Modeling the semi‐empirical electrotopological index in QSPR studies for aldehydes and ketones
Érica Silva Souza, Carlos Alberto Kuhnen, Berenice da Silva Junkes, Rosendo Augusto Yunes, Vilma Edite Fonseca Heinzen · Journal of Chemometrics · 2009
Abstract The semi‐empirical electrotopological index, ISET, used for quantitative structure–retention relationship (QSRR) models firstly developed for alkanes and alkenes, was remodeled for organic functions such as ketones and aldehydes. The ISET values for hydrocarbons are calculated through the atomic charge values obtained from a Mulliken population analysis using the semi‐empirical AM1 method and their correlation with the SETi values attributed to the different types of carbon atoms according to experimental data. For ketones and aldehydes the interactions between the molecules and the stationary phase are slowly increased relative to the hydrocarbons, due to the charge redistribution that occurs in the presence of heteroatoms. For these polar molecules the increase in the interactions was included in the calculation of the ISET values through the dipole moment of the whole molecule and also through an equivalent local dipole moment related to the net charges of the atoms of the CO and HCO functional groups. Our findings show that the best definition of an equivalent local dipole moment is clearly dependent on the specific features of the charge distribution in the polar region of the molecules (e.g. ketones and aldehydes), which allows them to be distinguished. Thus, the QSRR models for 15 aldehydes and 42 ketones obtained using the remodeled ISET were of good quality as shown by the statistical parameters. The ability of this remodeled index to include charge distribution and structural details opens a new way to study the correlations between the molecular structure and retention indices in gas chromatography. Copyright © 2009 John Wiley & Sons, Ltd.