Comparative Gas Chromatographic–Mass Spectrometric Evaluation of Hop (Humulus lupulus L.) Essential Oils and Extracts Obtained Using Different Sample Preparation Methods

The main aim of investigations was to identify chemotypes and determine differences between some domestic hop varieties and wild hops, which were collected from some regions of Lithuania and cultivated at the same edafoclimatic conditions in hops collection of Kaunas Botanical Garden of Vytautas Magnus University. One of objectives was to compare essential oils of hops (2 years harvest) by the evaluation of volatiles content. Among the main components of hop essential oils monoterpenes (β-myrcene) and sesquiterpenes (α-humulene and β-caryophyllene) were determined using gas chromatography coupled with mass spectrometry (GC-MS). Retention parameters (tR, calculated retention index, and Kovats retention index) and m/z value of molecular ion for selected compounds from hop essential oils were determined. Samples were prepared by applying solid phase microextraction (SPME), supercritical fluid extraction (SFE) and accelerated solvent extraction (ASE). The steam distillation was used to obtain hop essential oils. The chemometric comparison of domestic and wild hops based on GC-MS analysis data was carried out. The obtained statistical results allow us to classify the investigated wild forms and domestic varieties of hops according to the similarities of their chemotypes. The concentration of β-myrcene, α-humulene in hop essential oils obtained from cones 2 years harvests is much higher than other volatile organic compounds (15.2–23.7 % in total contribution). In analysed essential oils β-farnesene is a constituent in higher quantity of hop essential oils obtained from cones from second time harvest than from cones from first harvest. This can be explained by the year-to-year vegetation conditions difference.