RESUMO
Hop terpenes might be oxidized during kettle boiling into more water soluble compounds that could contribute to 'hoppy' aroma of kettle hopped lager beers. Our current research proves that the boiling process induces significant changes in the hop oil volatile profile. The discrimination between volatile profiles of unboiled and boiled hop essential oil was evaluated via principal component and cluster analysis (PCA and CA). HS-SPME-GC-MS analysis revealed quantitative changes (e.g. increases in the levels of oxygenated α-humulene and ß-caryophyllene derivatives) as well as qualitative changes (i.e. detection of compounds, not found in unboiled hop essential oil) in the hop oil volatile profile upon boiling. Many of these compounds were previously found in lager beer and may therefore contribute to beer flavor. Interestingly, the analytical difference between unboiled and boiled hop essential oil proved to be more pronounced as the initial hop essential oil concentration used for boiling was increased. In addition, lager beers spiked with boiled hop oil were described as 'hoppy/spicy' during sensory evaluations. Therefore, the newly formed products and hop oil constituents that are characterized by an increased recovery after boiling, are candidate compounds for 'hoppy' aroma in real brewing practice.
RESUMO
The volatile composition of novel varietal oxygenated sesquiterpenoid hop oil fractions ("spicy essences") was characterized by headspace solid-phase microextraction in combination with gas chromatography-mass spectrometry. Oxygenated sesquiterpenes represent the major chemical compound class, accounting for at least 65% of the total volatile fraction. In addition to oxygenated sesquiterpenes, spicy hop essences consist of several ketones, sesquiterpene and monoterpene hydrocarbons, and a relatively high number of unidentified compounds. On the basis of their relative composition, spicy hop essences can be fully differentiated according to their varietal origin. Multidimensional gas chromatography in combination with time-of-flight mass spectrometry on spicy hop essence cv. Spalter Select further demonstrated the enormous complexity of this particular hop oil fraction. The aromagram obtained via gas chromatography-olfactometry comprised nine odor-active regions described in terms of "citrus", "green", "haylike", "earthy", "woody", and "spicy". 2-Undecanone, 2-tridecanone, γ-cadinene, α-calacorene, calarene, humuladienone, caryolan-1-ol, caryophyllene oxide enantiomers, and humulene epoxide II are tentatively identified in the odor-active zones.
