基于新型分子距边矢量ν与多元统计方法对于烷烃13C NMR化学位移和(CSS)估计与预测的深入研究

波谱学杂志 ›› 2001, Vol. 18 ›› Issue (4): 363-375.

基于新型分子距边矢量ν与多元统计方法对于烷烃¹³C NMR化学位移和(CSS)估计与预测的深入研究

袁晓燕^1,3, 余丹辉², 刘树深¹, 曹晨忠⁴, 谌其亭⁵, 李志良^1,5*

1.重庆大学化学化工学院, 重庆 400044; 2.岳阳市卫生局汨罗药检所, 岳阳 411026; 3.长沙大学物理与化学系, 长沙 410003; 4.湘潭师范学院化学系, 湘潭 4112 00; 5.长沙电力大学应用化学系, 长沙 410004

收稿日期:2001-04-05 修回日期:2001-08-31 出版日期:2001-12-05 发布日期:2001-12-05
作者简介:袁晓燕(1952-)，女,理学学士,教授,高级访问学者.
基金资助:
国家春晖计划项目教育部启动基金(1998) 及霍英东基金(1998) 资助课题.

ON FURTHER INVESTIGATION INTO ESTIMATION AND PREDICTION OF CHEMICAL SHIFT SUM OF CARBON-13 NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY IN ALKANES BASED ON A NOVEL MOLECULAR DISTANCE-EDGE VECTOR (VMDE OR ν)

YUAN Xiao-yan^1,3, YU Dan-hui², LIU Shu-shen¹, CAO Chen-zhong⁴, CHEN Qi-ting⁵, LI Zhi-liang^1,5*

1.College of Chemistry and Chemical Engineering (CECCE), Chongqing University , Chongqing 400044;
2.Miluo Institute of Pharmaceutical Monitoring and Management, Yueyang Bureau of Hygience and Health, Miluo 411126;
3.Department of Physics and Chemistry, Changsha University, Changsha 410007;
4.Department of chemistry, Xiangtan Normal University, Xiangtan 411100;
5.Department of Applied Chemistry, Changsha Electrical Power College, Chang sha 410004

Received:2001-04-05 Revised:2001-08-31 Online:2001-12-05 Published:2001-12-05
About author:*Correspondence author.
Supported by:
国家春晖计划项目教育部启动基金(1998) 及霍英东基金(1998) 资助课题.

摘要/Abstract

摘要：

基于本实验室提出一种新型以势能形式表达的分子距边矢量, 深入地系统研究了核磁共振碳-13谱化学位移和(CSS)规律以及分子拓扑指数矢量在定量结构波谱关系(QSSR)中的应用. 借助多种计量化学方法包括多元线性回归、逐步多元回归、主成分回归、主筛选回归等进行分子拟模和定量相关研究, 发现烷烃¹³C NMR 化学位移和(CSS)与其分子距边矢量及路径长度指数有良好线性相关性, 回归方程及其统计参数为: CSS=bν+cp₃=∑_^mj=0b_jν_j+b₁₁p₃=b₀ν+b₁ν₁+b₂ν₂+b₃ν₃+b₄ν₄+b₅ν₅+b₆ν₆+b₇ν₇+b₈ν₈+b₉ν₉+b₁₀ν₁₀+b₁₁p₃=-13.576+22.179ν₁+28.407ν₂+25 .950ν₃+26.690ν₄+14.498ν₅+5.726ν₆-5.379ν₇-3.214ν₈-15.021ν₉ -25.710ν₁₀+12.278p₃ n=63, R=0.997, EV=99.68%, RMS=3.7348, SD=4.1 18, F= 773.116, U=144228.844, Q=864.938; CV: R²_CV=0.980, EV=98.83%, RMS=7.126 1, SD_CV=7.634, F_CV=221.720, U_CV=142121.891, Q_CV=2971 .896. 结果良好.

关键词: 分子模建模拟, 分子距边矢量ν, 化学结构参数化, 核磁共振碳谱, 烷烃化学位移和(CSS), 定量构谱关系

Abstract:

Based on a novel molecular distance-edge vector (VMDE,ν), expressed in the form of potential energy and developed in our laboratories, further syst ematic studies were made on the regularity of chemical shift sum (CSS) for c arbo n-13 nuclear magnetic resonance ¹³C NMR). With aid of several chemom etrical techniques including multiple linear regression (MLR), stepwise multiple regressi on (SMR) and principal component regression (PCR), various molecular modelling e quations were established to correlate chemical shift sum (CSS) of carbon-13 nucl ear magnetic resonance ¹³C NMR) excellently to the molecular distance-edge vec tor (VMDE) together with the path count of three bonding segment (C-C-C) as foll ows, whose very good results were obtained for the modelled estimation and accur ate prediction with cross validation (CV) of leave-one-out (LOO) procedure: CSS=bν+cp₃=∑^m_j₌₀b_jν_j+b₁₁p₃=b₀ν+b₁ν₁+b₂ν₂+b₃ν₃+b₄ν₄+b₅ν₅+b₆ν₆+b₇ν₇+b₈ν₈+b₉ν₉+b₁₀ν₁₀+b₁₁p₃=-13.576+22.179ν₁+28.407ν₂+25 .950ν₃+26.690ν₄+14.498ν₅+5.726ν₆-5.379ν₇-3.214ν₈-15.021ν₉ -25.710ν₁₀+12.278p₃ n=63, R=0.997, EV=99.68%, RMS=3.7348, SD=4.1 18, F= 773.116, U=144228.844, Q=864.938; CV: R²_CV=0.980, EV=98.83%, RMS=7.126 1, SD_CV=7.634, F_CV=221.720, U_CV=142121.891, Q_CV=2971 .896. Some reliable correlation models have been developed by using the adjoin structural descriptors through combination of the MDE vector (ν vector) and molecu lar path counts of length three (p₃).

Key words: Molecular modelling and simulation, Molecular distance-edge vector ν, Chemical structural parameterization, Chemometrics and chemoinformatics, Multip le linear regression (MLR), Stepwise multiple regression (SMR), Principal comp onent regression (PCR), Carbon-13 nuclear magnetic resonance spectroscopy ¹³C NMR), Cross validation, Chemical shift sum of alkanes, Quantitative struc ture-spectrum relationships (QSSR)

中图分类号:

O482.53⁺2

袁晓燕, 余丹辉, 刘树深, 曹晨忠, 谌其亭, 李志良. 基于新型分子距边矢量ν与多元统计方法对于烷烃¹³C NMR化学位移和(CSS)估计与预测的深入研究[J]. 波谱学杂志, 2001, 18(4): 363-375.

YUAN Xiao-yan, YU Dan-hui, LIU Shu-shen, CAO Chen-zhong, CHEN Qi-ting, LI Zhi-liang. ON FURTHER INVESTIGATION INTO ESTIMATION AND PREDICTION OF CHEMICAL SHIFT SUM OF CARBON-13 NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY IN ALKANES BASED ON A NOVEL MOLECULAR DISTANCE-EDGE VECTOR (VMDE OR ν)[J]. Chinese Journal of Magnetic Resonance, 2001, 18(4): 363-375.

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基于新型分子距边矢量ν与多元统计方法对于烷烃¹³C NMR化学位移和(CSS)估计与预测的深入研究

ON FURTHER INVESTIGATION INTO ESTIMATION AND PREDICTION OF CHEMICAL SHIFT SUM OF CARBON-13 NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY IN ALKANES BASED ON A NOVEL MOLECULAR DISTANCE-EDGE VECTOR (VMDE OR ν)

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