Quantitative Structure–Retention Relationships for Polycyclic Aromatic Hydrocarbons and their Oligoalkynyl‐Substituted Derivatives

Abstract

Reversed‐phase high‐performance liquid chromatography (RP‐HPLC) has been carried out for a series of unsubstituted polycyclic aromatic hydrocarbons (PAHs) and the corresponding ethynyl, 1,3‐butadiynyl, and 1,3,5‐hexatriynyl derivatives. Theoretical values of the isotropic polarizability and several polarity descriptors have been computed for each compound by using semiempirical models and density functional theory (DFT), with the aim of evaluating linear functions as quantitative structure–retention relationships (QSRRs). The polarity has been described by using either the permanent electric dipole moment, the subpolarity, or a topological electronic index. Three types of partial atomic charges have been used to calculate the subpolarity and a topological index. The choice of the theoretical model, of the polarity descriptor, and of the partial atomic charges is discussed and the resulting QSRRs are compared. Calculating the retention times from the polarizability and the topological electronic index (AM1, PM3, or DFT‐B3LYP/6–31+G(d,p)) gives the best agreement with the experimental values.

Accurate Prediction of Gas Chromatographic Retention Times via Density Functional Theory Calculations: A Case Study Using Brominated Flame Retardants

“…However, decabromo DE is still used in Brazil, Iran, and New Zealand . Additionally, “novel” brominated flame retardant formulations have been used as replacement and are becoming more prevalent in the environment . PBDEs may enter the environment through emissions from manufacturing processes, volatilization from various products that contain PBDEs, recycling wastes and leachate from waste disposal sites …”

“…There have been many studies demonstrating the applicability of theoretical methods to accurately predict the chromatographic retention times of analytes . In fact, we have used COnductor‐like Screening MOdel for Realistic Solvents (COSMO‐RS) to predict the boiling points and the GC retention times of PBDEs and MeO‐PBDEs .…”