钼铁硫原子簇化合物的合成与结构化学IV: 双类立方烷化合物与酰氯的反应

报导了双类立方烷簇状化合物(Et4N)4[Mo2Fe7S8(SC6H5)12]与乙酰氯在乙腈中的反应, 结果获得不含Fe(SC6H5)3桥的双类立方烷化合物(Et4N)4[Mo2Fe6S8(SC6H5)9]. 反应用^1H NMR和元素分析表征. 这种类型的结构转换为首次所见, 从而对化合物中桥的松散结构提供了新的实验证据.     

含磷拟除虫菊酯的研究I:3-[1'-磷(膦)酸酯基-2'-氯代乙烯基]-2,-二甲基环丙烷羧酸酯的合成及其几何异构体的研究

本文合成了九个新型的含磷拟除虫菊酯类化合物和五个新的中间体, 研究了亚磷(膦)酸酯的取代基空间位阻对Perkow重排产物中几何异构体的影响, 结果表明:取代基位阻增大, 产物E/Z比值也增大。     

醋酸乙烯酯基桥连铁硫配合物(σ,π-μ-CH3CO2C=CH2)(μ-RS)Fe2CO)6的制备及结构鉴定

本文报道乙酰氯同[μ-CO)(μ-RS)Fe2(CO]Et3NH相作用生成了标题化合物, 除用碳氢分析, IR, 'HNMR及X衍射技术表征这类配合物的结构和构象外, 还对形成此类产物的过程进行了初步讨论。     

稀土(III)三硬脂酸盐LB膜的制备及结构研究

用直接在5×10^-^5mol.dm^-^3稀土(III)氯化物水溶液的液面上铺展稀土(III)三硬脂酸盐(简称LnSt~3)的方法,在疏水光学玻璃片上连续沉积了44层以上的含稀土(III)(La、Nd、Sm、Eu、Tb)硬脂酸盐LB膜,转移比为0.7-0.8。低角度X射线衍射(2θ=0.3-14ⅲ)结果表明,膜的结构为高度有序的层状结构,相邻稀土离子面的间距为4.7-4.8nm。X射线光电子能谱(XPS)证实了五种膜中分别含有La、Nd、Sm、Eu和Tb元素。此外,还对LnSt~3LB膜进行了红外光谱考察,表明在亚相中加入一定浓度的稀土离子能有效地抑止界面上LnSt~3的水解作用,为制备含稀土(III)离子的优质LB膜提供了依据。     

MICELLIZATION STUDIES OF DODECYL BENZENESULFONIC ACID AND ITS INTERACTION WITH POLYVINYLPYRROLIDONE

Dodecyl benzenesulfonic acid (DBSA) surfactant was used in the present study to find the effect of concentration on its electrical conductance in solution from 293-323K above and below the critical micelle concentration (CMC). The micellization parameters i.e. degree of counter ion binding (β), aggregation number (n) and number of counter ion micelle(m) were measured. The interaction of DBSA with polyvinylpyrrolidone (PVP) was also studied at 293K throughconductance and surface tension measure ments. A number of important parameters i.e. critical aggregation concentration (CAC), Gibb‘s free energy (△G) and binding ratio (R) were determined and the effect of NaCl on the CAC and polymer saturation point (PSP) was also investigated.     

Calcium Sulfate as High-Performance Filler for Polylactide (PLA) or How to Recycle Gypsum as By-product of Lactic Acid Fermentation Process

Reinforcing of polylactide (PLA) with fillers can be an interesting solution to reduce its global price and to improve specific properties. Starting from calcium sulfate (gypsum) as by-product of the lactic acid fermentation process, novel high performance composites have been produced by melt-blending PLA and this filler after a previous specific dehydration performed at 500°C for min. 1 h. Due to PLA sensitivity towards hydrolysis, it has first been demonstrated that formation of β-anhydrite II (AII) by adequate thermal treatment of calcium sulfate hemihydrate is a prerequisite. Then, the modification of filler interfacial properties with different coating agents such as stearic acid (SA) and stearate salts has been considered. The effect of surface treatment on molecular, thermal and mechanical properties has been examined together with the morphology of the resulting composites. To take advantage of the improved lubricity and better wetting characteristics, the filler was coated by up to 2% (by weight) SA. The coating of the filler leads to PLA–AII composites that surprisingly exhibit thermal stability, cold crystallization and enhanced impact properties. Such remarkable performances can be accounted for by the good filler dispersion as evidenced by SEM–BSE imaging of fractured surfaces. As far as tensile proprieties are concerned, notable utilization of uncoated filler or filler coated by stearate salts leads to PLA–AII composites characterized by higher tensile strength and Young's modulus values. The study represents a new approach in formulating new melt-processable grades with improved characteristic features by using PLA as polymer matrix.     

土槿皮三萜成分的研究

从土槿皮(Pseudolarix kaempferi, Gord.)中分到两个三萜成分, 经化学和光谱方法证明, 其一为具有羊毛甾烷母核的新三萜-3氧代-羊毛甾-7,23,25-三烯-23,26-环氧-27-羧酸, 命名为金钱松呋喃酸(1), 另一个为白桦脂酸(2), 此外, 还分到β-谷甾醇和β-谷甾醇-β-D-葡萄糖苷。     

二氢辅酶的电催化氧化: I: α-萘甲酰尼罗蓝修饰电极性能研究

新的电子传递中间体α-萘甲酰尼罗蓝(NNB)能强烈吸附在石墨上以构成修饰电极。在-0.5V至+0.6V(vs. SCE)电位区内, 固定化的NNB表观出相当可逆的氧化还原行为, 总反应中有2个电子和2个质子参加。在pH7.0缓冲溶液中其表面标准电位E°'为-170mV, 表观电子传递常数kg为3s^-^1。NNB对还原辅酶NADH的电化学氧化有明显催化作用, 可使氧化过电位降低550mV。NADH的电催化遵循EC机理, 催化反应步骤为速度决定步骤, 其速度常数为3×10^3dm^3.mol^-^1.s^-^1。NNB在中性和弱碱性介质中的稳定性优于其它电子传递中间体, 是有前途的电催化剂。     

酪氨酸-KBrO3-H2SO4体系化学振荡反应的研究

本文首次报道酪氨酸-KBrO3-H2SO4体系的非催化化学振荡反应及在Ce^36+等金属离子催化下的振荡反应, 研究了振荡反应产物及许多因素对振荡反应的影响,讨论了非催化振荡反应的控制机理。根据实验结果以及振荡反应的一般机理,对上述体系非催化振荡反应的机理作了初步的探索, 并用以对实验现象作了定性说明。     

聚醚型非离子表面活性剂的混合表面膜III, 环氧乙烷一环氧丙烷嵌段共聚物, 聚丙二醇与十六醇, 硬脂酸的二元混合物

本文进一步研究了环氧乙烷-环氧丙烷嵌段共聚物(L61和F68)、聚丙二醇(PPG)分别与十六醇(CA)、硬脂酸(SA)所形成的二元混合膜。根据对π-α实验结果的分析, 表明PPG-CA、PPG-SA、F68-SA和L61-SA的混合单分子膜是不相混溶的, 而L61-CA和F68-CA的混合单分子膜则是混溶的。