Multi-capillary column high-pressure photoionization time-of-flight mass spectrometry and its application for online rapid analysis of flavor compounds

High-pressure photoionization time-of-flight mass spectrometry (HPPI-TOFMS) is a versatile and highly sensitive analytical technique for online and real-time analysis of trace volatile organic compounds in complex mixtures. However, discrimination of isomers is usually a great challenge for the soft ionization method, and matrix effect is also inevitable under high pressure in the HPPI source. In this work, we describe a first attempt to develop a two-dimensional (2D) hyphenated instrument by coupling of a multi-capillary column (MCC) with a HPPI-TOFMS to overcome these problems. The capability of the MCC-HPPI-TOFMS for discrimination of isomeric compounds and elimination of the matrix effect was demonstrated by analyzing flavor mixtures. With the merits of fast separation, soft ionization and high detection sensitivity, satisfactory effects in the 2D analysis were achieved, despite the relatively low chromatographic resolution of MCC. As a result, three isomers, eucalyptol, L-menthone and linalool, in a flavor mixture were successfully categorized within 90 s, and the matrix effect caused by solvent ethanol was significantly eliminated as well. The limits of detection (LODs) down to sub-ppbv level were achieved for the investigated five flavor compounds without any enrichment process, and an excellent repeatability was obtained with the relative standard deviations (RSDs) of signal intensities <= 5%. The MCC-HPPI-TOFMS system was preliminarily applied for rapid and online analysis of flavor compounds in(t)he exhaled gas of a volunteer after mouth rinsing with a gargle product. The rapid changes of the three flavor compounds, as well as the steady endogenous metabolite acetone, in the exhaled gas were successfully determined with a time-resolution of only 1.5 min.