微波硫灯发射光谱的理论模拟

通过实验观测了微波硫灯的发光光谱. 利用从头计算的多组态准简并微扰理论方法, 采用cc-pVQZ基组计算了S2分子B3Σu--X3Σg-态和B″3Πu-X3Σg-态的跃迁矩及其振动态之间跃迁的弗兰克-康登因子, 导出了S2分子振动分辨发射谱. 同时, 利用含时密度泛函方法计算了Sn(n=2~8)分子的吸收谱. 将计算得到的S2分子振动分辨发射谱与实验所测得的光谱分布进行了比较分析, 解释了微波硫灯的宽谱区发光光谱的特性.     

木质素磺酸盐的分离提纯

以粗木质素磺酸钠为原料, 采用树脂法、超滤法、长链胺法和溶剂萃取法对其进行了提纯. 红外光谱、元素分析、凝胶渗透色谱等测试结果表明, 溶剂萃取法不能达到提纯目的; 树脂法、超滤法、长链胺法可除去相对分子量小于1000的杂质, 粗木质素磺酸钠经提纯后木质素磺酸钠的质量分数从59.0%提高到90%左右, 且提纯产品的重均分子量和数均分子量均增大, 分子量分布更均一. 从产品收率、提纯效果及提纯工艺等3方面分析表明, 长链胺法除糖效果最好, 提纯后糖含量下降了50%; 超滤法的收率最高, 可达31%, 且其提纯产品的重均分子量较高, 达到12000, 比粗木钠提高了1倍以上.     

L1 β-Lactamase催化反应机理研究

用混合量子力学和分子力学(QM/MM)方法和密度泛函理论讨论了L1 β-Lactamase催化Nitrocefin水解的过程, 研究结果表明, 反应为多步反应: 第一步亲核进攻反应为反应的决速步骤, 并且伴随着酰胺键的断裂, 第二步反应为质子迁移反应. 同时讨论了金属锌在反应中的作用.     

微波辐射条件下混合溶剂体系中AlPO4-5分子筛的晶貌控制

在微波辐射条件下于混合溶剂体系中实现了AlPO4-5分子筛晶体的形貌控制. 实验结果表明, AlPO4-5分子筛晶体的长径比(c/a)随体系中乙二醇与水体积比的增大而减小, 其长径比可以在1.7~6.3之间调变. 当在体系中加入晶种诱导时, 产物晶粒的大小随加入晶种量的增加和诱导时间的延长而明显减小. 在正丁醇与水的混合体系中, 当正丁醇与水的体积比达到5∶1时, 可以形成哑铃形的特殊晶貌.     

Comparison Between the Effects of 2-Selenium Bridged β-Cyclodextrin and Ebselen on Treating SHRsp Stroke

A glutathione peroxidase（GPX） mimic, 2-selenium bridged β-cyclodextrin（2-SeCD）, was synthesized. In order to examine its role and mechanism in treating stroke we chose stroke-prone spontaneously hypertensive rats（SHRsp） as animal model. 56 SHRsps of 8-week olds were randomly divided into several groups： test groups （low, moderate, high dose of 2-SeCD） and control groups（positive and negative）. After onset of the stroke, the rats in test groups were orally administrated with different amounts of 2-SeCD, the positive control group with ebselen, and the negative control group with drinking water. The treatment lasted two weeks, followed by observation of the rats for 10 days, meanwhile blood pressure, biochemical parameters of plasma, and the contents of nitric oxide（NO） and malondialdehyde（MDA） in plasma and brain were determined. The results show that there were significant differences in contents of NO and MDA in plasma and brain between the test groups（high, moderate dose of 2-SeCD） and negative control group. The NO contents of the test groups were obviously higher than that of the negative control group （P〈0.01）. The MDA contents of the test groups（high, moderate dose of 2-SeCD） were obviously lower than that of the negative control group（P〈0.01）. The mechanism of 2-SeCD in treating stroke was discussed, which maybe related to the increase of NO and the decrease of MDA in plasma and brain tissue, but the exact mechanism should be further studied. Moreover, the tendencies of changes in systolic blood pressure, contents of NO and MDA, and other physiological parameters for the test groups were shown to be much better than the corresponding parameters for the positive group（the group with ebselen）（P〈0.05）, indicating that the treatment effect of 2-SeCD is better than that of ebselen.     

乳液聚合中聚苯胺膜形成的动力学研究

以(NH4)2S2O8(APS)为氧化剂,十二烷基苯磺酸(DBSA)同时为乳化剂和掺杂剂,采用乳液聚合方法制备聚苯胺膜(PANIfilm),用石英晶体微天平(QCM)实时监测聚苯胺膜的形成过程,并对其动力学过程进行研究.结果表明,聚苯胺成膜反应对APS是0.5级,对苯胺是1级,聚苯胺膜增长速率随温度的升高而增加,而聚苯胺膜的最终沉积量却减小,表观活化能Ea=41.15kJ/mol,与均相溶液聚合成膜法的结果相近;随着DBSA浓度的增加,聚苯胺膜增长速率减小,而最终的沉积量增大.     

高炉渣非晶态含量的定量分析方法研究

通过X-ray衍射方法对高炉渣中非晶态与晶态的含量进行了定量分析研究。定量分析过程包括标准样品制备、配样与衍射以及数据处理分析。数据处理包括非晶态衍射峰及晶态峰在一定衍射角度内的积分、线性拟合与定量系数确定。提出了X-ray衍射方法所用的高炉渣标准样品的制备方法,包括100％非晶态标样和100％晶态标样。提出了由100％非晶态和100％晶态为标准样品时,高炉渣中非晶态含量的测定方法,适用于非晶态含量较高(>80%)的高炉渣的定量分析。结合数学处理和X-ray衍射结果,可得到原始高炉渣中非晶态含量和晶态含量,以及相应的比例系数,适用于非晶态含量高的高炉渣(>90%)。     

双4,6-二甲基嘧啶-2-巯基衍生物的水相合成

2-巯基-4,6-二甲基嘧啶与碘(或卤代烷)在水溶液中反应合成了4种双4,6-二甲基嘧啶-2-巯基衍生物,其结构经1H NMR,IR,MS,元素分析和单晶X射线衍射表征.     

煤粉燃烧过程中灰膜形成比例实验研究

煤焦颗粒燃烧过程中,灰膜形成显著影响其燃烧特性.因此,本文借助高温沉降炉研究了 61～75,75～90和90～125 μm三种粒径黄陵烟煤在1273和1673 K温度下的燃烧特性与灰膜形成比例;借助扫描电镜(SEM)详细观测空心微珠颗粒内部结构,提出灰膜比例计算公式,并分析温度,粒径和碳转化率对灰膜比例的影响.结果表明...     

Theoretical Studies on the N-Phenylpyrrolidine Formation Mechanism Based on the Reaction of Phenylamine with 1,4-Butanediol

The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.