Molecular structure retention relationships in comprehensive two‐dimensional gas chromatography

Comprehensive two‐dimensional gas chromatography (GC×GC) offers new opportunities to develop relationships between molecular structure and retentions in the two dimensional (2D) separation space defined by the GC×GC retention in each dimension. Whereas single dimension GC provides only one retention property for a solute, and hence the specific relationship between retention and chemical property is not readily apparent or derivable, the 2D presentation of compounds in GC×GC provides a subtle and exquisite correlation of chemical property and retention unlike any other GC experiment. The ‘orthogonality’ of the two separation dimensions is intimately related to the manner in which different separation mechanisms, available through use of two dissimilar phases, are accessible to the different chemical compounds or classes in a sample mixture, and indeed the specific chemical classes present in the sample. The GC×GC experiment now permits various processes such as chemical decompositions, molecular interconversions, various non‐linear chromatography effects, and processes such as slow reversible interactions that may arise with stationary phases or in the injector or column couplings, to be identified and further investigated. Here, we briefly review implementation of the GC×GC method, consider the molecular selectivity of GC×GC, and highlight a selection of molecular processes that can be probed by using GC×GC.