Comparison of chemometric methods for the screening of comprehensive two-dimensional liquid chromatographic analysis of wine

Two chemometric methods are compared for the rapid screening of comprehensive two-dimensional liquid chromatographic (LC × LC) analysis of wine. The similarity index and Fisher ratio methods were both found to be able to distinguish geographical variability and to determine potentially significant peaks for further quantitative and qualitative study. An experimental data set consisting of five different wine samples and multiple simulated data sets were analyzed in the investigation of the screening methods. Several statistical analyses are employed in the understanding and verification of the results from the similarity index and Fisher ratio methods. The sum rank difference (SRD) method was used to compare the rankings of the two different methods as applied to the different data sets and to determine the amount of variability associated with the ranking of the peak differences. The major advantage the similarity index method offers is that it is an unsupervised method; no a priori knowledge of the samples (i.e., class identification) is required, while the Fisher ratio method is supervised. Both methods are rapid and require little user intervention other than the determination of a threshold for inclusion/exclusion of compounds from further analysis.

SI and FR plots for LC × LC-DAD chromatograms of geographically different wine samples.Figure optionsDownload as PowerPoint slideHighlights
► We compare two chemometric techniques for rapid screening of LC × LC-DAD.
► The Fisher ratio and similarity index methods were compared.
► Significant concentration differences of peaks between sample types were determined.
► Various chromatographic conditions were found to have an effect on both methods.