Theoretical prediction of the Kovat's retention index for oxygen-containing organic compounds using novel topological indices

For the retention index of polar compounds, polar groups in molecules would participate in polar interactions between eluents and stationary phases and thus would be expected to make large and separate contributions to the total retention index (RI). The characterization of the structural feature will help to elucidate the quantitative structure-retention relationship (QSRR). In this paper, on the basis of the PEI index previously developed by Cao, two novel molecular polarizability effect index, modified molecular polarizability index (MPEIm) and modified inner molecular polarizability index (IMPEIm were proposed to predict the GC retention of a variety of oxygen-containing organic compounds with diverse chemical structures on OV-1 and SE-54 stationary phases. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. Simple linear regression equations between the RI and the topological indices were established for each stationary phase separately (R > 0.99). Statistical analysis showed that the QSRR models have high internal stability and good predictive ability for external groups. The molecular properties known to be relevant for GC retention data, such as molecular size, branching and polar functional groups were well covered by the generated descriptors. The models with topological indices were compared with those based on quantum-chemical descriptors. It is observed that topological indices produce better correlations with Koval's retention index. The results indicate the efficiency of presented indices in the structure-retention index correlations of complex compounds with polar multi-functional groups. (C) 2007 Elsevier B.V. All rights reserved.