Development of a novel comprehensive analytical method for volatile compounds using supercritical fluid chromatography/mass spectrometry with a highly cross-linked styrene divinylbenzene polymer-based column

•Highly cross-linked styrene divinylbenzene (SDVB) polymer-based column brought excellent retention and separation of volatile compounds especially the esters and non-polar terpenes in SFC.•Although retention mechanism based on π-π interactions of SDVB and Phenyl column is similar, higher specific area of novel SDVB column than that of Phenyl column contributed to the better retention.•The results provided reasons to not only further develop the profiling of volatile compounds on analytical-scale but also the purification and production on prep-scale. Analytical techniques to determine volatile compounds such as flavor, aroma, and fragrances are in high demand due to their wide range of applications in industry, the chemical properties of them are very diverse. Supercritical fluid chromatography (SFC) is capable of high speed, high peak capacity separation and has a high separation coverage. It is also an advantageous for preparative purifications due to its unique mobile phase conditions. However, there is no column commercially available for SFC that is suitable to comprehensively separate volatile compounds. SFC is limited to the use of silica-based columns due to weak retentions and polymer-based column issues such as pressure, swelling and shrinkage tolerances. This study demonstrated comprehensive analytical method for volatile in SFC using a highly cross-linked styrene divinylbenzene (SDVB) polymer-based column, newly developed for SFC. In this study, 23 typical volatile compounds with a wide variety of chemical properties were selected as model compounds. The newly developed SDVB column showed, compared to conventional silica-based columns (k > 0.3), an excellent overall and substantial improved retentions (k > 1.6) under SFC mobile phase conditions. It was also able to retain esters (hydroxy acetate, pentyl butylate, methyl salicylate) and non-polar terpenes (limonene, pinene) that did not show sufficient retention in any other commercially available silica-based columns. Aldehydes reacting on NH2 column due to Schiff base formation were also successfully eluted. It was confirmed that SDVB column provided comprehensive separation and wide coverage for volatile compounds.