1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me₂SiSiMe₂)[Me₄CpMo(CO)₃-Li⁺]₂(I),I与冰醋酸作用,随即分别与CCl₄,NBS及I₂反应,生成相应的铝卤化合物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃X]₂[X=Cl(1),Br(2),I(3)].I与CH₃I反应,在钼原子上发生烃基化,得到产物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃Me]₂(4);I与单质I₂直接反应,生成脱硅桥产物Me₄Cp(CO)>₃I(5).经元素分析、IR及¹HNMR表征了化合物1-5的结构。     

Biosorption of Cadmium by Phanerochaete Chrysosporium

The biosorption properties of cadmium(Ⅱ) by pre-treated biomass of Phanerochaete chrysosporium in the form of pellet were investigated. It was found that formaldehyde cross-linking and subsequent alkaline treatment could significantly improve the adsorption capacity of the biomass compared to other sorts of treatments, such as calcium chloride treatment, HCl treatment and,acetone treatment. Biosorption capacity of cadmium was examined as a function of physical and chemical factors including the pH of the metal solution pellet size, temperature and biomass concentration. The cadmium removal efficiency was strongly affected by pH. The maximal adsorption occurred around pH4.5. The pellet size also had a marked influence on the cadmium removal efficiency and the optimum size was the diameter range of 1.5-2.0 mm. The effect of biosorption temperature on cadmium uptake was inconspicuous between 25℃ and 35℃, but there was a notable decrease in cadmium uptake when the temperature reached 40℃. The cadmium removal efficiency increased as the biomass concentration when the initial cadmium ion concentration was 10 mg/L. When the biomass concentration was 2 g/L,the removal efficiency was 99.56%. However, the augment of the. removal efficiency was not obvious when the biomass concentration was more than 2 g/L. On the optimum conditions mentioned above,cadmium concentration could be reduced from 10 ppm down to 0.04 ppm that was below the Chinese National Waste Water Integrated Discharge Standard. In the biosotption process, most of the metal uptake happened during a short period immediately after the adsorption process started. It was observed that the biomass pellets had already adsorbed 83.36% of the total amount of cadmium finally adsorbed within the initial 10 minutes. The cadmium uptake rate decreased gradually afterwards. Sorption equilibrium could almost be established in 12 hours. This indicated that biosorption might consist of two processes:a fast surface binding process opcurring first and a slow membrane diffusion process taking place subsequently.     

Study of Competitive Chelating Reaction between Lanthanum and Tribromoarsenazo in the Medium of Weak acid by Capillary Zone Electrophoresis

Study of chelating reaction in solution is one hot and difficult field in coordination chemistry, and HPLC and CE have been used to study the kinetics of fast equilibrium in this field successfully. However, these methods are used for studying relative simple reaction systems presently^[1-3]. This-paper describes a new application of CE for studying complication competitive chelating reaction in fluid-phase, which is difficult to be studied by conventional methods. Two kind metal chelate complexes of lanthanum reacted with TBA formed under the condition of critic acid were observed in real time by simultaneous technique of CE-PTI spectrometry. The tendency of the conversion between these chelates as functions of the mole ratio of the reagent and the metal, pH value and the elapsing time was investigated. Kinetic equation of competitive chelating reaction between the TBA-La (Ⅲ) and La (Ⅲ) -critic acid was established too. As shown in tablel, It was found this competitive chelating reaction following second-order reaction, and reaction constant k=5.55 L·mol^-1·S^-1.     

截断切割问题的数学模型

本文就 1 997年全国大学生数学建模竞赛中 B题所给的截断切割问题建立了一个数学模型 ,并给出了求解的方法 .     

铝化物金属间化合物中自由电子密度、微观缺陷及其键组成

通过测量Ni₅₀Al₅₀,Ti₅₀Al₅₀,Fe₆₀Al₄₀,Fe₇₂Al₂₈合金和高定向石墨晶体的正电子寿命谱参数,分别计算了这些样品基体和缺陷态的自由电子密度.结果表明,合金基体的自由电子密度较低,合金中金属键和共价键共存.以具有确定键组成的石墨晶体作为参照,计算了这些合金中分别参与形成金属键和共价键的价电子数占总价电子数的百分比.不同的合金具有不同的键组成,Ni₅₀Al₅₀,Ti₅₀Al₅₀和Fe₆₀Al₄₀合金中的共价键成分都比较高,均高于Fe₇₂Al₂₈合金中的共价键成分.金属间化合物中的成键特征对其晶体结构和晶界结构有较大的影响.共价键成分高的合金中,其晶界缺陷处的自由电子密度较低.讨论了自由电子密度、微观缺陷和键组成对合金力学性能的影响.     

以分子印迹聚合物为固定相手性拆分1,1′-联-2-萘酚及其衍生物

以(R)-(+)-1,1′-联-2-萘酚为模板分子,4-乙烯基吡啶为功能单体合成了分子印迹聚合物,将其作为高效液相色谱的固定相,研究其手性识别特性。对该固定相的手性拆分的色谱条件进行了优化。实验结果表明,合成的印迹聚合物对(R)-(+)-1,1′-联-2-萘酚具有较强的亲和力和特定的选择性,能有效拆分1,1′-联-2-萘酚对映体,分离因子最高达到12.25。通过优化色谱条件,该分子印迹聚合物还能对与1,1′-联-2-萘酚结构相似的衍生物5,6,7,8,5′,6′,7′,8′-八氢-1,1′-联-2-萘酚和1,1′-联萘-2-氨基-2′-酚进行手性拆分,分离因子分别达到1.51和2.40。     

高速逆流色谱分离同分异构体

应用高速逆流色谱法对同分异构体的分离纯化进行研究。实验结果表明,以正己烷-乙酸乙酯-水(体积比为1∶10∶10)为两相溶剂系统,上相为固定相,下相为流动相,进行二次高速逆流色谱分离,可从茶多酚中分离出g级的儿茶素同分异构体——(-)-表没食子儿茶素没食子酸酯(EGCG)和(-)-没食子儿茶素没食子酸酯(GCG),其高效液相色谱纯度均在98%以上。选择四氯化碳-氯仿-甲醇-水(体积比为7∶3∶7∶3)为溶剂系统,下相为固定相,上相为流动相,经一次高速逆流色谱即可将药物中间体溴代苯胺同分异构体进行有效的分离。     

硅烷化衍生-气相色谱/质谱法分析糖氨反应中的2,6-脱氧果糖嗪

糖氨反应混合物之所以被广泛地用于炯草行业以改善或者增强卷烟烟气,关键在于其含有大量的吡嗪类化合物,而2-（1′,2′,3′,4′-四羟基丁基）-6-（2″,3″,4″-三羟基丁基）-吡嗪,或称2,6-脱氧果糖嗪（简称2,6-DOF,结构见图1-a）就是糖氨反应的重要产物之一。该化合物的相对分子质量较大（Mr304）,挥发性低,多羟基极性强,无法直接进行气相色谱／质谱（GC／MS）表征。本文先对2,6-DOF进行三甲基硅烷化预处理,然后用GC／MS对其进行定性和粗略的定量检测。该方法可有效地用于糖氨反应实验的跟踪。     

基于修正的Magnus方法的高振荡动力系统的数值积分方法

基于建立于一般线性动力系统上的Magnus数值积分方法,针对随时间而高频率振荡的二阶动力系统,给出了有效的修正Magnus数值积分算法．首先,将二阶动力系统重新表示为一阶系统的形式,通过引进新变量进行参考坐标变换,使动力系统的高振荡性质保留在新形式内;进而基于局部线性化技术用修正的Magnus方法求解新形式下的系统方程;最后,通过一系列数值实验说明了文中方法的有效性．     

空心微米镍球的表面改性及微波吸附性能研究

采用特殊的化学镀方法对已制备的空心微米镍球进行表面组装, 成功地在该镍球表面包覆了一层蜂窝状包覆钴层. 通过FESEM, TEM, XRD衍射表征了该包覆镍球, 观察到均匀包覆钴层的网眼构造和密集孔隙结构. 用BET气体吸附法、同轴线法对该镍球比表面积和微波性能进行了研究. 研究表明, 蜂窝状包覆钴层提高了粒子的比表面积, 同时表面镀钴提高了镍球的复介电常数值, 从而能增加粒子对电磁波的电介质损耗, 提高粒子在微波频率范围内对电磁波的反射吸收.