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Electronic Structure and Circular Dichroism of Natural Alboatisins Isolated from Aerial Parts of Isodon Albopilosus: DFT and TDDFT Study
Gao-zhang Gou*,Bo Zhou,Ling Shi,Shao-ming Chi,Xian-lan Chen,Wei Liu*
Author NameAffiliationE-mail
Gao-zhang Gou* School of Science, Honghe University, Mengzi 661199, ChinaKey Laboratory of Natural Pharmaceutical and Chemical Biology of Yunnan Province, Mengzi 661199, China hhxylxyhxx@126.com 
Bo Zhou School of Science, Honghe University, Mengzi 661199, China  
Ling Shi School of Science, Honghe University, Mengzi 661199, China  
Shao-ming Chi College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China  
Xian-lan Chen School of Science, Honghe University, Mengzi 661199, China  
Wei Liu* School of Science, Honghe University, Mengzi 661199, ChinaKey Laboratory of Natural Pharmaceutical and Chemical Biology of Yunnan Province, Mengzi 661199, China liuwei4728@163.com 
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.
Key words:  Alboatisin, Optical activity, Density functional theory, Circular dichroism, Cotton effect
FundProject:
天然Alboatisin电子结构和圆二色谱的密度泛函理论研究
苟高章*,周波,石玲,迟绍明,陈显兰,刘卫*
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VCD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.
关键词:  Alboatisin,旋光度,圆二色谱,密度泛函理论,论科顿效应
DOI:10.1063/1674-0068/28/cjcp1503045
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