Alternatives To Malt Brewing
Alternatives To Malt Brewing
a r t i c l e i n f o a b s t r a c t
Article history: Background: Due to the competitiveness of the beer market, breweries are under pressure to lower the
Received 11 March 2016 cost of beer production. They have also attempted to widen their offers by developing new, innovative
Received in revised form products to meet consumer demand. To achieve these goals, they have increasingly replaced malt with
16 January 2017
various less expensive adjuncts. It is estimated that up to 85e90% of beer worldwide is now produced
Accepted 2 May 2017
Available online 8 May 2017
with adjuncts.
Scope and approach: The use of adjuncts may cause negative as well as positive changes to the quality of
the nal product. It is therefore important to understand the impact of particular adjuncts on the
Keywords:
Beer
different properties of beer in order to ensure appropriate use. In this review, both the positive and
Adjunct negative consequences are discussed of the partial replacement of malt with other carbohydrate sources
Unmalted grain during beer production.
Barley Key ndings and conclusions: Novel analytical methods and research developments have shed new light
Corn on the impact of adjuncts on beer characteristics. Appropriately chosen adjuncts can contribute to lighter
Syrup colours, improved colloidal or foam stability and prolongation of beer shelf-life. The avour prole can
also be changed by altering the sugar and amino acid spectra in wort. However, negative consequences
may also result from the use of adjuncts. With appropriate processing and the application of commercial
enzymatic preparations during wort and beer production these threats can be minimized.
2017 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tifs.2017.05.001
0924-2244/ 2017 Elsevier Ltd. All rights reserved.
2 P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9
The inclusion of even a little unmalted raw material in the grist the endosperm of grains following the separation of germs and
can alter the sensory properties of beer. Thus, it is possible to obtain bran (Annemller & Manger, 2013, pp. 1e80; Szwed, Tomaszewska-
a product of new avour and aroma without having to change the Ciosk, & Blazewicz, 2014). A wide variety of syrups may also be
production line (Kordialik-Bogacka, Bogdan, & Diowksz, 2014; used, with different compositions of fermentable (glucose, maltose,
Piddocke, Kreisz, Heldt-Hansen, Nilsen, & Olsson, 2009; Yeo & maltotriose) and non-fermentable (maltotetraose and higher oli-
Liu, 2014). It is estimated that a 30% substitution of malt with gosaccharides) sugars, depending on the degree of starch hydro-
unmalted corn allows for an 8% reduction in the cost of beer pro- lysis they have undergone. Syrups are often categorized according
duction (Poreda, Czarnik, Zdaniewicz, Jakubowski, & Antkiewicz, to their dextrose equivalent value (DE value), which corresponds to
2014). The addition of sugar syrups or granulated sugar, mean- the percentage content of reducing sugars, calculated as glucose
while, provides a simple way to increase wort gravity. High-gravity (although this does not provide a full picture of the sugar spectrum
fermentation is more cost-effective and is now common practice in in the syrup and consequently of the fermentability of the sup-
the brewing industry (Piddocke et al., 2011). The use of adjunct can plemented wort) (Stewart, 2006). Maltose-rich syrups are prefer-
also inuence the price of the nal product due to tax regulations, able to glucose-rich syrups. In worts abundant in glucose, yeasts
such as in Japan where liquor tax is calculated according to malt have difculty adapting to metabolize maltose and maltotriose,
usage (Braun & Dishman, 2006; Goode & Arendt, 2006). In Ger- which slows or halts fermentation. Nowadays, starch-derived
many, Switzerland and Greece, where the German Purity Law syrups are widely used by large-scale breweries (Piddocke et al.,
(Reinheitsgebot) is applicable, beer can only be produced from 2009). Syrups allow to increase the strength of wort with no
malt, water, hops and yeast and other sources of starch and sugar additional investment in the brewery. Moreover, these adjuncts
are prohibited. Nevertheless, it is nowadays possible to produce enable to overcome problems with heterogeneity of raw grains, by
beer by taking even raw barley as the only source of extract ensuring the consistent composition of the wort and beer. They also
(Aastrup, 2010; Heldt-Hansen, Elvig, Scho nenberg, & Kreisz, 2011; reduce the space required to store cereal raw materials. Use of
Steiner, Auer, Becker, & Gastl, 2012). Supplementation of the syrups or sugar can provide savings in terms of energy and mate-
mashes with exogenous enzymatic preparations is necessary to rials. When syrups or sugar are used, the mash can be thinner,
break down the starch, proteins and cell wall components in the making extraction and separation of the wort from raw materials
grains (Steiner et al., 2012). easier. Due to the lower amounts of sludge in pitching wort, there is
The aim of this review is to discuss both the positive and also reduced soiling of yeast cells during fermentation.
negative consequences of the partial replacement of malt with Mash vessel adjuncts include products which are: (1) not pre-
other carbohydrate sources during beer production. cooked but can be directly mixed with grist, such as wheat ours,
(2) pre-cooked outside the brewery, such as aked maize or rice
2. Malt substitutes grits, micronized and torreed whole grains, aked wheat or
barley, and aked pearl barley, (3) require cooking in the brewery
The denition of an adjunct has changed over the years. during mashing, such as rice, maize or sorghum grits and ours or
Currently, adjuncts are described as sources of extract other than rened starches from these materials (Meussdoerffer & Zarnkow,
malt (Atnafu & Abebaw, 2015; Briggs, Boulton, Brookes, & Stevens, 2009). This division is associated with the different gelatinization
2004, pp. 34e200). Adjuncts can be divided according to their state temperatures of starches derived from various sources. In the case
of matter, into solids and liquids. The rst group comprises of adjunct starch (for example rice starch) which gelatinizes at
unmalted cereals such as barley, corn, rice and (of lesser impor- temperatures higher than those at which malt enzymes are active,
tance) wheat, oats, sorghum, rye, and triticale, together with prior starch gelatinization is necessary before the adjunct can be
unmalted pseudocereals (buckwheat, amaranth, quinoa), cassava, mixed with the malt mash (Glatthar, Heinisch, & Senn, 2005;
teff and granulated sugar (sucrose) (Annemller & Manger, 2013, Goode et al., 2005; Meussdoerffer & Zarnkow, 2009; Poreda et al.,
pp. 1e80; Goode & Arendt, 2006). All except for granulated sugar 2014). This requires a cereal cooker, an additional vessel in the
require being hydrolized in the mashing process with malt or brewhouse, if infusion mashing is performed. When cooking grits
exogenous microbial enzymes. For this reason, they are called mash (in particular rice), it is preferable to use exogenous a-amylase or a
vessel adjuncts. Liquid adjuncts include sucrose-based syrups, portion of highly enzymatic, ground malt. Gelatinization of raw
derived from sugar cane or sugar beet, and hydrolyzed starch cereals can also take place in the mash vessel before the intro-
syrups (wort extenders), as well as malt extracts and syrups ob- duction of the malt grits with water. Nevertheless, this procedure
tained from hydrolyzed cereals (wort replacements). Apart from prolongs wort production (Krottenthaler, Back, & Zarnkow, 2009;
carbohydrates, the latter contain nitrogenous compounds and Meussdoerffer & Zarnkow, 2009).
minerals and their composition is similar to that of brewing wort. The use of rice is now mostly limited to Asian countries, due to
Malt extracts, supplied as hopped and unhopped, are popular its high price. Broken grains, a by-product of rice grown for human
among home brewers and micro-breweries. Liquid adjuncts and consumption, are used. Before further processing, de-husking and
granulated sugar contain soluble sugars and can be added to boiling degerming are required (Stewart, 2006). A mixture of different
nished wort. They are therefore called copper or kettle adjuncts. varieties is usually delivered, which results in considerable uctu-
These are commonly used to produce high-gravity worts, which ation in terms of starch gelatinization temperature and the dura-
serve to increase the capacity of the brewhouse and as a result the tion of wort separation. Rice is considered to give beer a neutral,
production capacity of the whole brewery. Their application also dry, light and clean avour (Pliansrithong, Usansa, & Wanapu,
enables wort fermentability to be adjusted easily (Piddocke et al., 2013). A fuller avoured beer is obtained with corn. Before corn
2009; Piddocke et al., 2011). Sucrose is used both in solid and can be processed into grits or akes for brewing purposes, the oil-
liquid forms, as dissacharide or invert sugar after hydrolysis (a rich germs have to be removed (Annemller & Manger, 2013, pp.
mixture of glucose and fructose). Nevertheless, concentrated so- 1e80; Meussdoerffer & Zarnkow, 2009; Yeo & Liu, 2014). When a
lutions of sugar tend to crystallize, which requires warm handling brewery uses a lauter tun, there cannot be excessive amounts of
and storage, at 40e50 C (Briggs et al., 2004, pp. 34e200). rice or corn in the grist, because the rice used is de-husked and corn
Iodine-negative starch hydrolysates from corn, wheat or rice are grits do not contain husks, which serve as a lter layer during
produced off-line by enzymatic and/or acid hydrolysis and can have lautering (Meussdoerffer & Zarnkow, 2009). In the case of wheat,
a similar sugar composition to malt worts. These are prepared from which is rich in pentosans which increase viscosity, coarse grinding
P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9 3
is recommended to alleviate wort ltration problems (Faltermaier, (Annemller & Manger, 2013, pp. 1e80). Nevertheless, it has been
Waters, Becker, Arendt, & Gastl, 2014). reported that brewing with up to 50% barley adjuncts and enzymes
It is worth highlighting that when raw barley is used as an can produce beer with good attenuation and avour stability (Kunz,
adjunct, its quality specication is different from that of barley used Mller, Mato-Gonzales, & Methner, 2012).
for malting. The viability of the grains (germination energy and Processing oats used in quantities of up to 20% enables pro-
capacity) is unimportant, but the protein content must be high. duction of good quality wort, without the need for exogenous en-
Raw barley is tough and therefore wet milling systems are rec- zymes (Schnitzenbaumer & Arendt, 2014). It is even feasible to
ommended for grinding. The processing of unmalted barley often produce acceptable beers with up to 40% oats and without exoge-
requires the supplementing of mash with exogenous hemi- nous enzymes, but on condition that the oats are hammer-milled
cellulases, owing to the high concentration of hemicelluloses and (Schnitzenbaumer, Kerpes, Titze, Jacob, & Arendt, 2012). However,
gums in grains (10.3% d. m.) (Annemller & Manger, 2013, pp. the replacement of 20e40% barley malt with hammer-milled oats
1e80). The hemicellulose contents of corn and rice are 4.2% d. m. increases the b-glucan content of the mash and decreases the
and 2.3% d. m., respectively (Annemller & Manger, 2013, pp. ltration/lautering rate signicantly (Schnitzenbaumer & Arendt,
1e80). In barley malt, the cell walls, which are mainly composed of 2013; Schnitzenbaumer et al., 2012).
hemicelluloses, are degraded during malting. Pre-cooked adjuncts
are easily handled and provide higher extract yields than raw 3. Wort extract
materials, due to the fact they contain gelatinized starch and partly
degraded hemicelluloses. It is very easy to process aked rice or During malting, enzymes responsible for the degradation of
maize and yield high extracts, even in infusion mashes. However, it insoluble high-molecular weight components in the grains to sol-
is not currently economical to use these particular adjuncts uble low-molecular compounds are synthesized and activated.
(Krottenthaler et al., 2009). Adjuncts lack predominantly or wholly hydrolytic enzymes.
Wheat our can be used directly in infusion mashes. To obtain a Moreover, their structures are compact, rather than modied (as in
higher extract, however, the our can be pre-soaked or pre-cooked, malt), which hinders enzyme action (Hbner, O'Neil, Cashman, &
usually at 96 C to avoid frothing (Briggs et al., 2004, pp. 34e200). Arendt, 2010; Schnitzenbaumer & Arendt, 2013; Steiner et al.,
This also ensures the gelatinization of its small starch granules. 2012). The application of mash vessel adjuncts usually leads to
Wheat our is obtained almost completely from endosperm. The decreased extract content in wort. Lower levels of malt in the grist
germ and bran are removed, which results an increase in the starch generates a smaller pool of enzymes involved in the hydrolysis of
content and a decrease in the protein, ash and fat contents, with as malt components such as starch or proteins and the components of
a consequence a higher extract yield (Stewart, 2006). Dealing with cell walls (Donkelaar, Noordman, Boom, & Goot, 2015; Kordialik-
our can be difcult, requiring specialized equipment, such as Bogacka et al., 2014). However, in good quality malt there is a
special hoppers and conveyers (Briggs et al., 2004, pp. 34e200). slight excess of enzymes, which can also degrade compounds
As has been already mentioned, the chemical composition of introduced through the addition of adjuncts (Ryder & Power, 2006).
particular adjuncts varies, which has an impact on beer quality. It is When larger amounts of malt are substituted, the use of exogenous
essential to understand these relations in order to adjust the pro- enzymatic preparations becomes necessary. Starch gelatinization
duction process, for example by selecting appropriate enzymatic performed at higher temperatures than with typical mash also
preparations or the optimal mashing programme (Faltermaier et al., contributes to the breakdown of starch by amylolytic enzymes. The
2014; Glatthar et al., 2005; Malomo, Ogunmoyela, Oluwajoba, & use of either wheat, oats or raw barley in amounts over 20% without
Adekoyeni, 2012). the application of exogenous enzymes causes a decrease in the
The proportion of mash vessel adjuncts in the grist depends on extract content of wort and consequently lowers the nal alcohol
many factors, including the type and quality of the adjunct, the content in beer (Depraetere, Delvaux, Coghe, & Delvaux, 2004;
pretreatment method, the use of enzymatic preparations, the Kordialik-Bogacka et al., 2014; Lowe, Ulmer, Van Sinderen, &
quality of the malt, the mashing procedure and the wort separation Arendt, 2004; Schnitzenbaumer & Arendt, 2014). Enzymatic prep-
system. When large quantities of cereal adjuncts are used, it is arations can counteract this problem. By virtue of high starch
recommended to employ mash lters to reduce wort separation content in corn (73%) and rice (75%), in contrast, their addition
time. Without use of enzyme preparations during mashing, the results in a higher level of extract in worts as well as higher
proportion of corn or rice grits in the grist should not exceed attenuation (Annemller & Manger, 2013, pp. 1e80; Poreda et al.,
30e40%. Levels of malt substitution above 40% require the appli- 2014).
cation of a-amylase (Annemller & Manger, 2013, pp. 1e80; Cooper, Wort is a complex medium which ensures effective yeast
Evans, Yousif, Metz, & Koutoulis, 2016). However, with such grist growth. It is mostly composed of carbohydrates (approximately
mixtures separation of wort in the lauter tun can be difcult. 90% of wort solids) and nitrogenous compounds (approximately 5%
Good sorghum processability can be achieved only with the use of wort solids), inorganic ions, phosphates, lipids, organic acids,
of exogenous enzymes (Schnitzenbaumer, Karl, & Arendt, 2013). polyphenols, vitamins, nucleic acid derivatives. Maltose (43e45%)
Brewing with up to 50% wholegrain sorghum our is feasible even is the most abundant sugar in all-malt wort, followed by malto-
with infusion mashing, but the use of sorghum grain requires pre- triose (11e13%), monosaccharides (7e9%) and sucrose (3e4%)
gelatinization of its starch by cooking (Schnitzenbaumer, Kaspar, (Lodolo, Kock, Axcell, & Brooks, 2008). Non-fermentable carbohy-
Titze, & Arendt, 2014). Even with the use of commercial enzyme drates are also present in wort, including dextrins (20e30% of the
mixtures, separation of wort in the lauter tun is impossible with carbohydrate fraction), arabinose, xylose, ribose, isomaltose, pan-
over 25% sorghum (Annemller & Manger, 2013, pp. 1e80). ose and isopanose (Kunz, Seewald, Brandt, & Methner, 2013;
For processing of barley adjuncts in quantities of less than Palmer, 2006). As chemoorganotrophic organisms, yeasts require
10e20%, the enzyme activity of barley malt is sufcient. Larger an organic source of carbon. Glucose, fructose, sucrose, maltose,
quantities of barley adjuncts require use of microbial b-glucanase to maltotriose, galactose and rafnose (a bottom-fermenting yeast)
avoid lautering and ltration problems (Annemller & Manger, are metabolized by brewing yeast. There is a strict order of sugar
2013, pp. 1e80; Goode & Arendt, 2006). At levels of adjunct over uptake (Lodolo et al., 2008; Rautio & Londesborough, 2003;
25%, exogenous proteinase is additionally required, and at levels Stewart, Hill, & Russel, 2013). The most readily utilized are taken
above 50% other enzymes, including a-amylase are needed up rst. Assimilation begins with sucrose, followed by glucose and
4 P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9
fructose and then by maltose and trisaccharide maltotriose Pliansrithong et al., 2013). Amino acids, like sugars, are utilized
(Espinoza-Ramrez, Perez-Carrillo, & Serna-Saldvar, 2014; Gibson sequentially (Lodolo et al., 2008; Stewart et al., 2013). According to
et al., 2008; Lodolo et al., 2008). Sucrose, glucose and fructose are the order of their uptake, they are classied into four groups.
known as primary fermentable sugars. Brewing yeasts switch to Arginine, asparagine, aspartate, glutamate, glutamine, lysine, serine
metabolizing other sugars once primary fermentable sugars have and threonine (group A) are taken up as rst, followed by histidine,
been largely consumed (Stewart et al., 2013). Maltose uptake re- isoleucine, leucine, methionine and valine (group B). Alanine,
quires the synthesis in yeast cells of maltose permease, which glycine, phenylalanine, tyrosine, tryptophan (group C) and
transports the maltose intact across the cellular membrane using ammonia are only utilized following the depletion of group A
energy generated from ATP hydrolysis, and a-glucosidase, which amino acids (Lekkas, Stewart, Hill, Taidi, & Hodgson, 2005, 2007;
splits maltose to two glucose residues (Russell, 2006). Maltotriose Tenge, 2009). Proline alone represents group D. Despite being
is also assimilated intact by independent permease and then present in large quantities in wort, proline can be only assimilated
hydrolysed by a-glucosidase. In contrast to sucrose, glucose and by brewing yeast during fermentation under nitrogen-limited
fructose, energy (ATP conversion to ADP) is required for active conditions (Gibson, 2011; Lodolo et al., 2008).
maltose and maltoriose uptake. Maltotriose is not assimilated by The application of adjunct may change the proportion of the
yeast cells until approximately 50% of maltose has been depleted different amino acids in wort. In a study by Aastrup (2010), the
(Gibson et al., 2008; Lodolo et al., 2008). complete replacement of malt by unmalted barley lead to a 15%
The shift in the sugar composition of wort which results from increase in quickly absorbed amino acids and a decrease ranging
the introduction of adjuncts can have a signicant inuence on from 8% to 28e30% in non-adsorbed amino acid (proline). This
yeast growth and fermentation performance (Gibson, 2011). Thus, a phenomenon was also observed by Heldt-Hansen et al. (2011).
high concentration of sucrose or glucose in wort, as a consequence Therefore, they recommended a distinct level of FAN in worts
of the application of either glucose or sucrose syrups to wort or produced completely from unmalted barley (9e14 mg/L/Plato) and
granulated sugar to obtain high gravity wort, can retard or even in all-malt worts (10e18 mg/L/Plato) to achieve comparable
suppress maltose and maltotriose utilization during fermentation fermentation performance. When available nitrogen sources are
(Gibson, Lawrence, Leclaire, Powell, & Smart, 2007; Piddocke et al., limited in wort produced with adjunct, the uptake of specic amino
2011). This is particularly important when stored yeasts are pitched acids by yeast proceeds in a different way from that in all-malt wort
into wort, since only yeasts harvested immediately after the main and the degree of FAN utilisation is higher.
fermentation and inoculated into new wort are suitable for Amino-acids limitation in wort may stimulate the utilization of
metabolizing maltose and maltotriose (Gibson, 2011). Moreover, peptides. Yeast growth is deteriorated in media containing di-
increased wort gravity poses a threat to fermentation performance. peptides in comparison with media in which amino acids or
It is associated both with elevated osmotic pressure and the dilu- ammonium sulphate are the sole nitrogen sources. Up to 400
tion of essential nutrients such as amino acids, minerals, fatty acids different dipeptides and 8000 tripeptides are believed to be present
and vitamins (Gibson, 2011; Stewart et al., 2013). A deterioration of in all-malt wort (Lekkas, Stewart, Hill, Taidi, & Hodgson, 2007).
yeast viability, growth and fermentation performance has been Such complexity makes understanding how these compounds are
observed in highly concentrated media by D'Amore (1992) and utilized more difcult. It is also believed that low-molecular-weight
Cahill, Murray, Walsh, and Donnelly (2000). Studies by Piddocke peptides have a negative inuence on foam stability (Lekkas et al.,
et al. (2009) also conrm that increased gravity of wort caused by 2009).
the addition of glucose or maltose syrups causes decrease in yeast The lower FAN level obtained with the addition of raw cereals
growth rate, elongation of the lag phase which precedes the syn- results from the negligible activity of enzymes which degrade high-
thesis of ethanol, incomplete sugar uptake and increased concen- molecular-weight proteins, often rendering them insoluble in the
trations of ethyl acetate and isoamyl acetate in beer. Moreover, wort from which they are separated during ltration with other
when the fermentation performance of worts supplemented with insoluble materials. Moreover, some cereals, such as corn and rice,
glucose and maltose syrups were compared, maltose-enriched are not as protein-rich as raw barley and consequently barley malt.
wort was found to provide a higher yeast cell growth rate, Syrups and granulated sugar, meanwhile, do not introduce any
improved wort fermentability and superior beer avour (Piddocke nutrients, such as nitrogenous compounds, other than carbohy-
et al., 2009). It was also shown that the viability of yeast grown in drates (Stewart, 2006). The nitrogen limitation observed in worts
maltose medium was higher than that in glucose medium (Stewart, obtained with the addition of adjuncts, in particular in high gravity
2006). This explains why maltose syrups are preferred for high- worts, can lead to poor yeast viability and retarded or sluggish
gravity brewing. fermentation (Piddocke et al., 2009; Yano, Hideki, et al., 2008).
Nevertheless, adjuncts can also change the composition of nitrog-
4. Nitrogenous compounds and their inuence on yeast enous compounds in worts signicantly, determining for example
growth and beer avour which amino acids or peptides become predominant (Yano, Hideki,
et al., 2008). It should be noted that due to adjunct use the con-
Malt replacements, whether mash vessel or kettle adjuncts, centration of other nutrients, such as inorganic ions or vitamins, is
decrease the content of nitrogen-containing substances, including also altered, which has a further impact on yeast growth (Stewart
both high molecular compounds and nitrogen sources for brewing et al., 2013).
yeast (Depraetere et al., 2004; Glatthar et al., 2005; Kunz et al., The concentration and proportion of individual assimilable ni-
2012; Poreda et al., 2014; Schnitzenbaumer & Arendt, 2013; trogen sources also has a profound inuence on the production of
Steiner et al., 2012; Yano, Hideki, Imai, Ogawa, & Ohochi, 2008). higher alcohols, esters, vicinal diketones (diacetyl, 2,3-
Due to the limited extracellular proteolytic activity of yeast, only pentanedione) and H2S (Lodolo et al., 2008). Excess FAN in wort
amino acids, ammonium ions and some di- and tripeptides are leads to increased synthesis of higher alcohols (e.g. iso-butanol) in
assimilable. Free amino nitrogen (FAN) is utilized for the synthesis beer, which are formed from intermediates in amino acid catabolic
of enzymatic and structural proteins, which are necessary for yeast pathways (valine in this case) (Gibson, 2011). In turn, higher alco-
growth and other metabolic reactions. An adequate level of FAN is hols are precursors of the most important esters. Therefore, the FAN
necessary for efcient yeast multiplication and good fermentation content has to be high enough to guarantee adequate yeast growth
performance (Lekkas, Hill, Taidi, Hodgson, & Stewart, 2009; but not so high that it stimulates the formation of excessive
P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9 5
amounts of fermentation by-products, mainly higher alcohols products and Strecker aldehydes which form during malt kilning
(Pires, Teixeira, Branyik, & Vicente, 2014). The concentration of (Palmer, 2006).
certain individual amino acids in wort can also have an impact on
beer avour. It is thought that higher valine concentrations in wort 5. Dimethyl sulphide (DMS)
and consequently a higher valine uptake and intracellular con-
centration in yeast cells causes less diacetyl to be produced during Dimethyl sulphide at high concentrations gives beer the unde-
fermentation (Bra nyik, Vicente, Dosta lek, & Teixeira, 2008; sirable avour of cooked sweetcorn. Barley malt is said to be the
Krogerus & Gibson, 2013; Shen, Wang, Liu, Li, & Li, 2014). Diace- main source of S-methylmethionine (SMM), which is a DMS pre-
tyl gives a butter aroma associated with the avour of immature cursor (Gresser, 2009). Thus, a lower proportion of malt in the grist
beer. can decrease DMS content in wort. On the other hand, DMS pre-
Changes in the composition and quantity of amino acids that cursors are also present in adjuncts such as unmalted cereals
result from the use of adjuncts can thus alter the avour of beer. (Russell, 2006). It has been shown that the precursors of DMS in
This is mainly related to the formation of higher alcohols, rst, and corn, for example, can be completely converted to DMS during wort
then esters, in different amounts than in all-malt beer (Kordialik- boiling. Moreover, it should be remembered that cereals which
Bogacka et al., 2014). The lower concentrations of amino acids contain starch with high gelatinization temperatures, should be
and small peptides in worts produced with adjuncts can give beers gelatinized in a cereal cooker before being mixed into the mash.
a much more delicate taste. The structure and quantity of carbo- This step accelerates the breakdown of DMS precursors and the
hydrate can also have an inuence on beer avour. High-gravity subsequent evaporation of DMS (Poreda et al., 2014). Thus, the
brewing is associated with disproportionately high concentra- replacement of malt by an adjunct can alter the DMS concentration
tions of esters, mainly ethyl acetate and isoamyl acetate (Bra nyik in beer.
et al., 2008; Piddocke et al., 2009). Acetate esters, including ethyl
acetate and isoamyl acetate, are the predominant esters in beer. 6. Polyphenols, avour and colloidal stability
Ethyl acetate imparts a fruity avour and isoamyl acetate a banana
avour. Excessive concentrations of these esters is considered to Polyphenols are secondary metabolites of plants, which contain
have a negative inuence on the avour of beer (Pires et al., 2014; at least one aromatic ring linked to the hydroxyl group or other
Rossi, Sileoni, Perrettib, & Marconi, 2013). During the fermentation structural elements. Polyphenols can be divided into four cate-
of wort supplemented with glucose syrups, higher amounts of ac- gories, according to the type and number of their phenolic residues:
etate esters are produced than with all-malt wort or wort supple- phenolic acids, avonoids, stilbenes and lignans (Aaron &
mented with maltose syrups, even in the case of similar FAN levels Shellhammer, 2010). In beer, 70e80% of polyphenols are derived
(Piddocke et al., 2009). The reason for this is not fully understood. It from barley malt and the rest from hops (Callemien & Collin, 2008;
may be connected with inhibition by maltose of the transport of Jerkovic, Nguyen, Timmermans, & Collin, 2008). The substitution of
volatile compounds from yeast cells or with the formation of lower malt by adjuncts usually leads to decreased polyphenol content,
amounts of acetyl-CoA during metabolism of maltose (Briggs et al., and not only in the case of liquid adjuncts, which are composed
2004, pp. 34e200). Thus, due to the limited availability of acetyl- mainly of sugars and devoid of polyphenols. In research by
CoA, which is a substrate in ester production, smaller amounts of Depraetere et al. (2004), the use of 40% unmalted wheat in the grist
esters are produced. For worts at normal gravity (12e14 P) sup- caused an up to twofold decrease in the polyphenol content of beer.
plementation with liquid adjuncts also leads to higher ester content In studies by Kunz, Woest, Lee, Mller, and Methner (2011),
in beer (Piddocke et al., 2009). decreased polyphenol content in the nal product was further
Low molecular nitrogenous compounds, in particular amino observed with the use of raw barley, although only with a high
acids and low molecular peptides, also have an impact on beer proportion of barley (75 or 90%). For example, in beer produced
colour, as they take part in Maillard and Strecker reactions with 75% barley, the polyphenol content was 143 mg/l, versus
(Vanderhaegen et al., 2003). Maillard compounds include hetero- 157 mg/l for all-malt beer. A similar trend was observed with the
cyclic compounds, which are formed in complex and differential use of unmalted barley by Yano et al. (2008). These authors found
reactions between reducing sugars and proteins, peptides, amino only a small difference between the polyphenol content in all-malt
acids and amines. Excessively high concentrations of Maillard wort and wort obtained with barley.
compounds lead to darkening, as well as to premature ageing and Polyphenols have been widely reported to be strong antioxi-
the appearance of a bready, stale avour (Saison, Schutter, dants (Fumi, Galli, Lambri, Donadini, & De Faveri, 2011; Leitao et al.,
Uyttenhove, Delvaux, & Delvaux, 2009). Therefore, a lower con- 2012). However, there is disagreement regarding the role of poly-
centration of low molecular nitrogenous compounds, as a result of phenols as antioxidants in wort and beer. Polyphenols constitute
adjunct application, can limit the formation of compounds which numerous molecules with different structures and act through
deteriorate beer aroma, taste and colour. In studies by Kunz et al. various mechanisms. Polyphenols with low molecular weight are
(2012), barley malt in the grist was replaced with raw barley in generally considered to have antioxidant capacity. As their molec-
proportions from 10 to 90%. It was observed that as the amount of ular weight increases, their activity decreases (Krottenthaler, 2009).
unmalted barley in the grist was increased, the oxidative stability of Polyphenols may function as free radical scavengers, reducing
beer improved owing to the lower content of specic intermediate agents, singlet oxygen quenchers and chelators of divalent transi-
Maillard reaction products, which accelerate radical generation. tion metals such as iron and copper. Polyphenols can release
Moreover, lower amounts of specic oxidative indicators (2- electrons to free radical species easily, generating phenoxy radicals,
methyl- and 3-methyl-butanal) were synthesized during beer which are relatively stable (Vanderhaegen, Neven, Verachtert, &
storage. Studies by Steiner et al. (2012) showed an almost twofold Derdelinckx, 2006). On the other hand, they may also act as pro-
reduction in the formation of aging compounds in beer produced oxidants, by transferring electrons to transition metal ions. They
completely with unmalted barley in comparison with all-malt beer. can reduce Fe (III) to Fe (II) and Cu (II) to Cu (I), metals which are
Decreased FAN content also means a smaller pool of precursors for prone to oxidation via Fenton and Haber-Weiss reactions. Flavan-3-
Strecker aldehydes, which are generated during beer aging (Bra nyik ols, proanthocyanidins and avonols may potentially promote the
et al., 2008). Adjuncts result in not only lower FAN levels in wort in formation of radical oxygen species (Aaron & Shellhammer, 2010;
comparison to malt but also generate fewer Maillard reaction Vanderhaegen et al., 2006).
6 P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9
Polyphenols also have an inuence on beer avour. Polyphenols important determinant of enzymatic activity and as a result for
in the avonoid family provide beer with astringency and impact extract recovery. It is recommended to acidify adjunct mashes to a
the overall aroma of hops. Therefore, the level of these compounds pH value of around 5.4e5.5. This results in higher attenuation,
in beer can affect both avour and avour stability (Aaron & reduced viscosity and better lautering. It also helps to maintain
Shellhammer, 2010). acceptable levels of colouring during boiling and enhances the
High molecular polyphenols play a role in haze formation. activity of phosphatases, thereby increasing the buffering capacity
During the brewing process, polyphenols should bind haze-active of the wort. Further acidication of the boiling wort is desirable
proline-rich proteins into stable complexes, which precipitate and before casting, since it is benecial for the precipitation of unstable
can be removed (Iimure et al., 2009; Robinson et al., 2007). How- proteins and gives a pleasant bitterness to the beer without
ever, without proper treatment colloidal haze can form in beer harming the bitterness yield. Lower buffering capacity results in
through the formation of protein-polyphenol complexes during larger decreases in pH during fermentation, and as a consequence
beer storage (Rehmanji, Gopal, & Mola, 2005). Chill (non-perma- provides green beer with a lower pH value. Low pH favours the
nent) haze disappears after warming but during further storage breakdown of a-acetolactate, known as potential diacetyl, into
strong bonds can be formed between condensed polyphenols, free diacetyl, which is then reduced by yeast to acetoin and 2,3-
called tannoids, and proteins, leading to irreversible haze butanediol. The degradation of diacetyl below its avour threshold
(Dienstbier, Gabriel, Sladk, & Sigler, 2011; Steiner, Becker, & Gastl, is a prerequisite for beer maturation. Lower pH values can therefore
2010). Thus, there are two ways in which adjuncts can affect shorten the maturation time needed for diacetyl reduction.
colloidal stability. They can contribute to lowering both the amount With regard to the inuence of particular adjuncts on pH wort,
of haze-active proteins, due to decreased proteolytic activity the literature concerning raw barley is equivocal. Introduction of
(Donkelaar et al., 2015; Ferrari, Baronchelli, Stanca, & Gianinetti, unmalted barley has been reported to result in worts with both
2010; Gupta, Abu-Ghannam, & Gallagher, 2010; Steiner et al., higher and lower pHs (Annemller & Manger, 2013, pp. 1e80; Lowe
2012), and polyphenols in beer (Kunz et al., 2011; Yano et al., 2008). et al., 2004). Use of oats or sorghum increases the pH of wort
This usually results in improved beer colloidal stability. Studies by (Kordialik-Bogacka et al., 2014; Schnitzenbaumer & Arendt, 2013,
Depraetere et al. (2004) show that the substitution of malt with 40% 2014; Schnitzenbaumer et al., 2013; Schnitzenbaumer et al., 2012).
wheat decreases the risk of permanent haze formation more
effectively than a 20% substitution. The application of rice gives a 9. Foam stability
similar effect. The use of syrups, which are devoid of polyphenols
and proteins, can also improve the colloidal stability of beer Beer foam stability is mainly dependent on the interaction of
(Meussdoerffer & Zarnkow, 2009; Yano et al., 2008). proteins/polypeptides originating from malt and iso-a-acids from
hops (Bamforth, 2004; Blasco, Vin ~ as, & Villa, 2011). High molecular
7. b-glucan weight proteins/polypeptides, including protein Z, lipid transfer
protein 1 (LTP1), hordeins and barley dimeric a-amylase inhibitor-1
During malting, enzymes are synthesized and activated which (BDAI-1) have all been demonstrated to be effective at stabilizing
degrade the components of cell walls (including b-glucan and beer foam (Iimure et al., 2009; Kordialik-Bogacka & Ambroziak,
arabinoxylans). Due to the lack of these enzymes, undegraded b- 2007; Kordialik-Bogacka & Antczak, 2011). However, hydrophobic
glucan is present in unmalted cereals and higher amounts of b- polypeptides have been shown to be the key foam-positive com-
glucan are released into the wort than when malt only is used. In pounds and the balance between polypeptides derived from albu-
particular, greater quantities of b-glucan can be extracted if nely mins and hordeins to play a decisive role (Bamforth & Milani,
ground grains are used for mashing (Lu & Li, 2006; Lu, Li, & Gu, 2004). Malt is a source not only of foam-promoting proteins, but
2005). b-glucan can cause production problems in breweries such also of other foam-positive and foam-negative components, such as
as viscous wort, slow wort separation, low extract recovery, slow b-glucan, melanoidins, polyphenols and lipids (Bravi, Benedetti,
beer ltration, the risk of haze, and the need for large quantities of Marconi, & Perretti, 2014). The precise role of b-glucan, melanoi-
lter-aids (Steiner et al., 2010; Tgel, Runyon, Galindo, & Nilsson, dins, polyphenols in stabilizing foam is a matter of long running
2015). These effects were conrmed by Glatthar et al. (2005); debate (Combe, Ang, & Bamforth, 2013; Evans et al., 2011; Gresser,
Kordialik-Bogacka et al. (2014); Kunz et al. (2011) and 2009).
Schnitzenbaumer and Arendt (2014) in processes involving barley, If unmalted cereals are used to replace malt in the grist, the
triticale or oats. To minimize the undesirable impact of b-glucan, it chemical composition of the wort and beer is altered, including the
is necessary to use malt with high b-glucanase activity or apply content of proteins/polypeptides and lipids, which are of utmost
either microbial b-glucanase or cellulase to the mash importance for foam stability (Annemller & Manger, 2013, pp.
(Schnitzenbaumer & Arendt, 2013). Corn, wheat and rice, which 1e80). Unmalted cereals contain proteins that are not degraded
have much lower levels of b-glucan than barley malt, should not during malting, and wort may therefore contain high-molecular-
increase wort and beer viscosity (Blazewicz & Zembold-Gula, 2007; weight proteins/polypeptides, which may have a positive effect
Lyu, Nam, Lee, & Lee, 2013; Meussdoerffer & Zarnkow, 2009). In on beer foam stability (Depraetere et al., 2004; Steiner et al., 2012).
mashes made with wheat, rye or triticale, pentosans may more It has been shown that the more barley grains are modied during
commonly give rise to production problems (Glatthar et al., 2005). malting (i.e. the higher the Kolbach index) the lower is beer foam
The use of syrups, which do not contain either b-glucans or arabi- stability (Evans & Bamforth, 2008). Nevertheless, research has not
noxylans, does not cause such problems and even may reduce been conclusive concerning the impact of particular adjuncts on
difculties arising from the processing of under-modied or inho- foam stability. It has been claimed for instance that despite the
mogeneous malts (Yano et al., 2008). On the other hand, b-glucan similar protein contents in wheat and barley, wheat contributes a
can contribute positively to palate-fullness. greater amount of high-molecular-weight proteins to wort.
Depraetere et al. (2004) demonstrated that wheat possesses foam-
8. pH active compounds and can improve the foam stability of beer
produced from over-modied malt, but when wheat grist was
Adjuncts usually have an inuence on mash and wort pH due to mixed with malt with high foaming potential beer foam stability
their reduced buffering capacity. The pH value of the mash is an deteriorated.
P. Bogdan, E. Kordialik-Bogacka / Trends in Food Science & Technology 65 (2017) 1e9 7
Others have indicated that b-glucans and arabinoxylans from render processing more difcult. A risk when using mash vessel
wheat may reduce the drainage of liquid from foam by increasing adjuncts is that there may be insufcient quantities of enzymes
the viscosity of beer and consequently increase foam stability from the malt to perform saccharication of starch or to degrade
(Depraetere et al., 2004). Yano et al. (2008) found that substituting gums and hemicellulose, causing ltration problems. There may
malt with 20 or 40% raw barley improved foam stability by up to also be insufcient quantities of enzymes to break down proteins
20%. This may be associated with the greater amount of high- and ensure an appropriate level of FAN in wort, and of foam-
molecular-proteins in wort produced with unmalted barley. These positive polypeptides in beer. One of the most signicant disad-
authors also found the use of syrups to be detrimental for foam vantages of using adjunct is, in fact, the low content of assimilable
stability, but only when used in quantities above 25%. This may be nitrogenous compounds available for the yeast. This can have a
surprising, if one takes into account the fact that syrups do not negative inuence on beer fermentation. Most problems connected
contribute any positive compounds from the point of view of foam with the ineffective breakdown of polymers from raw grains can be
stability. However, they also do not contain foam-damaging com- overcome, however, by the application of exogenous enzymes.
ponents such as lipids, diluting their levels in the nal product.
Moreover, as Bamforth (2004) shows, in all-malt beer there can be
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