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水分子(簇)和水溶剂对脯氨酸铜(Ⅱ)对映异构的影响 被引量:2
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作者 刘芳 辛志荣 +5 位作者 范艳洁 李心雨 潘宇 杨清荟 姜春旭 王佐成 《中山大学学报(自然科学版)(中英文)》 CAS CSCD 北大核心 2022年第5期105-116,共12页
采用密度泛函理论的M06和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水分子(簇)和水溶剂对气相S-脯氨酸二价铜配合物(S-Pro·Cu(Ⅱ))对映异构的影响。研究发现:S-Pro·Cu(Ⅱ)的对映异构可在5个通道a、b、c、d和e实现,a、... 采用密度泛函理论的M06和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水分子(簇)和水溶剂对气相S-脯氨酸二价铜配合物(S-Pro·Cu(Ⅱ))对映异构的影响。研究发现:S-Pro·Cu(Ⅱ)的对映异构可在5个通道a、b、c、d和e实现,a、b和c通道分别是α-H直接以O、Cu、N为桥迁移;c和d通道是Cu与羰基O双齿配位后,α-H以O为桥以及O和N联合为桥迁移(其中α-H以Cu为桥迁移是氢负离子迁移,其他为氢质子迁移)。势能面计算表明:孤立的S-Pro·Cu(Ⅱ)在b和c通道的对映异构有明显的优势,反应活化能分别是153.4和160.3 kJ·mol^(−1)。水汽环境下c通道最具优势,反应活化能是143.7 kJ·mol^(−1),b通道最具劣势,在该通道的对映异构不能实现。水溶剂效应使c通道的反应活化能降到89.9 kJ·mol^(−1)。结果表明:脯氨酸铜(Ⅱ)在气相和水汽相下可以保持其手性特征,在水液相下容易对映异构。 展开更多
关键词 脯氨酸 二价铜离 水分() 水溶剂 对映异构 密度泛函理论 过渡态 能垒
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A simplified adsorption model for water vapor adsorption on activated carbon 被引量:2
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作者 姚小龙 李立清 +1 位作者 李海龙 马卫武 《Journal of Central South University》 SCIE EI CAS 2014年第4期1434-1440,共7页
A simplified model was developed to describe the water vapor adsorption on activated carbon. The development of the simplified model was started from the original model proposed by DO and his co-workers. Two different... A simplified model was developed to describe the water vapor adsorption on activated carbon. The development of the simplified model was started from the original model proposed by DO and his co-workers. Two different kinds of carbon materials were prepared for water vapor adsorption, and the adsorption experiments were conducted at different temperatures(20-50 °C) and relative humidities(5%-99%) to test the model. It is shown that the amount of adsorbed water vapor in micropore decreases with the temperature increasing, and the water molecules form larger water clusters around the functional group as the temperature is up to a higher value. The simplified model describes reasonably well for all the experimental data. According to the fitted values, the parameters of simplified model were represented by the temperature and then the model was used to calculate the water vapor adsorption amount at 25 °C and 35 °C. The results show that the model can get relatively accurate values to calculate the water vapor adsorption on activated carbon. 展开更多
关键词 water vapor adsorption activated carbon model
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