Modeling chromatographic parameters by a novel graph theoretical sub-structural approach.

A novel approach to the study of quantitative relationships between chromatographic parameters and the chemical structure is introduced. It is based on the computation of the spectral moments of the topological bond matrix by using different weights as diagonal entries of this matrix. The main advantage of the present approach is that the quantitative contributions of the structural fragments of molecules to the chromatographic parameters studied can be obtained explicitly. By using this approach we study two data sets: one composed of 156 alkanes and the other of 81 oxygen-containing organic molecules. In both cases excellent quantitative structure-chromatographic retention relationships were obtained. The contributions of the different fragments to the chromatographic retention were generated obtaining tables of additive contributions to the properties studied. The physicochemical interpretation of the results on the basis of the retention mechanisms is also analyzed in light of this new approach.