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-  2019 

水液相环境下氢氧根水分子簇催化布洛芬旋光异构及质子的作用 Optical Isomerism of Ibuprofen Catalyzed by Hydroxyl-Water Cluster and Roles of Protons in the Water Liquid Phase Environment

Keywords: 布洛芬,旋光异构,氢氧根,质子,密度泛函,过渡态,从头算,自洽反应场

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Abstract:

采用基于密度泛函理论的B3LYP方法和从头算的MP2方法,结合自洽反应场理论的SMD模型,研究了布洛芬(Ibu)分子2种稳定构象的旋光异构反应。研究发现:Ibu的旋光异构有氢氧根拔α-氢和氢氧根水分子簇联合拔α-氢两种机理。势能面计算表明:对于构象1,氢氧根拔α-氢时旋光异构的决速步骤能垒为42.69kJ·mol~(-1),氢氧根水分子簇联合拔α-氢时旋光异构的决速步骤能垒为48.83kJ·mol~(-1);对于构象2,氢氧根拔α-氢时旋光异构的决速步骤能垒为38.73kJ·mol~(-1),氢氧根水分子簇联合拔α-氢时旋光异构的决速步骤能垒为50.72kJ·mol~(-1)。质子的存在会使Ibu旋光异构反应的后半程变成无势垒放热反应。结果表明,水液相碱性环境下布洛芬分子可以较快地旋光异构,质子与氢氧根离子共存会使Ibu旋光异构的反应速度更快

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