Chromatographic retention behaviour of monosubstituted benzene derivatives on porous graphitic carbon and octadecyl-bonded silica studied using molecular modelling and quantitative structure–retention relationships

The retention behaviour of a series of 28 monosubstituted benzenes, representing a diverse range of functional groups and substituent shape, were investigated using porous graphitic carbon (PGC) and octadecyl-bonded silica (ODS) stationary phases. For the majority of analytes retention on PGC was greater than on ODS, and in most cases this effect occurred at both pH 2.5 and 7.0. The main trends observed on PGC (in comparison with ODS) were: (i) similar or reduced retention of low polarity molecules such as the hydrocarbon and halogenated analytes; (ii) increased retention of conjugated analytes with extended planarity; (iii) increased retention of polar and charged species; and (iv) substantial increases in retention for selected polar and negatively charged analytes, including some ionised and unionised acid analytes. Poor retention of positively charged analytes was observed on both stationary phases. Molecular modelling studies have explored the geometry of π–π stacking interactions in retention on PGC and have highlighted the strong retention of large conjugated analytes, with extended planar conformations, which can interact with the graphite surface with cofacial geometry. Quantitative structure–retention relationships showed the importance of hydrophobic (π) and electronic factors (e.g. mean polarisability and LUMO energy) in retention on PGC, whilst retention on ODS was correlated to hydrophobicity (log P and π).

► Study of mechanism of separation on PGC using retention, molecular modelling & QSRR. ► 28 monosubstituted benzenes, including ionisable and charged analytes, studied. ► Increased retention of conjugated, polar and charged analytes seen on PGC. ► Molecular modelling and QSRR studies provide insights into mechanism of retention.