Web Release Date: June 23,
Comparison of Odor-Active Compounds in the Spicy Fraction
of Hop (Humulus lupulus L.) Essential Oil from Four Different
Varieties

and
Department of Food Science, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand, and Australian Centre for Research on Separation Science, Department of Applied Chemistry, RMIT University, G.P.O. Box 2476V, Melbourne, Victoria 3001, Australia
Received for review March 14, 2007. Revised manuscript received May 16, 2007. Accepted May 20, 2007. G.T.E. acknowledges the Tertiary Education Commission, New Zealand, for providing scholarship funding. P.J.M. gratefully acknowledges the ongoing support of Leco Australia.

Abstract:
The "spicy" character of hops is considered to be a desirable attribute in beer, associated with "noble
hop aroma". However, the compounds responsible have yet to be adequately identified. Odorants in
four samples of the spicy fraction of hop essential oil were characterized using gas chromatography-olfactometry (GC-O) and CharmAnalysis. Four hop varieties were compared, namely, Target, Saaz,
Hallertauer Hersbrucker, and Cascade. Odor-active compounds were tentatively identified using
comprehensive two-dimensional gas chromatography (GC×GC) combined with time-of-flight mass
spectrometry (TOFMS). An intense "woody, cedarwood" odor was determined to be the most potent
odorant in three of the four spicy fraction samples. This odor coincided with a complex region where
between 8 and 13 compounds were coeluting in each of the four spicy fractions. The peak responsible
was determined by (i) correlating peak areas with Charm values in eight hop samples and (ii) heart-cut multidimensional gas chromatography-olfactometry (MDGC-O). The compound responsible was
tentatively identified as 14-hydroxy-
-caryophyllene. Other important odorants identified were geraniol,
linalool,
-ionone, and eugenol.
Keywords: Humulus lupulus L.; gas chromatography-olfactometry; comprehensive two-dimensional gas chromatography; time-of-flight mass spectrometry; multidimensional gas chromatography; hop aroma; character-impact odorants
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