Method for reducing the ambiguity of comprehensive two-dimensional chromatography retention times

Comprehensive two-dimensional chromatography generates a two-dimensional chromatogram from a one-dimensional signal array. This process can only be done unambiguously when the range of secondary retention times is less than the modulation period. However, complex samples often produce wider ranges of secondary retention times. Peaks with retention times that exceed the modulation period are said to be “wrapped-around”. A simple algorithm has been developed that determines absolute retention times when wrap-around occurs. A sample is first analyzed under standard modulation conditions and then re-analyzed with a modulation period that is increased by an integer fraction of the original modulation period. Retention shifts along the secondary axis are used to determine absolute retention times. A theoretical analysis has been performed to optimize the implementation conditions and characterize the technique limitations. The efficacy of this algorithm has been tested through a series of isothermal GC × GC separations. This method has been found to be particularly useful during the initial stages of method development.