Enhanced multi-stir bar sorptive extraction for wine analysis: Alteration in headspace mode.

Multi-stir bar sorptive extraction (multi-SBSE) represents a viable alternative for recent trends in sample preparation based on a combination of extraction techniques. In this case, increased amount of sorbent and its extended polarity range could advance quality of experimental data obtained in foodomics or metabolomics investigations. With this in mind, it was developed multi-SBSE procedure suitable for authentication of botrytized wine produced in different countries of Tokaj wine region. A design of headspace mode of multi-SBSE was modified to provide additional agitation of a stir bar. An expanded profile of wine samples was obtained with the application of EG-Silicone and PDMS coated stir bars in headspace and direction immersion mode, respectively. Multivariate optimization based on central composite design was selected to determine the influence of various experimental parameters, including extraction temperature enhancing headspace extraction. In our case, proper description of the optimization results required application of a third-order polynomial model, which highlighted dominant influence of salt addition for extraction in both modes. Due to a large number of extracted compounds, comprehensive two-dimensional gas chromatography (GC × GC) was used for assessment of wine samples. Such approach allows reveleaing the presence of sulphur containing compounds, diols, ketone derivatives and methoxybenzenes linking a specific geographical origin. At the same time, the results obtained for compounds common for all the samples were processed with principal component analysis (PCA). Considerable progress for discrimination of the botrytized wines was mainly achieved with combined data from EG-Silicone and PDMS extraction.