装体为有机模板,研究在气-液界面仿生合成SiO2膜的过程。考察了影响成膜的订因素并优化了操作条件,进而仿生合成了孔结构梯度分布的无机膜。SEM与孔径分布表征,表明所制备的SiO2膜顶层孔径为1.9nm,底部的则为25nm,膜的比表面积为313.5m^2·g^-1。     

The Effects of Morphological Properties of Henequen Fiber Irradiated by EB on the Mechanical and Thermal Properties of Henequen Fiber/PP Composites

The aim of this study was to investigate the effects of electron beam (EB) irradiation on the morphological properties, crystallinity and surface area of henequen fiber and on the mechanical and thermal properties of henequen fiber reinforced polypropylene (PP) composites. The structure of henequen fiber was characterized by X-ray diffraction, mercury porosimetry and BET surface area analysis. The EB irradiation of 10 kGy led to the increasing of crystalline and surface pore area of henequen fiber, which contributed to the number of interlocking places with PP. From the results of tensile and impact strength tests, the highest value was observed for the composite reinforced with the henequen fiber treated with EB dose of 10 kGy, decreasing overall as EB dose increased. This tendency was also shown by coefficient of thermal expansion (CTE) measurements, but the value of CTE decreased until 50 kGy, meaning that a large total surface area can provide many interlocking places and so improve adhesion between fiber and matrix. Therefore, it can be concluded that the optimum pore surface area by 10 kGy irradiation contributes to successful mechanical interlocking between fiber and matrix and consequently enhances the mechanical and thermal properties of the composites.     

Henequen/poly(butylene succinate) biocomposites: electron beam irradiation effects on henequen fiber and the interfacial properties of biocomposites

Henequen natural fiber-reinforced poly(butylene succinate) biocomposites were prepared through a resin microdroplet formation on a single fiber and also fabricated by a compression molding technique using chopped henequen fibers, surface-treated with electron beam irradiation (EBI) at various dosages. The effect of EBI treatment on the surface characteristics and dynamic mechanical properties of henequen fibers was investigated using SEM, XPS and DMA methods, respectively. Also, the interfacial behavior of biocomposites was explored through a single fiber microbonding test and fracture surface observations. The result indicates that the interfacial shear strength (IFSS) of biocomposites greatly depends on the EBI treatment level on the henequen fiber surface. This study also suggests that appropriate modification of natural fiber surfaces at an optimum EBI dosage significantly contributes to improving the interfacial properties of biocomposites.     

同系列电子给体与同系列电受体电荷转移络合作用的研究

用电子吸收光谱法, 研究了五个电子受体系列和三个电子给体系列以及非同系列的给、受体共48个化合物间的弱电荷转移络合作用。发现所研究的同系列给体与同一受体作用; 或同系列受体与同一给体作用; 或同系列给体与同系列受体作用, 一般存在着明显的CT络合与表观不络合的现象。通常情况下, 同系序数大的化合物呈现表观不络合;有时, 同系序数大和小的化合物, 即同系物的两头均呈现表观不络合现象, 对此种现象用给、受体间前线分子轨道能级关系进行了讨论。     

可溶性聚[3-(2,2,3,3-四氟丙氧基)噻吩]的光谱性质

研究了中性和经FeCI3掺杂后聚[3-(2, 2, 3, 3-四氟丙氧基)噻吩](P3FT)溶液的光谱性质。中性P3FT具有特殊的溶剂色效应, 其甲醇 溶液的溶剂化吸收带强度随P3FT浓度增大而增强, 该吸收带是高分子链与链之间的相互作用(即聚合物的聚集态结构)的反映。用电子光谱跟踪FeCI3掺杂P3FT的过程, 结果表明, P3DT随着掺杂程度的增大, 载流子由极化子转变成双极化子, 且双极化子的能级位于禁带中间, 与孤子相似。     

三核钼原子簇化合物的EPR和电子结构

本文报道一个新的三核钼原子簇化合物在室温和77K固态和液态的EPR谱,这些谱均呈现出a,b两套谱线的叠加,分析谱线的强度比,线宽和谱参数,认为g值较大的a谱归属于三核钼原子簇化合物,而b谱归属于单核钼杂质。从由X射线晶体结构方法确定的空间结构出发,三核钼原子簇化合物可能有两种分子形式:Mo3(μ3-S)(μ2-S)3Cl[S2P(OEt)2]4 1Mo3(μ3-S)(μ2-S)(μ2-Cl)2Cl[S2P(OEt)2]4 2分别用简单量子化学理论和EHMO法计算出未配对电子所处的分子轨道,求出g1和g1,并与EPR实验值相比较,认为该化合物的分子式应为2,簇骼{Mo3}属七电子体系,在77K温度下,其未配对电子主要局域在三个钼原子所组成的近似等腰三角形簇骼的顶点钼原子周围。     

异构化的π-丁二烯二羰基(乙氧基芳基卡宾)铁配合物的质谱研究

1964年Fischer等报道了第一个过渡金属卡宾配合物以来,为数众多的过渡金属配合物已被合成和鉴定。最近我们合成了一系列异构化的π-丁二烯二羰基(乙氧基芳基卡宾)铁配合物,并研究了它们的红外光谱和核磁共振谱。本文报道这类新型配合物的低分辨电子轰击电离(EI)质谱,探讨其可能的断裂途径。它们的EI质谱表明,存在一系列具有结构信息的特征离子,相应的特征峰有助于配合物的结构鉴定。根据红外光谱分析和X-射线晶体结构分析,这些新型配合物具有下面两种结构类型,其中3为B型结构,其它均为A型结构。     

Photoinduced electron transfer between adamantanamine-(OCH2CH2)n-phenothiazine and mono-6-p-nitrobenzoyl-β-cyclodextrin

A series of adamantanamine-(OCH₂CH₂)_n-phenothiazine (n = 0, 1, 2, 3) electron donors was synthesized. Photoinduced electron transfer was observed in the supramolecular complex of the phenothiazine derivatives with p-nitrobenzoyl-β-cyclodextrin (NBCD) through binding of the adamantyl group by the NBCD cavity, which is stabilized clearly via hydrophobic interactions in aqueous solution. Detailed Stern–Volmer constants were measured and they were partitioned into dynamic Stern–Volmer quenching constants and static binding constants. The results revealed an efficient electron transfer process inside the supramolecular systems compared to that controlled by diffusion. This observation also indicates that the chain length will influence the electron transfer efficiency of a supramolecular donor–acceptor system.