Almaguer Et Al-2014-Journal of The Institute of Brewing

Review article Institute of Brewing & Distilling
Received: 12 April 2014 Revised: 7 June 2014 Accepted: 6 July 2014 Published online in Wiley Online Library: 26 September 2014
(wileyonlinelibrary.com) DOI 10.1002/jib.160
Humulus lupulus – a story that begs to be told.

A review
Cynthia Almaguer,1,2 Christina Schönberger,3 Martina Gastl,1*
Elke K. Arendt2 and Thomas Becker1
The hop cones of the female plant of the common hop species Humulus lupulus L. are grown almost exclusively for the
brewing industry. Only the cones of the female plants are able to secrete the fine yellow resinous powder (i.e. lupulin glands).
It is in these lupulin glands that the main brewing principles of hops, the resins and essential oils, are synthesized and accu-
mulated. Hops are of interest to the brewer since they impart the typical bitter taste and aroma to beer and are responsible
for the perceived hop character. In addition to the comfortable bitterness and the refreshing hoppy aroma delivered by hops,
the hop acids also contribute to the overall microbial stability of beer. Another benefit of the hop resins is that they help en-
hance and stabilize beer foam and promote foam lacing. In an attempt to understand these contributions, the very complex
nature of the chemical composition of hops is reviewed. First, a general overview of the hop chemistry and nomenclature is
presented. Then, the different hop resins found in the lupulin glands of the hop cones are discussed in detail. The major hop
bitter acids (α- and β-acids) and the latest findings on the absolute configuration of the cis and trans iso-α-acids are discussed.
Special attention is given to the hard resins; the known δ-resin is reviewed and the ε-resin is introduced. Recent data on the
bittering potential and the antimicrobial properties of both hard resin fractions are disclosed. Attention is also given to the
numerous essential oil constituents as well as their contributions to beer aroma. In addition to the aroma contribution of
the well-known essential oil compounds, a number of recently identified sulfur compounds and their impact on beer aroma
are reviewed. The hop polyphenols and their potential health benefits are also addressed. Subsequently, the importance of
hops in brewing is examined and the contributions of hops to beer quality are explained. Finally, the beer and hop market
of the last century, as well as the new trends in brewing, are discussed in detail. Hop research is an ever growing field of central
importance to the brewing industry, even in areas that are not traditionally associated with hops and brewing. This article
attempts to give a general overview of the different areas of hop research while assessing the latest advances in hop science
and their impact on brewing. Copyright © 2014 The Institute of Brewing & Distilling
Keywords: Humulus lupulus L.; hops; hard resins; hop chemistry; hop market; varietal acreage; brewing
Introduction knowledge of hops. Hop research covers all matters related to

hops, from breeding and growing to harvesting and drying as
Brewing science is an extremely broad field dedicated to the well as their chemistry and their impact on beer quality. As a
study of all aspects of beer and its production process. It spans result of progress in analytical techniques, our knowledge of
many disciplines and applications of interest to the practical hops has advanced tremendously, leading to improvements
brewer. At its most simple it encompasses the study of malt, and new product development in the hop and brewing indus-
yeast and hops (Humulus lupulus L.). Through research and tries. Although a considerable amount of research has been
collaboration, a number of major breakthroughs have been done on a great variety of hop constituents and their function
achieved in the brewing field. Research in brewing plays a in brewing, much remains a matter of debate, in particular, the
predominant role in the brewing industry in part because it chemical background of hoppy aroma (1–4) and the influence of
provides information about the properties and composition of hop polyphenols on the organoleptic properties of beer (5–7).
the materials used. By understanding and then applying this Ultimately, the brewer and brewing chemists understand what
knowledge to practice, brewers may tailor new beers in which the hop substances can do; however, to some extent, it remains
specific properties are enhanced or suppressed for specific
purposes.
Compared with the large quantities of malt required in beer
production, the amount of hops needed is significantly smaller. * Correspondence to: Martina Gastl, Lehrstuhl für Brau- und Getränketechnologie,
Technische Universität München Weihenstephan, Weihenstephaner Steig 20,
This minor ingredient has, however, a crucial impact on beer
85354 Freising, Germany. E-mail: [email protected]
quality and, thus, hops are of paramount importance for beer
brewing. The complex chemistry associated with hop sub- 1
Lehrstuhl für Brau- und Getränketechnologie, Technische Universität München
stances and their function in brewing has been the subject of Weihenstephan, Weihenstephaner Steig 20, 85354 Freising, Germany
extensive investigation for over a century. Yet, surprisingly, 2
Department of Food and Nutritional Sciences, National University of
greater understanding of the chemical character of the hop Ireland, University College Cork, College Road, Cork, Ireland
compounds is still needed. Recent findings have not only helped
3
strengthen the existing research but also have improved our
289
Barth Innovations, Freiligrathstr. 7/9, 90482 Nuremberg, Germany
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling
C. Almaguer et al.
Institute of Brewing & Distilling
unclear how they do it. It is intended in the following to evaluate Hop cones
and review the available literature on this subject and, thus, pro-
vide the current status of hop research. The inflorescences of the female plants form the hop cones
(strobile) (11) used by the brewing industry. The hop cone consists
of stipular petal-like structures called ‘bracts’ and ‘bracteoles’
around a central axis or strig. At the base of the bracteoles, the
Hop botany lupulin glands are formed as the hop ripens. Only the cones of
The genus Humulus is made up of dioecious, perennial, climbing the female plants are able to secrete the fine yellow resinous pow-
vines (8). This genus belongs to the Cannabaceae family of the der known as lupulin glands. It is in these lupulin glands that the
Urticales order which in 2003 was incorporated into the natural main brewing principles of hops, the resins and essential oils, are
order of Rosales (9). The only other genus in the family is synthesized and accumulated (8,10). In 1821, Ives assigned the
Cannabis (see Fig. 1) represented solely by C. sativa (i.e. Indian name ‘lupulin’ to this yellow powder; he was the first one to
hemp, marijuana or hashish) (10). For years it was believe observe that it is in the lupulin where the bitter and aromatic sub-
that the genus Humulus was only represented by two species, stances of hops are stored (15). The lupulin glands are only weakly
the ‘common hop’, Humulus lupulus L., and the ‘Japanese attached to the hop cones, therefore, hops have to be handled
hop’, H. japonicus Zieb. et Zucc (11). In 1936, the species carefully to avoid losing the valuable hop components (14).
Humulus yunnanensis Hu was first described; however, it In most commercial hop growing areas worldwide the seed
remained a relatively unknown species thought to have orig- content in hops is regulated. Male hops are physically removed
inated at high elevations in the Yunnan province of southern from the hop fields to avoid the fertilization of the female plants
China. Previous to Small’s study, it had been almost univer- and, thus, the production of seeds. In most parts of the world,
sally unappreciated and identified as H. lupulus. It was in seeds are considered by brewers to be undesirable. It is believed
1978 that Small identified H. yunnanensis as a species of its that oxidation of the seed fatty acids produce off-flavours in
own (12). Currently more is known of the H. japonicus species; beer (16). Further, it has been proven that seedless hops are
this is an annual plant indigenous in China, Japan and the generally richer in essential oils and resins than seeded ones
neighbouring islands. For brewing purposes it is of no value (i.e. higher brewing value) (10). However, male plants are
as its hops are devoid of lupulin glands (11). H. japonicus is essential in hop breeding programmes to develop new varie-
widely cultivated as a strong climber, often used in gardens ties through controlled hybridization.
as a decorative, leafy screen (8).
Hop harvesting and drying
In late summer or early autumn, when the hop cones have
Hop cultivation ripened and the resin content is highest, the hops are harvested.
The hop cones of the female plant of the common hop species At harvest the moisture present in hops is about 75–80%; at such
Humulus lupulus L. are grown almost exclusively for the brewing high moisture level not only do the hop compounds change
industry. About 97% of worldwide cultivated hops are destined rapidly but they also go mouldy quickly. Thus, the hop cones
for brewing purposes. The world hop production is dominated are carefully dried in the oast house or kiln at temperatures
by Germany and the USA. The hop production of both countries between 60–75 °C to reduce the moisture content to about
accounts for about 75–80% of the total hop output (13). Suc- 10% (17). After cooling and conditioning the hops are com-
cessful cultivation of the hop plant requires optimal growth pressed and packed into bales. These bales are stored cold until
conditions, especially with respect to the length of daylight, required for use, either sale or processing into hop products.
summer temperature, annual rainfall and soil fertility (14). The
hop plant is grown throughout most moderate climate regions
of the world; these are located between latitudes 35° and 55°
Chemical composition of hops
of the Northern and Southern Hemispheres (8). More than 60% Whole hop cones comprise several components, such as resins,
of the hop area under cultivation is located in Germany and essential oils, proteins, polyphenols, lipids, waxes, cellulose and
the USA (13). The largest hop growing areas include the amino acids (10,18). The typical overall average chemical compo-
Hallertau region in Germany and the states of Washington, sition of fresh dried hop cones is shown in Table 1. The leafy
Oregon and Idaho in the USA. Other hop growing countries nature of the hop petals ensures the presence of ubiquitous
are the Czech Republic, Poland, Slovenia, England, Ukraine, substances such as proteins, carbohydrates and polyphenols
China, South Africa, Australia and New Zealand. (8,19). The brewing value of hops is primarily attributed to the
precursors of the flavour- and bitter-active compounds found
in the resins secreted by the lupulin glands. The hop essential
oils are also important to the brewer as they provide flavour
and aroma characteristics to the beer.
Hop chemistry
Hop resin nomenclature
It is in the lupulin glands of the female hop cone that the main
brewing principles, the resins and the essential oils, are synthe-
sized (10). The characteristic resins of hops include many
290
Figure 1. Classification of the hop plant (8,9).
wileyonlinelibrary.com/journal/jib Copyright © 2014 The Institute of Brewing & Distilling J. Inst. Brew. 2014; 120: 289–314
Humulus lupulus – a story that begs to be told
Table 1. Average chemical composition of achieving a total purification of the resins (24). Currently, the
dried hop cones (8,10,18,19,28) method most commonly used for fractionation of hop resins is
a modified version of Wöllmer’s protocol (25–27). In Fig. 2 the
Constituent Amount (%) composition and most recent nomenclature of the hop resins
are shown. Depending on the hop variety and growing condi-
Total resins 15–30 tions, the total resin content can range between 15 and 30%
Essential oil 0.5–3 of the total weight of the dried hops (28). The total resin is de-
Proteins 15 fined as the fraction soluble in diethyl ether and cold
Monosaccharides 2 methanol. The requirement that the total resins should be solu-
Polyphenols (tannins) 4 ble in cold methanol is designed to exclude the hop waxes,
Pectins 2 which will slowly crystallize from cold methanol (29). For the
Amino acids 0.1 extraction of the total resin, cold methanol is specified because
Waxes and steroids traces–25 the hot solvent dissolves or disperses waxes (22).
Ash 8 The hop total resins can be further divided into soft and hard
Moisture 10 resins. Compared with the soft resins, the hard resin content in
Cellulose, etc. 43 whole hop cones is low; it ranges between 3 and 5%, while
the soft resins comprise 10–25% of the total weight of dried
substances; Hayduck originally separated the hop resins into α-, hops (28). The amounts of soft and hard resins recovered by fur-
β- and γ-fractions on the basis of their solubility in different solvents ther fractionation of the total resins are 90 and 10%, respectively
and their ability to form a precipitate with lead acetate (20). Over (30,31). These values may vary as the total resin composition is
the years, the hop resin nomenclature constantly changed and dependent on the hop variety and hop product. The chemical
already in 1897 the term γ-resin had become obsolete, and ever and physical properties of the soft and hard resins differ from
since this fraction has been more commonly referred to as hard one another. A soft-resin enriched extract purified from cultivar
resins (21). In 1957, the situation was clarified by joint proposals (cv.) Hallertauer Taurus (H. Taurus) type 90 pellets is shown in
of the European Brewery Convention (EBC) and the American Fig. 3(A). The soft resin extract usually displays a distinct yellow
Society of Brewing Chemists (ASBC) (22). It was then revised in hue. The soft resins are able to produce a thick, viscous, very
1969 by the Nomenclature Sub-committee of the Hops Liaison dense fluid, whose consistency is comparable to that of honey.
Committee (23) and has not changed since then. The dark green powder shown in Fig. 3(B) is the hard resin ex-
tract prepared from cv. H. Taurus CO2 spent hop material (i.e.
hop powder remaining from the supercritical CO2 extraction).
Depending on the hop variety and hop product, the colour of
Hop resins the purified extracts may vary. When preparing the resin rich ex-
Total resins tracts, the varietal characteristics are revealed through the ex-
Several resin extraction methods were developed over the years, tract’s colour. However, the consistency of the extracts is not
but all seemed to be flawed and further proved the difficulty of affected by the hop variety or hop product used.
Figure 2. Classification and nomenclature of hop resins (8,19,28).

291
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib
C. Almaguer et al.
isomerized during the boiling process into the more water

soluble and bitter iso-α-acids (Fig. 4). Only traces of the α-acids
survive into the finished beer; the largest loss of α-acids occurs
when the hops are added to the wort kettle. Each of the α-acids
undergoes isomerization to produce the corresponding iso
compound. The major constituents comprising the iso-α-acids
are isohumulone, isocohumulone and isoadhumulone. Each
α-acid yields in fact two iso-α-acids as these occur as diaste-
reoisomers in their cis and trans forms (35). Although the isom-
erization process has been known since the late 1920s (36)
and has been extensively studied by many research groups
over the years (37–47), the configuration of the iso-α-acids
had remained speculative. In a recent study (48), the absolute
configuration of the cis and trans iso-α-acids was determined
by X-ray crystallography. The configuration of ( )-humulone
Figure 3. Comparison of cv. H. Taurus hop resins. (A) A soft resin enriched extract
purified from cv. H. Taurus hop pellets T90. The hard resins extracted from cv. H. was determined as (6S), thus the conserved stereocentre dur-
Taurus CO2 spent hop material are shown in (B). ing isomerization is C4, while cis and trans iso-α-acids differ
stereochemically at C5.
In further studies on the α-acid composition, traces of other α-
Soft resins acids were found in hops. In 1955, Verzele identified a fourth
To date, it is generally accepted that the total soft resin is soluble component, prehumulone, by partition chromatography.
in hexane and that the bulk of the brewing and bittering value Verzele also established that the component eluting last in the
of the hop is found in this fraction. The total soft resins consist chromatographic separation of the hop α-acids was
of α-acids and the β-fraction (i.e. β-acids and uncharacterized posthumulone (49,50). As previously mentioned, the composi-
soft resins). The term ‘resin’ is used as the base available in tion of the α-acids is characteristic of the hop variety; however
spite of the recognition that the two main groups of constitu- it is further dependent on the harvesting time. It was deter-
ents (i.e. α-acids and β-acids) are crystalline and not resinous mined by Verzele that, independent of the hop variety, the levels
in nature (22). The α-acids can be readily separated from the of prehumulone and posthumulone are higher when the hops
total soft resins by their ability to form an insoluble lead salt with are harvested late (14).
lead(II) acetate in methanol (10). Prior to 1952, the α-acid fraction
of hops was believed to consist almost entirely of a single com- β-Fraction. β-Acids. The β-fraction of the total soft resins can
ponent, known as humulone (32). Rigby and Bethune used be further divided into β-acids and uncharacterized soft resins.
countercurrent distribution to establish that the α-acids are, in The less acidic β-acids can be isolated from hops by removing
fact, mixtures of homologues and analogues. In addition to the stronger α-acids first with lead(II) acetate (51). Lupulone, a
humulone, two other substances are present in substantial β-acid constituent, was first isolated from hops by Lermer in
amounts, cohumulone and adhumulone (33,34). Trace amounts 1863 (52,53). Compared with the α-acids, the β-acids have been
of two other α-acids, prehumulone and posthumulone, are also subjected to less extensive studies. Up until the 1950s, humulone
found in hops. The composition of the α-acid fraction varies and lupulone were the only known hop acids. It was later
greatly among the hop varieties. established that, like the α-acids, the β-acids are a mixture of
analogues. The compounds in the β-acid series bear the same
α-Acids. It is well established that the α-acids are by far the relation as the α-acid constituents and, thus, these are termed
most important constituents of the hop resins. Upon addition analogously. The β-acid group is composed of lupulone and four
of hops to the wort kettle, the α-acids are extracted and thermally congeners: colupulone, adlupulone, prelupulone and postlupulone
Figure 4. Chemical structures of the hop α-acids. Thermally induced isomerization occurs during wort boiling to produce the diastereomeric trans- and cis-iso-α-acids,
292
these are the main bittering acids in beer (48).
(see Fig. 5). In 1956, it was established by Howard and Tatchell that the percentage of soft resin falls while that of the hard resin
the β-acids are always richer in colupulone than the α-acids are in increases (58). In 1964, Ashurst et al. (59) inconclusively ad-
cohumulone (54). dressed the question of what constituents are responsible for
The β-acids show poor solubility in water (52), and while the the bittering ability of stored hops when the α-acids have been
α-acids undergo isomerization during wort boiling, the β-acids transformed into other substances. At that point, it had been
do not. The wort properties (i.e. low pH) do not favour β-acid recognized for many years that the resins of the hop undergo
solubility and as a result only trace amounts are transferred several changes during storage: the α- and β-acids become
into beer. Previous to the studies of Haseleu et al. (55,56) the oxidized, the products still being analytically classed as soft
β-acids were believed to be lost in the brewing process and, resins, while further oxidation results in gradual transformation
thus, did not contribute to beer bitterness. Haseleu et al. were to hard resins. Thus, the α- and β-acids decrease continually
able to identify a number of bitter tasting β-acid transformation during storage while the amount of uncharacterized soft resin
products that are generated during wort boiling, thereby increases at first and then decreases as the hard resin steadily
proving that, in addition to the α-acids, the β-acids are potential increases (59,60). While some authors (19,58) automatically con-
bitter taste precursors present in the hop soft resins. sidered oxidized soft resins to be hard resins, others (32,59–61)
considered the uncharacterized soft resins in old hops to be
Uncharacterized soft resins. The uncharacterized soft resins is the intermediate deterioration products of the α- or β-acids
considered a non-specific hop fraction (29). This fraction consists which, upon further oxidation, will ultimately turn into hard
of the portion of the total soft resins remaining after the α-acids resins. It is believed that these intermediate deterioration
have been precipitated and the β-acids are allowed to crystallize products have brewing value, but the exact role of the oxidation
out (10). Hitherto, the constituents of the uncharacterized soft products, be it oxidized soft resins or hard resins, in the brewing
resins have not been characterized as any specific compound. process is not fully understood (32,60).
Essential oil components and hop wax are also found in this frac-
tion. This is possible since the hop oils are soluble in ether and α-Hard resin and β-hard resin. Hitherto, the complex nature
light petroleum. Although most of the hop wax is removed, of the total hard resin has not been conclusively characterized.
the separation of hop wax from the cold methanolic solution is In the early 1960s, Burton and Stevens proposed two fractions
slow and normally incomplete; as a result, traces of wax occur in derived from the total hard resin, the α-hard resin and the β-hard
this fraction (10). The uncharacterized soft resins can be further di- resin fraction (58). The α-hard resin fraction represents a small
vided into α-soft resins and β-soft resins. These terms are reserved part of the hard resins capable of forming an insoluble lead salt
for substances that may later be identified as having arisen from when treated with a lead acetate solution (58). Using ion-
the α-acids or the β-acids, respectively (22). The brewing value of exchange chromatography it was possible to perform further
the uncharacterized soft resins remains unknown. fractionation of the α-hard resin. Some of the collected
fractions of the α-hard resin were believed to be α-acids that
did not completely precipitate earlier in the fractionation (10).
Hard resins
However the term α-hard resin does not imply that all the
By definition the hard resin is the portion of the total resin that is
material is derived from the α-acids but that, like the α-acids, it
soluble in methanol and diethyl ether but insoluble in hexane
gives an insoluble lead salt (58). The β-hard resin is the major
and low boiling paraffinic hydrocarbons (29). It is generally
portion of the total hard resin; unlike the α-hard resin, this
accepted that the hard resins arise by oxidation of the soft resin;
fraction fails to give an insoluble lead salt (10,58). Xanthohumol
however, it is neither well defined nor proven conclusively what
accounts for the bulk of the β-hard resin. With the exception of
the hard resins consist of. In 1956, Schild and Raum found hard
xanthohumol, the precise chemical identity of the hard resins
resins in hops at the earliest stage of development (57); there-
is not well understood (8).
fore it is necessary to differentiate between the native hard resin
of hops and that which arises by autoxidation of the soft resin
during kilning and storage (10). Unfortunately, hitherto, no dis- Xanthohumol. Xanthohumol is the most abundant prenylated
tinction has been made between the deterioration or oxidation chalcone present in the hop lupulin glands and naturally found
products and the natural hard resin constituents of fresh hops in the hard resins. Many of the native hard resins are made up
(32). However, given that the soft resins are prone to oxidation, of prenylflavonoids (8). Xanthohumol was first isolated from hops
this results in a challenging task. As hops age during storage, by Power, Tutin and Rogerson in 1913 (62). Xanthohumol is the
only known naturally occurring methylated hop resin (10). In
the last decade, on account of the wide range of potential health
benefits, xanthohumol has been the source of numerous investi-
gations (63–65). Although xanthohumol is the major compound
in hop hard resins, only trace amounts are found in beer as it is
lost in significant quantities in the conventional brewing process.
During the brewing process, the thermal isomerization of
chalcones into flavones takes place and xanthohumol is cyclized
to isoxanthohumol (see Fig. 6). Attempts to increase the amount
of xanthohumol present in the finished beer have been made by
several brewing scientists. To achieve this, brewing trials using
xanthohumol enriched extracts were carried out (66–69).
δ-Hard resin. In 1952, Walker et al. (70) found a water-soluble

Figure 5. Chemical structures of the hop β-acids. portion of the hard resin that also had a bitter character. They
293
C. Almaguer et al.
fractions were collected as brittle powdery material. The frac-

tions could be further differentiated based on their bittering
potential as well as their antimicrobial properties. The more
non-polar fractions (i.e. δ 9–δ 11) proved to be more active
than the polar fractions. No pure compounds were isolated
from any of the recovered fractions (73).
Bausch et al. (74) also conducted research on the δ-resin of
Figure 6. Chemical structures of xanthohumol (chalcone) and isoxanthohumol
hops. In their studies, they were able to quantify the δ-resin in
(flavone). During the brewing process, the thermal isomerization of chalcones into fresh green hops. However, they observed that not all sub-
flavones takes place and xanthohumol is cyclized to isoxanthohumol. stances present in the δ-resin extracted from aged hops were
found in that of fresh hops. The δ-resin was found in all hop
fractions. Small amounts of crude δ-resin were isolated from
termed this portion of the total hard resin the δ-resin. An raw α-acids and pure α-acids, 2.3 and 1.4%, respectively. In their
aqueous solution of the δ-resin was described to be intensely trials, the hop fractions were artificially aged by subjecting the
bitter yet the taste was pleasant. In their study, Walker et al. samples to extreme temperatures and high moisture levels.
collected evidence to determine that the δ-resin is produced When the raw α-acids and pure α-acids were separately heated
by oxidation of a non-water-soluble constituent of the hop at 70 °C for 8 h (90% moisture level), the δ-resin increased to 32
resins. Additionally, data from preliminary chromatographic and 40.6%, respectively. The δ-resin content in the β-fraction of
examination of the δ-resin indicate that it is not homogeneous hops was 1.15%; after forced aging this increased to 8.3%. Upon
(70). In a later study, Abson et al. (71) developed a method for forced aging of the β-fraction, the δ-resin slightly increased, as
estimating the δ-resin content in hops. In their experiments, they opposed to the α-acids, where large amounts of δ-resin were
observed that this fraction accumulates during the storage of produced. The δ-resin content in the hard resin of hops was
hops. However, they could not find any direct relationship 22.3%; upon accelerated aging it increased to 23%, thus
between the percentage decrease in the α-soft resin (i.e. α-acids) suggesting that δ-resin found in the hard resins is relatively
and the amount of δ-resin accumulated during the same stable. Moreover, no further oxidation products were gene-
period of time. From this observation it could be inferred that rated from the δ-resin. Finally, in picking trials of 1962, Bausch
the δ-resin is not the sole product of changes occurring in the et al. monitored the δ-resin content and composition of hops
α-soft resin. In the analysed hop samples, they found δ-resin during a 6 week period. Some substances were no longer
contents varying from 0.6% to about 4%. From their results, found in the δ-resin of all samples harvested a month or more
it could be concluded that the δ-resin content in hops, just after the first sample was harvested. It was also observed that
like most hop constituents, is variety dependent. Further, the the δ-resin content of the hop cones significantly decreased
formation of δ-resin upon storage varies among the different during drying (74).
hop varieties (71).
Jackson and Walker (72) were able to separate the total δ-resin Hulupones. A new group of bitter substances was identified by
into several non-crystalline fractions. In their preliminary fraction- Spetsig et al. in the late 1950s. It was observed that the β-acids
ation of the δ-resin by column chromatography, they isolated six are readily oxidized to the strong bitter-tasting hulupones. It
fractions (δI–δVI). Small-scale experiments indicated that these was also established that, for the conversion of β-acids to
were not single substances. Moreover, they collected evidence to hulupones to take place, an oxidizing agent was required (75).
determine that in terms of chemical reaction the fractions were When these substances were examined by reversed-phase
qualitatively similar. All fractions exhibited the same association chromatography, three peaks that elute before the α-acids were
of chemical functions: unsaturation, enolic/phenolic acidity and detected (75–77). Like the humulones and lupulones, the
carbonyl (ketone) activity. From the crude δ-resin, two major frac- hulupones also consist of a series of analogues. The names
tions were recovered, δII (66.3%) and δIII (22.5%). In an attempt to cohulupone, hulupone and adhulupone were assigned to the
fully characterize both fractions, further chromatography was individual compounds; the prefixes have the same significance
performed. Based on its solubility in benzene and light petroleum, as in the humulone and lupulone series. Hulupone concentra-
a significant portion of δII is believed to be residues of the soft tions have been reported to be between 0.5 and 3.0% of the
resin. Contrary to δII, fraction δIII showed the same solubility weight of the dried cones. In contrast to the hard resins, no
characteristics as the hard resins. Fractionation of δIII by partition hulupones were detected in fresh hops (76,78). When the course
between immiscible solvents yielded four subfractions (δIII A, δIII of the hulupones was monitored during the brewing process, it
EA, δIII B and δIII E). It was further observed that neither the total was found that the bulk of the hulupones is usually retained in
δ-resin nor the fractions isolated from the crude δ-resin are totally the spent hops that remain after wort boiling. However a con-
soluble in water. However, when using any solvent to suspend the siderable fraction is transferred to the wort in its unchanged
fractions, water was required to achieve complete solubility. form, that is, the hulupones in wort exist in the form of salts
Jackson and Walker were not able to identify any pure compounds (75,76,78). At least in the 1960s, it appeared that the hulupones
in the δ-resin. However, from the recorded observations on the commonly contributed to a little over 5% of the bittering princi-
similarity in chemical behaviour of the fractions, it was possible ples in beer (78). Owing to the complex nature of the substances,
for them to conclude that some basic type of structure predomi- these three compounds are challenging to classify. As men-
nates amongst the δ-resin components (72). tioned previously, it is generally accepted that the hard resins
In a recent study, 11 fractions were recovered from the total arise by oxidation of the soft resins. Although hulupones are
δ-resin. The isolated fractions could be distinguished based on autoxidation products of the β-acids, when present in hops,
their physical properties and their solubility. The more polar these are soluble in all organic acids, and therefore components
fractions were recovered as thick resins while the non-polar of the soft resin (78).
294
Hulupinic acid. Hulupones are degradation products of the β-acids, was also established that the ε-resin composition is variety
yet these can only be considered to be an intermediate oxida- dependant, that is, some compounds are only found in certain
tion state. Further oxidation of the hulupones will result in the hop varieties (85).
non-bitter hulupinic acid (see Fig. 7) (79,80). In 1964, Burton The bitter intensities of the δ-resin, ε-resin and total hard resin
and Stevens isolated a crystalline product from the α-hard were tested and compared. To do this, each hop resin was
resin and suggested the name hulupinic acid for this com- separately suspended at its natural concentration ratio in 5%
pound (58,79). When a solution of cohulupone in ethanol aqueous ethanol. Subsequently, to simulate a beer-like matrix,
was heated under reflux while a stream of oxygen was passed the pH of all solutions was adjusted to 4.4 with trace amounts of
through it, it was possible to isolate hulupinic acid after aqueous formic acid (1% in water). The trained panellists were
3 days. Surprisingly, autoxidation of hulupone and cohulupone asked to rate the bitter intensity of all samples on a six-point
in an ethanolic solution gave the same hulupinic acid (79); sensory scale ranging from not detectable (0) to extreme (5). The
exactly the same transformation product was obtained from ε-resin was considered by the panellists to be six times more
adhulupone by similar treatment (81). From the evidence bitter than the δ-resin. The bitter intensity conferred by the
gathered, it was possible to state that the acyl side chain (i.e. R ε-resin was comparable to that delivered by the total hard resin
group) must have been removed and possibly replaced by a (data not shown). The results collected from the tasting sessions
hydroxyl group during the oxidation process (14,79). It was also revealed that, at least in a water matrix, the ε-resin can deliver a
determined that the amount of hulupinic acid increased with perceivable bitterness (85). However, it must be borne in mind that
the age of the hops. Nevertheless, at the time, the highest de- the sensory bitterness is relative to the matrix.
tected hulupinic acid concentration in aged hops was <0.05% The 11 isolated fractions from the total ε-resin could be
(58,79). The solubility of the hulupinic acid was tested in water distinguished based on their physical properties and their solu-
and it was established to be approximately 1 g/L at pH 4.0 and bility. Unlike the isolated δ-resin fractions, all ε fractions were col-
it increased to 2 g/L at pH 5.0 (58). Based on this information, it lected as powdery material. From the crude ε-resin, two major
is expected to find low amounts of hulupinic acid in the finished fractions were recovered: ε 10 (31.3%) and ε 11 (22.9%). In this
beers. Although hulupinic acid is the ultimate oxidation product study, the bittering potential and the antimicrobial properties
of the β-acids and moreover this compound was isolated from of the 11 ε fractions were assessed. From the collected data it
the α-hard resin, owing to its solubility in water, hulupinic acid was possible to classify the fractions based on their activity.
is classified as a component of the δ-resin (58). The highly polar fractions ε 1 and ε 2 showed no activity. Gener-
ally, there was a good relationship among the bittering potential
ε-Hard resin. Previous to a recent study (73), no data have been and the inhibitory activity of the ε fractions. As the fractions be-
reported in the literature regarding the ε-resin of the total hard came more non-polar, the bitter intensity as well as the antimi-
resin. In this study, a portion of the hard resin which was not sol- crobial activity of the ε fractions increased (82).
uble in water yet had a bitter character was found. This portion Almost 100 fractions were recovered by additional purification
of the hard resin was termed the ε-resin (73,82,83). It was found and fractionation of the ε-resin. In addition, it was possible to iso-
that the ε-resin accounts for up to 80% of the total hard resin late over 20 pure compounds from the ε-resin (73,83). As before,
composition; however, like most hop constituents, this is variety sensory evaluations and microbiology tests were conducted
dependent (83). Like the total δ-resin, the ε-resin is not homoge- with these fractions. From the collected data it was possible to
nous. When further fractionation of the ε-resin was done, 11 classify the subfractions and pure compounds based on their
crude fractions were recovered. In the current study, a method bittering intensity as well as their inhibitory effect. The bitter
was developed for the large-scale production of the ε-extract intensity scale ranged from high bitterness to low bitterness. In
(84). Upon characterization of the ε-resin enriched extract, com- a similar manner the antimicrobial activity scale was broken
pounds that are usually found in the commercially available down into three levels, ranging from high inhibition to no
xanthohumol extracts were also identified in the produced inhibition. Multidimensional scaling was used to determine the
extract. Highly polar compounds were not detected in the similarities among the subfractions, as a result, eight clusters
ε-extract; moreover, the xanthohumol and isoxanthohumol were generated (data not shown) (73). Ultimately, through the
content in the ε-extract was found to be significantly lower. It screening and selection of the hop fractions, it is possible to
Figure 7. Chemical structure of hulupones and hulupinic acid. Oxidation of hulupones yields hulupinic acid.
295
C. Almaguer et al.
tailor brews to comply with the consumer’s requests without within the individual varieties were observed. In some varieties,
compromising the microbial stability of the beer. certain components are affected by the environmental conditions
in which they were grown, in which they were grown; in particular
country of origin. These oil compounds will either be present in
Hop essential oils higher amounts or not present at all. Additionally, year to year
Like the hop resins, the essential oils are secondary metabolites variations in the hop oil composition may be observed within
of the hop plant secreted in the lupulin glands. By definition, the the same variety (105,106,109). Van Opstaele et al. studied the
hop oil fraction is the portion of the hop material that is volatile. impact of the varietal character of the fractions associated with
These volatile aroma compounds are considered ‘essential’ since the floral note (2) and the spicy (or herbal) note (3). Independent
they give hops their characteristic smell. While the hop resins of the variety the hop oil fractions were extracted from these
give beer its bitterness, the essential oils give beer aroma and fractions deliver similar flavour characters to beer: floral or spicy.
flavour. Dried hops contain 0.5–3.0% of essential oil (29,86,87); The chemical composition of these hop oil fractions is, however,
it has been reported that this relatively small volatile fraction is a variety dependent.
complex mixture of over 200 components. While only 200 com-
pounds had been conclusively identified in the late 1990s, capillary
Hydrocarbons
gas chromatography analysis revealed up to 400 peaks in a chro-
matogram recorded at high detector sensitivity (51). By the begin- In Fig. 8, a general overview of some of the known hop oil com-
ning of the century, the total number of identified and chemically pounds is shown. The contribution of most of these compounds
characterized compounds found in hops was 440. In a more recent continues to be controversial. The bulk of the hop oil is made up
study, comprehensive multidimensional gas chromatography of hydrocarbons and oxygenated components. The hydrocar-
(GC × GC) with flame ionization detection was applied; from bons can be classified into three groups: aliphatic hydrocarbons,
the collected data, it was suggested that there may be over monoterpenes and sesquiterpenes (100). The hydrocarbon
1000 different compounds in the hop oil fraction (88). group is very volatile (i.e. lower boiling fraction) and will readily
Almost 200 years ago, it was independently recognized by oxidize and polymerize (92). The solubility of hydrocarbons in
Loiseleur-Deslongchamps (89) and Hanin (90) that hop cones water, wort and beer is very low; additionally, most of these
are very aromatic. Loiseleur-Deslongchamps described the hop compounds are lost by evaporation during the boiling process;
aroma to be garlic-like. A few years later, the first attempts to as a result only trace amounts are found in beer (110,111).
characterize the hop oil were made by Payen and Chevallier.
The volatile oils were first distilled from the hop cones and the
β-Myrcene
distillate was further separated into two fractions (91). However,
the first systematic examination of the essential oil of hops was Of the hydrocarbon fraction, the most important and abun-
done by Chapman from 1895 to 1929 (92–98). It is now known dant monoterpene is β-myrcene (Fig. 9A); it may account for
that the content and composition of the total essential oil of 30–60% of the total oil content (99,111–113). In 1895, β-myrcene
hops are affected by numerous factors such as hop variety, was first obtained from bay oil by Power and Kleber. In 1903,
growth conditions, time of picking (ripeness), drying conditions, Chapman recognized that the properties of one of the isolated
aerial oxidation, age and storage conditions (99). There is evi- hop oil compounds were the same as those of the acyclic terpene
dence to suggest that the yield may also be slightly influenced β-myrcene. By directly comparing the properties of the unknown
by seasonal effects (91). compound with those of β-myrcene extracted from oil of bay, it
As of 1980, the chemical composition of the hop essential oils was possible to conclude that β-myrcene is also found in the
has been conventionally described under three main chemical hop oil fraction (95). β-Myrcene is the main component res-
groups, the hydrocarbons, the oxygenated compounds and the ponsible for imparting the pungent smell to fresh hops (51).
sulfur-containing components (100). It has been established that Other monoterpenes present in the hop oil fraction in sig-
the hop essential oil profile depends on the hop variety. In par- nificantly lower amounts are ocimene, β-pinene, limonene and
ticular, the amounts of hydrocarbons and oxygenated com- ρ-cymene, among others (10).
pounds vary according to the hop variety and age (101). In the
late 1950s, Howard and Slater (99) recognized that, independent
Sesquiterpenes
of the country in which the hops were grown, there was a vari-
etal uniformity in the general pattern observed in the composi- In the hydrocarbon fraction, the major components of the
tion of the hydrocarbon fraction. A decade later, Likens and sesquiterpene group are α-humulene, β-caryophyllene and
Nickerson (101,102) and Buttery and Ling (103) confirmed that β-farnesene. These sesquiterpenes have higher boiling points
the essential oil of several hop varieties displayed good varietal than the monoterpenes. This high-boiling group is domi-
uniformity in their chemical composition. Likens and Nickerson nated by α-humulene and β-caryophyllene (114). β-Myrcene
established that certain components or ratios of components plus these two hydrocarbons make 80–90% of the total
in the hop oil are highly specific for the individual varieties. essential oil in hops (95). α-Humulene, the most abundant
In 1990, Kenny (104) published a key for the varietal char- sesquiterpene found in hops, was one of the first compounds
acterization of hops based on six ratios calculated from the to be identified in hop oil; the structure of the compound is
amounts of 10 essential oil components. Other varietal iden- shown in Fig. 9(B) (92). The second most important sesquiterpene
tification models, based on the hop oil analysis and composi- found in hops is β-caryophyllene (see Fig. 9C) (92). Although it
tion, were proposed by Kralj et al. (105), Kovačevič and Kač was suspected as early as 1895 that β-caryophyllene could be
(106,107) and Perpète et al. (108). From their collected data present in the essential oil fraction of hops, it was not until
they were also able to propose hop cultivar markers. It was 1949 when this component was conclusively identified in hop
only recently that differences in the essential oil composition oil by Šorm et al. (115). When a typical hop oil chromatogram is
296
297
Figure 8. Hop oil composition (10,100,126).
C. Almaguer et al.
A later study by Murphey and Probasco (124) confirmed the

findings of Howard and Slater. It further proved that the harvest
point can considerably affect the aroma quality of hops. In all
hop varieties studied, the total essential oil content continued
to increase throughout the sampling period. The higher
total oil content is primarily due to β-myrcene synthesis.
The β-myrcene content in most late harvested samples increased
Figure 9. Structures of some terpenes present in hop essential oil. (A) β-Myrcene, from negligible amounts to almost 50% of the total oil content.
the most abundant monoterpene present in fresh hop oil. The most important The β-caryophyllene and α-humulene concentrations of all late-
sesquiterpenes are α-humulene (B) and β-caryophyllene (C). In (D) is shown stage harvested samples decreased by more than half of the early
β-farnesene; this compound is only found in some hop varieties.
stage content. Recently, the effect of the time of harvest and loca-
tion on the hop essential oil composition of two American aroma
examined, it can be observed that much of the material is hop varieties were compared (125). Contrary to previous studies
accounted for in three elution bands. The substance responsible where the increase in the total oil content was primarily attributed
for the first peak is β-myrcene; β-caryophyllene elutes much later to β-myrcene synthesis, Sharp and Shellhammer were able to de-
and shortly after, the peak for α-humulene appears (86). In Fig. 9D, termine other hop compounds responsible for the increase in the
the chemical structure of β-farnesene, an acyclic sesquiterpene, is oil quantity. This increase was strongly correlated with α-pinene, β-
shown. This compound was first isolated by Šorm et al. from pinene, limonene, methyl heptanoate and linalool.
Žatec (Saaz) hops (115,116). Unlike β-myrcene and α-humulene
and β-caryophyllene; β-farnesene is only found in certain hop
varieties and usually in low amounts (99,117). Oxygenated compounds
Howard and Slater investigated hop oil production during the The hydrocarbon fraction of hop oil is quantitatively eluted from
ripening period. To do this, samples were picked at defined silica gel by light petroleum; a second fraction containing the
intervals during the ripening of hops and the essential oil oxygenated compounds will elute once ether is applied. Al-
fraction was examined (118). The essential oil fraction was though the oxygenated fraction is found in substantially lower
isolated from these hop samples by steam distillation and amounts [ca. 30% of the total essential oil (126)], the composi-
analysed by gas chromatography. A portion of the hop oil tion of this fraction is more complex than the hydrocarbon one
extract was divided into two fractions by adsorption chromatog- (86). In the oxygenated fraction a large number of components
raphy and then analysed separately by gas chromatography. are found; however, most of these are present below their odour
From their results it was concluded that the total oil content threshold concentrations. Normally, the oxygenated compounds
rises steadily during ripening (99). It was observed that, for most of the hop oil comprise two major portions that are termed the
varieties, the oil develops at a later stage than the resins (118). ‘volatile’ and ‘non-volatile’ portions. The former consists of a
Stevens et al. (119) isolated the essential oils using steam distilla- complex mixture of compounds with boiling points lower than
tion and analysed them by gas chromatography. They were the that of α-humulene. Since the boiling point of the non-volatile
first to report that the essential oils continue to be synthesized fraction is higher than that of α-humulene in early hop oil exam-
until harvest. They also observed that the production of the es- ination, this portion was more challenging to analyse (99). How-
sential oil components present in ripe hops does not start before ever, these higher boiling substances are of interest to the
resin development is completed (119). Since many hops were brewer since these will most likely be retained in the wort after
picked when resin development was complete but before oil boiling and they may eventually find their way into the finished
production had ceased (120), the hop quality in earlier times beer (117). The total oxygenated fraction is a complex mixture of
cannot be compared with the current one. From the picking alcohols, aldehydes, acids, ketones, epoxides and esters. In 1981,
trials, it was seen that the proportion of β-myrcene rose rapidly Sharpe and Laws reported 60 aldehydes or ketones, 70 esters, 50
throughout the ripening period. The β-myrcene content alcohols, 25 acids and 30 oxygen heterocyclic compounds in
increased from an almost negligible figure to 36%. The propor- hop oil (100); since then, the list has significantly increased.
tions of β-farnesene and β-caryophyllene remained compara- It was observed by Howard and Slater that, as hops aged, the
tively constant. Unexpectedly, the α-humulene content of hops oil became richer in oxygenated components at the expense of
fell significantly from 79 to 42% (118). From the collected data the hydrocarbons. In addition, oxidation resulted in non-volatile
it could also be concluded that the β-myrcene content is directly oxygenated compounds at the expense of the hydrocarbons,
proportional to the proportion of cohumulone and colupulone and as a result the proportion of β-myrcene decreased. Finally,
found in the hop resins (99). In another study, Rigby and non-volatile oxygenated compounds were produced with a
Bethune isolated the hop essential oils by steam distillation concomitant loss of some of the volatile ones (99). The effects
and separated them into different fractions by countercurrent of autoxidation of β-myrcene were studied in detail by
distribution. By means of the chromatostrip and chromaplate Dieckmann and Palamand (127). It was reported that autoxida-
technique (121) as well as gas chromatography (122), they tion proceeds in four reaction classes: cyclization, oxidation,
collected data to show that hops with high cohumulone had disproportionation and polymerization. Over 40 compounds
high β-myrcene; conversely, hops with high humulone had a were found to be produced from the autoxidation of β-myrcene.
high α-humulene content (122,123). It was also recognized by
Howard and Slater that a high β-myrcene proportion generally
accompanied a low α-humulene content. Based on these conclu- Linalool
sions, there was enough evidence to suggest that there may be The alcohols of the essential oil fraction can be classified into
a common intermediate in the biosynthesis of β-myrcene and three groups: terpene alcohols, sesquiterpene alcohols and
the α-acids and β-acids (99). aliphatic/aromatic alcohols (100). The major constituents of the
298
alcohol fraction are 2-methylbutanol and linalool with lower as 1-hexanal and (Z)-3-hexenal are responsible for delivering
amounts of geraniol, nerolidol, nerol and terpineol (10). The most the green and grassy notes to beer (137). Among the acids,
abundant terpene alcohol is linalool, and like many essential oil it has been reported that only a few free acids are present
components, it was first identified in 1903 by Chapman (95). Linal- in hop oil (100). The fatty acids of hop such as 2-methylbutyric
ool is considered an important hop aroma indicator substance in acid are linked with a cheesy aroma (138). The first ketone to
beer (111). The contribution of linalool to the hop aroma profile be characterized by Šorm et al. in 1947 was undecan-2-one
is dependent on the hop treatment. It is unlikely that linalool will (116). It was first identified in 1928 by Chapman and termed
make a contribution to the aroma profile of the beer if the wort luparone (97); this term is no longer used. This compound,
is traditionally hopped (i.e. beginning of the boil). The contribution also known as methyl nonyl ketone, was found in the late
of linalool to hop aroma in beer is more perceivable when a late 1950s to be the most abundant oxygenated component in
hop addition is done. Only minor linalool contributions are most hop oils (122). It has been reported that this hop oil
detected in dry hopped beers (128). Linalool is a hydration product component gives a floral flavour to beer (139). Many other ke-
of β-myrcene (128); it is also a chiral compound; therefore there are tones were later reported to be present in hops by Jahnsen
two stereoisomers: (R)-( )-linalool and (S)-(+)-linalool (see Fig. 10A (126) and Guadagni (130), among others.
and B). Both enatiomeric forms are found in the hop essential oil The oxygenated hop sesquiterpenoids, in particular humulene
fraction. It has been shown that (R)-linalool is more flavour-active epoxide II, have been associated with the spicy or herbal hop
and, of the total linalool content, the (R)-form is usually present character (140). Efforts have been made to unravel the nature
in hops between 92 and 94% (129). of this spicy note. However, owing to the very complex chemical
Linalool is usually considered to be responsible for the floral composition of the spicy hop character and the lack of reference
character in beer. The odour threshold concentration of compounds to verify the analytical data, many of the com-
linalool in water was first reported by Guadagni et al. to be pounds responsible for this hop character remain unknown.
6 ppb (i.e. 6 μg/L) (130); however in beer this value increases Eyres et al. (141) and Nielsen (142) were able to tentatively iden-
to 10 ppb (111). Sensory threshold values are highly depen- tify 14-hydroxy-β-caryophyllene and caryophylla-3,8-(13)-dien-5-
dent on the olfactory properties and the structures of the β-ol, respectively, as highly odour-active compounds responsible
molecules, but also on the matrix in which they are tested for the spicy character of hops. More recently, Van Opstaele et al.
(131). The composition of the beer matrix (i.e. lower pH and (3) were able to associate another 22 oxygenated sesquiter-
sugar profile) plays a key role in the determination of thresh- penes to the spicy fraction of hops. Among these 22
olds as it exerts an effect on the presence or absence of constituents, eight compounds were tentatively identified as
sensation of the hop compounds (132). In addition to the testing α-humulene or β-caryophyllene oxidation products. The pre-
matrix, other odour-active substances can also interact and cause cise identity of 10 of these compounds remains unknown. Of
strong changes in the odour thresholds of these compounds the 12 tentatively identified oxygenated hop sesquiterpenoids,
(131). The data found in the available literature for the flavour humulene epoxide II appeared to be the most predominant
threshold values of linalool in beer vary significantly. In 1975, constituent, followed by ( )-caryophyllene oxide. Other tenta-
Meilgaard reported a flavour threshold in beer of 80 ppb and de- tively identified compounds associated with the spicy or
scribed it as having an aniseed and terpenoid flavour (133). A few herbal character of hops are humuladienone, caryolan-1-ol,
years later, Peacock and Deinzer reported a flavour threshold globulol, viridiflorol, 10-epi-α-cadinol and τ-cadinol (3). Goiris
value of 27 ppb and characterized it as floral and citrusy et al. (143) determined the flavour threshold of the enriched
(134,135). More recently a value of 8 ppb was reported by Kaltner sesquiterpenoid hop oil fraction in beer to be 5 ppb; however,
et al. (136). Independent of the threshold, linalool is one of the an addition of 20 ppb was usually preferred by the panellists.
few hop oil components that is universally accepted as being The total ester fraction represents a complex mixture having a
flavour-active in beer (128). wide boiling range (86). The esters are probably the most
important of all the hop oil components owing to their contribu-
tion to hop aroma and flavour (100). It was independently
Other oxygenated compounds reported by Wright and Connery (144) and others that esters
Jahnsen (114) suggested that a whole series of aldehydes of hop oil are the constituents more closely associated with
occurs in hop essential oils. It was shown that aldehydes such quality. It was also noted that oils with high ester content, low
acid and low volatile reducing power had a more delicate
and pleasant aroma (121). Naya and Kotake reported that the
β-myrcene-rich varieties show high contents of esters (145).
Many esters such as 2-methylpropyl isobutyrate are known for
their fruity and floral notes (138).
Sulfur compounds
The essential oil of hops contains only trace amounts of sulfur
compounds. However, since these have potent aromas and
low odour thresholds they may easily influence the overall fla-
vour of beer (146). The volatile organosulfur substances afford
the most detrimental hop flavours to beer (147). These com-
Figure 10. Structures of some oxygenated compounds found in hop essential oils.
pounds have very low sensory thresholds; values can be as low
(A) (R)-linalool, the active stereoisomer of linalool. In (B) the mirror image of (R)-linalool as 0.1 ppb (148). In general, these components impart undesir-
able sulfury, cooked vegetable, musty, cabbage-like and onion-
299
is shown, the (S)-form is less odour-active and is also present in lower amounts.
C. Almaguer et al.
like flavours to beer (100,148). The methyl thioesters impart un- in the hop cone petals and strig and, with the exception of the
pleasant cheesy, cooked vegetable and sulfury aromas. In prenylflavonoids (e.g. xanthohumol), not in the lupulin glands
addition to these aromas, the methylthiomethyl thioesters also (8). The polyphenol fraction represents a vast class of com-
impart onion-like and garlic-like odours. The rubbery and pounds with widely varying structural characteristics (154).
garlic-like off-flavours in beer are imparted by 2,3,5-trithiahexane Chemically, these are substances that are built up by multiple
and 3,3-dimethylallyl methyl sulfide, respectively (148). Many phenol units. Although they are a very heterogeneous group
studies have shown that a broad range of odours can be of substances, the polyphenols share a common structural ele-
produced by the sulfur compounds; however, most of them ment: an aromatic ring with at least two hydroxyl groups (155).
are considered to be undesirable off-flavours. The thioester The composition of the polyphenols depends on the hop
responsible for the truffle aroma is S-methyl-2-methyl variety, cultivation area, harvesting technique and degree of
thiobutanoate (149). Green and fruity notes are associated with aging (154). It has been reported that aged hops contain higher
S-methyl thiohexanoate; this substance has also been reported levels of polyphenols than fresh ones (156). It has also been
to produce a pineapple odour (150). Another aroma delivered shown that certain polyphenolic substances are unique to a
by the organosulfur compounds is that of roasted meat; this specific hop variety (157).
note is imparted by 2-methyl-3-furanethiol (147). Another inter- Analysing hop samples by high-performance liquid
esting sulfur containing class is S-methylthiomethyl thioesters, chromatography–diode array detection, Forster et al. found over
which represents a new class that has not been isolated from 100 compounds in the polyphenol fraction of hops (158). Hop
any other natural source (151). Recently, an S-cysteine conjugate, polyphenols can be classified into flavonols (e.g. quercetin),
S-3(1-hydroxyhexyl) cysteine, was identified for the first time in flavan-3-ols (i.e. flavanols or flavanoids, e.g. catechin), phenolic
Cascade hops. The exact aroma character of this compound carboxylic acids (e.g. ferulic acid), and other polyphenolic
has not been conclusively defined (152). compounds (e.g. prenylflavonoids and multifidol glucosides)
(see Fig. 11) (159). Flavonols (Fig.12C) and flavan-3-ols (Fig. 12D)
are derived from the structure of flavone (see Fig. 12B) and as
4-Mercapto-4-methylpentan-2-one such are classified as flavonoids (Fig. 12A), a subgroup of
Of particular interest to the brewer and brewing chemist has polyphenols (155). Some polyphenols are unique to hops; that
been the intense muscat-like (i.e. grape) character found in is, they have not yet been found in any other natural source.
some beers. These muscat-like characteristics were attributed Some of these polyphenolic substances hitherto found only in
to 4-mercapto-4-methylpentan-2-one (4MMP). This compound hops are multifidol glucosides and prenylflavonoids such as
can only be found in specific hop varieties and has been xanthohumol, desmethylxanthohumol, 6-prenylnaringenin and
shown to have an extremely low threshold value in beer 8-prenylnaringenin (159,160).
1.5 ppt (i.e. 1.5 ng/L) (137). It has also been documented that In general, aroma hops contain a higher amount of low
4MMP produces aromas reminiscent of blackcurrant and cat molecular weight polyphenols than bittering hops (161). The
urine (109,153). The growing location and conditions have reason for this is that an increase in α-acid content can only be
the most noticeable effect on the levels of thioesters and obtained at the expense of the polyphenol content (162). Most
sulfur compounds (151). Interestingly, 4MMP was detected in polyphenols in wort are derived from malt; however, about
hop cultivars grown in the USA, Australia and New Zealand. 20–30% of the polyphenols found in the wort come from
This compound was, however, not found to be present in the hop material (139). The importance of the hop polyphenols
the same cultivar grown in Europe (109). in the brewing process is due not only to their contribution to
flavour but also to their role in the production, by protein–
polyphenol interaction, of non-biological haze, which limits the
Hop polyphenols shelf-life of bottled beers (10). Since hop polyphenols can be very
easily oxidized, they act as strong antioxidants (155). They do this
Polyphenols are another secondary metabolite of the hop plant; by reacting as free radicals scavengers, by inhibiting lipoxy-
hop polyphenols comprise up to 4% of the total weight of dried genases, or by acting as metal chelators (163). Low-molecular-
hop cones. Similar to most hop constituents, the level of weight polyphenols are natural antioxidants and account to a
polyphenols is variety dependant. These are to be found mostly great extent for the reducing power of wort, thereby protecting
Figure 11. Constituents of the hop polyphenol fraction (159).

300
Figure 13. Chemical structures of two protonated aglycones. Quercetin (A) and
kaempferol (B) are structurally very similar; quercetin has an extra hydroxyl group
on the flavonoid unit.
differentiation are the quercetin and kaempferol glycosides;

Figure 12. Chemical structures of the backbones of the hop polyphenols. (A) The the other phenolic components are less cultivar specific (155).
backbone of the flavonoids from which all other structures are derived from.
Flavonols and flavan-3-ols (C and D, respectively) are two classes of flavonoids
derived from the structure of flavone (B).
Flavan-3-ols
beer against oxidation and improving the taste stability. Higher- The polyphenol solubility in wort and beer is not the same for all
molecular-weight polyphenols contribute to the colour of beer compounds. As expected, the hydrophilic groups of substances
and to haze formation (154). such as hydroxybenzoin, hydroxycinnamic acids, flavan-3-ols
and proanthocyanidins have a high solubility. The prenyl-
flavonoids (e.g. xanthohumol) are more difficult to bring into
solution. However the flavonoids have an intermediate solubility
Flavonoids
(161). A portion of the hop polyphenolic material is composed of
water soluble substances such as catechin and epicatechin
Flavonols
flavan-3-ols (Fig. 14A and B, respectively). These are the mono-
Approximately 20% of the total hop polyphenols consist of meric building blocks of dimers, trimers and higher polymeric
low-molecular-weight substances or monomer substances structures sometimes having as many as 20 or more basic units.
such as the phenolic carboxylic acids as well as the flavonoids These polymers, known as proanthocyanidins or condensed
and their glycosides (Table 2). Hop flavonoids consist mainly tannins, may also contain gallocatechin and epigallocatechin
of catechins and their polymers, proanthocyanidins, quercetin as extension units (166). Chemically, molecules that consist of
(Fig. 13A) and kaempferol (Fig. 13B) (164). The two protonated up to eight monomer units (oligomers) are referred to as
aglycones, quercetin and kaempferol, do not occur in free forms proanthocyanidins. Tannins (polymers), however, consist of a
in hops but only in glycosidically bound forms (i.e. bound to higher number of monomers (111). Proanthocyanidins (see
sugars) (155,165). The more hydrophilic protonated quercetin Fig. 14C) are flavan-3-ol oligomers and polymers that give
glycosides elute earlier than protonated kaempferol glycosides anthocyanidins upon acid depolymerization reactions (167).
when the glycosidic residues are the same. The glycosides of These are the most reactive substances of the polyphenol frac-
quercetin elute earlier because of the extra hydroxyl group on tion (139). While the proanthocyanidins may contain catechin
the flavonoid unit (165). Of the known flavonols, quercetin has and epicatechin as monomers or as terminal and extension
the highest antioxidative potential (164). Later eluting glycosides, units, gallocatechin and epigallocatechin were only found to
such as kaempferol, are more prominent in aroma hops (165). be subunits but not terminal units of the polymers (166). Hop
Hitherto, the most suitable polyphenols for cultivar proanthocyanidins have received special attention in the
Table 2. Composition of hop polyphenols and their concen-

trations in hops (155)
Substances and substance groups Amount (%)

Phenolic carboxylic acids
Benzoic acid derivatives <0.01
Cinnamic acid derivatives 0.01–0.03
Flavonoids
Xanthohumol 0.20–1.70
8-,6-Prenylnaringenin <0.01
Quercetin 0.05–0.23
Kaempferol 0.02–0.24
Catechins and epicatechins 0.03–0.30
Oligomeric proanthocyanidins 0.20–1.30
Acylphloroglucinol derivatives (multifidols) 0.05–0.50
Higher molecular substances Figure 14. Chemical structures of catechin (A) and epicatechin ( B). These are
Catechin tanning agents and tannins 2.00–7.00 water soluble flavan-3-ols and are the monomeric building blocks for higher
301
polymeric substances such as proanthocyanidins (C).
C. Almaguer et al.
brewing industry because they contribute to haze formation Multif idol glucosides
(168). As previously mentioned, the proanthocyanidins or
The naturally occurring acylphloroglucinol 1-[(2-methylbutyryl)-
tannins are a group of water soluble polyphenolic compounds
phloroglucinyl]-β-D-glucopyranoside, commonly known by its
(139). In beer these proanthocyanidins will slowly react with
trivial name ‘multifidol glucoside’, was first isolated from the
the proteins present to form a non-biological haze. These
latex of Jatropha multifida L. The term ‘multifidol’ is used to refer
insoluble precipitates will ultimately limit the shelf-life of
just to the aglycon. This compound is known to be immuno-
bottled beers (29).
logically active and have curative properties (173). Multifidols
do not occur in the free form but are, like many other
polyphenols, glycosidically bound (159). Recently four
Other polyphenolic compounds monoacylphloroglucinol-glucopyranosides and one aglycon
were isolated from hops. The occurrence in hop cones of all these
Prenylf lavonoids compounds but one was first reported in 2005 (174,175). Similar
to the α-acids and β-acids of hops, multifidols are acylphlo-
The major component of the prenylflavonoids in fresh hops is roglucinol derivatives with different side chains. The identified
the chalcone xanthohumol. A smaller amount of desmethyl- compounds were named according to the nomenclature of the
xanthohumol is also found in the lupulin glands of hops. hop bitter acids. Based on the structure of the multifidol
The prenylchalcones, xanthohumol and desmethylxanthohumol, glucosides homologue, the prefix ‘co-’, ‘n-’ or ‘ad-’ is assigned
are naturally present in hops and they are precursors of (structures shown in Fig. 16). The isolated hop multifidol gluco-
the isomeric flavanones (169). During the brewing process, sides demonstrate anti-inflammatory activity in vitro (174).
these prenylchalcones are largely converted into their
isomeric flavanones: isoxanthohumol and prenylnaringenins,
respectively (67). While xanthohumol can only cyclize to Resveratrol
isoxanthohumol (see above Fig. 6), desmethylxanthohumol
gives a mixture of 6-prenylnaringenin and the 1:1 racemate of (±) In 2005, Callemien et al. (176) mentioned for the first time the
8-prenylnaringenin (Fig. 15) (29,170,171). The estrogenic race- presence of three cardioprotective stilbenes (a class of phenolic
mate of (±)8-prenylnaringenin is often referred to simply as compounds) in hops: trans-resveratrol, trans-piceid and cis-
8-prenylnaringenin or ‘hopein’. The term hopein was coined piceid (Fig. 17A–D, respectively). cis-Resveratrol (see Fig. 17B)
in 2001 by De Keukeleire. Of the prenylnaringenins, the most im- was absent in the fresh hop cones and pellets of all tested hop
portant one is 8-prenylnaringenin. This compound was reported varieties (177). However, evidence was gathered to prove that
as the most active (in vitro) phytoestrogen known in the plant cis-resveratrol is generated from cis-piceid (the resveratrol
kingdom (172). Phytoestrogens are a plant form of the oestrogen glucoside) during storage (178,179). Similar to many hop con-
hormone and these can help prevent cardiovascular diseases stituents, the stilbene content in hops is affected by the variety,
and cancer (159). Of the other prenylflavonoids found in hops,
6-prenylnaringenin displayed only very weak estrogenic activ-
ity. Moreover, while isoxanthohumol was only weakly active,
xanthohumol proved to be completely inactive in terms of
estrogenic activity (172). Additional health benefits of the
estrogenic properties of hops were reviewed by Chadwick
et al. (171). It was not until 1988 that the chemical structure
of 8-prenylnaringenin, the principal estrogenic component of
hops, was for the first time correctly established by Hänsel
and Schulz (170). The presence of the estrogenic properties
of hops had long been known. However the report by
Milligan et al. may be regarded as the beginning of the mod-
ern, unambiguous understanding of the in vitro estrogenic
activity of hops (172). Figure 16. Chemical structures of the multifidol glucosides.
Figure 15. Chemical structures of desmethylxanthohumol, 6-prenylnarigenin and 8-prenylnaringenin. During the brewing process, the thermal isomerization of chalcones
into flavones takes place and desmethylxanthohumol is converted into the isomeric flavanones.
302
Figure 17. The chemical structures of the stilbenes trans- and cis-resveratrol are shown in (A) and (B), respectively. These compounds are generated from the resveratrol
glucosides trans-piceid (C) and cis-piceid (D), respectively.
harvest year and geographical origin, among other factors. of polyphenols, the quality and temporal intensity of bitterness
Except for very high oxygen-sensitive hop varieties, the lower was similar, but not identical, to that from iso-α-acids. As the
the α-acid content, the higher the resveratrol potential (177). It levels of polyphenols were increased, the produced bitterness
is well known that the biologically active ingredient of red wine was harsher and more astringent. At the highest tested levels
is resveratrol. Recently, the cardioprotective effects of wine have the bitterness was considered to be harsh, medicinal or metallic.
been attributed to this compound (180,181). Compared with In this study it was found that beers with 200 mg/L of polyphe-
grapes, the concentration in hops is low; up to 2 mg/kg of nols were rated as more bitter than beers with 10 mg/L iso-α-
trans-resveratrol has been found in fresh hop cones (182). acids (186). Another beer quality aspect that should not be
trans-Resveratrol is much more hydrophobic than other hop disregarded is mouthfeel. In 1995 Forster et al. (158) recognized
polyphenols (176), and thus difficult to transfer to the finished that hop polyphenols have a positive impact on the fullness of
beer. However its importance should not be disregarded since beer. Before 2007 no conclusive study had been conducted
trans-resveratrol has been linked to various health benefits. As regarding the influence of hop polyphenols on the mouthfeel
a phenolic compound, resveratrol contributes to the antioxidant of beer. In 2007, Aerts et al. (5) filed an application for a US
potential and thereby may play a role in the prevention of Patent (0254063 A1). Their data not only confirmed that hop
human cardiovascular diseases. Resveratrol has also been shown polyphenols positively enhance the mouthfeel of beer but also
to modulate the metabolism of lipids, and to inhibit the that the impact on mouthfeel is subject to varietal differences
oxidation of low-density lipoproteins and the aggregation of (5). Recently Goiris et al. (6) summarized these findings and
platelets. Moreover, as a phytoestrogen, resveratrol may provide focused on the contribution of the different hop polyphenol
cardiovascular protection. This compound also possesses anti- classes to the fullness of beer. Their results showed that the
inflammatory and anticancer properties (181). A thorough prenylated flavonoid-rich extract as well as the flavonol
review of the health benefits of resveratrol was published in glycoside-rich extract positively enhance the mouthfeel of beer.
2006 by Baur and Sinclair (183). The presence of trans-resveratrol The addition of a proanthocyanidin rich extract to beer had no
and cis-resveratrol as well as trans-piceid and cis-piceid was perceivable impact on the mouthfeel but caused unwanted as-
confirmed in beer. Of 110 analysed commercial beers, trans- tringency. Of the three hop polyphenol-rich extracts, beers with
resveratrol was found to be the most abundant stilbene in beer. added flavonol glycosides were preferred by the panellists (6).
The highest trans-resveratrol concentration detected in beer was
66.74 μg/mL. Although resveratrol is a naturally occurring
phenolic phytoalexin with potential health benefits, these
effects depend on the ingested amount and the bioavailability
Hop varieties
of the compounds (184). At its most simple, hop varieties have traditionally been classified,
based on their chemical composition, as ‘bittering hops’ and
‘aroma hops’. This distinction is important as the brewer may
Polyphenols in beer
benefit from proper selection of particular hop varieties to add
Hop polyphenols can provide both bitterness and astringency, subtle tastes and flavours to the beers. Recent proposals suggest
depending on their degree of polymerization. It has been a more refined classification of hop varieties. On the basis of α-acid
reported by Peleg et al. (185) that, in a water matrix, as the content, the bittering hops are further subdivided into ‘bittering
degree of polymerization increases, maximum bitterness inten- hops’, ‘high alpha’ and ‘super high alpha’ varieties. Based on the
sity is perceived and total duration decreases whereas astrin- hop oil composition, aroma hops are classified as ‘fine aroma hops’
gency increases. Peleg et al. also noticed that the monomers and ‘aroma hops’. At the time of harvest, the long-term average
were significantly higher in bitterness than the dimers, which α-acid content in the bittering varieties and aroma varieties is in
were significantly higher than the trimers (185). In a recent study the range of 10–20 and 2–10%, respectively. Some of the most
(186), brewing trials were conducted using a polyphenol-rich important traded bittering hop varieties on the world market are
extract derived from CO2 spent hop material. It was shown that Hallertauer Magnum, Hallertauer Taurus, Herkules, Galena,
the bitterness produced by the polyphenols interacts with the Nugget, Millennium and CTZ (Columbus, Tomahawk, Zeus). The
bitterness delivered by the iso-α-acids. For a beer with low levels representative aroma hop varieties are Hallertauer Perle, Hallertauer
303
C. Almaguer et al.
Tradition, Spalter Select, Hallertauer Mittelfrüh, Hersbruck Flavour hops

Hersbrucker, Tettnang Tettnanger, Saaz and Cascade (87).
Recently certain hop varieties have gained increasing popularity
in the hop and brewing industry. These varieties are referred to
as ‘flavour hops’. Currently, the term is not uniformly used but
Varietal acreage in Germany mostly refers to varieties originating in the USA, Australia and
New Zealand. Recently, Germany and other countries have also
In 2011, Germany became the world’s leading hop producer by
started cultivating these varieties. The term was coined about
volume displacing the USA. The 2008, 2009 and 2012 crops
20 years ago by the president of the American Association of
caused the greatest α-acid surplus the world has ever experi-
Brewers, Charles N. Papazian (155). Flavour hops describe varie-
enced. As a result of this historic hop glut, hop acreages were
ties that are designed to impart bold tastes as well as distinct
forced to decline in nearly all countries. In recent years, Germany
aroma and flavour characteristics to beer. The flavour profile of
has shouldered much of the brunt of the needed global hop
these varieties is commonly related to tropical and fruity notes.
acreage reduction and hop production (187). While in most
Unlike aroma and bittering hops, flavour hops are not associated
countries the hop acreage continues to decline, in 2011, the
with their α-acid content nor their yield. Owing to the complex-
USA offset this trend by significantly expanding the hop acreage
ity, hitherto, there has been no conclusive scientific definition of
(from 3,736 to 5,123 ha) assigned to aroma varieties (188).
flavour hops. However it has been suggested that a flavour hop
Since 1990, the total hop area under cultivation in Germany has
variety can be both an aroma and a bittering hop. Moreover,
remained between 16,000 and 23,000 ha. The largest hop culti-
hop varieties that have been traditionally classified as aroma or
vated areas (>22,500 ha) occurred from 1991 to 1993; conversely,
bittering varieties could now be reclassified as flavour hops. Four
between 2003 and 2007 the area under cultivation did not surpass
flavour hop selections that have been recently released for
18,000 ha. In Fig. 18 the breakdown of the cultivated hop catego-
cultivation in Germany are Polaris, Hallertauer Blanc, Mandarina
ries in the overall hop acreage is shown. The total acreage planted
Bavaria and Hüll Melon (189). The most popular flavour hops in
with aroma hop varieties has remained relatively constant. It repre-
the USA are Cascade, Simcoe, Centennial and Citra. Galaxy, Ella
sents between 50 and 60% of the total hop cultivated area in
(formerly known as Stella), Summer, Topaz and Vic Secret are
Germany. The occasional decline in area allotted for aroma hops
the flavour hop varieties cultivated in Australia (190). Nelson
is a consequence of fields not being cultivated rather than farmers
Sauvin, Kazbek and Aramis are being grown in New Zealand,
switching to other hop varieties. The acreage for traditional
the Czech Republic and France, respectively (188). By increasing
bittering varieties (e.g. Northern Brewer) has suffered a significant
the range of hop varieties available to the brewer, the brewing
decrease over the years. In the early 1990s, 30% of the total area
industry is provided with endless creative possibilities and hence
was planted with bittering varieties; currently, <2% is used for
the global beer portfolio can be expanded.
growing bittering hops. The reduction in the area designated for
traditional bittering hops resulted as a consequence of the
introduction of the high-alpha varieties (e.g. Hallertau Magnum).
The decline of the cultivated area with bittering hops was parallel
Hops and brewing
to the increase of acreage used for high-alpha hops. Currently, In the past 100 years global beer production increased sevenfold
about 55% of the land is planted with aroma hops and 40% of (Fig. 19). In 1911, 273 million hectolitres (hL) of beer were pro-
the acreage is used to cultivate high-alpha varieties. Of the duced; by 2013 world beer production had reached a new re-
remaining 5%, <2% is assigned to the bittering varieties. cord of 1960 million hL. In the last four decades (1970–2010)
global beer production tripled, from 630 million to 1846 million
hL (191). In general, world beer production has experienced a
very steady increase except for three representative periods, in
which owing to the political and economic situation, beer pro-
duction and consumption significantly decreased. First, the
1914–1918 war ravaged Europe, altered the political map and
Figure 18. Hop acreage development in Germany since 1990. The black section
shows the total hop area under cultivation for the aroma varieties. The acreage area
for the bittering varieties is represented by the light grey section. The high α varieties
were only cultivated as of 1990; the dark grey section shows the area under cultiva-
tion. The total hop area under cultivation in Germany is represented by the black dots.
The observed discrepancies are due to other minor varieties, which are not included in Figure 19. World beer production 1911–2013 (191,195). Missing data not avail-
able owing to the political situation at that time.
304
the graph. The data for 2013 are the estimated values (191,195).
Table 3. World market key data (191,195)
Crop Hop area under Hop production Beer production Crop Hop area under Hop production Beer production Crop Hop area under Hop production Hop α Beer production
year cultivation (ha)a (t)b (million hL)c year cultivation (ha) (t) (million hL) year cultivation (ha) (t) production (t) (million hL)
1880 89,000 68,600 — 1924 50,482 67,975 159 1969 67,291 94,876 5276 605
1881 89,000 68,800 — 1925 55,322 58,755 174 1970 70,666 102,589 6038 630
1882 89,063 43,000 — 1926 64,199 58,115 171 1971 75,042 96,050 5377 658
1883 103,641 81,200 — 1927 78,639 72,190 180 1972 78,015 105,013 6170 689
1884 115,402 80,400 — 1928 81,122 67,815 187 1973 81,329 118,301 7469 743
1885 119,513 87,950 — 1929 78,558 83,425 187 1974 82,037 111,176 6631 771
1886 120,798 86,850 1930 57,788 61,215 199 1975 80,584 113,503 7234 802
J. Inst. Brew. 2014; 120: 289–314

—
1887 115,800 77,750 — 1931 50,397 48,485 178 1976 78,197 107,533 6012 826
1888 116,900 69,250 — 1932 41,816 41,960 157 1977 78,563 116,892 7049 848
1889 114,000 103,400 — 1933 47,806 51,870 170 1978 77,599 109,440 6456 874
1890 114,730 65,000 — 1934 52,548 55,400 185 1979 79,733 121,867 7142 909
1891 115,739 79,300 — 1935 55,391 61,610 191 1980 86,926 120,611 7269 931
1892 114,958 80,850 — 1936 53,945 59,116 206 1981 94,739 131,017 8049 950
1893 117,411 73,050 — 1937 53,792 63,358 218 1982 97,462 146,115 8471 968
1894 117,000 112,400 — 1938 53,017 59,846 220 1983 95,665 132,742 7540 972
1895 115,000 106,800 — 1939 — — — 1984 92,821 128,728 8175 968
1896 112,589 89,750 — 1940 — — — 1985 86,855 124,050 7056 984
1897 105,685 83,650 — 1941 — — — 1986 84,220 112,466 7199 1016
1898 100,461 74,300 — 1942 — — — 1987 87,393 118,341 8080 1044
1899 110,415 107,650 254 1943 — — — 1988 89,875 117,363 7276 1076
1900 106,758 77,400 — 1944 — — — 1989 90,177 118,551 7290 1104
1901 107,684 91,300 — 1945 — — — 1990 91,271 114,416 6864 1142
1902 108,240 75,550 261 1946 — — — 1991 91,409 130,060 8612 1165
1903 107,241 77,900 261 1947 — — — 1992 91,835 122,379 7537 1163
1904 113,304 77,750 263 1948 41,749 49,481 — 1993 91,121 137,275 9099 1190
1905 115,401 123,900 263 1949 44,569 53,449 251 1994 86,786 121,323 6907 1214
1906 116,176 80,300 — 1950 48,272 68,157 265 1995 81,466 126,686 7831 1248
1907 115,978 95,800 — 1951 50,110 73,297 287 1996 76,967 124,379 9300 1269
1908 115,106 101,350 — 1952 50,257 67,141 302 1997 70,290 112,192 8773 1300
1909 97,379 46,200 — 1953 47,742 68,921 308 1998 60,111 94,610 7245 1301
1910 94,761 79,850 — 1954 48,194 64,605 323 1999 57,427 95,450 7393 1365
1911 93,832 67,400 273 1955 45,818 63,394 343 2000 58,991 96,715 8294 1392
1912 98,026 98,650 293 1956 52,200 58,049 352 2001 58,903 99,214 8646 1424
Copyright © 2014 The Institute of Brewing & Distilling

1913 101,103 75,400 295 1957 54,522 66,693 377 2002 56,237 100,932 8749 1443
1914 89,397 97,250 290 1958 63,346 81,196 385 2003 53,500 87,056 6722 1479
1915 78,492 67,300 — 1959 65,258 83,356 402 2004 50,693 92,266 8103 1552
1916 66,414 57,800 — 1960 63,956 81,333 418 2005 50,273 94,385 7903 1603
1917 46,546 42,550 — 1961 62,494 68,458 439 2006 49,466 85,585 7103 1696
1918 40,516 20,800 117 1962 66,410 80,943 455 2007 50,455 91,584 7663 1787
1919 40,516 37,700 — 1963 96,790 91,834 471 2008 57,297 111,175 10,242 1819
1920 48,312 56,200 127 1964 70,967 93,066 510 2009 56,747 113,669 10,952 1818
1921 52,955 40,750 138 1965 71,494 92,001 515 2010 52,156 99,879 9475 1846
1922 51,277 53,700 133 1966 71,600 94,371 529 2011 48,528 100,604 10,348 1925
1923 47,842 35,400 137 1967 70,895 94,127 547 2012 46,971 89,090 9139 1951
1968 68,203 91,909 570 2013d 46,300 81,300 8000 1960
a
ha, Hectare = 10,000 m2;
b
t, metric ton = 1,000 kg;
c
million hL = 100,000,000 L;
d
2013 = estimated data.
wileyonlinelibrary.com/journal/jib
305
C. Almaguer et al.
had a severe effect on the beer market. During this period, beer respective hop producing areas according to alpha values. The
consumption worldwide was more than halved. Shortly after- α-acid production represents the actual hop supply available to
wards, American brewers were affected by the Prohibition Act the brewers (194). In the hop market, a key indicator is the aver-
of 1919, which stayed in force until 1933. Beer production in age hopping rate, which unfortunately has undergone a steady
the USA reached a low of 3.6 million hL in 1926. Finally, Europe decline since it was first recorded. Since 1970 the hopping rate
was again thrown into turmoil during the 1939–1945 war, and has fallen by nearly 60% (Fig. 21). In the last four decades from
beer consumption in Germany fell from 50 million hL in 1939 1970 to 2010, the average α-acid addition in beer has decreased
to 5.8 million hL in 1949 (192,193). Since 1948, world beer pro- from 9.6 to 4.1 g α/hL (191). From 1970 to 1980, the hopping rate
duction has experienced a steady increase. dropped almost by 2 g α/hL, from 9.6 to 7.8 g α/hL. When
The hop grower knows that every hop season is unique and looking at the world market critically, it may be inferred that, ow-
different from all the other ones, and that year-to-year fluctua- ing to the alpha deficit before 1980 and the resulting increase in
tions are normal (194). The size of the world hop crops partly re- hop prices, as well as the better utilization of the bittering sub-
flects the demand of brewers as well as the events surrounding stances, a reduction of the alpha rate became possible world-
the hop harvest (detailed data in Table 3). A particular example is wide (197). Moreover, today China, not the USA, is the world’s
the very large world crop in 1905, which resulted in enormous biggest beer producer. Unfortunately beer in these new beer-
surpluses and a corresponding decline in prices below actual producing countries is less heavily hopped. The reduction of
production costs. This, in turn, caused a reduction in acreage beer bitterness around the world is the result of changing tastes
and consequent recovery in prices during 1908–1910. Such cy- in today’s consumer society. These new trends partly explain the
cles were not new to the hop industry and have been experi- decline in the hopping rate (194). In addition to lowering the bit-
enced many times (Fig. 20) (192). Another factor that forces terness levels in mainstream beers, the hopping rate has de-
hop growers to adjust acreage is the introduction of production creased owing to the use of hops with higher α-acid levels and
quotas (194). Until 1930, acreage under cultivation was signifi- the increased use of more sophisticated hop products that
cantly larger than total hop production volume. Except for the achieve higher utilization levels (193). Another factor is the mod-
1963 hop crop, as of 1948 a clear trend may be observed: smaller ernization of the brewing industry worldwide (198). The decline
areas under cultivation achieve a higher hop production yield. in the hopping rate from 1980 to 1990 was not as drastic as that
This change may be attributed to the introduction of more pro- in the decade before or in the two following decades. In 1990
ductive hop varieties with a higher α-acid content. In 2013, with the hopping rate was 6.9 g α/hL, almost 1 g α/hL less than in
approximately 46,000 ha, the hop industry had the smallest acre- 1980. By 2000, the hop addition was 5.6 g α/hL and by 2010 it
age under cultivation since 1955. Although the area under culti- was 4.1 g α/hL. The reduction was 1.3 and 1.5 g α/hL, respec-
vation continues to shrink, the varieties being grown are tively. In 2012, the hopping rate increased to 4.3 g α/hL and it
delivering increasingly high yields in terms of both quantity is expected to continue to increase. This recent increase in the
and alpha. In 2013, the total volume of hop production is esti- hopping rate is primarily attributed to the growing craft brewing
mated to be 81,300 metric tons (t) with an estimated alpha yield sector.
of 8,000 t (195). Since 2008 record levels of high alpha yields have
been achieved, above 10,000 t. In 2009, the hop crop provided
an unparalleled boom; the alpha production was 10,952 t (196).
Hop contributions to beer
This higher alpha yield per hectare requires an acreage reduc- In 1891, Moritz and Morris (199) gave five reasons for adding
tion and possibly variety replacements in order to avoid a crop hops to beer: (a) to impart the distinctive bitter taste and aroma
surplus and ultimately a market imbalance. (i.e. hoppy character); (b) to precipitate certain nitrogenous con-
The growing interest in bittering compounds and the analyti- stituents of the wort (i.e. break formation); (c) to act as a filter aid
cal properties of hops on the part of the brewing industry in the hop back (i.e. clarify the wort); (d) to confer antibacterial
prompted Joh. Barth & Sohn in 1970 to attempt to list the properties to beer; and (e) to assist in the sterilization of the
Figure 20. The world hop crop 1880–2013. The black area represents the total
hop production volume in metric tons. The grey area illustrates the cultivated
acreage (191,195). Missing data not available owing to the political situation at
Figure 21. Average world hopping rate in g α/hL for the last 40 years (191).
306
that time.
wort. A century later, Hughes and Simpson (200) extended the 1960 Harold et al. (209) were the first to demonstrate the
list by including two other benefits: (f) to enhance and stabilize occurrence of hop oil in beer. After examining the volatile portion
beer foam; and (g) to promote foam lacing. As mentioned Harold et al. were able to clearly show the presence in beer of
above, the brewing value of hops is primarily attributed to the β-myrcene, methyl nonyl ketone and α-humulene, as well as a
presence of resins, essential oils and polyphenols. number of unidentified hop oil constituents (209).
No one single component of the hop oil fraction is responsible
for the hoppy character in beer. The combination of many com-
Bitterness
pounds is necessary for the characteristic hop aroma. In 1963
Many complex reactions occur during the boiling of wort with Guadagni et al. suggested that this contribution is due to the
hops in the brewery. In addition to the transformations involving additive or synergistic effects of many components (i.e. hop oil
carbohydrates, proteins, polyphenols and various polymeric sub- compounds and volatile fermentation products) (210). In 1966
stances, the hop bitter principles are extracted, thereby under- Hashimoto (211) and Buttery and Ling (212) suggested that the
going intricate transformations and interactions with other volatile hop components with sufficient solubility in water to
constituents (201). Bitterness is one of the most readily be retained in boiling wort may cause the hoppy aroma in beer.
discerned sensory attributes of beer as far as the consumer is They further established that the hoppy aroma is not derived
concerned (202). Over the years, the chemical changes in the directly from the hop oil itself, but from certain volatile water
hop resins during wort boiling have been thoroughly studied soluble compounds that are produced partly from the hop
and therefore adequately profiled. These studies were crucial resins, as decomposition products (207). It was later shown that
since the chemistry of hop extraction during wort boiling deter- terpene and sesquiterpene hydrocarbons, the major compo-
mines to a great extent the flavour and the quality of the fin- nents of hop oil, are rarely found in beer. Therefore, these are
ished beer (201). By far the most important chemical not considered to be responsible for hoppy flavours in kettle-
conversion occurring during wort boiling is the thermal isomer- hopped beer. On the other hand, the oxidation products of
ization of the α-acids into the more soluble and bitter iso-α-acids. these hydrocarbons are commonly found in beer and have
The α-acids yield two iso-α-acids, as these occur as diastereo- been suggested to contribute to the hoppy character
isomers in their cis and trans forms (35). For a given pair of cis- (134,138,213,214). The aromas derived from the hop essential
and trans-isomers, the cis-component is significantly more bitter oils are usually described in terms of fruity, floral, citrus, grassy
than its trans-counterpart. It has also been established that the and spicy (or herbal) notes. To the brewer, these differences in
isohumulones are more bitter than the isocohumulones (202). the hoppy character are important since they help profile the
Of the six major iso-α-acids present in beer, the most bitter many existing beer styles.
compound is cis-isohumulone and the least bitter one is trans-
isocohumulone (203). As mentioned previously, the characteris-
tic beer bitter taste is attributed to components formed
Microbial stability
from the hop resins during wort boiling, mainly the iso-α-acids.
Over 85% of the perceived pleasant bitterness in beer is deliv- Hop bitter acids exhibit an inhibitory effect on bacteria; thus
ered by the iso-α-acids (204). However, other hop substances, they play a major role in enhancing the preservative properties
such as hop polyphenols and oxidation products of the β-acids of beer. It was shown as early as 1888 that hops contribute to
(i.e. hulupones) also contribute to beer bitterness. the microbial stability of beer and protect beer from infections
(20). Thereafter the antibacterial activity of the hop compounds
and the hop resistance of lactic acid bacteria have been
Aroma
extensively investigated. In 1937, Shimwell discovered that the
In addition to giving the pleasant bitter taste, hops impart a antibiotic properties and bacteriostatic power of hops are
characteristic ‘hoppy’ aroma to beer. The hop chemistry associ- restricted to Gram-positive bacteria, while the Gram-negative
ated with the hoppy character of beer is very complex. However, species were mostly unaffected by the hop acids (215). It was
since the advent and utilization of gas chromatography, much later found that hop acids are also mildly antifungal (on selected
has been learned regarding the composition of the hop oil fraction fungi species) (216) and antiprotozoal (217). Among the Gram-
and its contribution to beer. It is known that, after the vigorous positive bacteria some species of lactic acid bacteria are less
boiling of hops in the kettle, very little hop oil constituents will sensitive (i.e. more resistant) to hop compounds and are able
remain in the wort in their native form. Most of the essential oil to grow in beer. Shimwell reported that the antiseptic potency
compounds are highly volatile and poorly soluble in wort; how- of the hop acids increases at lower pH (215). Shimwell later
ever, their presence in beer depends on the chemical properties proposed that the antibacterial activity of the hop constituents
of the specific essential oil component and the hopping technol- is associated with permeability changes of the bacterial cell wall
ogy used. After boiling for 90 min, 85–95% of the essential oil in (218). Almost 35 years later, Teuber and Schmalreck (219)
hops has evaporated from the kettle and the rest has polymerized showed that hop compounds and their derivatives cause leak-
to form resinous substances. As a result, the hop oil components age of the cell plasma membrane in the aerobic organism
are hardly retained in the wort in their native form. Further, during Bacillus subtilis. This results in complete inhibition of the active
the fermentation process there is a considerable loss or transfor- transport of sugars and amino acids. Subsequent inhibition of
mation of the hop oils retained in the wort (4,205). These hop oil the respiratory chain and of protein, RNA and DNA synthesis
components disappear to a large extent by adsorption on yeast occurs as a secondary event. However, this organism cannot
and the filter mass (206,207). A detailed review of the biotransfor- grow in beer and beer spoilage bacteria differ from B. subtilis
mations of hop-derived aroma compounds by yeast upon fermen- in the physiology of their cell membranes (220). Therefore this
tation was published in 2012 by Praet et al. (208). Some hop oil cannot be considered the mechanism by which hop bitter acids
constituents survive unchanged through to the finished beer. In inhibit the growth of beer spoiling bacteria.
307
C. Almaguer et al.
Another major breakthrough in understanding the preserva- and maltotriose (227). Therefore, in order for bacteria to survive
tive value of the hop bitter acids occurred in the 1990s. In the and grow in beer, several mechanisms are involved in their
early 1990s, Simpson established one of the molecular mecha- resistance to the adverse conditions of the hostile environment.
nisms by which beer spoilage bacteria are inhibited (221,222). Of particular importance is the resistance to hops as this is a
In an earlier study Simpson and Smith showed that the undisso- prerequisite for lactic acid bacteria to be able to grow in beer,
ciated forms of hop compounds and hop-derived compounds thereby causing beer spoilage. Ultimately, hop resistance of
are mainly responsible for the antibacterial activity. The ionized lactic acid bacteria requires multiple defence mechanisms
forms of such compounds have a negligible effect on lactic acid (228). Following the studies of Simpson, several mechanisms
bacteria (223). The practical implication of this finding is that involved in the hop resistance of lactobacilli were proposed.
small variations in beer pH cause large changes in the antibacte- Sami et al. (229) were the first to identify horA as one of the
rial activity of the hop bitter acids in beer (220). It had been genes responsible for hop resistance. They used horA as a
known for some time that the antibacterial activity of certain genetic marker and developed a rapid and accurate polymerase
hop compounds and their derivatives is influenced by the pH chain reaction method for the prediction of beer spoiling
of the test medium (218,224). However, the relationship was first lactobacilli (230). The putative protein product of horA, HorA, has
placed on a quantitative basis by Simpson and Smith (223). They an ATP-binding (adenosine-5′-triphosphate) domain, a consensus
established the dependence of the inhibitory effect of hops on sequence for an ATP-binding cassette transporter reported to be
the pH of the medium; low pH favours antibacterial activity located in the cytoplasm, and six hydrophobic regions that are
but high pH reduces it (220). The antibacterial activity of trans- large enough to span the plasma membrane. The HorA protein
isohumulone is enhanced by the addition of monovalent cations acts as a multidrug resistance transporter that excretes the hop
(e.g. K+, Na+, NH+4 , Rb+, Li+). However the presence of divalent compounds into the outer medium. Therefore, the bacteriostatic
cations (e.g. Mg2+, Mn2+, Ni2+, Ca2+) reduces the antibacterial effect of the iso-α-acids may be counteracted by the HorA protein,
activity of trans-isohumulone (223). which mediates cellular extrusion of iso-α-acids or other toxic
It was also observed by Simpson that trans-isohumulone molecules that accumulate intracellularly in the presence of the
causes an increase in proton permeability, thus suggesting that hop compounds. From the collected data, Sami et al. suggested
it acts as an ionophore of the mobile-carrier type (221). Iono- that a multidrug resistance pump contributes to the resistance
phores are antimicrobial agents that increase the permeability mechanisms to hop compounds of lactic acid bacteria (229).
of cell membranes to specific ions. Hop compounds as iono- The horA gene was shown by Sami et al. (229) to function as a
phores inhibit the growth of Gram-positive bacteria by primary multidrug transporter; this implies that the gene is de-
catalysing the exchange of protons (i.e. H+) for cellular divalent pendent on ATP-binding. A few years later, Suzuki et al. (231)
cations, such as Mn2+, in an electroneutral process. Changes in found another defence mechanism that is not mediated by the
the intracellular pH are induced by ionophores (225). This reduc- horA gene. Upon biochemical characterization of a hop resistant
tion in intracellular pH leads to inhibition of nutrient transport Lactobacillus brevis strain two conclusions were drawn: first, that
and starvation of the affected organisms (220). In Lactobacillus the second hop resistance mechanism is mediated by proton
species, trans-isohumulone dissipates effectively the transmem- motive force (PMF)-dependent multidrug transporter and sec-
brane pH gradient of non-growing cells and reduces their ability ond that this defence mechanism may be induced upon lactic
to accumulate L-[U-14C]leucine; further it causes leakage of the acid bacteria. The genetic marker found to mediate the horA-
accumulated leucine. Conversely, the membrane potential is independent hop resistance mechanism is ORF5 (232). The
only dissipated to a smaller extent (221). Some components of ORF5 identified encodes a protein with putative 11–12 transmem-
the cell plasma membrane may be responsible for conferring brane domains, a feature that is consistent with the previously
hop resistance on beer spoiling lactic acid bacteria. Such compo- reported PMF-dependent multidrug transporters (233). Similar to
nents could act to restrict the ability of trans-isohumulone to the horA properties, the presence or absence of ORF5 was highly
conduct protons or divalent cations across the plasma membranes correlated with the beer spoilage ability of L. brevis strains (232).
of the bacteria or could increase the rate at which protons are Two other genetic markers that mediate hop resistance in lactic
expelled from the cell interior (222). A clear complication in hop acid bacteria were found. The first one is horB, which is a regulator
inhibition research is the complexity of the chemical composition that modulates the transcription of genes that encode multidrug
of hops. This is due not only to compound variation on account of transporters; the other is the horC gene, which encodes a
consecutive chemical conversions but also to the variations of the PMF-dependent multidrug transporter (234,235). From all the
natural product (223). It has been shown that resistance to hop collected data it was possible for Suzuki et al. to suggest that
bitter acids is a unique character associated only with beer the beer spoilage ability of lactic acid bacteria is acquired by
spoilage lactic acid bacteria. The expected cross resistance to other horizontal transfer of hop resistance genes (233).
proton ionophores could not be detected. The lack of cross resis- Other putative hop resistance mechanisms include the contri-
tance to other antibacterial agents suggests that the mechanism bution of the hitA (hop-inducible cation transporter) gene, which
of resistance includes features that discriminate on the basis of encodes for HitA, a divalent cation transporter. This gene has
molecular structure rather than, or in addition to, physicochemical been shown to be present in most beer spoiling lactobacilli
properties. Cross resistance between different hop acids suggests (236). It was also hypothesized that genes responsible for the
that the most important structural feature in this respect is the production of teichoic acid in the cell wall also contribute to
β-triketone group (226). hop resistance in beer spoiling lactic acid bacteria strains (237).
Beer is a very unfavourable medium for the growth of most The proton translocating, membrane-bound ATPase was
Gram-positive microorganisms owing to the presence of alcohol, suggested to ameliorate the protonophoric actions of hop bitter
hop compounds, high carbon dioxide level, relatively low pH, acids by pumping out the intracellular protons in an ATP-
extremely reduced oxygen content and the presence of only dependent manner (238). The hop resistance of beer spoiling
trace amounts of nutrient substances such as glucose, maltose lactic acid bacteria is a complex phenomenon yet to be fully
308
understood. The collected evidence indicates that cell walls and (202,253–258) have looked into the effect of different hop com-
cytoplasmic membranes play an important role in defending pounds on foam properties. It has been revealed that hydro-
beer spoiling lactic acid bacteria from the bactericidal effects phobicity is the key factor in determining the effectiveness
of the hop bitter acids (239). of a hop compound to stabilize beer foam. These hydrophobic
In a more recent study, Haakensen et al. (240) confirmed that compounds have the tendency to leave the beer and concen-
lactic acid bacteria species that harbour the horA gene are more trate in the foam, thereby increasing foam stability (259).
likely to spoil beer than those that do not. The horA gene has It has been known for a number of years that the bitter iso-α-
been conclusively shown to function as a multidrug transporter acids, derived from the α-acids of hops, are a major contributor
(241). Therefore, the presence of the horA gene is a significant to the improvement in beer foam stability (255). It was further
predictor to assess the beer spoilage ability of lactobacilli observed by Diffor et al. that, of the iso-α-acid analogues,
isolates. Throughout the years, three other putative beer isohumulone provides a more stable foam than isocohumulone
spoilage associated genes have been suggested; these are hitA, (253). This difference is attributed to the lower solubility of
horC and ORF5 (233,235,236,242,243). Recently, it was found that isohumulone at beer pH, which results in its greater tendency
hitA and horC are not predictive of an organism’s ability to grow to associate with other foam-forming constituents in the beer.
in beer. However the presence of hitA, horC or both in addition This, however, does not mean that isocohumulone has a
to horA is indicative of the ability of a microorganism to grow negative effect on foam, but rather that isohumulone provides
rapidly in beer. The horA and hitA genes code for primary- and a more stable foam (260). Other natural but minor hop com-
secondary-type multidrug transporters, respectively (244). The ponents such as isoadprehumulone, dihydroisohumulone,
primary-active, ATP-binding cassette multidrug transporters are tetrahydroisocohumulone and tetrahydroisohumulone have
dependent on ATP-binding/hydrolysis, whereas secondary- been suggested to promote foam stability and lacing (255).
active multidrug transporters are coupled to the proton motive
force that exists across the cytoplasmic membrane (245). In Cling
another study by Haakensen et al. (241) Pediococcus isolates As beer is being consumed, the texture of the foam changes from
were screened for beer spoilage genes. Two genes, bsrA and bsrB being liquid to almost solid; this solid or dry foam can adhere to
(beer spoilage related) were highly correlated with the beer the glass surface. The ability of the foam to adhere to the glass wall
spoilage ability and hop resistance of Pediococcus isolates. These is known as foam ‘cling’ or ‘lacing’ (261). In 1964, Glenister and
bsrA and bsrB genes were not found in any Lactobacillus isolates, Segel (262) raised the importance of the primary and secondary
regardless of whether they were able to grow in beer or not. This cling. The primary cling is created once the initial foam head is
makes them the first genetic markers capable of differentiating allowed to collapse. The secondary cling is the pattern that is
between beer spoilage lactobacilli and pediococci (246). Like formed when the consumer, at intervals, removes the beer from
horA, bsrA and bsrB are both primary-type ATP-binding cassette the glass. From their observations, they concluded that the differ-
multidrug resistance genes (241). ences between commercial beers as to their secondary cling are
The mechanisms of hop resistance of beer spoiling Lactobacillus frequently more striking than to those of primary cling. It is well
brevis have also been studied on the proteomic level. The gathered documented that hops contribute in a positive manner to foam
evidence suggests that the stress caused to the bacteria by hop cling. While beer foam is enhanced by the presence of hop
compounds is not only associated with proton motive force substances, lacing will not occur unless hop compounds are pres-
depletion but it also implies that there is a limitation of divalent ent (202,263). To date, there are no defined standards for cling
cations. More specifically, hop compounds inhibit the bacteria’s measurements. Further it may be supposed that the perception
metabolism by reducing the intracellular manganese concen- of what constitutes good lacing is a subjective matter (259), yet
tration, thereby causing a conflictive regulation of the energy this foam quality aspect cannot be disregarded.
metabolism (247). The specific role of the single hop resistance
mechanisms described in the literature is not fully understood,
particularly since none of the defence mechanisms confers hop
resistance in the absence of other (unknown) mechanisms of
Summary
hop resistance. This suggests that the resistance of lactobacilli With a view to increasing the understanding of the nature of hops,
isolates towards hop compounds requires multiple interdepen- research has focused on the chemical composition of hops and
dent resistance mechanisms (248,249). their brewing properties. Plentiful research has been conducted
on identifying and elucidating the structures of specific hop com-
pounds and their impact on beer quality. Although much is known
Foam
about hops and their function in brewing, new aspects continue to
Hop acids not only contribute to beer bitterness, but also play an be revealed. Extensive international research continues to be
essential role in achieving beer foam formation and stability. The actively conducted by respected scientists and institutions in
role of hops for beer foam is to stabilize the foam complexes countries all around the world. In these new aspects of hop
(250). It is well recognized that foam is an important quality research, while much has been achieved, much more remains to
factor in the beer production process. According to MEBAK be done to resolve outstanding issues. It must be borne in mind
(Mitteleuropäischen Brautechnischen Analysenkommision) stan- that any progress at all in these new aspects is pioneering. Hop sci-
dards, a good foam stability for a ‘Vollbier’ (full beer; 11.0–15.9°P) ence has provided brewers with one of the main ways of meeting
is a head retention time between 220 and 300 s (251). The foam the abiding need to understand the nature of hops. While hop re-
suppressor–enhancer properties of the hop acids have long been search has been changing and progressing as times change, to the
known. In 1976, the first observations on the role of the iso-α-acids brewing scientist, the profound mystery of hops remains revering
of hops in the structure of beer foam were documented by Fly and and reinvigorating. Humulus lupulus has a complex story yet to be
Chicoye (252). Following their studies, numerous researchers fully understood but, undeniably, one worth telling and retelling.
309
C. Almaguer et al.
25. Anger, H.-M. (2006) Brautechnische Analysenmethoden der

References Mitteleuropäischen Brautechnischen Analysenkommission,
1. Hofte, A. J. P., van der Hoven, R. A. M., Fung S. Y., Verpoorte, R., Selbstverlag: Freising.
Tjaden, U. R., and van der Greef, J. (1998) Characterization of hop 26. Wöllmer, W. (1916) Über die Bitterstoffe des Hopfens, Ber. Deutsch.
acids by liquid chromatography with negative electrospray ioniza- Chemisch. Gesellsch. 49, 780–794.
tion mass spectrometry, J. Am. Soc. Brew. Chem. 56, 118–122. 27. Wöllmer, W. (1925) Über die Bitterstoffe des Hopfens, Ber. Deutsch.
2. Van Opstaele, F., Causmaecker, B. D., Aerts, G., and Cooman, L. D. Chemisch. Gesellsch. 58, 672–678.
(2012) Characterization of novel varietal floral hop aromas by 28. Hough, J. S., Briggs, D. E., Stevens, R., and Young, T. W. (1982)
headspace solid phase microextraction and gas chromatography– Malting and Brewing Science Volume 2: Hopped Wort and Beer, 2nd
mass spectrometry/olfactometry, J. Agric. Food Chem. 60, edn, Chapman Hall: New York.
12270–12281. 29. Briggs, D. E., Boulton, C. A., Brookes, P. A., and Stevens, R. (2004) The
3. Van Opstaele, F., Praet, T., Aerts, G., and Cooman, L. D. (2013) Char- chemistry of hop constituents, in Brewing – Science and Practice
acterization of novel single-variety oxygenated sesquiterpenoid pp. 255–305, CRC Press: Boca Raton, FL.
hop oils fractions via headspace solid-phase microextraction and 30. Almaguer, C., Gastl, M., and Becker, T. (2010) The brewing potential
gas chromatography–mass spectrometry/olfactometry, J. Agric. of hop hard resins, in European Brewery Convention Hop Symposium
Food Chem. 61, 10555–10564. 2010, Wolnzach.
4. Takoi, K., Itoga, Y., Takayanagi, J., Kosugi, T., Shioi, T., Nakamura, T., 31. Dresel, M. (2013) Struktur und sensorischer Beitrag von
and Watari, J. (2014) Screening of geraniol-rich flavor hop and Hopfenhartharzen zum Bittergeschmack von Bier sowie zellbasierte
interesting behavior of β-citronellol during fermentation under Studien zu deren Resorption und Metabolismus, Verlag Dr. Hut: Munich.
various hop-addition timings, J. Am. Soc. Brew. Chem. 72, 22–29. 32. Rigby, F. L. (1958) The practical significance of recent develop-
5. Aerts, G., Cooman, L. D., Rouck, G. D., and Goiris, K. (2007) Use of ments in the chemical analysis of hops, Brew. Dig. 33, 50–59.
Hop Polyphenols in Beer, C12C11/00 (2006.01), Chemisch en 33. Rigby, F. L., and Bethune, J. L. (1952) Cohumulone, a new hop
Biochemisch Onderzoekscentrum. constituent, J. Am. Chem. Soc. 74, 6118–6119.
6. Goiris, K., Jaskula-Goiris, B., Syryn, E., Van Opstaele, F., De Rouck, G., 34. Rigby, F. L., and Bethune, J. L. (1955) Components of the lead-
Aerts, G., and De Cooman, L. (2014) The flavoring potential of hop precipitable fraction of Humulus lupulus, Adhumulone, J. Am. Chem.
polyphenols in beer, J. Am. Soc. Brew. Chem. 72, 135–142. Soc. 77, 2828–2830.
7. Aron, P. M., and Shellhammer, T. H. (2010) A discussion of polyphe- 35. Spetsig, L. O. (1958) On the rearrangement products of humulone,
nols in beer physical and flavour stability, J. Inst. Brew. 116, 369–380. Acta Chem. Scandinav. 12, 592–593.
8. Roberts, T. R., and Wilson, R. J. H. (2006) Hops, in Handbook of Brewing, 36. Windisch, W., Kolbach, P., and Schleicher, R. (1927) Über die
2nd edn (Priest, F. J., and Stewart, G. G., Eds) pp. 177–280, Taylor & Umwandlung der α-Hopfenbittersäure (Humulon) beim Kochen in
Francis: Boca Raton, FL. wässerigen Lösungen verschiedener [H] und über die Natur der
9. Bremer, B., Bremer, K., Chase, M. W., Reveal, J. L., Soltis, D. E., Soltis, dabei entstehenden Stoffe, Wochenschrift für Brauerei 44, 453–459.
P. S., Stevens, P. F., Anderberg, A. A., Fay, M. F., Goldblatt, P., Judd, 37. Howard, G. A., Slater, C. A., and Tatchell, A. R. (1957) Chemistry of
W. S., Källersjö, M., Kårehed, J., Kron, K. A., Lundberg, J., Nickrent, hop constituents XI. Some observations on the isomerization of
D. L., Olmstead, R. G., Oxelman, B., Pires, J. C., Rodman, J. E., Rudall, humulone, J. Inst. Brew. 63, 237–248.
P. J., Savolainen, V., Sytsma, K. J., van der Bank, M., Wurdack, K., 38. Hildebrand, R. P. (1964) The isomerization of humulone, Tech. Q.
Xiang, J. Q.-Y., and Zmarzty, S. (2003) An update of the angiosperm Master Brew. Assoc. Am. 1, 142–147.
phylogeny group classification for the orders and families of 39. Burton, J. S., Stevens, R., and Elvidge, J. A. (1964) Chemistry of hop
flowering plants: APG II, Bot. J. Linn. Soc. 141, 399–436. constituents XXII. Proton magnetic resonance spectroscopy of
10. Stevens, R. (1967) The chemistry of hop constituents, Chem. Rev. isohumulone A, J. Inst. Brew. 70, 345–352.
67, 19–71. 40. Spetsig, L. O. (1964) Isolation and characterization of two
11. Percival, J. (1905) The hop plant, in The Hop and its Constituents – A isohumulone isomers, J. Inst. Brew. 70, 440–445.
Monograph on the Hop Plant (Chapman, A. C., Ed.) pp. 1–9, The 41. Clarke, B. J., and Hildebrand, R. P. (1965) The isomerization of
Brewing Trade Review: London. humulone I. Isolation of photoisohumulone, J. Inst. Brew. 71, 26–36.
12. Small, E. (1978) A numerical and nomenclatural analysis of morpho- 42. Verzele, M., Anteunis, M., and Alderweireldt, F. (1965)
geographic taxa of Humulus, System. Bot. 3, 37–76. Isohumulones, J. Inst. Brew. 71, 232–239.
13. Raiser, T. C. (2011) Commercial aspects of hops, Lecture presented at 43. Clarke, B. J., Hildebrand, R. P., and White, A. W. (1976) The applica-
the 1st Hops Academy, Nürnberg, Germany. tion of salt formation in the chemistry and technology of hop
14. Verzele, M., and Keukeleire, D. D. (1991) Chemistry and Analysis of resins, J. Inst. Brew. 82, 212–217.
Hop and Beer Bitter Acids, Vol. 27, Elsevier: Amsterdam. 44. Malowicki, M. G., and Shellhammer, T. H. (2005) Isomerization and
15. Ives, A. W. (1821) An experimental inquiry in the chemical proper- degradation kinetics of hop (Humulus lupulus) acids in a model
ties and economical and medicinal virtues of the Humulus lupulus, wort-boiling system, J. Agric. Food Chem. 53, 4434–4439.
or common hop, Ann. Phil. 17, 194–202. 45. Malowicki, M. G., and Shellhammer, T. H. (2006) Factors affecting
16. Harrison, J. (1971) Effect of hop seeds on beer quality, J. Inst. Brew. hop bitter acid isomerization kinetics in a model wort boiling
77, 350–352. system, J. Am. Soc. Brew. Chem. 64, 29–32.
17. Briant, L. (1905) The cold storage of hops, in The Hop and its 46. Jaskula, B., Kafarski, P., Aerts, G., and Cooman, L. D. (2008) A kinetic study
Constituents – A Monograph on the Hop Plant (Chapman, A. C., Ed.) on the isomerization of hop α-acids, J. Agric. Food Chem. 56, 6408–6415.
pp. 51–60, The Brewing Trade Review: London. 47. Jaskula, B., Goiris, K., Van Opstaele, F., Rouck, G. D., Aerts, G., and
18. Verzele, M. (1986) Centenary Review – 100 Years of hop chemistry Cooman, L. D. (2009) Hopping technology in relation to α-acids
and its relevance to brewing, J. Inst. Brew. 92, 32–48. isomerization yield, final utilization, and stability of beer bitterness,
19. Palamand, S. R., and Aldenhoff, J. M. (1973) Bitter tasting com- J. Am. Soc. Brew. Chem. 67, 44–57.
pounds of beer. Chemistry and taste properties of some hop resin 48. Urban, J., Dahlberg, C. J., Carroll, B. J., and Kaminsky, W. (2013)
compounds, J. Agric. Food Chem. 21, 535–543. Absolute configuration of beer’s bitter compounds, Angew. Chem.
20. Hayduck, M. (1888) Über die bitteren und harzigen Bestandteile Int. Edn 52, 1553–1555.
des Hopfens, Wochenschrift für Brauerei 5, 937–947. 49. Verzele, M. (1955) Sur la séparation du complexe ’humulone’ par
21. Briant, L., and Meacham, C. S. (1897) Estimation of resin in hops, chromatographie de partage, Bull. Soc. Chim. Belges 64, 70–86.
J. Fed. Inst. Brew. 3, 233–236. 50. Verzele, M. (1958) Posthumulone, a new ‘alpha acid’, Bull. Soc. Chim.
22. ASBC and EBC (1957) Hop resin nomenclature, J. Inst. Brew. 63, Belges 67, 278–279.
286–288. 51. Velde, N. V. D., and Verzele, M. (1986) High performance liquid
23. Committee, Nomenclature Sub-Committte: Hops Liasion Commit- chromatography of hop and beer extracts with photodiode array
tee (N. S.-C. H. L). (1969) Recommendations concerning nomencla- detection, J. Inst. Brew. 92, 584–587.
ture of hop resin components, J. Inst. Brew. 75, 340–342. 52. Lermer, J. C. (1863) Der Bitterstoff des Hopfens, Krystallinisch rein
24. Tartar, H. V., and Bradley, C. E. (1912) A comparative study of Dargestellt, Polytechn. J. 169, 54–65.
methods for the determination of hard and total soft resins in hops, 53. Lermer, J. C. (1863) Notizen – 1. Krystallisirter Bitterstoff des
J. Ind. Eng. Chem. 4, 209–212. Hopfens, J. Prakt. Chem. 90, 254.
310
54. Howard, G. A., and Tatchell, A. R. (1956) Development of resins 80. Regan, J. P., and Elvidge, J. A. (1969) Chemistry of hop constituents.
during the ripening of hops, J. Inst. Brew. 62, 251–256. Part XXXIII. Reactions of β-acids, J. Inst. Brew. 75, 10–14.
55. Haseleu, G., Intelmann, D., and Hofmann, T. (2009) Structure deter- 81. Brown, P. M., Burton, J. S., and Stevens, R. (1964) Chemistry of hop
mination and sensory evaluation of novel bitter compounds constituents. Part XXI. Adhulupone and analogues of hulupone,
formed from β-acids of hop (Humulus lupulus L.) upon wort boiling, J. Chem. Soc. (Resumed) 1964, 4774–4778.
Food Chem. 116, 71–81. 82. Almaguer, C., Gastl, M., and Becker, T. (2012) Charakterisierung
56. Haseleu, G., Intelmann, D., and Hofmann, T. (2009) Identification antimikrobiell wirksamer Verbindungen in der Hopfen-
and RP-HPLC-ESI-MS/MS quantitation of bitter-tasting β-acid trans- Hartharzfraktion, in 45. Technologisches Seminar, Freising.
formation products in beer, J. Agric. Food Chem. 57, 7480–7489. 83. Dresel, M., and Hofmann, T. (2012) Revealing the impact of hops
57. Schild, E., and Raum, H. (1956) Papierchromatographische Studien hard resin on the beers’ bitterness, in 10th International Trends in
über die Bittersäuren und Harze des Hopfens, Brauwissenschaft Brewing, Ghent.
9, 150–160. 84. Schulmeyr, J., Dresel, M., and Hofmann, T. (2012) Hop Resin-based
58. Burton, J. S., and Stevens, R. (1965) Evaluation of hops – XI. The Substance, Patent EP2668256A1, WO2012100953A1 published
hard resin and presence of hulupinic acid, J. Inst. Brew. 71, 51–56. Aug 2, 2012. Joh. Barth & Sohn.
59. Ashurst, P. R., and Whitear, L. (1965) Hop resins and beer flavour. IV. 85. Dresel, M., and Hofmann, T. (2014) Structural and sensory characteriza-
Observations concerning hard resin, J. Inst. Brew. 71, 46–50. tion of key bitter compounds from the hard resin of hops (Humulus
60. Laws, D. R. J. (1968) Hop resins and beer flavour V. The significance lupulus L.) and their occurrence in hop products, and beers produced
of oxidized hop resins in brewing, J. Inst. Brew. 74, 178–182. with an extract enriched with those compounds (unpublished data).
61. Howard, G. A., and Slater, C. A. (1960) Ion-exchange chromatogra- 86. Howard, G. A. (1957) Evaluation of hops – V. The essential oil of
phy of hop resins and its application to the preparation of extracts hops, J. Inst. Brew. 63, 126–138.
for bittering beer, J. Inst. Brew. 66, 305–312. 87. Steinberg, A. S. (2011) Hops, in Lecture presented at the 1st Hops
62. Power, F. B., Tutin, F., and Rogerson, H. (1913) CXXXV – The constit- Academy, pp. 1–40, Nürnberg.
uents of hops, J. Chem. Soc. 103, 1267–1292. 88. Roberts, M. T., Dufour, J.-P., and Lewis, A. C. (2004) Application of
63. Gerhäuser, C. (2005) Review – Broad spectrum antiinfective poten- comprehensive multidimensional gas chromatography combined
tial of xanthohumol from hop (Humulus lupulus L.) in comparison with time-of-flight mass spectrometry (GC × GC-TOFMS) for high
with activities of other hop constituents and xanthohumol metab- resolution analysis of hop essential oil, J. Sep. Sci. 27, 473–478.
olites, Mol. Nutr. Food Res. 49, 827–831. 89. Loiseleur-Deslongchamps, J. L. A. (1819) Manuel des Plantes Usuelles
64. Stevens, J. F., and Page, J. E. (2004) Xanthohumol and related Indigénes, ou Historie Abrégée des Plantes de France, Vol. 2 Chez
prenylflavonoids from hops and beer: To your good health! Phyto- Méquignon Ané, Pere: Paris.
chemistry 65, 1317–1330. 90. Hanin, L. (1819) Cours de Matiere Médicale, Vol. 1, Chez Croullebois: Paris.
65. Magalhães, P. J., Carvalho, D. O., Cruz, J. M., Guido, L. F., and Barros, A. A. 91. Bullis, D. E., and Likens, S. T. (1962) Hop oil… Past and present,
(2009) Fundamentals and health benefits of xanthohumol, a natural Brew. Dig. 37, 54–59.
product derived from hops and beer, Nat. Prod. Commun. 4, 591–610. 92. Chapman, A. C. (1895) VIII – Essential oil of hops, J. Chem. Soc. Trans.
66. Wunderlich, S., Zücher, A., and Back, W. (2005) Enrichment of 67, 54–63.
xanthohumol in the brewing process, Mol. Nutr. Food Res. 49, 874–881. 93. Chapman, A. C. (1895) LXXX – Some derivatives of humulene,
67. Stevens, J. F., Taylor, A. W., Clawson, J. E., and Deinzer, M. L. (1999) J. Chem. Soc., Trans. 67, 780–784.
Fate of xanthohumol and related prenylflavonoids from hops to 94. Chapman, A. C. (1898) The essential oil of hops, J. Fed. Inst. Brew.
beer, J. Agric. Food Chem. 47, 2421–2428. 4, 224–235.
68. Magalhães, P. J., Dostalek, P., Cruz, J. M., Guido, L. F., and Barros, A. 95. Chapman, A. C. (1903) LVII – Essential oil of hops, J. Chem. Soc.,
A. (2008) The impact of a xanthohumol-enriched hop product on Trans. 83, 505–513.
the behavior of xanthohumol and isoxanthohumol in pale and dark 96. Chapman, A. C. (1928) CVI – On the chemical individuality of humulene,
beers: A pilot scale approach, J. Inst. Brew. 114, 246–256. J. Chem. Soc. (Resumed) 785–789. Available at: http://pubs.rsc.org/en/
69. Biendl, M., Methner, F.-J., Stettner, G., and Walker, C. (2004) Brewing Content/ArticleLanding/1928/JR/jr9280000785#!divAbstract
trials with a xanthohumol-enriched hop product, Brauwelt Int. 97. Chapman, A. C. (1928) CLXXII – The higher-boiling constituents of the
22, 182–185. essential oil of hops, J. Chem. Soc. (Resumed) 1303–1306. Available at:
70. Walker, T. K., Zakomorny, M., and Blakebrough, N. (1952) ‘Delta http://pubs.rsc.org/en/content/articlelanding/1928/JR/jr9280001303#!
resin,’ a water-soluble, bitter, bacteriostatic portion of resin of hops, divAbstract
J. Inst. Brew. 58, 439–442. 98. Chapman, A. C. (1929) The essential oil of hops, J. Inst. Brew.
71. Abson, J. W., Saleh, M. S. E., and Walker, T. K. (1954) Further obser- 35, 247–255.
vations on the δ-resin of hops and a method for its estimation, 99. Howard, G. A., and Slater, C. A. (1957) Evaluation of hops – VII. Com-
J. Inst. Brew. 60, 42–46. position of the essential oil of hops, J. Inst. Brew. 63, 491–506.
72. Jackson, C. P., and Walker, T. K. (1959) Studies on the delta resin of 100. Sharpe, F. R., and Laws, D. R. J. (1981) The essential oil of hops – A
hops – I. Isolation and preliminary fractionation of δ resin and some review, J. Inst. Brew. 87, 96–107.
observations respecting its nature and composition, J. Inst. Brew. 101. Likens, S. T., and Nickerson, G. B. (1967) Identification of hop
65, 497–503. varieties by gas chromatographic analysis of their essential oils.
73. Almaguer, C., Gastl, M., Dresel, M., Hofmann, T., and Becker, T. Constancy of oil composition under various environmental influ-
(2012) A study of the functionality of hop epsilon-resins as a novel ences, J. Agric. Food Chem. 15, 525–530.
brewing product, Oral presentation at the World Brewing Congress, 102. Likens, S. T., and Nickerson, G. B. (1965) Identification of the varietal
Portland, OR. Abstract 14. origin of hop extracts, Proc. Am. Soc. Brew. Chem. 23, 23–29.
74. Bausch, H. A., Rothenbach, E. F., and Müke, O. (1966) Die δ-Harze 103. Buttery, R. G., and Ling, L. C. (1967) Identification of hop varieties by
des Hopfens, Nahrung 10, 123–133. gas chromatographic analysis of their essential oils. Capillary gas
75. Spetsig, L. O., Steninger, M., and Brohult, S. (1957) The resolution of chromatography patterns and analyses of hop oils from American
hop bitter substances by reversed-phase partition chromatogra- grown varieties, J. Agric. Food Chem. 15, 531–535.
phy, in Proc. Eur. Brew. Conv. Congr., Copenhagen pp. 22–26, 104. Kenny, S. T. (1990) Identification of U.S.-grown hop cultivars by hop
Elsevier: Amsterdam. acid and essential oil analyses, J. Am. Soc. Brew. Chem. 48, 3–8.
76. Spetsig, L. O., and Steninger, M. (1960) Hulupones, a new group of 105. Kralj, D., Zupanec, J., Vasilj, D., Kralj, S., and Pšeničnik, J. (1991) Variability
hop bitter substances, J. Inst. Brew. 66, 413–417. of essential oils of hops, Humulus lupulus L., J. Inst. Brew. 97, 197–206.
77. Spetsig, L. O., and Steninger, M. (1956) Resolution of mixtures of 106. Kovačevič, M., and Kač, M. (2001) Solid-phase microextraction of
cohumulone, humulone and adhumulone by reversed phase parti- hop volatiles: Potential use for determination and verification of
tion chromatography, J. Inst. Brew. 62, 333–336. hop varieties, J. Chromatogr. A 918, 159–167.
78. Stevens, R., and Wright, D. (1961) Evaluation of hops – X. Hulupones 107. M. Kovačevič, and Kač, M. (2002) Determination and verification of
and the significance of β-acids in brewing, J. Inst. Brew. 67, 496–501. hop varieties by analysis of essential oils, Food Chem. 77, 489–494.
79. Burton, J. S., Stevens, R., and Elvidge, J. A. (1964) 185. Chemistry of 108. Perpète, P., Mélotte, L., Dupire, S., and Collin, S. (1998) Varietal
hop constituents. Part XVIII. Hulupinic acid, J. Chem. Soc. (Resumed) discrimination of hop pellets by essential oil analysis I. Comparison
1964, 952–955. of fresh samples, J. Am. Soc. Brew. Chem. 56, 104–108.
311
C. Almaguer et al.
109. Kishimoto, T., Kobayashi, M., Yako, N., Iida, A., and Wanikawa, A. 137. Kishimoto, T., Wanikawa, A., Kono, K., and Shibata, K. (2006) Com-
(2008) Comparison of 4-mercapto-4-methylpentan-2-one contents parison of the odor-active compounds in unhopped beer and
in hop cultivars from different growing regions, J. Agric. Food Chem. beers hopped with different hop varieties, J. Agric. Food Chem.
56, 1051–1057. 54, 8855–8861.
110. Sanchez, N. B. (1990) Analytical and sensory evaluation of hop 138. Van Opstaele, F., Goiris, K., Syryn, E., Rouck, G. D., Jaskula, B.,
varieties, Masters Thesis, pp. 1–163, Oregon State University: Clippeleer, J. D., Aerts, G., and Cooman, L. D. (2006) Hop: Aroma
Portland, OR. and bitterness perception, Cerevisia 31, 167–188.
111. Biendl, M., Engelhard, B., Forster, A., Gahr, A., Lutz, A., Mitter, W., 139. Neve, R. A. (1991) Hops, Chapman and Hall: London.
Schmidt, R., and Schönberger, C. (2012) Hopfen von Anbau bis 140. Kowaka, K., Fukuoka, Y., Kawasaki, H., and Asano, K. (1983) The true
zum Bier, Fachverlag Hans Carl: Nürnberg. value of aroma hops in brewing, in Proc. Eur. Brew. Conv. Congr.,
112. Thompson, M. L., Marriott, R., Dowle, A., and Grogan, G. (2010) Bio- London, pp. 71–78, IRL Press: Oxford.
transformation of β-myrcene to geraniol by a strain of Rhodococcus 141. Eyres, G. T., Marriott, P. J., and Dufour, J.-P. (2007) Comparison of
erythropolis isolated by selective enrichment from hop plants, Appl. odor-active compounds in the spicy fraction of hop (Humulus
Microb. Cell Physiol. 85, 721–730. lupulus L.) essential oil from four different varieties, J. Agric. Food
113. Barth-Haas-Group. Hop varieties – From Australia to USA. Available Chem. 55, 6252–6261.
at: http://www.barthhaasgroup.com/en/varieties-and-products/ 142. Nielsen, T. P. (2009) Character-impact hop aroma compounds in
hop-varieties (accessed June 2014). ale, in Hop Flavor and Aroma: Proceedings of the 1st Interna-
114. Jahnsen, V. J. (1963) Composition of hop oil, J. Inst. Brew. tional Brewers Symposium (Shellhammer, T. H., Ed.) pp. 59–78,
69, 460–466. St Paul, MN.
115. Šorm, F., Mleyiva, J., Arnold, Z., and Pilva, J. (1949) Terpenes. XIII 143. Goiris, K., Ridder, M. D., Rouck, G. D., Boeykens, A., Van Opstaele, F.,
Sesquiterpenes from the essential oil of hops, Collect. Czech. Chem. Aerts, G., Cooman, L. D., and Keukeleire, D. D. (2002) The oxygen-
Commun. 14, 699–715. ated sesquiterpenoid fraction of hops in relation to the spicy hop
116. Šorm, F., Mleyiva, J., and Arnold, Z. (1949) Terpenes. XII. Composi- character of beer, J. Inst. Brew. 108, 86–93.
tion of the oil of hops, Collect. Czech. Chem. Commun. 14, 693–698. 144. Wright, R. G., and Connery, F. E. (1951) Studies of hop quality, Proc.
117. Roberts, J. B., and Stevens, R. (1962) Composition and biogenesis of Am. Soc. Brew. Chem. 21, 87–101.
essential oil of hops, J. Inst. Brew. 68, 420–427. 145. Naya, Y., and Kotake, M. (1972) The constituents of hops (Humulus
118. Howard, G. A., and Slater, C. A. (1958) Effect of ripeness and drying lupulus L). VII. The rapid analysis of volatile components, Bull. Chem.
of hops on the essential oil, J. Inst. Brew. 64, 234–237. Soc. Japan 45, 2887–2891.
119. Stevens, R., Roberts, J. B., and Williams, I. H. (1961) Treatment of 146. Guadagni, D. G., Buttery, R. G., and Okano, S. (1963) Odour thresh-
hops (Humulus lupulus, L.) with gibberellic acid: Effect of olds of some organic compounds associated with food flavours,
spraying with gibberellic acid on yield and composition, Nature J. Sci. Food Agric. 14, 761–765.
191, 360–361. 147. Lermusieau, G., and Collin, S. (2003) Volatile sulfur compounds in
120. Howard, G. A. (1963) The composition and brewing value of hop oil, hops and residual concentrations in beer – A review, J. Am. Soc.
Brew. Dig. Sept., 50–53. Brew. Chem. 61, 109–113.
121. Rigby, F. L., and Bethune, J. L. (1955) Separation of the aromatic 148. Seaton, J. C., Suggett, A., and Moir, M. (1981) The flavor contribu-
constituents of hops, Proc. Am. Soc. Brew. Chem. 13, 174–183. tion of sulfur compounds in hops, Tech. Q. Master Brew. Assoc.
122. Rigby, F. L., and Bethune, J. L. (1957) Analysis of hop oil by gas– Am. 18, 26–30.
liquid partition chromatography, J. Inst. Brew. 63, 154–161. 149. Gijs, L., Piraprez, G., Perpète, P., Spinnler, E., and Collin, S. (2000)
123. Rigby, F. L., and Bethune, J. L. (1957) The aromatic constituents Retention of sulfur flavours by food matrix and determination of
of hops. III. Analysis of the 1956 crop, Proc. Am. Soc. Brew. sensorial data independent of the medium composition, Food
Chem. 15, 66–69. Chem. 69, 319–330.
124. Murphey, J. M., and Probasco, G. (1996) The development of 150. Berger, C., Martin, N., Collin, S., Gijs, L., Khan, J. A., Piraprez, G.,
brewing quality characteristics in hops during maturation, Tech. Spinnler, H. E., and Vulfson, E. N. (1999) Combinatorial approach
Q. Master Brew. Assoc. Am. 33, 149–159. to flavor analysis. 2. Olfactory investigation of a library of S-
125. Sharp, D. C. (2013) Harvest maturity of Cascade and Willamette Methyl thioesters and sensory evaluation of selected components,
hops, Masters Thesis, pp. 1–56, Oregon State University: Portland, J. Agric. Food Chem. 47, 3274–3279.
OR. 151. Seaton, J. C., and Moir, M. (1987) Sulphur compounds and their im-
126. Jahnsen, V. J. (1962) Complexity of hop oil, Nature 196, 474–475. pact on beer flavour, in European Brewery Convention – Hops, pp.
127. Dieckmann, R. H., and Palamand, S. R. (1974) Autoxidation of some 130–145, Fachverlag Hans Carl, Nürnberg.
constituents of hops. I. The monoterpene hydrocarbon, myrcene, 152. Gros, J., Peeters, F., and Collin, S. (2012) Occurrence of odorant
J. Agric. Food Chem. 22, 498–503. polyfunctional thiols in beers hopped with different cultivars. First
128. Peacock, V. E. (2010) The value of linalool in modeling hop aroma in evidence of an S-cysteine conjugate in hop (Humulus lupulus L.),
beer, Tech. Q. Master Brew. Assoc. Am. 47, 29–32. J. Agric. Food Chem. 60, 7805–7816.
129. Kaltner, D., Steinhaus, M., Mitter, W., Biendl, M., and Schieberle, P. 153. Mestres, M., Busto, O., and Guasch, J. (2000) Analysis of organic
(2003) (R)-Linalool als Schlüsselaromastoff für das Hopfenaroma sulfur compounds in wine aroma, J. Chromatogr. A 881, 569–581.
in Bier und sein Verhalter während der Bieralterung, Monatsschrift 154. Benitez, J. L., Forster, A., Keukeleire, D. D., Moir, M., Sharpe, F. R.,
für Brauwissenschaft 56, 192–196. Verhagen, L. C., and Westwood, K. T. (1997) European Brewery
130. Guadagni, D. G., Buttery, R. G., and Harris, J. (1966) Odour intensities Convention Manual of Good Practice – Hops and Hop Products,
of hop oil components, J. Sci. Food Agric. 17, 142–144. Getränke-Fachverlag Hans Carl: Nürnberg.
131. Marsili, R. T. (2006) Application of sensory-directed flavor-analysis 155. Institut für Pflanzenbau und Pflanzenzüchtung, A. H. (2012) Annual
techniques, in Sensory-directed Flavor Analysis (Marsili, R., Ed.) Report 2011 – Special Crops: Hops. Available at: http://www.
pp. 55–80, CRC Press: Boca Raton, FL. hopfenforschung.de/hopfen_annual_report_2012.pdf.
132. Kaltner, D., and Mitter, W. (2006) Possible impact of hops on taste 156. Hornsey, I. S. (1999) Brewing, The Royal Society of Chemistry:
and drinkability of beer, in European Brewery Convention Sympo- Cambridge.
sium ‘Drinkability’, Edinburgh, Fachverlag Hans Carl: Nürnberg. 157. Schmidt, R., and Beck, B. (2007) Low molecular polyphenols in beer
133. Meilgaard, M. C. (1975) Flavor chemistry of beer: Part II: Flavor and influenced by different hop varieties, in IHGC Scientific Commission,
threshold of 239 aroma volatiles, Tech. Q. Master Brew. Assoc. Am. Tettnang.
12, 151–168. 158. Forster, A., Beck, B., and Schmidt, R. (1995) Investigations on hop
134. Peacock, V. E., and Deinzer, M. L. (1981) Chemistry of hop aroma in polyphenols, in Proc. Eur. Brew. Conv. Congr., Brussels, pp. 143–150,
beer, J. Am. Soc. Brew. Chem. 39, 136–141. IRL Press: Oxford.
135. Peacock, V. E., Deinzer, M. L., Likens, S. T., Nickerson, G. B., and 159. Biendl, M. (2009) Hops and health, Tech. Q. Master Brew. Assoc. Am.
McGill, L. A. (1981) Floral hop aroma in beer, J. Agric. Food 46, 1–7.
Chem. 29, 1265–1269. 160. Stevens, J. F., Miranda, C. L., Buhler, D. R., and Deinzer, M. L. (1998)
136. Kaltner, D., Thum, B., Forster, C., and Back, W. (2000) Hopfen, Chemistry and biology of hop flavonoids, J. Am. Soc. Brew. Chem.
Brauwelt 140, 704–706. 56, 136–145.
312
161. Forster, A., Beck, B., and Schmidt, R. (1999) Hop polyphenols – do C. (2011) Determination of resveratrol and piceid in beer matrices by
more than just cause turbidity in beer, Hopfenrundschau Int. 1999/ solid-phase extraction and liquid chromatography-tandem mass
2000, 68–74. spectrometry, J. Chromatogr. A 1218, 698–705.
162. Kammhuber, K. (2005) Differentiating between the world range of 185. Peleg, H., Gacon, K., Schlich, P., and Noble, A. C. (1999) Bitterness
hop varieties according to bitter compounds and polyphenols, and astringency of flavan-3-ol monomers, dimers and trimers,
Hopfenrundschau Int. 2005/2006, 42–46. J. Sci. Food Agric. 79, 1123–1128.
163. Mikyška, A., Hrabák, M., Hašková, D., and Šrogl, J. (2002) The role of 186. McLaughlin, I. R., Lederer, C., and Shellhammer, T. H. (2008) Bitter-
malt and hop polyphenols in beer quality, flavour and haze ness-modifying properties of hop polyphenols extracted from
stability, J. Inst. Brew. 108, 78–85. spent hop material, J. Am. Soc. Brew. Chem. 66, 174–183.
164. Kammhuber, K. (2006) Quercetin and kaempferol – Two flavonoids 187. Dornbusch, H., Drexler, G., König, W., Vilches, R., and Ward, I. L.
which are present in hops with positive properties for health, (2012) World harvest report, New Brew., 40–62.
Hopfenrundschau Int. 2006/2007, 52–55. 188. Barth-Haas-Group (2013) The Barth Report (2012/2013), pp. 1–32.
165. Sägesser, M., and Deinzer, M. (1996) HPLC–ion spray–tandem mass 189. Barth-Haas-Group (2012) The Barth Report (2011/2012), pp. 1–32.
spetrometry of flavonol glycosides in hops, J. Am. Soc. Brew. Chem. 190. Barth-Haas-Group (2011) The Barth Report (2010/2011), pp. 1–32.
54, 129–134. 191. Barth-Haas-Group (1909–2014) The Barth Report (1909–2014).
166. Taylor, A. W., Barofsky, E., Kennedy, J. A., and Deinzer, M. L. (2003) 192. Barth, H. J., Klinke, C., and Schmidt, C. (1994) Der große Hopfenatlas:
Hop (Humulus lupulus L.) proanthocyanidins characterized by mass Geschichte und Geographie einer Kulturpflanze, Joh. Barth & Sohn:
spectrometry, acid catalysis, and gel permeation chromatography, Nürnberg.
J. Agric. Food Chem. 51, 4101–4110. 193. Moir, M. (2000) Hops – A millennium review, J. Am. Soc. Brew. Chem.
167. Li, H.-J., and Deinzer, M. L. (2006) Structural identification and distri- 58, 131–146.
bution of proanthocyanidins in 13 different hops, J. Agric. Food 194. Barth, H. J. (2005) 1950–2005: Hop trade – Events and trends in the
Chem. 54, 4048–4056. hop market in Germany and the USA from 1950 to the present day,
168. Moll, M., Fonknechten, G., Carnielo, M., and Flayeux, R. (1984) Hopfenrundschau Int. 2005/2006, 66–77.
Changes in polyphenols from raw materials to finished beer. Tech. 195. Barth-Haas-Group (2013/2014) The Barth Report (unpublished).
Q. Master Brew. Assoc. Am. 21, 79–87. 196. Barth-Haas-Group (2010) The Barth Report (2009/2010), pp. 1–32.
169. Keukeleire, J. D., Ooms, G., Heyerick, A., Roland-Ruiz, I., Bockstaele, 197. Barth-Haas-Group (1981) The Barth Report (1980/1981), pp. 1–20.
E. V., and Keukeleire, D. D. (2003) Formation and accumulation of 198. Barth-Haas-Group (2001) The Barth Report (2000/2001), pp. 1–28.
α-Acids, β-Acids, desmethylxanthohumol, and xanthohumol during 199. Moritz, E. R., and Morris, G. H. (1891) A Text-book of the Science of
flowering of hops (Humulus lupulus L.), J. Agric. Food Chem. Brewing, E. & F. N. Spon: London.
51, 4436–4441. 200. Hughes, P. S., and Simpson, W. J. (1993) Production and composi-
170. Hänsel, R., and Schulz, J. (1988) Desmethylxanthohumol: tion of hop products, Tech. Q. Master Brew. Assoc. Am. 30, 146–154.
Isolierung aus Hopfen und Cyclisierung zu Flavanonen, Archiv 201. Keukeleire, D. D. (1993) The effects of hops on flavour stability and
Pharm. 321, 37–40. beer properties, Cerevisia Biotechnol. 18, 33–46.
171. Chadwick, L. R., Pauli, G. F., and Farnsworth, N. R. (2006) The 202. Hughes, P. (2000) The significance of iso-α-acids for beer quality –
pharmacognosy of Humulus lupulus L. (hops) with an emphasis Cambridge Prize Paper, J. Inst. Brew. 106, 271–276.
on estrogenic properties, Phytomedicine 13, 119–131. 203. Hughes, P. S., and Simpson, W. J. (1996) Bitterness of congeners
172. Milligan, S. R., Kalita, J. C., Heyerick, A., Rong, H., Cooman, L. D., and and stereoisomers of hop-derived bitter acids found in beer,
Keukeleire, D. D. (1999) Identification of potent phytoestrogen in J. Am. Soc. Brew. Chem. 54, 234–237.
hops (Humulus lupulus L.) and beer, J. Clin. Endocrinol. Metab. 83, 204. Meilgaard, M. (1960) Hop analysis, Cohumulone factor and the
2249–2252. bitterness of beer: Review and critical evaluation, J. Inst. Brew.
173. Kosasi, S., Sluis, W. G. V. D., and Labadie, R. P. (1989) Multifidol 66, 35–50.
and multifidol glucoside from the latex of Jatropha multifida, 205. Takoi, K., Koie, K., Itoga, Y., Katayama, Y., Shimase, M., Nakayama, Y.,
Phytochemistry 28, 2439–2441. and Watari, J. (2010) Biotransformation of hop-derived monoter-
174. Bohr, G., Gerhäuser, C., Knauft, J., Zapp, J., and Becker, H. (2005) pene alocohols by lager yeasts and their contribution to the flavor
Anti-inflammatory acylphloroglucinol derivatives from hops of hopped beer, J. Agric. Food Chem. 58, 5050–5058.
(Humulus lupulus), J. Nat. Prod. 68, 1545–1548. 206. Laws, D. R. J., McGuinness, J. D., and Rennie, H. (1972) The losses of
175. Vancraenenbroeck, R., Vanclef, A., and Lontie, R. (1965) bitter substances during fermentation, J. Inst. Brew. 78, 314–321.
Caractérisation de flavonols et d’un glucoside de la 207. Kuroiwa, Y., Kokubo, E., and Hashimoto, N. (1973) Advanced hop
phloroisobutyrophénone dans le houblon, in Proc. Eur. Brew. Conv. chemistry in connection with beer flavor, Tech. Q. Master Brew.
Congr., Stockholm, pp. 360–371, Elsevier, Amsterdam. Assoc. Am. 10, 215–219.
176. Callemien, D., Jerkovic, V., Rozenberg, P., and Collin, S. (2005) Hop as 208. Praet, T., Van Opstaele, F., Jaskula-Goiris, B., Aerts, G., and
an interesting source of resveratrol for brewers optimization of the Cooman, L. D. (2012) Biotransformations of hop-derived aroma
extraction and quantitative study by liquid chromatography/ compounds by Saccharomyces cerevisiae upon fermentation,
atmospheric pressure chemical ionization tandem mass spectrome- Cerevisia 36, 125–132.
try, J. Agric. Food Chem. 53, 424–429. 209. Harold, F. V., Hildebrand, R. P., Morieson, A. S., and Murray, P. J.
177. Jerkovic, V., Callemien, D., and Collin, S. (2005) Determination of (1960) Influence of hop oil constituents on the flavour and aroma
stilbenes in hop pellets from different cultivars, J. Agric. Food Chem. of beer, J. Inst. Brew. 66, 395–398.
53, 4202–4206. 210. Guadagni, D. G., Buttery, R. G., Okano, S., and Burr, H. K. (1963)
178. Jerkovic, V., and Collin, S. (2007) Fate of resveratrol and piceid Additive effect of sub-threshold concentrations of some organic
through different hop processings and storage times, J. Agric. Food compounds associated with food aromas, Nature 200, 1288–1289.
Chem. 56, 584–590. 211. Hashimoto, N. (1970) Hop constituents responsible for the hoppy
179. Jerkovic, V., and Collin, S. (2009) The cis-resveratrol concentration is flavor of beer – Part I, Rep. Res. Lab. Kirin Brewery Co. Ltd 13, 1–16.
proposed as a new indicator of the hop freshness, Brew. Sci. 212. Buttery, R. G., and Ling, L. C. (1966) The chemical composition of
62, 141–146. the volatile oil of hops, Brew. Dig. 41, 71–77.
180. Siemann, E. H., and Creasy, L. L. (1992) Concentration of the 213. Tressl, R., Engel, K. H., Kossa, M., and Köppler, H. (1983) Characteri-
phytoalexin resveratrol in wine, Am. J. Enol. Viticult. 43, 49–52. zation of tricyclic sesquiterpenes in hop (Humulus lupulus, var.
181. Frémont, L. (2000) Minireview – Biological effects of resveratrol, Life Hersbrucker Spät), J. Agric. Food Chem. 31, 892–897.
Sci. 66, 663–667. 214. Fukuoka, Y., and Kowaka, M. (1983) Identification of compounds
182. Jerkovic, V., and Collin, S. (2007) Occurrence of resveratrol and imparting hoppy flavor to beer, Rep. Res. Lab. Kirin Brewery Co. Ltd
piceid in American and European hop cones, J. Agric. Food Chem. 26, 31–36.
55, 8754–8758. 215. Shimwell, J. L. (1937) On the relationship between the staining
183. Baur, J. A., and Sinclair, D. A. (2006) Therapeutic potential of properties of bacteria and their reaction towards hop antiseptic –
resveratrol: the in vivo evidence, Nat. Rev. Drug Discov. 5, 493–506. Part I and II, J. Inst. Brew. 43, 111–118.
184. Chiva-Blanch, G., Urpi-Sarda, M., Rotchés-Ribalta, M., Zamora-Ros, R., 216. Mizobuchi, S., and Sato, Y. (1985) Antifungal activities of hop bitter
Llorach, R., Lamuela-Raventos, R. M., Estruch, R., and Andrés-Lacueva, resins and related compounds, Agric. Biol. Chem. 49, 399–403.
313
C. Almaguer et al.
217. Srinivasan, V., Goldberg, D., and Haas, G. J. (2004) Contributions to 240. Haakensen, M. C., Butt, L., Chaban, B., Deneer, H., Ziola, B., and
the antimicrobial spectrum of hop constituents, Econ. Bot. Dowgiert, T. (2007) horA-Specific real-time PCR for detection of
58, S230–S238. beer-spoilage lactic acid bacteria, J. Am. Soc. Brew. Chem.
218. Shimwell, J. L. (1937) On the relationship between the staining 65, 157–165.
properties of bacteria and their reaction towards hop antiseptic – 241. Haakensen, M., Vickers, D. M., and Ziola, B. (2009) Susceptibility of
Part III, J. Inst. Brew. 43, 191–195. Pediococcus isolates to antimicrobial compounds in relation to
219. Teuber, M., and Schmalreck, A. F. (1973) Membrane leakage in hop-resistance and beer-spoilage, BMC Microbiol. 9, 190.
Bacillus subtilis 168 induced by the hop constituents lupulone, 242. Fujii, T., Nakashima, K., and Hayashi, N. (2005) Random amplified
humulone, isohumulone and humulinic acid, Arch. Microbiol. polymorphic DNA-PCR based cloning of markers to identify the
94, 159–171. beer-spoilage strains of Lactobacillus brevis, Pediococcus damnosus,
220. Simpson, W. J. (1993) Cambridge Prize Lecture – Studies on the Lactobacillus collinoides and Lactobacillus coryniformis, J. Appl.
sensitivity of lactic acid bacteria to hop bitter acids, J. Inst. Brew. Microbiol. 98, 1209–1220.
99, 405–411. 243. Suzuki, K., Ozaki, K., and Yamashirta, H. (2004) Genetic marker for
221. Simpson, W. J. (1993) Ionophoric action of trans-isohumulone on differentiating beer-spoilage ability of Lactobacillus paracollinoides
Lactobacillus brevis, J. Gen. Microbiol. 139, 1041–1045. strains, J. Appl. Microbiol. 97, 712–718.
222. Simpson, W. J., and Fernandez, J. L. (1994) Mechanism of resistance 244. Haakensen, M., Schubert, A., and Ziola, B. (2008) Multiplex PCR for
of lactic acid bacteria to trans-isohumulone, J. Am. Soc. Brew. Chem. putative Lactobacillus and Pediococcus beer-spoilage genes and
52, 9–11. ability of gene presence to predict growth in beer, J. Am. Soc. Brew.
223. Simpson, W. J., and Smith, A. R. W. (1992) Factors affecting Chem. 66, 63–70.
antibacterial activity of hop compounds and their derivatives, 245. Venter, H., Shahi, S., Balakrishnan, L., Velamakanni, S., Bapna, A.,
J. Appl. Bacteriol. 72, 327–334. Woebking, B., and Veen, H. W. v. (2005) Similarities between ATP-
224. Walker, T. K., and Blakebrough, N. (1952) Bacteriostatic power of dependent and ion-coupled multidrug transporters, Biochem. Soc.
humulone boiling-product, J. Inst. Brew. 58, 13–24. Trans. 33, 1008–1011.
225. Simpson, W. J. (1993) Application of in vivo bioluminescence to 246. Haakensen, M., Pittet, V., Morrow, K., Schubert, A., Ferguson, J.,
the study of ionophoretic action, J. Bioluminesc. Chemiluminesc. and Ziola, B. (2009) Ability of novel ATP-binding cassette multi-
8, 147–152. drug resistance genes to predict growth of Pediococcus isolates
226. Fernandez, J. L., and Simpson, W. J. (1993) Aspects of the resis- in beer, J. Am. Soc. Brew. Chem. 67, 170–176.
tance of lactic acid bacteria to hop bitter acids, J. Appl. 247. Behr, J., Israel, L., Gänzle, M. G., and Vogel, R. F. (2007) Proteomic ap-
Bacteriol. 75, 315–319. proach for characterization of hop-inducible proteins in Lactobacil-
227. Sakamoto, K., and Konings, W. N. (2003) Beer spoilage bacteria and lus brevis, Appl. Environ. Microbiol. 72, 3300–3306.
hop resistance, Int. J. Food Microbiol. 89, 105–124. 248. Behr, J. (2008) Mechanisms of hop inhibition, tolerance and adapta-
228. Behr, J., Gänzle, M. G., and Vogel, R. F. (2006) Characterization of a tion in Lactobacillus brevis, in Lehrstuhl für Technische Mikrobiologie,
highly hop-resistant Lactobacillus brevis strain lacking hop trans- pp. 1–141, Technische Universität München: Germany.
port, Appl. Environ. Microbiol. 72, 6483–6492. 249. Behr, J., and Vogel, R. F. (2009) Mechanisms of hop inhibition: Hop
229. Sami, M., Yamashita, H., Hirono, T., Kadokura, H., Kitamoto, K., Yoda, ionophores, J. Agric. Food Chem. 57, 6074–6081.
K., and Yamasaki, M. (1997) Hop-resistant Lactobacillus brevis 250. Schönberger, C., and Kostelecky, T. (2011) 125th Anniversary
contains a novel plasmid harboring a multidrug resistance-like Review: The role of hops in brewing, J. Inst. Brew. 117, 259–267.
gene, J. Ferment. Bioeng. 84, 1–6. 251. Miedaner, H. (2002) Brautechnische Analysenmethoden der
230. Sami, M., Yamashita, H., Kadokura, H., Kitamoto, K., Yoda, K., and Mitteleuropäischen Brautechnischen Analysenkommission, 4th edn
Yamasaki, M. (1997) A new and rapid method for determination Selbstverlag: Freising.
of beer-spoilage ability of lactobacilli, J. Am. Soc. Brew. Chem. 252. Fly, W. H., and Chicoye, E. (1977) The effect of countercurrent distri-
55, 137–140. bution fractions of hop extracts on beer foam, J. Am. Soc. Brew.
231. Suzuki, K., Sami, M., Kadokura, H., Nakajima, H., and Kitamoto, K. Chem. 35, 69–72.
(2002) Biochemical characterization of horA-independent hop re- 253. Diffor, D. W., Likens, S. T., Rehberger, A. J., and Burkhardt, R. J. (1978)
sistance mechanism in Lactobacillus brevis, Int. J. Food Microbiol. The effect of isohumulone/isocohumulone ratio on beer head
76, 223–230. retention, J. Am. Soc. Brew. Chem. 36, 63–65.
232. Suzuki, K., Koyanagi, M., and Yamashita, H. (2004) Genetic charac- 254. Simpson, W. J., and Hughes, P. S. (1994) Stabilization of foams by
terization of non-spoilage variant isolated from beer-spoilage hop-derived bitter acids. Chemical interactions in beer foam,
C
Lactobacillus brevis ABBC45 , J. Appl. Microbiol. 96, 946–953. Cerevisia Biotechnol. 19, 39–44.
233. Suzuki, K., Ozaki, K., and Yamashita, H. (2004) Comparative analysis 255. Smith, R. J., Davidson, D., and Wilson, R. J. H. (1998) Natural foam
of conserved genetic markers and adjacent DNA regions identified stabilizing and bittering compounds derived from hops, J. Am.
in beer-spoilage lactic acid bacteria, Lett. Appl. Microbiol. Soc. Brew. Chem. 56, 52–57.
39, 240–245. 256. Keukeleire, D. D. (2000) Fundamentals of beer and hop chemistry,
234. Suzuki, K., Iijima, K., Ozaki, K., and Yamashita, H. (2005) Isolation of a Quím. Nova 23, 108–112.
hop-sensitive variant of Lactobacillus lindneri and identification of 257. Weiss, A., Schöneberger, C., Mitter, W., Biendl, M., Back, W., and
genetic markers for beer spoilage ability of lactic acid bacteria, Krottenthaler, M. (2002) Sensory and analytical characterisation of
Appl. Environ. Microbiol. 71, 5089–5097. reduced, isomerised hop extracts and their influence and use in
235. Iijima, K., Suzuki, K., Ozaki, K., and Yamashita, H. (2006) horC confers beer, J. Inst. Brew. 108, 236–242.
cc
beer-spoilage ability on hop-sensitive Lactobacillus brevis ABBC45 , 258. Kunimune, T., and Shellhammer, T. H. (2008) Foam-stabilizing ef-
J. Appl. Microbiol. 100, 1282–1288. fects and cling formation patterns of iso-α-acids and reduced
236. Hayashi, N., Ito, M., Horiike, S., and Taguchi, H. (2001) Molecular iso-α-acids in lager beer, J. Agric. Food Chem. 56, 8629–8634.
cloning of a putative divalent-cation transporter gene as a new 259. Wilson, R. J. H., Roberts, T. R., Smith, R. J., Bradley, L. L., and Moir, M.
genetic marker for the identification of Lactobacillus brevis (1998) The inherent foam stabilising and lacing properties of some
strains capable of growing in beer, Appl. Microbiol. Biotechnol. minor, hop-derived constituents of beer, in European Brewery Con-
55, 596–603. vention Symposium Beer Foam Quality, pp. 188–207, Verlag Hans
237. Yasui, T., and Yoda, K. (1997) Purification and partial characteriza- Carl Getränke-Fachverlag: Amsterdam.
tion of an antigen specific to Lactobacillus brevis strains with beer 260. Heintz, O. E. (1987) Aspects of beer foam formation and head
spoilage activity, FEMS Microbiol. Lett. 151, 169–176. retention, Tech. Q. Master Brew. Assoc. Am. 24, 58–60.
238. Sakamoto, K., Veen, H. W. v., Saito, H., Kobayashi, H., and Konings, 261. Bamforth, C. (2003) Beer – Tap into the Art and Science of Brewing,
W. N. (2002) Membrane-bound ATPase contributes to hop resis- 2nd edn Oxford University Press: New York.
tance of Lactobacillus brevis, Appl. Environ. Microbiol. 68, 5374–5378. 262. Glenister, P. R., and Segel, E. (1964) Foam evaluation. I. Primary cling;
239. Suzuki, K., Asano, S., Iijima, K., and Kitamoto, K. (2008) Sake and secondary cling; foam strength, Proc. Am. Soci. Brew. Chem. 22, 55–59.
beer spoilage lactic acid bacteria – A Review, J. Inst. Brew. 263. Almaguer, C., Gastl, M., Arendt, E. K., and Becker, T. (2012) Contribu-
114, 209–223. tions of hop hard resins to beer quality, Brew. Sci. 65, 118–129.
314

Almaguer Et Al-2014-Journal of The Institute of Brewing

Uploaded by

Copyright:

Available Formats

Almaguer Et Al-2014-Journal of The Institute of Brewing

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Almaguer Et Al-2014-Journal of The Institute of Brewing

Uploaded by

Copyright:

Available Formats

Review article Institute of Brewing & Distilling

(wileyonlinelibrary.com) DOI 10.1002/jib.160

Humulus lupulus – a story that begs to be told.

Introduction knowledge of hops. Hop research covers all matters related to

Barth Innovations, Freiligrathstr. 7/9, 90482 Nuremberg, Germany

Figure 1. Classiﬁcation of the hop plant (8,9).

Figure 2. Classiﬁcation and nomenclature of hop resins (8,19,28).

isomerized during the boiling process into the more water

these are the main bittering acids in beer (48).

δ-Hard resin. In 1952, Walker et al. (70) found a water-soluble

fractions were collected as brittle powdery material. The frac-

Figure 8. Hop oil composition (10,100,126).

A later study by Murphey and Probasco (124) conﬁrmed the

Figure 11. Constituents of the hop polyphenol fraction (159).

differentiation are the quercetin and kaempferol glycosides;

Table 2. Composition of hop polyphenols and their concen-

Substances and substance groups Amount (%)

polymeric substances such as proanthocyanidins (C).

Tradition, Spalter Select, Hallertauer Mittelfrüh, Hersbruck Flavour hops

J. Inst. Brew. 2014; 120: 289–314

Copyright © 2014 The Institute of Brewing & Distilling

25. Anger, H.-M. (2006) Brautechnische Analysenmethoden der

You might also like