基于药效团模型设计的PAEs分子拉曼特征振动光谱衍生增强研究  

Derivatization Enhanced Raman Characteristic Vibration Spectrum of PAEs Based on Pharmacophore Model

作　　者：邱尤丽 辛美玲 李鱼 

机构地区：[1]华北电力大学环境科学与工程学院,北京102206 [2]华北电力大学资源环境系统优化教育部重点实验室,北京102206

出　　处：《光谱学与光谱分析》2018年第2期441-447,共7页Spectroscopy and Spectral Analysis

基　　金：国家"十一五"科技支撑项目(2008BAC43B01);中央高校基金项目(2017XS058)资助

摘　　要：对17个PAEs训练集分子、五个PAEs测试集分子,应用Discovery Studio软件构建PAEs分子拉曼特征振动光谱的3DQSAR药效团模型,并对PAEs分子(以环境优先控制污染物DMP,DBP和DNOP为例)进行9种常见的疏水基团取代反应,同时利用密度泛函理论B3LYP/6-31G(d)计算气态环境中取代前后PAEs的拉曼特征振动光谱,筛选PAEs拉曼特征振动光谱显著增强的衍生物。研究结果表明:药效团模型(Hypo1)具有最大的相关系数(R^2)0.83、最小的均方根值(RMS)0.182和总消耗值(total cost)71.865,且Configuration值为12.68(<17),说明所构建模型具有显著性及较好的预测能力;获得基于Hypo 1药效团模型设计的PAEs分子衍生物23个:DMP(9),DBP(9)和DNOP(5),上述衍生物分子正频计算值均大于0,说明所设计的PAEs分子衍生物结构稳定,其中DMP-CH_2CH_3,DBP-Cl,DNOP-C_6H_5的拉曼特征振动光谱峰强较DMP,DBP和DNOP分别增大了6.25倍、2.05倍、1.56倍,说明PAEs分子衍生化对其拉曼特征振动光谱峰强具有显著增强作用。此外,利用密度泛函理论在相同的基组水平下计算了PAEs分子衍生物的取代反应能垒(以DNOP为例),取代反应的难易程度:—CH_2CH_2CH_3>—C_6H_5>—NO_2>—SH>—Cl,可作为筛选PAEs分子衍生化拉曼光谱增强反应的依据,并为建立增强PAEs分子拉曼光谱的检测技术提供理论支撑。In this paper,3DQSAR pharmacophore models of PAEs Raman characteristic vibration spectrum were established by Discovery Studio software for 17phthalic acid esters were used as training set and 5phthalic acid esters used as test set.The substitution reaction of PAEs（take environmental priority controlled pollutants DMP,DBP and DNOP for example）used the optimal pharmacophore model built by Hypo 1and 9kinds of common hydrophobic groups.At the same time,the Raman characteristic vibration spectrum of PAEs and derivatives in gaseous environment were calculated by using density functional theory at B3LYP/6-31g（d）level,which was to screen derivative reaction of PAEs Raman characteristic vibration spectrum enhanced significantly.The results showed that the pharmacophore model（Hypo 1）was significant and had good predictive abilities with the greatest correlation coefficient（R^2）of 0.83,the smallest value of root mean square（RMS）of 0.182and the total cost of71.865,the configuration value of 12.68（〈17）.There were 23PAEs derivatives based on Hypo 1,including 9DMP derivatives,9DBP derivatives,5DNOP derivatives,and the positive frequencies of derivative molecules were greater than 0,which illustrate the structure of PAEs derivatives were stable.The Raman characteristic vibration spectrum intensity of DMP-CH2CH3,DBP-Cl,DNOP-C6H5increased comparing with DMP,DBP,DNOP by 6.25times,2.05times and 1.56times respectively,which indicated that PAEs derivatization had significantly enhanced effect on Raman characteristic vibration spectrum intensity.In addition,the substitution reaction energy barriers of PAEs derivatives were calculated by using density functional theory at B3LYP/6-31g（d）level,（take DNOP for example）,and the substitution reaction order of the substituent—C6H5,—CH2CH2CH3,—SH,—Cl,—NO2and DNOP molecule was—CH2CH2CH3〉—C6H5〉—NO2〉—SH〉—Cl,which can be uesd as the basis of screening PAEs molecular derivatization enhanced Raman spectrum reaction and provide theoretical

关 键 词：邻苯二甲酸酯 药效团模型 拉曼特征振动光谱 衍生增强 环境检测 

分 类 号：O657.3[理学—分析化学]