In this article, a detailed study on hop alpha-acid isomerization kinetics is presented. Because of the complex wort matrix and interfering interactions occurring during real wort boiling (i.e., trub formation and alpha-acids/iso-alpha-acids complexation), this investigation on alpha-acid isomerization kinetics was performed in aqueous buffer solution as a function of time (0-90 min) and heating temperature (80-100 degrees C). Rate constants and activation energies for the formation of individual iso-alpha-acids were determined. It was found that iso-alpha-acid formation follows first-order kinetics and Arrhenius behavior. Differences in activation energies for the formation of trans- and cis-isomers were noticed, the activation energy for the formation of trans-iso-alpha-acids being approximately 9 kJmol (-1) lower.

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A pleasant and consistent bitterness is an essential flavour attribute of beer. Hop-derived iso-α-acids are largely responsible for beer bitterness and accurate determination of these primary flavour compounds is very important in relation to quality control. The most widely used way to determine beer bitterness is based on spectrophotometry, measuring the absorbance of an iso-octane extract of acidified beer. However, this approach is far from specific as it measures all of the extracted compounds, including non-bittering principles. For that particular reason, High Performance Liquid Chromatography (HPLC) is increasingly applied for the quantitative determination of hop-derived iso-α-acids and, if present, reduced iso-α-acids. However, to obtain accurate data on beer bitterness profiles, both quantitative sample preparation and state-of-the-art HPLC are essential. In this paper, several extraction procedures based on solid phase extraction (SPE) and liquid-liquid extraction (LLE), respectively, were evaluated and an optimised extraction methodology using H 3 PO 4 for sample acidification prior to extraction is presented. The proposed extraction/HPLC methodology allows for the quantitative recovery and analysis of hop-derived beer bitterness.

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