A regression model for calculating the second dimension retention index in comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry

• A novel model for calculating the second dimensional retention index in GC × GC/TOF–MS.
• Three different criteria were introduced to calculate the optimal magnitude of parameters.
• The proposed method outperformed the literature reported methods in extrapolation capability with fewer parameters.

Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC/TOF–MS) system has become a key analytical technology in high-throughput analysis. Retention index has been approved to be helpful for compound identification in one-dimensional gas chromatography, which is also true for two-dimensional gas chromatography. In this work, a novel regression model was proposed for calculating the second dimension retention index of target components where n-alkanes were used as reference compounds. This model was developed to depict the relationship among adjusted second dimension retention time, temperature of the second dimension column and carbon number of n-alkanes by an exponential nonlinear function with only five parameters. Three different criteria were introduced to find the optimal values of parameters. The performance of this model was evaluated using experimental data of n-alkanes (C7–C31) at 24 temperatures which can cover all 0–6 s adjusted retention time area. The experimental results show that the mean relative error between predicted adjusted retention time and experimental data of n-alkanes was only 2%. Furthermore, our proposed model demonstrates a good extrapolation capability for predicting adjusted retention time of target compounds which located out of the range of the reference compounds in the second dimension adjusted retention time space. Our work shows the deviation was less than 9 retention index units (iu) while the number of alkanes were added up to 5. The performance of our proposed model has also been demonstrated by analyzing a mixture of compounds in temperature programmed experiments.