无环醇^(13)C NMR化学位移与其结构参数的定量关系  

Quantitative Relationship Between ~13(C) Nuclear Magnelic Resonance Chemical Shift and Structural Parameters of Acyclic Alcohol

作　　者：戴益民[1,2,3] 李浔[1,3] 梁波[1] 杨道武[1,3] 曹忠[1,3] 黄可龙[2] 

机构地区：[1]长沙理工大学化学与生物工程学院,长沙410004 [2]中南大学化学化工学院,长沙410083 [3]湖南省电力与交通材料保护重点实验室,长沙410004

出　　处：《分析化学》2009年第12期1754-1758,共5页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(Nos.20775010;50803008);国家"863"计划项目(No.2008AA05Z405);湖南省科技攻关项目(No.2008GK3063);湖南省教育厅科学研究基金(No.09C066)资助

摘　　要：用新颖的原子拓扑矢量YC、原子平衡电负性qe、结构信息参数[NHi(i=α,β)]和γ校正参数对63个无环饱和脂肪醇的局部化学微环境进行了结构表征,并对化合物13C NMR化学位移进行了QSSR研究。采用偏最小二乘回归得到模型的复相关系数R和标准偏差S分别为0.9915和2.4827;对353个碳原子13C NMR化学位移的实验值与计算值的平均绝对误差仅为2.01×10-6。同时,采用留分法(Leave-molecule-out)和外检验方法测试模型的内部稳定性和外部预测能力。与文献结果比较,本研究所用参数少,且计算简便。A newly developed topological vector of atom Yc, equilibrium electro-negativity of atom qe, molecular structural information parameter [N^iH（i=α,β）] and γ calibration parameter were used to describe the local chemical microenvironment of 63 acyclic alcoholic compounds. Quantitative structural spectrum relation-ships （QSSR） was systematically made on relationship between ^13C NMR chemical shifts of 353 carbon atoms and their molecular structure descriptors. By partial least square regression （PLS）, the statistical results indicated that the model correlation coefficient and standard error were 0.9915 and 2.4827, respectively. And the average absolute error was only 2.01×10^-6 between the calculated and experimental chemical shifts for 353 carbon atoms. To validate the estimation stability for internal samples and the predictive capability for external samples of resulting models, leave-molecule-out （LMO） cross validation （CV） and external validation were performed. Compared with the reported result, not only the number of descriptors employed in this study was much fewer, but also the calculation was much easier.

关 键 词：醇 碳-13核磁共振 化学位移 分子结构参数 定量结构-波谱关系 

分 类 号：O623.412[理学—有机化学]