AEIV结合AHSI用于饱和脂肪酮类物质的13C NMR谱模拟

波谱学杂志 ›› 2006, Vol. 23 ›› Issue (2): 241-246.

AEIV结合AHSI用于饱和脂肪酮类物质的¹³C NMR谱模拟

1.重庆大学化学化工学院，重庆 400044；2.重庆大学生物医学工程教育部与重庆市重点实验室，重庆 400044

收稿日期:2005-10-11 修回日期:2005-12-09 出版日期:2006-06-05 发布日期:2006-06-05
基金资助:
霍英东基金[1998-7-6]，国家春晖计划教育部启动基金[1999-1-4/38]及重庆大学创新基金[2003-5-6]资助项目.

Estimation and Prediction of ¹³C Chemical Shifts of Saturated Ketones: A Quantitative Structure-Spectrum Relationship Study

1.College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044; 
2.Key Laboratory of Biomedical Engineering of Educational Ministry and Chongqing City, Chongqing 400044

Received:2005-10-11 Revised:2005-12-09 Online:2006-06-05 Published:2006-06-05
Supported by:
霍英东基金[1998-7-6]，国家春晖计划教育部启动基金[1999-1-4/38]及重庆大学创新基金[2003-5-6]资助项目.

摘要/Abstract

摘要：

应用一种反映分子局部微环境描述子——原子电性相互作用矢量（vector of atomic electronegative interaction，AEIV）和原子杂化状态指数（Atomic Hybridation State Index， AHSI）对饱和脂肪酮类化合物的55种分子中的153个¹³C NMR谱建模模拟，应用多元线性回归方法得到定量结构波谱关系(QSSR)模型的复相关系数R_MM=0.997，标准偏差为SD_MM=7.155. 采用留一法交互检验的结果是R_CV=0.993，SD_CV=10.195. 并随机抽出三部分分子进行检验，得到的相关系数分别是R_MM1=0.996，R_MM2=0.996，R_MM3=0.999. 研究结果表明使用AEIV和AHSI所建模型预测能力是相当稳定的.

关键词: ¹³C核磁共振波谱模拟, 原子电性作用矢量(VAEI), 定量结构波谱关系(QSSR)

Abstract:

A multiple linear regression model for calculating ¹³C chemical shifts in saturated ketones from the structural indices namely the atomic electronegative interaction (AEIV) vector and the atomic hybridation state index (HSI) was established using the ¹³C chemical shifts of 153 carbon atoms in 55 saturated alphatic ketones as the training set. The estimation correlation coefficient (R) and the standard deviation (SD) of molecular modeling (MM) were R_MM=0.997 and SD_MM=7.155, respectively. Leave-one-out (LOO) cross-validation (CV) was used to measure the prediction capability of the model, resulting in a correlation coefficient (R_CV) of 0.993 and a standard deviation (SD_CV) of 10.195. Furthermore, the validity of this method was tested using the ¹³C chemical shifts of three sets of saturated ketones selected randomly as the test sets, resulting in correlation coefficients of 0.996, 0.996 and 0.999, respectively. The results show that the model based on AEIV and HSI can be used to predict ¹³C chemical shifts in saturated ketones satisfactorily and with sufficient stability.

Key words: atomic electronegativity interaction vector, ¹³C chemical shift, NMR, saturated ketones, quantitative structure spectroscopy relationship

中图分类号:

O461

张巧霞, 周鹏, 李根容, 李志良. AEIV结合AHSI用于饱和脂肪酮类物质的¹³C NMR谱模拟[J]. 波谱学杂志, 2006, 23(2): 241-246.

ZHANG Qiao-Xia, ZHOU Peng, LI Gen-Rong, LI Zhi-Liang. Estimation and Prediction of ¹³C Chemical Shifts of Saturated Ketones: A Quantitative Structure-Spectrum Relationship Study[J]. Chinese Journal of Magnetic Resonance, 2006, 23(2): 241-246.

参考文献

[1] Beger R D，Freeman J P，Lay Jr J O，et al. Use of ¹³C NMR Spectrometric Data to Produce a Predictive Model of Estrogen Receptor Binding Activity[J]. J Chem Inf Comp Sci，2001，41(1): 219-224.

[2] Beger R D，Bolton P H. Protein φ and ψ dihedrals restraints determined from multidimensional hypersurface correlations of backbone chemical shifts and their use in the determination of protein tertiary structures[J]. J Biomol NMR，1997，10(2): 129-142.

[3] Wishart D S，Sykes B D. Chemical shifts as a tool for structure determination[J]. Method Enzymol, 1994，239: 363-392.

[4] Kvasnicka V. An Application of Neural Networks in Chemistry Prediction of ¹³C NMR Chemical Shifts[J]. J Math Chem，1991，6(1): 63-76.

[5] Meng L Z(孟令芝)，He Y B(何永炳). Organic Spectrocmetric Analisys(有机波谱分析)[M]. Wuhan(武汉): Wuhan University Press(武汉大学出版社)，1997. 3.

[6] Zhang M J(张梦军)，Liao C Y(廖春阳)，Zhou L P(周丽平)，et al. On Prelininary Approach to Estimation and Prediction of Chemical Shift of ¹³C NMR Spectroscopy in Flavonoids on Vector of Atomic Flectronegative Distance(黄酮类化合物的原子电矩矢量表达及核磁共振碳谱模拟)[J]. Chinese J Magn Reson(波谱学志)，2002，19(3): 293- 300.

[7] Liu S S，Liu H J，Yu B M，et al. Investigation on Quantitative Relationship between Chemical Shift of Carbon-13 Nuclear Magnetic Resonance Spectra and Molecular Topological Structure Based on a Novel Atomic Distance-Edge Vector (ADEV)[J]. J Chemom，2001，15(5): 427-438.

[8] Mei H(梅虎)，Zhou P(周鹏)，Li ZL(李志良)，et al. Calculation of ¹³C Chemical Shifts of Amino Acids Using Atomic Electronegativity Interaction Vector(原子电性作用矢量用于氨基酸化学位移计算). Chinese J Magn Reson(波谱学杂志), 2005，22(2): 163-172.

[9] Aylward G H，Findlay T J. SI chemical data(2nd ed)(SI化学数据手册)[M]. Beijing(北京): High Education Press(高等教育出版社)，1985. 94.

[10] Zhang H Q(张寒琦)，Chen Z(陈铮)，Lin Y J(林英杰)，et al. Handbook of chemical data(实用化学手册)[M]. Beijing(北京): Science Press(科学出版社)，2001. 682-723.

[11] Hall L H，Kier L B. Electrotopological state index for atom types:a novel combination of electronic，topological，and valence state information[J]. J Chem Inf Comp Sci, 1995，35(6): 1 039-1 045.

[12] Yu D Q(于德泉)，Yang J S(杨峻山)，Xie J X(谢晶曦). Handbook of Analytical Chemistry: Vol.5. Spectroscopy of nuclear magnetic resonance(分析化学手册第五分册:核磁共振波谱分析[M]. Beijing(北京): Chemical Industry Press(化学工业出版社)，1989. 832-834.

[13] Shen Q F(沈其丰). ¹³C spectrometry of nuclear magnetic resonance(核磁共振碳谱)[M]. Beijing(北京): Peking University Press(北京大学出版社), 1988. 267-270.

[14] Breitmaier E(E.布里特梅尔)，Voelter W(W.沃尔特)[著]. Liu L X(刘立新)，Tian Y Z(田雅珍)[译]. ¹³C spectrometry of nuclear magnetic resonance(碳13核磁共振波谱学)[M]. Dalian(大连): Dalian University of Technology Press(大连理工大学出版社), 1986. 135-148.

[15] Golbraikh A，Tropsha A. Beware of q2[J]. J Mol Graph Model, 2002，20(4): 269-276.

[16] Tropsha A，Gramatica P，Gombar V K. The importance of being earnest:validation is the absolute essential for successful application and interpretation of QSPR models[J]. QSAR Comb Sci，2003，22(1): 69-77.

[17] Gramatica P，Pilutti P，Papa E. Validated QSAR prediction of OH tropospheric degradation of VOCs:splitting into trainingtest sets and consensus modeling[J]. J Chem inf Comp Sci, 2004，44(5): 1 794-1 802.

AEIV结合AHSI用于饱和脂肪酮类物质的¹³C NMR谱模拟

Estimation and Prediction of ¹³C Chemical Shifts of Saturated Ketones: A Quantitative Structure-Spectrum Relationship Study

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 1

编辑推荐

Metrics

本文评价