Estimation of Kováts Retention Indices Using Group Contributions

We have constructed a group contribution method for estimating Kováts retention indices by using observed data from a set of diverse organic compounds. Our database contains observed retention indices for over 35,000 different molecules. These were measured on capillary or packed columns with polar and nonpolar (or slightly polar) stationary phases under isothermal or nonisothermal conditions. We neglected any dependence of index values on these factors by averaging observations. Using 84 groups, we determined two sets of increment values, one for nonpolar and the other for polar column data. For nonpolar column data, the median absolute prediction error was 46 (3.2%). For data on polar columns, the median absolute error was 65 (3.9%). While accuracy is insufficient for identification based solely on retention, it is suitable for the rejection of certain classes of false identifications made by gas chromatography/mass spectrometry.

[1]  Stephen E. Stein,et al.  Estimation of normal boiling points from group contributions , 1994, J. Chem. Inf. Comput. Sci..

[2]  M. Jalali-Heravi,et al.  Artificial neural network modeling of Kováts retention indices for noncyclic and monocyclic terpenes. , 2001, Journal of chromatography. A.

[3]  G. Tarján,et al.  Twenty-fifth anniversary of the retention index system in gas—liquid chromatography , 1983 .

[4]  Petr Buryan,et al.  Structure—retention correlations of isomeric alkylphenols in gas—liquid chromatography , 1990 .

[5]  J. Wolfowitz,et al.  An Introduction to the Theory of Statistics , 1951, Nature.

[6]  F. Raushel,et al.  Calculation of retention indices for benzene and benzene derivatives on the basis of molecular structure , 1972 .

[7]  Satoru Mihara,et al.  Correlation between molecular structures and retention indices of pyrazines , 1987 .

[8]  W. P. Eckel,et al.  Making sense of nontarget compound data from GC-MS library searches , 2000 .

[9]  G. Tarján,et al.  Thirtieth anniversary of the retention index according to Kováts in gas-liquid chromatography , 1989 .

[10]  Palagiri Tulasamma,et al.  Quantitative structure and retention relationships for gas chromatographic data: application to alkyl pyridines on apolar and polar phases. , 2006, Journal of molecular graphics & modelling.

[11]  Antonije Onjia,et al.  Prediction of the Lee retention indices of polycyclic aromatic hydrocarbons by artificial neural network. , 2006, Journal of chromatography. A.

[12]  E. Kováts,et al.  GAS CHROMATOGRAPHISCHE CHARAKTERISIERUNG ORGANISCHER VERBINDUNGEN , 1958 .

[13]  H. Vandendool,et al.  A GENERALIZATION OF THE RETENTION INDEX SYSTEM INCLUDING LINEAR TEMPERATURE PROGRAMMED GAS-LIQUID PARTITION CHROMATOGRAPHY. , 1963, Journal of chromatography.

[14]  K W Schramm,et al.  A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs). , 2000, Chemosphere.

[15]  Adam Voelkel,et al.  Retention indices and thermodynamic functions of solution for model non-ionic surfactants in standard stationary phases determined by gas chromatography , 1987 .

[16]  Valeri I. Babushok,et al.  On the Relationship Between Kováts and Lee Retention Indices , 2004 .

[17]  C T Peng,et al.  Prediction of retention indices. V. Influence of electronic effects and column polarity on retention index. , 1991, Journal of chromatography. A.

[18]  Tobias Kind,et al.  Use of boiling point-Lee retention index correlation for rapid review of gas chromatography-mass spectrometry data , 2003 .

[19]  C T Peng,et al.  Prediction of retention indexes. I. Structure-retention index relationship on apolar columns. , 1988, Journal of chromatography.

[20]  R. L. Brown,et al.  Development of a database of gas chromatographic retention properties of organic compounds. , 2007, Journal of chromatography. A.

[21]  S. Stein.  An integrated method for spectrum extraction and compound identification from gas chromatography/mass spectrometry data , 1999 .

[22]  Gareth J. Price,et al.  Prediction of retention in gas-liquid chromatography using the UNIFAC group contribution method: II. Polymer stationary phases , 1991 .

[23]  Subhash C. Basak,et al.  Prediction of gas chromatographic retention indices using variable connectivity index , 2001 .

[24]  Dmitrii V. Tchekhovskoi,et al.  The critical evaluation of a comprehensive mass spectral library , 1999, Journal of the American Society for Mass Spectrometry.

[25]  M. B. Evans,et al.  Recent developments in the gas chromatographic retention index scheme , 1989 .