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天然Alboatisin电子结构和圆二色谱的密度泛函理论研究(英文)

Electronic Structure and Circular Dichroism of Natural Alboatisins Isolated from Aerial Parts of Isodon Albopilosus:DFT and TDDFT Study

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【作者】 苟高章周波石玲迟绍明陈显兰刘卫

【Author】 Gao-zhang Gou;Bo Zhou;Ling Shi;Shao-ming Chi;Xian-lan Chen;Wei Liu;School of Science,Honghe University;Key Laboratory of Natural Pharmaceutical and Chemical Biology of Yunnan Province;College of Chemistry and Chemical Engineering,Yunnan Normal University;

【机构】 红河学院理学院化学系云南省天然药物和化学生物重点实验室云南师范大学化学化工学院

【摘要】 采用蒙特卡罗MMFF94分子力学力场方法搜索一类新发现的生物活性分子Alboatisin A~C的稳定构象,用梯度校正的B3LYP方法,计算其稳定构象的旋光度、振动圆二色谱(VCD)、电子圆二色谱(ECD)等光学活性,并从微观的角度对VCID谱和ECD谱中强或弱的正或负康登效应进行归属.从分子结构、电子结构和分子振动分析了分子手性的微观起源.结果表明,计算与实验的旋光度值相吻合,OH的取代位置与数目可调控旋光度发生在手性骨架上的振动或电子跃迁转移是手性光谱产生的重要原因.Alboatisin的圆二色谱是手性骨架变形振动的光谱响应,是不对称电子跃迁的光谱响应结果.

【Abstract】 The stable conformations of a series of bioactive molecules,(—)-alboatisins A—C,are identified via Monte Carlo searching with the MMFF94 molecular mechanics force field.Then,the optical rotation(OR) values,vibrational circular dichroism(VCD),and electronic circular dichroism(ECD) spectra were calculated using the gradient-corrected density functional theory method.The vibrational and transition modes of molecular chirality were explored in terms of their microscopic origin.The calculated specific rotations are in agreement with the experimental values.From the OR analysis,it was concluded that optical rotation values are regulated by hydroxyl substitution.Vibrations occurring on the chiral skeleton may cause strong absorption in VCD spectra;VCD spectra are thus the spectral response to deformation vibrations on the chiral carbon skeleton.The lowest-energy negative Cotton effect is caused by σ→π~* transition.Frontier molecular orbital analysis showed that strong ECD absorptions are produced when the dominant transition on the chiral skeleton is asymmetric;ECD spectra show the result of transitions lacking asymmetry on the chiral skeleton.

【基金】 supported by the National Natural Science Foundation of China(No.61361002 and No.21262049);the"Chun Hui"Plan of Chinese Ministry Education(No.Z2011125);the Scientific Research Foundation of Education Department of Yunnan Province(No.2013FZ121);the Youth Program of Yunnan Province(No.2014FD054);the Chemistry of Key Construction Disciplines for Master Degree Program in Yunnan(No.HXZ1303);the Educational Reform Program of Honghe University(No.JJJG1412);the General Program of Yunnan Provincial Education Departmen(No.2015Y455)
  • 【文献出处】 Chinese Journal of Chemical Physics ,化学物理学报(英文版) , 编辑部邮箱 ,2015年06期
  • 【分类号】O629;O641.1
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