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

Brewing science is an extremely broad field dedicated to the
study of all aspects of beer and its production process. It spans
many disciplines and applications of interest to the practical
brewer. At its most simple it encompasses the study of malt,
yeast and hops (Humulus lupulus L.). Through research and
collaboration, a number of major breakthroughs have been
achieved in the brewing field. Research in brewing plays a
predominant role in the brewing industry in part because it
provides information about the properties and composition of
the materials used. By understanding and then applying this
knowledge to practice, brewers may tailor new beers in which
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.
This minor ingredient has, however, a crucial impact on beer
quality and, thus, hops are of paramount importance for beer
brewing. The complex chemistry associated with hop sub-
stances and their function in brewing has been the subject of
extensive investigation for over a century. Yet, surprisingly,
greater understanding of the chemical character of the hop
compounds is still needed. Recent findings have not only helped
strengthen the existing research but also have improved our
hops, from breeding and growing to harvesting and drying as
well as their chemistry and their impact on beer quality. As a
result of progress in analytical techniques, our knowledge of
hops has advanced tremendously, leading to improvements
and new product development in the hop and brewing indus-
tries. Although a considerable amount of research has been
done on a great variety of hop constituents and their function
in brewing, much remains a matter of debate, in particular, the
chemical background of hoppy aroma (1–4) and the influence of
hop polyphenols on the organoleptic properties of beer (5–7).
Ultimately, the brewer and brewing chemists understand what
the hop substances can do; however, to some extent, it remains
* Correspondence to: Martina Gastl, Lehrstuhl für Brau- und Getränketechnologie,
Technische Universität München Weihenstephan, Weihenstephaner Steig 20,
85354 Freising, Germany. E-mail: martina.gastl@tum.de
1
Lehrstuhl für Brau- und Getränketechnologie, Technische Universität München
Weihenstephan, Weihenstephaner Steig 20, 85354 Freising, Germany
2
Department of Food and Nutritional Sciences, National University of
Ireland, University College Cork, College Road, Cork, Ireland
3
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Barth Innovations, Freiligrathstr. 7/9, 90482 Nuremberg, Germany

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unclear how they do it. It is intended in the following to evaluate
and review the available literature on this subject and, thus, pro-
vide the current status of hop research.
Hop botany
The genus Humulus is made up of dioecious, perennial, climbing
vines (8). This genus belongs to the Cannabaceae family of the
Urticales order which in 2003 was incorporated into the natural
order of Rosales (9). The only other genus in the family is
Cannabis (see Fig. 1) represented solely by C. sativa (i.e. Indian
hemp, marijuana or hashish) (10). For years it was believe
that the genus Humulus was only represented by two species,
the ‘common hop’, Humulus lupulus L., and the ‘Japanese
hop’, H. japonicus Zieb. et Zucc (11). In 1936, the species
Humulus yunnanensis Hu was first described; however, it
remained a relatively unknown species thought to have orig-
inated at high elevations in the Yunnan province of southern
China. Previous to Small’s study, it had been almost univer-
sally unappreciated and identified as H. lupulus. It was in
1978 that Small identified H. yunnanensis as a species of its
own (12). Currently more is known of the H. japonicus species;
this is an annual plant indigenous in China, Japan and the
neighbouring islands. For brewing purposes it is of no value
as its hops are devoid of lupulin glands (11). H. japonicus is
widely cultivated as a strong climber, often used in gardens
as a decorative, leafy screen (8).
Hop cultivation
The hop cones of the female plant of the common hop species
Humulus lupulus L. are grown almost exclusively for the brewing
industry. About 97% of worldwide cultivated hops are destined
for brewing purposes. The world hop production is dominated
by Germany and the USA. The hop production of both countries
accounts for about 75–80% of the total hop output (13). Suc-
cessful cultivation of the hop plant requires optimal growth
conditions, especially with respect to the length of daylight,
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°
of the Northern and Southern Hemispheres (8). More than 60%
of the hop area under cultivation is located in Germany and
the USA (13). The largest hop growing areas include the
Hallertau region in Germany and the states of Washington,
Oregon and Idaho in the USA. Other hop growing countries
are the Czech Republic, Poland, Slovenia, England, Ukraine,
China, South Africa, Australia and New Zealand.
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Figure 1. Classification of the hop plant (8,9).
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C. Almaguer et al.
Hop cones
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
lupulin glands are formed as the hop ripens. Only the cones of
the female plants are able to secrete the fine yellow resinous pow-
der known as lupulin glands. It is in these lupulin glands that the
main brewing principles of hops, the resins and essential oils, are
synthesized and accumulated (8,10). In 1821, Ives assigned the
name ‘lupulin’ to this yellow powder; he was the first one to
observe that it is in the lupulin where the bitter and aromatic sub-
stances of hops are stored (15). The lupulin glands are only weakly
attached to the hop cones, therefore, hops have to be handled
carefully to avoid losing the valuable hop components (14).
In most commercial hop growing areas worldwide the seed
content in hops is regulated. Male hops are physically removed
from the hop fields to avoid the fertilization of the female plants
and, thus, the production of seeds. In most parts of the world,
seeds are considered by brewers to be undesirable. It is believed
that oxidation of the seed fatty acids produce off-flavours in
beer (16). Further, it has been proven that seedless hops are
generally richer in essential oils and resins than seeded ones
(i.e. higher brewing value) (10). However, male plants are
essential in hop breeding programmes to develop new varie-
ties through controlled hybridization.
Hop harvesting and drying
In late summer or early autumn, when the hop cones have
ripened and the resin content is highest, the hops are harvested.
At harvest the moisture present in hops is about 75–80%; at such
high moisture level not only do the hop compounds change
rapidly but they also go mouldy quickly. Thus, the hop cones
are carefully dried in the oast house or kiln at temperatures
between 60–75 °C to reduce the moisture content to about
10% (17). After cooling and conditioning the hops are com-
pressed and packed into bales. These bales are stored cold until
required for use, either sale or processing into hop products.
Chemical composition of hops
Whole hop cones comprise several components, such as resins,
essential oils, proteins, polyphenols, lipids, waxes, cellulose and
amino acids (10,18). The typical overall average chemical compo-
sition of fresh dried hop cones is shown in Table 1. The leafy
nature of the hop petals ensures the presence of ubiquitous
substances such as proteins, carbohydrates and polyphenols
(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
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Humulus lupulus – a story that begs to be told
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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).

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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.
Taurus CO2 spent hop material are shown in (B).
Soft resins
To date, it is generally accepted that the total soft resin is soluble
in hexane and that the bulk of the brewing and bittering value
of the hop is found in this fraction. The total soft resins consist
of α-acids and the β-fraction (i.e. β-acids and uncharacterized
soft resins). The term ‘resin’ is used as the base available in
spite of the recognition that the two main groups of constitu-
ents (i.e. α-acids and β-acids) are crystalline and not resinous
in nature (22). The α-acids can be readily separated from the
total soft resins by their ability to form an insoluble lead salt with
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-
ponent, known as humulone (32). Rigby and Bethune used
countercurrent distribution to establish that the α-acids are, in
fact, mixtures of homologues and analogues. In addition to
humulone, two other substances are present in substantial
amounts, cohumulone and adhumulone (33,34). Trace amounts
of two other α-acids, prehumulone and posthumulone, are also
found in hops. The composition of the α-acid fraction varies
greatly among the hop varieties.
α-Acids. It is well established that the α-acids are by far the
most important constituents of the hop resins. Upon addition
of hops to the wort kettle, the α-acids are extracted and thermally
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).
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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
was determined as (6S), thus the conserved stereocentre dur-
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-
acids were found in hops. In 1955, Verzele identified a fourth
component, prehumulone, by partition chromatography.
Verzele also established that the component eluting last in the
chromatographic separation of the hop α-acids was
posthumulone (49,50). As previously mentioned, the composi-
tion of the α-acids is characteristic of the hop variety; however
it is further dependent on the harvesting time. It was deter-
mined by Verzele that, independent of the hop variety, the levels
of prehumulone and posthumulone are higher when the hops
are harvested late (14).
β-Fraction. β-Acids. The β-fraction of the total soft resins can
be further divided into β-acids and uncharacterized soft resins.
The less acidic β-acids can be isolated from hops by removing
the stronger α-acids first with lead(II) acetate (51). Lupulone, a
β-acid constituent, was first isolated from hops by Lermer in
1863 (52,53). Compared with the α-acids, the β-acids have been
subjected to less extensive studies. Up until the 1950s, humulone
and lupulone were the only known hop acids. It was later
established that, like the α-acids, the β-acids are a mixture of
analogues. The compounds in the β-acid series bear the same
relation as the α-acid constituents and, thus, these are termed
analogously. The β-acid group is composed of lupulone and four
congeners: colupulone, adlupulone, prelupulone and postlupulone
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Humulus lupulus – a story that begs to be told
(see Fig. 5). In 1956, it was established by Howard and Tatchell that
the β-acids are always richer in colupulone than the α-acids are in
cohumulone (54).
The β-acids show poor solubility in water (52), and while the
α-acids undergo isomerization during wort boiling, the β-acids
do not. The wort properties (i.e. low pH) do not favour β-acid
solubility and as a result only trace amounts are transferred
into beer. Previous to the studies of Haseleu et al. (55,56) the
β-acids were believed to be lost in the brewing process and,
thus, did not contribute to beer bitterness. Haseleu et al. were
able to identify a number of bitter tasting β-acid transformation
products that are generated during wort boiling, thereby
proving that, in addition to the α-acids, the β-acids are potential
bitter taste precursors present in the hop soft resins.
Uncharacterized soft resins. The uncharacterized soft resins is
considered a non-specific hop fraction (29). This fraction consists
of the portion of the total soft resins remaining after the α-acids
have been precipitated and the β-acids are allowed to crystallize
out (10). Hitherto, the constituents of the uncharacterized soft
resins have not been characterized as any specific compound.
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
light petroleum. Although most of the hop wax is removed,
the separation of hop wax from the cold methanolic solution is
slow and normally incomplete; as a result, traces of wax occur in
this fraction (10). The uncharacterized soft resins can be further di-
vided into α-soft resins and β-soft resins. These terms are reserved
for substances that may later be identified as having arisen from
the α-acids or the β-acids, respectively (22). The brewing value of
the uncharacterized soft resins remains unknown.
Hard resins
By definition the hard resin is the portion of the total resin that is
soluble in methanol and diethyl ether but insoluble in hexane
and low boiling paraffinic hydrocarbons (29). It is generally
accepted that the hard resins arise by oxidation of the soft resin;
however, it is neither well defined nor proven conclusively what
the hard resins consist of. In 1956, Schild and Raum found hard
resins in hops at the earliest stage of development (57); there-
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-
tinction has been made between the deterioration or oxidation
products and the natural hard resin constituents of fresh hops
(32). However, given that the soft resins are prone to oxidation,
this results in a challenging task. As hops age during storage,
Figure 5. Chemical structures of the hop β-acids.
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the percentage of soft resin falls while that of the hard resin
increases (58). In 1964, Ashurst et al. (59) inconclusively ad-
dressed the question of what constituents are responsible for
the bittering ability of stored hops when the α-acids have been
transformed into other substances. At that point, it had been
recognized for many years that the resins of the hop undergo
several changes during storage: the α- and β-acids become
oxidized, the products still being analytically classed as soft
resins, while further oxidation results in gradual transformation
to hard resins. Thus, the α- and β-acids decrease continually
during storage while the amount of uncharacterized soft resin
increases at first and then decreases as the hard resin steadily
increases (59,60). While some authors (19,58) automatically con-
sidered oxidized soft resins to be hard resins, others (32,59–61)
considered the uncharacterized soft resins in old hops to be
the intermediate deterioration products of the α- or β-acids
which, upon further oxidation, will ultimately turn into hard
resins. It is believed that these intermediate deterioration
products have brewing value, but the exact role of the oxidation
products, be it oxidized soft resins or hard resins, in the brewing
process is not fully understood (32,60).
α-Hard resin and β-hard resin. Hitherto, the complex nature
of the total hard resin has not been conclusively characterized.
In the early 1960s, Burton and Stevens proposed two fractions
derived from the total hard resin, the α-hard resin and the β-hard
resin fraction (58). The α-hard resin fraction represents a small
part of the hard resins capable of forming an insoluble lead salt
when treated with a lead acetate solution (58). Using ion-
exchange chromatography it was possible to perform further
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).
However the term α-hard resin does not imply that all the
material is derived from the α-acids but that, like the α-acids, it
gives an insoluble lead salt (58). The β-hard resin is the major
portion of the total hard resin; unlike the α-hard resin, this
fraction fails to give an insoluble lead salt (10,58). Xanthohumol
accounts for the bulk of the β-hard resin. With the exception of
xanthohumol, the precise chemical identity of the hard resins
is not well understood (8).
Xanthohumol. Xanthohumol is the most abundant prenylated
chalcone present in the hop lupulin glands and naturally found
in the hard resins. Many of the native hard resins are made up
of prenylflavonoids (8). Xanthohumol was first isolated from hops
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
portion of the hard resin that also had a bitter character. They
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Figure 6. Chemical structures of xanthohumol (chalcone) and isoxanthohumol
(flavone). During the brewing process, the thermal isomerization of chalcones into
flavones takes place and xanthohumol is cyclized to isoxanthohumol.
termed this portion of the total hard resin the δ-resin. An
aqueous solution of the δ-resin was described to be intensely
bitter yet the taste was pleasant. In their study, Walker et al.
collected evidence to determine that the δ-resin is produced
by oxidation of a non-water-soluble constituent of the hop
resins. Additionally, data from preliminary chromatographic
examination of the δ-resin indicate that it is not homogeneous
(70). In a later study, Abson et al. (71) developed a method for
estimating the δ-resin content in hops. In their experiments, they
observed that this fraction accumulates during the storage of
hops. However, they could not find any direct relationship
between the percentage decrease in the α-soft resin (i.e. α-acids)
and the amount of δ-resin accumulated during the same
period of time. From this observation it could be inferred that
the δ-resin is not the sole product of changes occurring in the
α-soft resin. In the analysed hop samples, they found δ-resin
contents varying from 0.6% to about 4%. From their results,
it could be concluded that the δ-resin content in hops, just
like most hop constituents, is variety dependent. Further, the
formation of δ-resin upon storage varies among the different
hop varieties (71).
Jackson and Walker (72) were able to separate the total δ-resin
into several non-crystalline fractions. In their preliminary fraction-
ation of the δ-resin by column chromatography, they isolated six
fractions (δI–δVI). Small-scale experiments indicated that these
were not single substances. Moreover, they collected evidence to
determine that in terms of chemical reaction the fractions were
qualitatively similar. All fractions exhibited the same association
of chemical functions: unsaturation, enolic/phenolic acidity and
carbonyl (ketone) activity. From the crude δ-resin, two major frac-
tions were recovered, δII (66.3%) and δIII (22.5%). In an attempt to
fully characterize both fractions, further chromatography was
performed. Based on its solubility in benzene and light petroleum,
a significant portion of δII is believed to be residues of the soft
resin. Contrary to δII, fraction δIII showed the same solubility
characteristics as the hard resins. Fractionation of δIII by partition
between immiscible solvents yielded four subfractions (δIII A, δIII
EA, δIII B and δIII E). It was further observed that neither the total
δ-resin nor the fractions isolated from the crude δ-resin are totally
soluble in water. However, when using any solvent to suspend the
fractions, water was required to achieve complete solubility.
Jackson and Walker were not able to identify any pure compounds
in the δ-resin. However, from the recorded observations on the
similarity in chemical behaviour of the fractions, it was possible
for them to conclude that some basic type of structure predomi-
nates amongst the δ-resin components (72).
In a recent study, 11 fractions were recovered from the total
δ-resin. The isolated fractions could be distinguished based on
their physical properties and their solubility. The more polar
fractions were recovered as thick resins while the non-polar
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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
hops. In their studies, they were able to quantify the δ-resin in
fresh green hops. However, they observed that not all sub-
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
raw α-acids and pure α-acids, 2.3 and 1.4%, respectively. In their
trials, the hop fractions were artificially aged by subjecting the
samples to extreme temperatures and high moisture levels.
When the raw α-acids and pure α-acids were separately heated
at 70 °C for 8 h (90% moisture level), the δ-resin increased to 32
and 40.6%, respectively. The δ-resin content in the β-fraction of
hops was 1.15%; after forced aging this increased to 8.3%. Upon
forced aging of the β-fraction, the δ-resin slightly increased, as
opposed to the α-acids, where large amounts of δ-resin were
produced. The δ-resin content in the hard resin of hops was
22.3%; upon accelerated aging it increased to 23%, thus
suggesting that δ-resin found in the hard resins is relatively
stable. Moreover, no further oxidation products were gene-
rated from the δ-resin. Finally, in picking trials of 1962, Bausch
et al. monitored the δ-resin content and composition of hops
during a 6 week period. Some substances were no longer
found in the δ-resin of all samples harvested a month or more
after the first sample was harvested. It was also observed that
the δ-resin content of the hop cones significantly decreased
during drying (74).
Hulupones. A new group of bitter substances was identified by
Spetsig et al. in the late 1950s. It was observed that the β-acids
are readily oxidized to the strong bitter-tasting hulupones. It
was also established that, for the conversion of β-acids to
hulupones to take place, an oxidizing agent was required (75).
When these substances were examined by reversed-phase
chromatography, three peaks that elute before the α-acids were
detected (75–77). Like the humulones and lupulones, the
hulupones also consist of a series of analogues. The names
cohulupone, hulupone and adhulupone were assigned to the
individual compounds; the prefixes have the same significance
as in the humulone and lupulone series. Hulupone concentra-
tions have been reported to be between 0.5 and 3.0% of the
weight of the dried cones. In contrast to the hard resins, no
hulupones were detected in fresh hops (76,78). When the course
of the hulupones was monitored during the brewing process, it
was found that the bulk of the hulupones is usually retained in
the spent hops that remain after wort boiling. However a con-
siderable fraction is transferred to the wort in its unchanged
form, that is, the hulupones in wort exist in the form of salts
(75,76,78). At least in the 1960s, it appeared that the hulupones
commonly contributed to a little over 5% of the bittering princi-
ples in beer (78). Owing to the complex nature of the substances,
these three compounds are challenging to classify. As men-
tioned previously, it is generally accepted that the hard resins
arise by oxidation of the soft resins. Although hulupones are
autoxidation products of the β-acids, when present in hops,
these are soluble in all organic acids, and therefore components
of the soft resin (78).
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Humulus lupulus – a story that begs to be told
Hulupinic acid. Hulupones are degradation products of the β-acids,
yet these can only be considered to be an intermediate oxida-
tion state. Further oxidation of the hulupones will result in the
non-bitter hulupinic acid (see Fig. 7) (79,80). In 1964, Burton
and Stevens isolated a crystalline product from the α-hard
resin and suggested the name hulupinic acid for this com-
pound (58,79). When a solution of cohulupone in ethanol
was heated under reflux while a stream of oxygen was passed
through it, it was possible to isolate hulupinic acid after
3 days. Surprisingly, autoxidation of hulupone and cohulupone
in an ethanolic solution gave the same hulupinic acid (79);
exactly the same transformation product was obtained from
adhulupone by similar treatment (81). From the evidence
gathered, it was possible to state that the acyl side chain (i.e. R
group) must have been removed and possibly replaced by a
hydroxyl group during the oxidation process (14,79). It was also
determined that the amount of hulupinic acid increased with
the age of the hops. Nevertheless, at the time, the highest de-
tected hulupinic acid concentration in aged hops was <0.05%
(58,79). The solubility of the hulupinic acid was tested in water
and it was established to be approximately 1 g/L at pH 4.0 and
it increased to 2 g/L at pH 5.0 (58). Based on this information, it
is expected to find low amounts of hulupinic acid in the finished
beers. Although hulupinic acid is the ultimate oxidation product
of the β-acids and moreover this compound was isolated from
the α-hard resin, owing to its solubility in water, hulupinic acid
is classified as a component of the δ-resin (58).
ε-Hard resin. Previous to a recent study (73), no data have been
reported in the literature regarding the ε-resin of the total hard
resin. In this study, a portion of the hard resin which was not sol-
uble in water yet had a bitter character was found. This portion
of the hard resin was termed the ε-resin (73,82,83). It was found
that the ε-resin accounts for up to 80% of the total hard resin
composition; however, like most hop constituents, this is variety
dependent (83). Like the total δ-resin, the ε-resin is not homoge-
nous. When further fractionation of the ε-resin was done, 11
crude fractions were recovered. In the current study, a method
was developed for the large-scale production of the ε-extract
(84). Upon characterization of the ε-resin enriched extract, com-
pounds that are usually found in the commercially available
xanthohumol extracts were also identified in the produced
extract. Highly polar compounds were not detected in the
ε-extract; moreover, the xanthohumol and isoxanthohumol
content in the ε-extract was found to be significantly lower. It
Figure 7. Chemical structure of hulupones and hulupinic acid. Oxidation of hulupones yields hulupinic acid.
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Institute of Brewing & Distilling
was also established that the ε-resin composition is variety
dependant, that is, some compounds are only found in certain
hop varieties (85).
The bitter intensities of the δ-resin, ε-resin and total hard resin
were tested and compared. To do this, each hop resin was
separately suspended at its natural concentration ratio in 5%
aqueous ethanol. Subsequently, to simulate a beer-like matrix,
the pH of all solutions was adjusted to 4.4 with trace amounts of
aqueous formic acid (1% in water). The trained panellists were
asked to rate the bitter intensity of all samples on a six-point
sensory scale ranging from not detectable (0) to extreme (5). The
ε-resin was considered by the panellists to be six times more
bitter than the δ-resin. The bitter intensity conferred by the
ε-resin was comparable to that delivered by the total hard resin
(data not shown). The results collected from the tasting sessions
revealed that, at least in a water matrix, the ε-resin can deliver a
perceivable bitterness (85). However, it must be borne in mind that
the sensory bitterness is relative to the matrix.
The 11 isolated fractions from the total ε-resin could be
distinguished based on their physical properties and their solu-
bility. Unlike the isolated δ-resin fractions, all ε fractions were col-
lected as powdery material. From the crude ε-resin, two major
fractions were recovered: ε 10 (31.3%) and ε 11 (22.9%). In this
study, the bittering potential and the antimicrobial properties
of the 11 ε fractions were assessed. From the collected data it
was possible to classify the fractions based on their activity.
The highly polar fractions ε 1 and ε 2 showed no activity. Gener-
ally, there was a good relationship among the bittering potential
and the inhibitory activity of the ε fractions. As the fractions be-
came more non-polar, the bitter intensity as well as the antimi-
crobial activity of the ε fractions increased (82).
Almost 100 fractions were recovered by additional purification
and fractionation of the ε-resin. In addition, it was possible to iso-
late over 20 pure compounds from the ε-resin (73,83). As before,
sensory evaluations and microbiology tests were conducted
with these fractions. From the collected data it was possible to
classify the subfractions and pure compounds based on their
bittering intensity as well as their inhibitory effect. The bitter
intensity scale ranged from high bitterness to low bitterness. In
a similar manner the antimicrobial activity scale was broken
down into three levels, ranging from high inhibition to no
inhibition. Multidimensional scaling was used to determine the
similarities among the subfractions, as a result, eight clusters
were generated (data not shown) (73). Ultimately, through the
screening and selection of the hop fractions, it is possible to
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tailor brews to comply with the consumer’s requests without
compromising the microbial stability of the beer.
Hop essential oils
Like the hop resins, the essential oils are secondary metabolites
of the hop plant secreted in the lupulin glands. By definition, the
hop oil fraction is the portion of the hop material that is volatile.
These volatile aroma compounds are considered ‘essential’ since
they give hops their characteristic smell. While the hop resins
give beer its bitterness, the essential oils give beer aroma and
flavour. Dried hops contain 0.5–3.0% of essential oil (29,86,87);
it has been reported that this relatively small volatile fraction is a
complex mixture of over 200 components. While only 200 com-
pounds had been conclusively identified in the late 1990s, capillary
gas chromatography analysis revealed up to 400 peaks in a chro-
matogram recorded at high detector sensitivity (51). By the begin-
ning of the century, the total number of identified and chemically
characterized compounds found in hops was 440. In a more recent
study, comprehensive multidimensional gas chromatography
(GC × GC) with flame ionization detection was applied; from
the collected data, it was suggested that there may be over
1000 different compounds in the hop oil fraction (88).
Almost 200 years ago, it was independently recognized by
Loiseleur-Deslongchamps (89) and Hanin (90) that hop cones
are very aromatic. Loiseleur-Deslongchamps described the hop
aroma to be garlic-like. A few years later, the first attempts to
characterize the hop oil were made by Payen and Chevallier.
The volatile oils were first distilled from the hop cones and the
distillate was further separated into two fractions (91). However,
the first systematic examination of the essential oil of hops was
done by Chapman from 1895 to 1929 (92–98). It is now known
that the content and composition of the total essential oil of
hops are affected by numerous factors such as hop variety,
growth conditions, time of picking (ripeness), drying conditions,
aerial oxidation, age and storage conditions (99). There is evi-
dence to suggest that the yield may also be slightly influenced
by seasonal effects (91).
As of 1980, the chemical composition of the hop essential oils
has been conventionally described under three main chemical
groups, the hydrocarbons, the oxygenated compounds and the
sulfur-containing components (100). It has been established that
the hop essential oil profile depends on the hop variety. In par-
ticular, the amounts of hydrocarbons and oxygenated com-
pounds vary according to the hop variety and age (101). In the
late 1950s, Howard and Slater (99) recognized that, independent
of the country in which the hops were grown, there was a vari-
etal uniformity in the general pattern observed in the composi-
tion of the hydrocarbon fraction. A decade later, Likens and
Nickerson (101,102) and Buttery and Ling (103) confirmed that
the essential oil of several hop varieties displayed good varietal
uniformity in their chemical composition. Likens and Nickerson
established that certain components or ratios of components
in the hop oil are highly specific for the individual varieties.
In 1990, Kenny (104) published a key for the varietal char-
acterization of hops based on six ratios calculated from the
amounts of 10 essential oil components. Other varietal iden-
tification models, based on the hop oil analysis and composi-
tion, were proposed by Kralj et al. (105), Kovačevič and Kač
(106,107) and Perpète et al. (108). From their collected data
they were also able to propose hop cultivar markers. It was
only recently that differences in the essential oil composition
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within the individual varieties were observed. In some varieties,
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
higher amounts or not present at all. Additionally, year to year
variations in the hop oil composition may be observed within
the same variety (105,106,109). Van Opstaele et al. studied the
impact of the varietal character of the fractions associated with
the floral note (2) and the spicy (or herbal) note (3). Independent
of the variety the hop oil fractions were extracted from these
fractions deliver similar flavour characters to beer: floral or spicy.
The chemical composition of these hop oil fractions is, however,
variety dependent.
Hydrocarbons
In Fig. 8, a general overview of some of the known hop oil com-
pounds is shown. The contribution of most of these compounds
continues to be controversial. The bulk of the hop oil is made up
of hydrocarbons and oxygenated components. The hydrocar-
bons can be classified into three groups: aliphatic hydrocarbons,
monoterpenes and sesquiterpenes (100). The hydrocarbon
group is very volatile (i.e. lower boiling fraction) and will readily
oxidize and polymerize (92). The solubility of hydrocarbons in
water, wort and beer is very low; additionally, most of these
compounds are lost by evaporation during the boiling process;
as a result only trace amounts are found in beer (110,111).
β-Myrcene
Of the hydrocarbon fraction, the most important and abun-
dant monoterpene is β-myrcene (Fig. 9A); it may account for
30–60% of the total oil content (99,111–113). In 1895, β-myrcene
was first obtained from bay oil by Power and Kleber. In 1903,
Chapman recognized that the properties of one of the isolated
hop oil compounds were the same as those of the acyclic terpene
β-myrcene. By directly comparing the properties of the unknown
compound with those of β-myrcene extracted from oil of bay, it
was possible to conclude that β-myrcene is also found in the
hop oil fraction (95). β-Myrcene is the main component res-
ponsible for imparting the pungent smell to fresh hops (51).
Other monoterpenes present in the hop oil fraction in sig-
nificantly lower amounts are ocimene, β-pinene, limonene and
ρ-cymene, among others (10).
Sesquiterpenes
In the hydrocarbon fraction, the major components of the
sesquiterpene group are α-humulene, β-caryophyllene and
β-farnesene. These sesquiterpenes have higher boiling points
than the monoterpenes. This high-boiling group is domi-
nated by α-humulene and β-caryophyllene (114). β-Myrcene
plus these two hydrocarbons make 80–90% of the total
essential oil in hops (95). α-Humulene, the most abundant
sesquiterpene found in hops, was one of the first compounds
to be identified in hop oil; the structure of the compound is
shown in Fig. 9(B) (92). The second most important sesquiterpene
found in hops is β-caryophyllene (see Fig. 9C) (92). Although it
was suspected as early as 1895 that β-caryophyllene could be
present in the essential oil fraction of hops, it was not until
1949 when this component was conclusively identified in hop
oil by Šorm et al. (115). When a typical hop oil chromatogram is
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297

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

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Figure 9. Structures of some terpenes present in hop essential oil. (A) β-Myrcene,
the most abundant monoterpene present in fresh hop oil. The most important
sesquiterpenes are α-humulene (B) and β-caryophyllene (C). In (D) is shown
β-farnesene; this compound is only found in some hop varieties.
examined, it can be observed that much of the material is
accounted for in three elution bands. The substance responsible
for the first peak is β-myrcene; β-caryophyllene elutes much later
and shortly after, the peak for α-humulene appears (86). In Fig. 9D,
the chemical structure of β-farnesene, an acyclic sesquiterpene, is
shown. This compound was first isolated by Šorm et al. from
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).
Howard and Slater investigated hop oil production during the
ripening period. To do this, samples were picked at defined
intervals during the ripening of hops and the essential oil
fraction was examined (118). The essential oil fraction was
isolated from these hop samples by steam distillation and
analysed by gas chromatography. A portion of the hop oil
extract was divided into two fractions by adsorption chromatog-
raphy and then analysed separately by gas chromatography.
From their results it was concluded that the total oil content
rises steadily during ripening (99). It was observed that, for most
varieties, the oil develops at a later stage than the resins (118).
Stevens et al. (119) isolated the essential oils using steam distilla-
tion and analysed them by gas chromatography. They were the
first to report that the essential oils continue to be synthesized
until harvest. They also observed that the production of the es-
sential oil components present in ripe hops does not start before
resin development is completed (119). Since many hops were
picked when resin development was complete but before oil
production had ceased (120), the hop quality in earlier times
cannot be compared with the current one. From the picking
trials, it was seen that the proportion of β-myrcene rose rapidly
throughout the ripening period. The β-myrcene content
increased from an almost negligible figure to 36%. The propor-
tions of β-farnesene and β-caryophyllene remained compara-
tively constant. Unexpectedly, the α-humulene content of hops
fell significantly from 79 to 42% (118). From the collected data
it could also be concluded that the β-myrcene content is directly
proportional to the proportion of cohumulone and colupulone
found in the hop resins (99). In another study, Rigby and
Bethune isolated the hop essential oils by steam distillation
and separated them into different fractions by countercurrent
distribution. By means of the chromatostrip and chromaplate
technique (121) as well as gas chromatography (122), they
collected data to show that hops with high cohumulone had
high β-myrcene; conversely, hops with high humulone had a
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-
sions, there was enough evidence to suggest that there may be
a common intermediate in the biosynthesis of β-myrcene and
the α-acids and β-acids (99).
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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
from negligible amounts to almost 50% of the total oil content.
The β-caryophyllene and α-humulene concentrations of all late-
stage harvested samples decreased by more than half of the early
stage content. Recently, the effect of the time of harvest and loca-
tion on the hop essential oil composition of two American aroma
hop varieties were compared (125). Contrary to previous studies
where the increase in the total oil content was primarily attributed
to β-myrcene synthesis, Sharp and Shellhammer were able to de-
termine other hop compounds responsible for the increase in the
oil quantity. This increase was strongly correlated with α-pinene, β-
pinene, limonene, methyl heptanoate and linalool.
Oxygenated compounds
The hydrocarbon fraction of hop oil is quantitatively eluted from
silica gel by light petroleum; a second fraction containing the
oxygenated compounds will elute once ether is applied. Al-
though the oxygenated fraction is found in substantially lower
amounts [ca. 30% of the total essential oil (126)], the composi-
tion of this fraction is more complex than the hydrocarbon one
(86). In the oxygenated fraction a large number of components
are found; however, most of these are present below their odour
threshold concentrations. Normally, the oxygenated compounds
of the hop oil comprise two major portions that are termed the
‘volatile’ and ‘non-volatile’ portions. The former consists of a
complex mixture of compounds with boiling points lower than
that of α-humulene. Since the boiling point of the non-volatile
fraction is higher than that of α-humulene in early hop oil exam-
ination, this portion was more challenging to analyse (99). How-
ever, these higher boiling substances are of interest to the
brewer since these will most likely be retained in the wort after
boiling and they may eventually find their way into the finished
beer (117). The total oxygenated fraction is a complex mixture of
alcohols, aldehydes, acids, ketones, epoxides and esters. In 1981,
Sharpe and Laws reported 60 aldehydes or ketones, 70 esters, 50
alcohols, 25 acids and 30 oxygen heterocyclic compounds in
hop oil (100); since then, the list has significantly increased.
It was observed by Howard and Slater that, as hops aged, the
oil became richer in oxygenated components at the expense of
the hydrocarbons. In addition, oxidation resulted in non-volatile
oxygenated compounds at the expense of the hydrocarbons,
and as a result the proportion of β-myrcene decreased. Finally,
non-volatile oxygenated compounds were produced with a
concomitant loss of some of the volatile ones (99). The effects
of autoxidation of β-myrcene were studied in detail by
Dieckmann and Palamand (127). It was reported that autoxida-
tion proceeds in four reaction classes: cyclization, oxidation,
disproportionation and polymerization. Over 40 compounds
were found to be produced from the autoxidation of β-myrcene.
Linalool
The alcohols of the essential oil fraction can be classified into
three groups: terpene alcohols, sesquiterpene alcohols and
aliphatic/aromatic alcohols (100). The major constituents of the
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Humulus lupulus – a story that begs to be told
alcohol fraction are 2-methylbutanol and linalool with lower
amounts of geraniol, nerolidol, nerol and terpineol (10). The most
abundant terpene alcohol is linalool, and like many essential oil
components, it was first identified in 1903 by Chapman (95). Linal-
ool is considered an important hop aroma indicator substance in
beer (111). The contribution of linalool to the hop aroma profile
is dependent on the hop treatment. It is unlikely that linalool will
make a contribution to the aroma profile of the beer if the wort
is traditionally hopped (i.e. beginning of the boil). The contribution
of linalool to hop aroma in beer is more perceivable when a late
hop addition is done. Only minor linalool contributions are
detected in dry hopped beers (128). Linalool is a hydration product
of β-myrcene (128); it is also a chiral compound; therefore there are
two stereoisomers: (R)-( )-linalool and (S)-(+)-linalool (see Fig. 10A
and B). Both enatiomeric forms are found in the hop essential oil
fraction. It has been shown that (R)-linalool is more flavour-active
and, of the total linalool content, the (R)-form is usually present
in hops between 92 and 94% (129).
Linalool is usually considered to be responsible for the floral
character in beer. The odour threshold concentration of
linalool in water was first reported by Guadagni et al. to be
6 ppb (i.e. 6 μg/L) (130); however in beer this value increases
to 10 ppb (111). Sensory threshold values are highly depen-
dent on the olfactory properties and the structures of the
molecules, but also on the matrix in which they are tested
(131). The composition of the beer matrix (i.e. lower pH and
sugar profile) plays a key role in the determination of thresh-
olds as it exerts an effect on the presence or absence of
sensation of the hop compounds (132). In addition to the testing
matrix, other odour-active substances can also interact and cause
strong changes in the odour thresholds of these compounds
(131). The data found in the available literature for the flavour
threshold values of linalool in beer vary significantly. In 1975,
Meilgaard reported a flavour threshold in beer of 80 ppb and de-
scribed it as having an aniseed and terpenoid flavour (133). A few
years later, Peacock and Deinzer reported a flavour threshold
value of 27 ppb and characterized it as floral and citrusy
(134,135). More recently a value of 8 ppb was reported by Kaltner
et al. (136). Independent of the threshold, linalool is one of the
few hop oil components that is universally accepted as being
flavour-active in beer (128).
Other oxygenated compounds
Jahnsen (114) suggested that a whole series of aldehydes
occurs in hop essential oils. It was shown that aldehydes such
Figure 10. Structures of some oxygenated compounds found in hop essential oils.
(A) (R)-linalool, the active stereoisomer of linalool. In (B) the mirror image of (R)-linalool
is shown, the (S)-form is less odour-active and is also present in lower amounts.
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling
Institute of Brewing & Distilling
as 1-hexanal and (Z)-3-hexenal are responsible for delivering
the green and grassy notes to beer (137). Among the acids,
it has been reported that only a few free acids are present
in hop oil (100). The fatty acids of hop such as 2-methylbutyric
acid are linked with a cheesy aroma (138). The first ketone to
be characterized by Šorm et al. in 1947 was undecan-2-one
(116). It was first identified in 1928 by Chapman and termed
luparone (97); this term is no longer used. This compound,
also known as methyl nonyl ketone, was found in the late
1950s to be the most abundant oxygenated component in
most hop oils (122). It has been reported that this hop oil
component gives a floral flavour to beer (139). Many other ke-
tones were later reported to be present in hops by Jahnsen
(126) and Guadagni (130), among others.
The oxygenated hop sesquiterpenoids, in particular humulene
epoxide II, have been associated with the spicy or herbal hop
character (140). Efforts have been made to unravel the nature
of this spicy note. However, owing to the very complex chemical
composition of the spicy hop character and the lack of reference
compounds to verify the analytical data, many of the com-
pounds responsible for this hop character remain unknown.
Eyres et al. (141) and Nielsen (142) were able to tentatively iden-
tify 14-hydroxy-β-caryophyllene and caryophylla-3,8-(13)-dien-5-
β-ol, respectively, as highly odour-active compounds responsible
for the spicy character of hops. More recently, Van Opstaele et al.
(3) were able to associate another 22 oxygenated sesquiter-
penes to the spicy fraction of hops. Among these 22
constituents, eight compounds were tentatively identified as
α-humulene or β-caryophyllene oxidation products. The pre-
cise identity of 10 of these compounds remains unknown. Of
the 12 tentatively identified oxygenated hop sesquiterpenoids,
humulene epoxide II appeared to be the most predominant
constituent, followed by ( )-caryophyllene oxide. Other tenta-
tively identified compounds associated with the spicy or
herbal character of hops are humuladienone, caryolan-1-ol,
globulol, viridiflorol, 10-epi-α-cadinol and τ-cadinol (3). Goiris
et al. (143) determined the flavour threshold of the enriched
sesquiterpenoid hop oil fraction in beer to be 5 ppb; however,
an addition of 20 ppb was usually preferred by the panellists.
The total ester fraction represents a complex mixture having a
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
reported by Wright and Connery (144) and others that esters
of hop oil are the constituents more closely associated with
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-
pounds have very low sensory thresholds; values can be as low
as 0.1 ppb (148). In general, these components impart undesir-
able sulfury, cooked vegetable, musty, cabbage-like and onion-
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like flavours to beer (100,148). The methyl thioesters impart un-
pleasant cheesy, cooked vegetable and sulfury aromas. In
addition to these aromas, the methylthiomethyl thioesters also
impart onion-like and garlic-like odours. The rubbery and
garlic-like off-flavours in beer are imparted by 2,3,5-trithiahexane
and 3,3-dimethylallyl methyl sulfide, respectively (148). Many
studies have shown that a broad range of odours can be
produced by the sulfur compounds; however, most of them
are considered to be undesirable off-flavours. The thioester
responsible for the truffle aroma is S-methyl-2-methyl
thiobutanoate (149). Green and fruity notes are associated with
S-methyl thiohexanoate; this substance has also been reported
to produce a pineapple odour (150). Another aroma delivered
by the organosulfur compounds is that of roasted meat; this
note is imparted by 2-methyl-3-furanethiol (147). Another inter-
esting sulfur containing class is S-methylthiomethyl thioesters,
which represents a new class that has not been isolated from
any other natural source (151). Recently, an S-cysteine conjugate,
S-3(1-hydroxyhexyl) cysteine, was identified for the first time in
Cascade hops. The exact aroma character of this compound
has not been conclusively defined (152).
4-Mercapto-4-methylpentan-2-one
Of particular interest to the brewer and brewing chemist has
been the intense muscat-like (i.e. grape) character found in
some beers. These muscat-like characteristics were attributed
to 4-mercapto-4-methylpentan-2-one (4MMP). This compound
can only be found in specific hop varieties and has been
shown to have an extremely low threshold value in beer
1.5 ppt (i.e. 1.5 ng/L) (137). It has also been documented that
4MMP produces aromas reminiscent of blackcurrant and cat
urine (109,153). The growing location and conditions have
the most noticeable effect on the levels of thioesters and
sulfur compounds (151). Interestingly, 4MMP was detected in
hop cultivars grown in the USA, Australia and New Zealand.
This compound was, however, not found to be present in
the same cultivar grown in Europe (109).
Hop polyphenols
Polyphenols are another secondary metabolite of the hop plant;
hop polyphenols comprise up to 4% of the total weight of dried
hop cones. Similar to most hop constituents, the level of
polyphenols is variety dependant. These are to be found mostly
Figure 11. Constituents of the hop polyphenol fraction (159).
300
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C. Almaguer et al.
in the hop cone petals and strig and, with the exception of the
prenylflavonoids (e.g. xanthohumol), not in the lupulin glands
(8). The polyphenol fraction represents a vast class of com-
pounds with widely varying structural characteristics (154).
Chemically, these are substances that are built up by multiple
phenol units. Although they are a very heterogeneous group
of substances, the polyphenols share a common structural ele-
ment: an aromatic ring with at least two hydroxyl groups (155).
The composition of the polyphenols depends on the hop
variety, cultivation area, harvesting technique and degree of
aging (154). It has been reported that aged hops contain higher
levels of polyphenols than fresh ones (156). It has also been
shown that certain polyphenolic substances are unique to a
specific hop variety (157).
Analysing hop samples by high-performance liquid
chromatography–diode array detection, Forster et al. found over
100 compounds in the polyphenol fraction of hops (158). Hop
polyphenols can be classified into flavonols (e.g. quercetin),
flavan-3-ols (i.e. flavanols or flavanoids, e.g. catechin), phenolic
carboxylic acids (e.g. ferulic acid), and other polyphenolic
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
such are classified as flavonoids (Fig. 12A), a subgroup of
polyphenols (155). Some polyphenols are unique to hops; that
is, they have not yet been found in any other natural source.
Some of these polyphenolic substances hitherto found only in
hops are multifidol glucosides and prenylflavonoids such as
xanthohumol, desmethylxanthohumol, 6-prenylnaringenin and
8-prenylnaringenin (159,160).
In general, aroma hops contain a higher amount of low
molecular weight polyphenols than bittering hops (161). The
reason for this is that an increase in α-acid content can only be
obtained at the expense of the polyphenol content (162). Most
polyphenols in wort are derived from malt; however, about
20–30% of the polyphenols found in the wort come from
the hop material (139). The importance of the hop polyphenols
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
shelf-life of bottled beers (10). Since hop polyphenols can be very
easily oxidized, they act as strong antioxidants (155). They do this
by reacting as free radicals scavengers, by inhibiting lipoxy-
genases, or by acting as metal chelators (163). Low-molecular-
weight polyphenols are natural antioxidants and account to a
great extent for the reducing power of wort, thereby protecting
J. Inst. Brew. 2014; 120: 289–314
Humulus lupulus – a story that begs to be told
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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
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).
beer against oxidation and improving the taste stability. Higher-
molecular-weight polyphenols contribute to the colour of beer
and to haze formation (154).
Flavonoids
Flavonols
Approximately 20% of the total hop polyphenols consist of
low-molecular-weight substances or monomer substances
such as the phenolic carboxylic acids as well as the flavonoids
and their glycosides (Table 2). Hop flavonoids consist mainly
of catechins and their polymers, proanthocyanidins, quercetin
(Fig. 13A) and kaempferol (Fig. 13B) (164). The two protonated
aglycones, quercetin and kaempferol, do not occur in free forms
in hops but only in glycosidically bound forms (i.e. bound to
sugars) (155,165). The more hydrophilic protonated quercetin
glycosides elute earlier than protonated kaempferol glycosides
when the glycosidic residues are the same. The glycosides of
quercetin elute earlier because of the extra hydroxyl group on
the flavonoid unit (165). Of the known flavonols, quercetin has
the highest antioxidative potential (164). Later eluting glycosides,
such as kaempferol, are more prominent in aroma hops (165).
Hitherto, the most suitable polyphenols for cultivar
the other phenolic components are less cultivar specific (155).
Flavan-3-ols
The polyphenol solubility in wort and beer is not the same for all
compounds. As expected, the hydrophilic groups of substances
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
(161). A portion of the hop polyphenolic material is composed of
water soluble substances such as catechin and epicatechin
flavan-3-ols (Fig. 14A and B, respectively). These are the mono-
meric building blocks of dimers, trimers and higher polymeric
structures sometimes having as many as 20 or more basic units.
These polymers, known as proanthocyanidins or condensed
tannins, may also contain gallocatechin and epigallocatechin
as extension units (166). Chemically, molecules that consist of
up to eight monomer units (oligomers) are referred to as
proanthocyanidins. Tannins (polymers), however, consist of a
higher number of monomers (111). Proanthocyanidins (see
Fig. 14C) are flavan-3-ol oligomers and polymers that give
anthocyanidins upon acid depolymerization reactions (167).
These are the most reactive substances of the polyphenol frac-
tion (139). While the proanthocyanidins may contain catechin
and epicatechin as monomers or as terminal and extension
units, gallocatechin and epigallocatechin were only found to
be subunits but not terminal units of the polymers (166). Hop
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).

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 C. Almaguer et al.
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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

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Humulus lupulus – a story that begs to be told
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.
Except for very high oxygen-sensitive hop varieties, the lower
the α-acid content, the higher the resveratrol potential (177). It
is well known that the biologically active ingredient of red wine
is resveratrol. Recently, the cardioprotective effects of wine have
been attributed to this compound (180,181). Compared with
grapes, the concentration in hops is low; up to 2 mg/kg of
trans-resveratrol has been found in fresh hop cones (182).
trans-Resveratrol is much more hydrophobic than other hop
polyphenols (176), and thus difficult to transfer to the finished
beer. However its importance should not be disregarded since
trans-resveratrol has been linked to various health benefits. As
a phenolic compound, resveratrol contributes to the antioxidant
potential and thereby may play a role in the prevention of
human cardiovascular diseases. Resveratrol has also been shown
to modulate the metabolism of lipids, and to inhibit the
oxidation of low-density lipoproteins and the aggregation of
platelets. Moreover, as a phytoestrogen, resveratrol may provide
cardiovascular protection. This compound also possesses anti-
inflammatory and anticancer properties (181). A thorough
review of the health benefits of resveratrol was published in
2006 by Baur and Sinclair (183). The presence of trans-resveratrol
and cis-resveratrol as well as trans-piceid and cis-piceid was
confirmed in beer. Of 110 analysed commercial beers, trans-
resveratrol was found to be the most abundant stilbene in beer.
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
of the compounds (184).
Polyphenols in beer
Hop polyphenols can provide both bitterness and astringency,
depending on their degree of polymerization. It has been
reported by Peleg et al. (185) that, in a water matrix, as the
degree of polymerization increases, maximum bitterness inten-
sity is perceived and total duration decreases whereas astrin-
gency increases. Peleg et al. also noticed that the monomers
were significantly higher in bitterness than the dimers, which
were significantly higher than the trimers (185). In a recent study
(186), brewing trials were conducted using a polyphenol-rich
extract derived from CO2 spent hop material. It was shown that
the bitterness produced by the polyphenols interacts with the
bitterness delivered by the iso-α-acids. For a beer with low levels
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling
Institute of Brewing & Distilling
of polyphenols, the quality and temporal intensity of bitterness
was similar, but not identical, to that from iso-α-acids. As the
levels of polyphenols were increased, the produced bitterness
was harsher and more astringent. At the highest tested levels
the bitterness was considered to be harsh, medicinal or metallic.
In this study it was found that beers with 200 mg/L of polyphe-
nols were rated as more bitter than beers with 10 mg/L iso-α-
acids (186). Another beer quality aspect that should not be
disregarded is mouthfeel. In 1995 Forster et al. (158) recognized
that hop polyphenols have a positive impact on the fullness of
beer. Before 2007 no conclusive study had been conducted
regarding the influence of hop polyphenols on the mouthfeel
of beer. In 2007, Aerts et al. (5) filed an application for a US
Patent (0254063 A1). Their data not only confirmed that hop
polyphenols positively enhance the mouthfeel of beer but also
that the impact on mouthfeel is subject to varietal differences
(5). Recently Goiris et al. (6) summarized these findings and
focused on the contribution of the different hop polyphenol
classes to the fullness of beer. Their results showed that the
prenylated flavonoid-rich extract as well as the flavonol
glycoside-rich extract positively enhance the mouthfeel of beer.
The addition of a proanthocyanidin rich extract to beer had no
perceivable impact on the mouthfeel but caused unwanted as-
tringency. Of the three hop polyphenol-rich extracts, beers with
added flavonol glycosides were preferred by the panellists (6).
Hop varieties
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
benefit from proper selection of particular hop varieties to add
subtle tastes and flavours to the beers. Recent proposals suggest
a more refined classification of hop varieties. On the basis of α-acid
content, the bittering hops are further subdivided into ‘bittering
hops’, ‘high alpha’ and ‘super high alpha’ varieties. Based on the
hop oil composition, aroma hops are classified as ‘fine aroma hops’
and ‘aroma hops’. At the time of harvest, the long-term average
α-acid content in the bittering varieties and aroma varieties is in
the range of 10–20 and 2–10%, respectively. Some of the most
important traded bittering hop varieties on the world market are
Hallertauer Magnum, Hallertauer Taurus, Herkules, Galena,
Nugget, Millennium and CTZ (Columbus, Tomahawk, Zeus). The
representative aroma hop varieties are Hallertauer Perle, Hallertauer
303
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 C. Almaguer et al.
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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).

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 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
Humulus lupulus – a story that begs to be told

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.
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had a severe effect on the beer market. During this period, beer
consumption worldwide was more than halved. Shortly after-
wards, American brewers were affected by the Prohibition Act
of 1919, which stayed in force until 1933. Beer production in
the USA reached a low of 3.6 million hL in 1926. Finally, Europe
was again thrown into turmoil during the 1939–1945 war, and
beer consumption in Germany fell from 50 million hL in 1939
to 5.8 million hL in 1949 (192,193). Since 1948, world beer pro-
duction has experienced a steady increase.
The hop grower knows that every hop season is unique and
different from all the other ones, and that year-to-year fluctua-
tions are normal (194). The size of the world hop crops partly re-
flects the demand of brewers as well as the events surrounding
the hop harvest (detailed data in Table 3). A particular example is
the very large world crop in 1905, which resulted in enormous
surpluses and a corresponding decline in prices below actual
production costs. This, in turn, caused a reduction in acreage
and consequent recovery in prices during 1908–1910. Such cy-
cles were not new to the hop industry and have been experi-
enced many times (Fig. 20) (192). Another factor that forces
hop growers to adjust acreage is the introduction of production
quotas (194). Until 1930, acreage under cultivation was signifi-
cantly larger than total hop production volume. Except for the
1963 hop crop, as of 1948 a clear trend may be observed: smaller
areas under cultivation achieve a higher hop production yield.
This change may be attributed to the introduction of more pro-
ductive hop varieties with a higher α-acid content. In 2013, with
approximately 46,000 ha, the hop industry had the smallest acre-
age under cultivation since 1955. Although the area under culti-
vation continues to shrink, the varieties being grown are
delivering increasingly high yields in terms of both quantity
and alpha. In 2013, the total volume of hop production is esti-
mated to be 81,300 metric tons (t) with an estimated alpha yield
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).
This higher alpha yield per hectare requires an acreage reduc-
tion and possibly variety replacements in order to avoid a crop
surplus and ultimately a market imbalance.
The growing interest in bittering compounds and the analyti-
cal properties of hops on the part of the brewing industry
prompted Joh. Barth & Sohn in 1970 to attempt to list 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
306
that time.
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C. Almaguer et al.
respective hop producing areas according to alpha values. The
α-acid production represents the actual hop supply available to
the brewers (194). In the hop market, a key indicator is the aver-
age hopping rate, which unfortunately has undergone a steady
decline since it was first recorded. Since 1970 the hopping rate
has fallen by nearly 60% (Fig. 21). In the last four decades from
1970 to 2010, the average α-acid addition in beer has decreased
from 9.6 to 4.1 g α/hL (191). From 1970 to 1980, the hopping rate
dropped almost by 2 g α/hL, from 9.6 to 7.8 g α/hL. When
looking at the world market critically, it may be inferred that, ow-
ing to the alpha deficit before 1980 and the resulting increase in
hop prices, as well as the better utilization of the bittering sub-
stances, a reduction of the alpha rate became possible world-
wide (197). Moreover, today China, not the USA, is the world’s
biggest beer producer. Unfortunately beer in these new beer-
producing countries is less heavily hopped. The reduction of
beer bitterness around the world is the result of changing tastes
in today’s consumer society. These new trends partly explain the
decline in the hopping rate (194). In addition to lowering the bit-
terness levels in mainstream beers, the hopping rate has de-
creased owing to the use of hops with higher α-acid levels and
the increased use of more sophisticated hop products that
achieve higher utilization levels (193). Another factor is the mod-
ernization of the brewing industry worldwide (198). The decline
in the hopping rate from 1980 to 1990 was not as drastic as that
in the decade before or in the two following decades. In 1990
the hopping rate was 6.9 g α/hL, almost 1 g α/hL less than in
1980. By 2000, the hop addition was 5.6 g α/hL and by 2010 it
was 4.1 g α/hL. The reduction was 1.3 and 1.5 g α/hL, respec-
tively. In 2012, the hopping rate increased to 4.3 g α/hL and it
is expected to continue to increase. This recent increase in the
hopping rate is primarily attributed to the growing craft brewing
sector.
Hop contributions to beer
In 1891, Moritz and Morris (199) gave five reasons for adding
hops to beer: (a) to impart the distinctive bitter taste and aroma
(i.e. hoppy character); (b) to precipitate certain nitrogenous con-
stituents of the wort (i.e. break formation); (c) to act as a filter aid
in the hop back (i.e. clarify the wort); (d) to confer antibacterial
properties to beer; and (e) to assist in the sterilization of the
Figure 21. Average world hopping rate in g α/hL for the last 40 years (191).
J. Inst. Brew. 2014; 120: 289–314
Humulus lupulus – a story that begs to be told
wort. A century later, Hughes and Simpson (200) extended the
list by including two other benefits: (f) to enhance and stabilize
beer foam; and (g) to promote foam lacing. As mentioned
above, the brewing value of hops is primarily attributed to the
presence of resins, essential oils and polyphenols.
Bitterness
Many complex reactions occur during the boiling of wort with
hops in the brewery. In addition to the transformations involving
carbohydrates, proteins, polyphenols and various polymeric sub-
stances, the hop bitter principles are extracted, thereby under-
going intricate transformations and interactions with other
constituents (201). Bitterness is one of the most readily
discerned sensory attributes of beer as far as the consumer is
concerned (202). Over the years, the chemical changes in the
hop resins during wort boiling have been thoroughly studied
and therefore adequately profiled. These studies were crucial
since the chemistry of hop extraction during wort boiling deter-
mines to a great extent the flavour and the quality of the fin-
ished beer (201). By far the most important chemical
conversion occurring during wort boiling is the thermal isomer-
ization of the α-acids into the more soluble and bitter iso-α-acids.
The α-acids yield two iso-α-acids, as these occur as diastereo-
isomers in their cis and trans forms (35). For a given pair of cis-
and trans-isomers, the cis-component is significantly more bitter
than its trans-counterpart. It has also been established that the
isohumulones are more bitter than the isocohumulones (202).
Of the six major iso-α-acids present in beer, the most bitter
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
from the hop resins during wort boiling, mainly the iso-α-acids.
Over 85% of the perceived pleasant bitterness in beer is deliv-
ered by the iso-α-acids (204). However, other hop substances,
such as hop polyphenols and oxidation products of the β-acids
(i.e. hulupones) also contribute to beer bitterness.
Aroma
In addition to giving the pleasant bitter taste, hops impart a
characteristic ‘hoppy’ aroma to beer. The hop chemistry associ-
ated with the hoppy character of beer is very complex. However,
since the advent and utilization of gas chromatography, much
has been learned regarding the composition of the hop oil fraction
and its contribution to beer. It is known that, after the vigorous
boiling of hops in the kettle, very little hop oil constituents will
remain in the wort in their native form. Most of the essential oil
compounds are highly volatile and poorly soluble in wort; how-
ever, their presence in beer depends on the chemical properties
of the specific essential oil component and the hopping technol-
ogy used. After boiling for 90 min, 85–95% of the essential oil in
hops has evaporated from the kettle and the rest has polymerized
to form resinous substances. As a result, the hop oil components
are hardly retained in the wort in their native form. Further, during
the fermentation process there is a considerable loss or transfor-
mation of the hop oils retained in the wort (4,205). These hop oil
components disappear to a large extent by adsorption on yeast
and the filter mass (206,207). A detailed review of the biotransfor-
mations of hop-derived aroma compounds by yeast upon fermen-
tation was published in 2012 by Praet et al. (208). Some hop oil
constituents survive unchanged through to the finished beer. In
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling
Institute of Brewing & Distilling
1960 Harold et al. (209) were the first to demonstrate the
occurrence of hop oil in beer. After examining the volatile portion
Harold et al. were able to clearly show the presence in beer of
β-myrcene, methyl nonyl ketone and α-humulene, as well as a
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-
pounds is necessary for the characteristic hop aroma. In 1963
Guadagni et al. suggested that this contribution is due to the
additive or synergistic effects of many components (i.e. hop oil
compounds and volatile fermentation products) (210). In 1966
Hashimoto (211) and Buttery and Ling (212) suggested that the
volatile hop components with sufficient solubility in water to
be retained in boiling wort may cause the hoppy aroma in beer.
They further established that the hoppy aroma is not derived
directly from the hop oil itself, but from certain volatile water
soluble compounds that are produced partly from the hop
resins, as decomposition products (207). It was later shown that
terpene and sesquiterpene hydrocarbons, the major compo-
nents of hop oil, are rarely found in beer. Therefore, these are
not considered to be responsible for hoppy flavours in kettle-
hopped beer. On the other hand, the oxidation products of
these hydrocarbons are commonly found in beer and have
been suggested to contribute to the hoppy character
(134,138,213,214). The aromas derived from the hop essential
oils are usually described in terms of fruity, floral, citrus, grassy
and spicy (or herbal) notes. To the brewer, these differences in
the hoppy character are important since they help profile the
many existing beer styles.
Microbial stability
Hop bitter acids exhibit an inhibitory effect on bacteria; thus
they play a major role in enhancing the preservative properties
of beer. It was shown as early as 1888 that hops contribute to
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
extensively investigated. In 1937, Shimwell discovered that the
antibiotic properties and bacteriostatic power of hops are
restricted to Gram-positive bacteria, while the Gram-negative
species were mostly unaffected by the hop acids (215). It was
later found that hop acids are also mildly antifungal (on selected
fungi species) (216) and antiprotozoal (217). Among the Gram-
positive bacteria some species of lactic acid bacteria are less
sensitive (i.e. more resistant) to hop compounds and are able
to grow in beer. Shimwell reported that the antiseptic potency
of the hop acids increases at lower pH (215). Shimwell later
proposed that the antibacterial activity of the hop constituents
is associated with permeability changes of the bacterial cell wall
(218). Almost 35 years later, Teuber and Schmalreck (219)
showed that hop compounds and their derivatives cause leak-
age of the cell plasma membrane in the aerobic organism
Bacillus subtilis. This results in complete inhibition of the active
transport of sugars and amino acids. Subsequent inhibition of
the respiratory chain and of protein, RNA and DNA synthesis
occurs as a secondary event. However, this organism cannot
grow in beer and beer spoilage bacteria differ from B. subtilis
in the physiology of their cell membranes (220). Therefore this
cannot be considered the mechanism by which hop bitter acids
inhibit the growth of beer spoiling bacteria.
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Another major breakthrough in understanding the preserva-
tive value of the hop bitter acids occurred in the 1990s. In the
early 1990s, Simpson established one of the molecular mecha-
nisms by which beer spoilage bacteria are inhibited (221,222).
In an earlier study Simpson and Smith showed that the undisso-
ciated forms of hop compounds and hop-derived compounds
are mainly responsible for the antibacterial activity. The ionized
forms of such compounds have a negligible effect on lactic acid
bacteria (223). The practical implication of this finding is that
small variations in beer pH cause large changes in the antibacte-
rial activity of the hop bitter acids in beer (220). It had been
known for some time that the antibacterial activity of certain
hop compounds and their derivatives is influenced by the pH
of the test medium (218,224). However, the relationship was first
placed on a quantitative basis by Simpson and Smith (223). They
established the dependence of the inhibitory effect of hops on
the pH of the medium; low pH favours antibacterial activity
but high pH reduces it (220). The antibacterial activity of trans-
isohumulone is enhanced by the addition of monovalent cations
(e.g. K+, Na+, NH+4 , Rb+, Li+). However the presence of divalent
cations (e.g. Mg2+, Mn2+, Ni2+, Ca2+) reduces the antibacterial
activity of trans-isohumulone (223).
It was also observed by Simpson that trans-isohumulone
causes an increase in proton permeability, thus suggesting that
it acts as an ionophore of the mobile-carrier type (221). Iono-
phores are antimicrobial agents that increase the permeability
of cell membranes to specific ions. Hop compounds as iono-
phores inhibit the growth of Gram-positive bacteria by
catalysing the exchange of protons (i.e. H+) for cellular divalent
cations, such as Mn2+, in an electroneutral process. Changes in
the intracellular pH are induced by ionophores (225). This reduc-
tion in intracellular pH leads to inhibition of nutrient transport
and starvation of the affected organisms (220). In Lactobacillus
species, trans-isohumulone dissipates effectively the transmem-
brane pH gradient of non-growing cells and reduces their ability
to accumulate L-[U-14C]leucine; further it causes leakage of the
accumulated leucine. Conversely, the membrane potential is
only dissipated to a smaller extent (221). Some components of
the cell plasma membrane may be responsible for conferring
hop resistance on beer spoiling lactic acid bacteria. Such compo-
nents could act to restrict the ability of trans-isohumulone to
conduct protons or divalent cations across the plasma membranes
of the bacteria or could increase the rate at which protons are
expelled from the cell interior (222). A clear complication in hop
inhibition research is the complexity of the chemical composition
of hops. This is due not only to compound variation on account of
consecutive chemical conversions but also to the variations of the
natural product (223). It has been shown that resistance to hop
bitter acids is a unique character associated only with beer
spoilage lactic acid bacteria. The expected cross resistance to other
proton ionophores could not be detected. The lack of cross resis-
tance to other antibacterial agents suggests that the mechanism
of resistance includes features that discriminate on the basis of
molecular structure rather than, or in addition to, physicochemical
properties. Cross resistance between different hop acids suggests
that the most important structural feature in this respect is the
β-triketone group (226).
Beer is a very unfavourable medium for the growth of most
Gram-positive microorganisms owing to the presence of alcohol,
hop compounds, high carbon dioxide level, relatively low pH,
extremely reduced oxygen content and the presence of only
trace amounts of nutrient substances such as glucose, maltose
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C. Almaguer et al.
and maltotriose (227). Therefore, in order for bacteria to survive
and grow in beer, several mechanisms are involved in their
resistance to the adverse conditions of the hostile environment.
Of particular importance is the resistance to hops as this is a
prerequisite for lactic acid bacteria to be able to grow in beer,
thereby causing beer spoilage. Ultimately, hop resistance of
lactic acid bacteria requires multiple defence mechanisms
(228). Following the studies of Simpson, several mechanisms
involved in the hop resistance of lactobacilli were proposed.
Sami et al. (229) were the first to identify horA as one of the
genes responsible for hop resistance. They used horA as a
genetic marker and developed a rapid and accurate polymerase
chain reaction method for the prediction of beer spoiling
lactobacilli (230). The putative protein product of horA, HorA, has
an ATP-binding (adenosine-5′-triphosphate) domain, a consensus
sequence for an ATP-binding cassette transporter reported to be
located in the cytoplasm, and six hydrophobic regions that are
large enough to span the plasma membrane. The HorA protein
acts as a multidrug resistance transporter that excretes the hop
compounds into the outer medium. Therefore, the bacteriostatic
effect of the iso-α-acids may be counteracted by the HorA protein,
which mediates cellular extrusion of iso-α-acids or other toxic
molecules that accumulate intracellularly in the presence of the
hop compounds. From the collected data, Sami et al. suggested
that a multidrug resistance pump contributes to the resistance
mechanisms to hop compounds of lactic acid bacteria (229).
The horA gene was shown by Sami et al. (229) to function as a
primary multidrug transporter; this implies that the gene is de-
pendent on ATP-binding. A few years later, Suzuki et al. (231)
found another defence mechanism that is not mediated by the
horA gene. Upon biochemical characterization of a hop resistant
Lactobacillus brevis strain two conclusions were drawn: first, that
the second hop resistance mechanism is mediated by proton
motive force (PMF)-dependent multidrug transporter and sec-
ond that this defence mechanism may be induced upon lactic
acid bacteria. The genetic marker found to mediate the horA-
independent hop resistance mechanism is ORF5 (232). The
ORF5 identified encodes a protein with putative 11–12 transmem-
brane domains, a feature that is consistent with the previously
reported PMF-dependent multidrug transporters (233). Similar to
the horA properties, the presence or absence of ORF5 was highly
correlated with the beer spoilage ability of L. brevis strains (232).
Two other genetic markers that mediate hop resistance in lactic
acid bacteria were found. The first one is horB, which is a regulator
that modulates the transcription of genes that encode multidrug
transporters; the other is the horC gene, which encodes a
PMF-dependent multidrug transporter (234,235). From all the
collected data it was possible for Suzuki et al. to suggest that
the beer spoilage ability of lactic acid bacteria is acquired by
horizontal transfer of hop resistance genes (233).
Other putative hop resistance mechanisms include the contri-
bution of the hitA (hop-inducible cation transporter) gene, which
encodes for HitA, a divalent cation transporter. This gene has
been shown to be present in most beer spoiling lactobacilli
(236). It was also hypothesized that genes responsible for the
production of teichoic acid in the cell wall also contribute to
hop resistance in beer spoiling lactic acid bacteria strains (237).
The proton translocating, membrane-bound ATPase was
suggested to ameliorate the protonophoric actions of hop bitter
acids by pumping out the intracellular protons in an ATP-
dependent manner (238). The hop resistance of beer spoiling
lactic acid bacteria is a complex phenomenon yet to be fully
J. Inst. Brew. 2014; 120: 289–314
Humulus lupulus – a story that begs to be told
understood. The collected evidence indicates that cell walls and
cytoplasmic membranes play an important role in defending
beer spoiling lactic acid bacteria from the bactericidal effects
of the hop bitter acids (239).
In a more recent study, Haakensen et al. (240) confirmed that
lactic acid bacteria species that harbour the horA gene are more
likely to spoil beer than those that do not. The horA gene has
been conclusively shown to function as a multidrug transporter
(241). Therefore, the presence of the horA gene is a significant
predictor to assess the beer spoilage ability of lactobacilli
isolates. Throughout the years, three other putative beer
spoilage associated genes have been suggested; these are hitA,
horC and ORF5 (233,235,236,242,243). Recently, it was found that
hitA and horC are not predictive of an organism’s ability to grow
in beer. However the presence of hitA, horC or both in addition
to horA is indicative of the ability of a microorganism to grow
rapidly in beer. The horA and hitA genes code for primary- and
secondary-type multidrug transporters, respectively (244). The
primary-active, ATP-binding cassette multidrug transporters are
dependent on ATP-binding/hydrolysis, whereas secondary-
active multidrug transporters are coupled to the proton motive
force that exists across the cytoplasmic membrane (245). In
another study by Haakensen et al. (241) Pediococcus isolates
were screened for beer spoilage genes. Two genes, bsrA and bsrB
(beer spoilage related) were highly correlated with the beer
spoilage ability and hop resistance of Pediococcus isolates. These
bsrA and bsrB genes were not found in any Lactobacillus isolates,
regardless of whether they were able to grow in beer or not. This
makes them the first genetic markers capable of differentiating
between beer spoilage lactobacilli and pediococci (246). Like
horA, bsrA and bsrB are both primary-type ATP-binding cassette
multidrug resistance genes (241).
The mechanisms of hop resistance of beer spoiling Lactobacillus
brevis have also been studied on the proteomic level. The gathered
evidence suggests that the stress caused to the bacteria by hop
compounds is not only associated with proton motive force
depletion but it also implies that there is a limitation of divalent
cations. More specifically, hop compounds inhibit the bacteria’s
metabolism by reducing the intracellular manganese concen-
tration, thereby causing a conflictive regulation of the energy
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
hop resistance. This suggests that the resistance of lactobacilli
isolates towards hop compounds requires multiple interdepen-
dent resistance mechanisms (248,249).
Foam
Hop acids not only contribute to beer bitterness, but also play an
essential role in achieving beer foam formation and stability. The
role of hops for beer foam is to stabilize the foam complexes
(250). It is well recognized that foam is an important quality
factor in the beer production process. According to MEBAK
(Mitteleuropäischen Brautechnischen Analysenkommision) stan-
dards, a good foam stability for a ‘Vollbier’ (full beer; 11.0–15.9°P)
is a head retention time between 220 and 300 s (251). The foam
suppressor–enhancer properties of the hop acids have long been
known. In 1976, the first observations on the role of the iso-α-acids
of hops in the structure of beer foam were documented by Fly and
Chicoye (252). Following their studies, numerous researchers
J. Inst. Brew. 2014; 120: 289–314 Copyright © 2014 The Institute of Brewing & Distilling
Institute of Brewing & Distilling
(202,253–258) have looked into the effect of different hop com-
pounds on foam properties. It has been revealed that hydro-
phobicity is the key factor in determining the effectiveness
of a hop compound to stabilize beer foam. These hydrophobic
compounds have the tendency to leave the beer and concen-
trate in the foam, thereby increasing foam stability (259).
It has been known for a number of years that the bitter iso-α-
acids, derived from the α-acids of hops, are a major contributor
to the improvement in beer foam stability (255). It was further
observed by Diffor et al. that, of the iso-α-acid analogues,
isohumulone provides a more stable foam than isocohumulone
(253). This difference is attributed to the lower solubility of
isohumulone at beer pH, which results in its greater tendency
to associate with other foam-forming constituents in the beer.
This, however, does not mean that isocohumulone has a
negative effect on foam, but rather that isohumulone provides
a more stable foam (260). Other natural but minor hop com-
ponents such as isoadprehumulone, dihydroisohumulone,
tetrahydroisocohumulone and tetrahydroisohumulone have
been suggested to promote foam stability and lacing (255).
Cling
As beer is being consumed, the texture of the foam changes from
being liquid to almost solid; this solid or dry foam can adhere to
the glass surface. The ability of the foam to adhere to the glass wall
is known as foam ‘cling’ or ‘lacing’ (261). In 1964, Glenister and
Segel (262) raised the importance of the primary and secondary
cling. The primary cling is created once the initial foam head is
allowed to collapse. The secondary cling is the pattern that is
formed when the consumer, at intervals, removes the beer from
the glass. From their observations, they concluded that the differ-
ences between commercial beers as to their secondary cling are
frequently more striking than to those of primary cling. It is well
documented that hops contribute in a positive manner to foam
cling. While beer foam is enhanced by the presence of hop
substances, lacing will not occur unless hop compounds are pres-
ent (202,263). To date, there are no defined standards for cling
measurements. Further it may be supposed that the perception
of what constitutes good lacing is a subjective matter (259), yet
this foam quality aspect cannot be disregarded.
Summary
With a view to increasing the understanding of the nature of hops,
research has focused on the chemical composition of hops and
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
about hops and their function in brewing, new aspects continue to
be revealed. Extensive international research continues to be
actively conducted by respected scientists and institutions in
countries all around the world. In these new aspects of hop
research, while much has been achieved, much more remains to
be done to resolve outstanding issues. It must be borne in mind
that any progress at all in these new aspects is pioneering. Hop sci-
ence has provided brewers with one of the main ways of meeting
the abiding need to understand the nature of hops. While hop re-
search has been changing and progressing as times change, to the
brewing scientist, the profound mystery of hops remains revering
and reinvigorating. Humulus lupulus has a complex story yet to be
fully understood but, undeniably, one worth telling and retelling.
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