Semi-empirical topological method for prediction of the gas chromatographic relative retention times of Polybrominated Diphenyl Ethers (PBDEs)

Abstract

Quantitative structure-retention relationship (QSRR) studies have proved to be a valuable approach in the prediction of the gas chromatographic relative retention time (GC-RRT) of organic chemicals. Polybrominated diphenyl ether (PBDE) congeners are now ubiquitous environmental pollutants. Of the 209 possible PBDE congeners, 126 have been synthesized and their retention-time data on seven different stationary phases has been determined [Korytár et al.:J Chromatography A 1065:239–249, (2005)]. To estimate and predict the GC-RRT values of all 209 PBDEs on different stationary phases, 17 molecular descriptors from the semi-experience algorithm in MOPAC program and the topological structures of PBDE molecules were calculated. By means of the VSMP (variable selection and modeling based on prediction) program [Liu et al.:J Chem Inf Comput Sci 43:964–969, (2003)], six optimal descriptors were selected to develop a QSRR model for the prediction of GC-RRT of PBDE. The descriptors contain some energy information (such as the energy of the lowest unoccupied molecular orbital and highest occupied molecular orbital) and topological information (the number of ortho-, meta-, and para- substituted bromine atoms) as well as the molecular weight (lnM _W ). All the models developed were cross-validated using leave-one-out (LOO). For seven GC stationary phases, the estimated correlation coefficients (r ²) are all more than 0.985 but for the column CP-Sil 19 (r ² = 0.9392) and LOO-validated correlation coefficients (q ²) all more than 0.985 but for the column CP-Sil 19 (q ² = 0.9345).