76 [J. Inst. Brew.

EFFECT OF KILNING ON MALT STARCH AND ON THE

DEXTRIN CONTENT OF RESULTING WORTS AND BEERS

By I. C. MacWilliam
{Brewing Industry Research Foundation, Nutfield, Redhill, Surrey)

Received 21th August, 1071

Examination of starches separated from green malt and from kilned malts of
colour ranging between 3 and 23 shows that only small amounts of "new" carbohydrate
linkages are formed in the starches during kilning, though the colour changes from
white to buff and the amount of contaminating protein increases. Nevertheless,
standard enzymic treatments show that the higher the colour value of the malt,
the less susceptible it is to attack by amylases, and the larger is the content of non-
fermentable, non-dialysable dextrin. Although the amount of non-dialysable dextrin
rises as the colour value of the malt increases, dextrin content of the derived wort is
not directly related to the enzymic activity of the malt Thus, the non-fermentable
dextrin of wort from malt of colour 3 is little higher than that of wort from green
malt, despite the considerably higher diastatic power of the latter. Head retention
values of draught and bottled beers from the green malt and kilned malts of colours
3,6 and 13 show no correlation with dextrin content.

Introduction and Discussion have also reported recently that kilning

Comparatively little information exists in
the literature on physical or chemical changes
undergone by malt starch during kilning.
Prolonged heating of starch in the preparation
of commercial "gums" and dextrins (e.g.,
for 24 h at 100° C followed by 3-5 h at 225° C)
liquifies the granular material to yield a
viscous, clear solution.3 The chemical struc
ture of the starch becomes altered, probably
owing to breaking of some of the normal
ee-1,4 and a-l,6-Unkages in the molecule
and the formation of 8-1,2-, /3-1.6-, and
possibly other bonds.4'8-".18 Such linkages
are not hydrolysed by the amylases, so that
the treated starch is degraded to a smaller
extent than the starting material. Although
temperatures used during the kilning of
malt, such as 24 h at 45-55° C and 5-15 h
between 75° and 90° C are considerably
lower than those employed in the production
of commercial gums, they might still be
sufficient to alter the properties of the starch,
possibly through the formation of "new"
linkages. In this investigation the presence
of "new" linkages in malt starch has been
sought, and their possible effect on beer
properties investigated. Results show that
only a very few such linkages are formed, and
these do not appear to affect the properties
of worts and beers. Other investigators8
produces no pronounced chemical or physical
alteration in malt starch.
The malts used were obtained from a single
batch of barley which was malted in the
normal way (see Experimental). Before
kilning, portions of green malt were with
drawn for analyses, isolation of starch and trial
brewing. The remainder was kilned and por
tions were withdrawn for similar examination
when the colours were 3, 6, 13, 20 and 23.
Decrease in diastatic power of the malts
(Table I) occurred progressively throughout
kilning, as would be expected, and some loss
of nitrogenous materials also occurred. The
difference in nitrogen content between the
green malt and the kilned malt of colour 13
was 0-12%. It could be considered that this
value falls within the limits of experimental
error (± 0-07%) for the Kjeldahl method"
but further examination of the nitrogen
content of malt as it varies during kilning
is clearly desirable. No changes were found10
in nitrogen content of a series of German
malts during kilning although the values for
the green malt were not quoted.
Examination of starches.—Separation of
starch was carried out by a physical pro
cedure (see Experimental) which removed
most of the protein. Analysis of the separa
ted starch (Table II) revealed changes
Vol. 78, 1972] macwilliam : effect of kilning on malt starch 77

TABLE I
Analyses op Malts

Malt used

Colour
Green
Malt properties malt 3 0 13

Moisture (%) . . 41-3 3-7 20 2-3

Hot water extract (lb/qr) 1040* 102-0 102-2 1010
Cold water extract (%) 10-4* 10-5 10-1 17-1
Diastatic power (°L) 131* 98 68 48
Nitrogen content (%) 1-60* 1-66 1-60 1-47
Index of nitrogen modification (%) . 43-7* 430 41-0 38-7

* Analysed on a freeze dried sample.

produced by kilning. The nitrogen content
showed a rapid rise when the malt was dried
to colour 3, but subsequently only small
further increases during kilning to colour 23.
It seems likely that a small proportion of
protein is denatured during kilning, becoming
insolubilized in a form difficult to remove
from the starch. Hydrolysis of the starches
with dilute acid, followed by examination of
the hydrolysates for material giving a blue
colour with ferric chloride-potassium ferri-
cyanide solution, showed that phenolic
material was also present, except in the case
of green malt.
Previous investigations on "new" linkages
formed in starch during the commerical
preparation of gums had employed periodate
oxidation18'18 and methylation techniques*-6
to examine the changes in structure of the
starch. In the present investigation purified
amyloglucosidase was employed; this, used
together with a-amylase11, degrades the
normal a-1,4, and oc-1,6 linkages present in
starch but does not hydrolyse other bonds.
"New" linkages formed by kilning would
not be broken by these enzymes but would
yield di- or higher saccharides, whilst the
rest of the molecule would yield glucose.
The amounts of undegraded material found
after treatment of the starches (Table II)
were very small but showed a rise in the
malts with colour values above 6 EBC units.
Some of the undegraded material remaining
after attack of the highly coloured malts was
probably a disaccharide since it occupied
a position on chromatograms between those
of maltose and isomaJtose. There was,
however, too little of this material to allow
its identity to be established.
The remainder of the unhydrolysed
material was immobile on chromatograms
and was, therefore, of larger molecular
weight. Little or none of the disaccharide
was released from green malt and the greatest
amount was found in the malts having
colours of 20 and 23. These results suggest
that small amounts of "new" linkages are
formed in malt starch during kilning and
these links are resistant to attack by amylo
glucosidase.

TABLE II
Properties of Starches Isolated from Malts

Carbohydrate not
degraded to glucose by
Colour of Nitrogen content amyloglucosidase (% of
Malt starch isolated (% dry matter) total carbohydrate)

Green White 003 001

Kilned malt colour 3 Off-white 0-28 001
.. 8 Off-white 0-30 0-02
„ 13 Very light buff 0-30 0-07
.. 20 Light buff 0-34 010
,. 23 Buff 0-30 0-10
 78 macwiixiam: effect of kilning on malt starch [J. Inst. Brew.
TABLE III
Yields of Non-fermentable Sugars from Malt Starches Attacked by Enzymes from Green
Malt

Percentage of non-
dialysablc dextrin in
Non-fermentable* Non-dial ysable non-fermentable
Source of starch carbohydrate dextrin* carbohydrate fraction

Green malt 18-4 6-4 29-4

Colour 3 22-1 7-3 230
6 23-4 7-9 33-8
13 26-2 91 34-7
20 30-7 10-4 33-9
23 35-1 11-2 31-7

• Results are percentages of the total carbohydrate employed, using degradation for 2 h at 65" C by enzymes
from green malt.

Conditions used in the enzyraic degrada intermediate in structure between dialysable

tion with amyloglucosidase (prolonged di
gestion at 37° C) are considerably more
favourable for complete hydrolysis of starch
than those which occur during normal
mashing of malt for 2h at 65° C. When
equal portions of enzymes extracted from
the green malt were added to the starches
and the digests were maintained for 2 h at
65° C, the extent of degradation, as reflected
by the yields of non-fermentable sugars and
of non-dialysable dextrins (Table III) was
lowest from the green malt starch and snowed
progressive increase in starches from malts
kilned for increased periods of time. The
amount of non-dialysable dextrin represented
about one-third of the non-fermentable
sugar in each case. This non-dialysable
dextrin gave no colour when iodine solution
was added to it and must represent material
sugars and the naturally-occurring amylopec-
tin and amylose. These intermediate mater
ials are also present in wort and beer (see
below).
Brewing trials.—Analyses of the hopped
worts (Table IV) showed that the contents
of non-fermentable sugar rose as the colour
of the malt increased. With the exception
of that for the green malt the content of
non-dialysable dextrin also increased as the
colour rose. The percentage of non-dialysable
dextrin in the non-fermentable carbohydrate
(Table IV) showed considerable variation
and no distinct trend emerged. This con
trasts with that of the laboratory examina
tion (Table III) in which the percentage of
non-dialysable dextrin remained close to
one-third of the total carbohydrate. Clearly
other factors must influence the amounts

TABLE IV
Analyses of Hopped Worts (S.G. 1040) Derived from Different Malts

Maltiised

Colour
Green
malt 3 6 13

Total carbohydrate (goitre) 1000 101-6 100-5 98-0

Fermentable carbohydrate (g/litre) 86-6 80S 78-9 74-6
Non-fermentable carbohydrate (g/litre) 13-3 150 21-7 23-6
Non-dialysable dextrin (g/litre) 100 7-6 8-8 10-5
Percentage of non-dialysable dextrin in non-
fermentable carbohydrate 75-2 60-7 41-1 44-8
Colour (EBC units) 6 11 16 29
Nitrogen content (mg/litre) 928 948 968 950
cc-Amino N content (mg/litre) 233 286 262 234
Bitterness (EBC units) 41-4 45-3 48-2 44-8
Vol. 78, 1972] macwilliam: effect of kilning on malt starch 79

and hence the proportions of non-dialysable
dextrins which are found in brewery mashes
compared with those in the laboratory.
The effects of these factors are also evident
when the percentages of fermentable and
non-fermentable carbohydrates (Table IV)
are considered in relation to the diastatic
powers of the malts (Table I). Increases in
the production of non-fermentable carbo
hydrate are clearly not in proportion to the
reductions in diastatic powers as kilning
progresses. For example, when the dia
static power falls by 32° L as green malt is
dried to malt of colour 3, the content of
non-fermentable carbohydrate increases by
1*7 g/litre, whereas when the diastatic power
falls by a further 30° L as the colour is
increased from 3 to 6, the content of non-
fermentable carbohydrate rises by 6-7 g/litre.
In view of these results it seems unlikely
that the very small differences found (Table
II) in the amounts of "new" linkages formed
in the starch as kilning proceeds have any
significant effect on the formation of non-
fermentable dextrins.
It seems likely from these results that
thickness of the mash, mode of sparging and
duration of hop boiling all may play a part in
producing minor variations which alter
the close relationship (see Table II) which
exists when strach is degraded with enzymes
in dilute solution without other substances
being present. The present results conform,
however, to the general trend that fermenta-
bility falls with fall in diastatic power.
Fermentation of the hopped worts (S.G.
1-040) and conditioning of the beers was
carried out in the same manner for each brew,
half of which was bottled and the other
half maintained in cask. Analyses of both
sets of beers (Table V) show that those from
green malt and kilned malts of colours 3 and
6 have very low final gravities and contain
only a small amount of residual fermentable
sugar. The amounts of non-fermentable
and non-dialysable carbohydrate are in all
cases slightly less than those in the corre
sponding worts. This may be due firstly
to a loss of fructose-containing sugars estima
ted as non-dialysable by the chromotagraphic
method used and secondly to the loss of
glucosan and pentosan in material sedimen-
ting during fermentation and conditioning.
Losses are similar in all cases (see Tables IV
and V) and are not likely to have any
marked effect on beer properties.

TABEL V
Analyses op Bbbrs Derived from Diffbrbnt Malts

Malt used
"Rnfctlwi
UVbllvU

(B)or Colour
Draught
Beer properties (D) Malt 3 6 13

Total carbohydrate (g/litre) D 13-3 16-7 21-6 27-4

Residual fermentable sugars
(g/litre) D M 2-8 1-3 4-8
Non-fermentable carbohydrate
(g/litrc) D 12-2 13-9 203 22-6
Non-dialysable dextrin (g/litre) . ■ D 7-4 6-0 6-7 91
Specific gravity B 3-02 4-38 5-95 9-58
D 301 404 6-40 8-96
Total nitrogen (mg/litre) B 537 616 598 668
D 526 646 693 680
Bitterness (EBC units) B 21-8 25-4 25-1 23-3
D 22-3 26-8 22-6 23-6
Head retention (half life, sec) B(l)* 89 98 91 108
B(2)» 92 81 86 86
D 91 106 93 101
Shelf life (weeks) B 14 > 11 12 12
Colour (EBC units) B 11 9 12 23
D 12 15 17 27
Flavour B "Green "Lager- "Pale "Mild
malt" like" alo" ale"

* (1) at bottling, (2) 6 weeks later.

80 macwilliam: effect of kilning on malt starch
The concentration of non-dialysable dex-
trins in the beers parallels that in the worts
but does not appear to show any corre
sponding relationship to other beer properties
(Table V). Head retention values are vari
able and showed no distinct trend. The
first values for the bottled beers (Table V)
were taken soon after bottling and the others
after 6 weeks. Those for the draught beers
were taken when the casks were opened 3
weeks after filling. It has been noted0
earlier that the head retention value of
beer rises to a peak soon after bottling and
falls gradually afterwards. Some of the
present results for bottled beer (Table V)
support this trend but further investigation
of the variation of head retention after
bottling is clearly desirable.
The head retention values do not show any
definite correlation with bitterness or nitrogen
content; thus the highest bitterness is found
in the beer from malt of colour 3 which also
contains the highest content of nitrogenous
substances. Shelf lives were greater than
11 weeks and flavours were clean but differed
considerably from one another (Table V).
Non-dialysable dextrins were isolated from
each beer, and added back at concentrations
of 0-2% to see whether such dextrins affected
head retention. Variations in head retention
values did not exceed ± 2 sec, suggesting
that the effect of non-dialysable dextrins on
head retention is negligible.
Experimental
Malts.—These were prepared on the J-cwt
scale in the Foundation's pilot malting
using a Proctor barley, with 0-25 ppm
gibberellic acid sprayed on at casting.
Analyses of malts were carried out by the
Recommended Methods of the Institute of
Brewing.14 A sample of the green malt
was freeze-dried to provide suitable material
for analysis.
Separation of starches.—The malts (500 g)
were boiled for 30 min in 80% ethanol, the
ethanol was removed by nitration, the grain
was ground in a bottom-drive laboratory
macerator (M.S.E. Ltd., Crawley, Sussex) and
the suspension was passed through a 100-
mesh sieve to remove fibrous material.
The specific gravity was adjusted to 1-030
with water and the suspension was centri-
fuged at 1500 rpm Two well-defined layers
were formed, a lower layer of almost pure
starch, and an upper layer of fine fibrous
[J. Inst. Brew.
material and gelatinous protein. The upper
layer was removed by scraping with a
spatula. The separation process was repeated
until the starch was free of other materials.
After refluxing the starch in methanol
containing 15% v/v/ water, the liquid was
removed by filtration and the solid dried in
air. Nitrogen contents of the starches were
determined by the Kjeldahl procedure.
Hydrolysis was- carried out by heating
starch (0-5 g) in 2-n sulphuric acid for 2 h at
100° C. After cooling, a mixture of 0-5%
w/v ferric chloride and 1% w/v potassium
ferricyanide (5 ml, 1:1) was added to a
portion to test for the presence of phenolic
compounds.
Enzymic degradation of starches.—(a) with
malt enzymes. These were extracted from
a fully-modified green malt (100 g) by
disruption in a bottom drive macerator (see
above) with 1% aqueous sodium chloride
solution (200 ml) for 2 min, followed by
stirring for a further 2 h. The mixture was
centrifuged, saturated with ammonium sul
phate and kept overnight. The precipitate
was separated by centrifugation, washed with
saturated ammonium sulphate solution and
redissolved in water. The solution was
dialysed for 48 h against running tap water
and finally made up to 200 ml with water.
The starches (0-1 g) were mixedwith enzyme
solution (10 ml) and maintained in a mashing
bath at 65° C for 2 h and were then boiled
to destroy enzymic activity. Non-ferment
able sugars were determined after chromato-
graphic separation,12 by means of the
anthrone reagent.6 Non-dialysable dextrins
were separated using cellophane tubing
(Visking Ltd.) and were also estimated using
the anthrone reagent.
(b) With amyloglucosidase.—Purified amylo-
glucosidase (0-1 g) which was free of /?-
glucosidase activity, was mixed with water
(10 ml) and filtered. Portions (2 ml) of the
filtrate were mixed with salivary oc-amylase
(1 ml),13 water (7 ml) and starch (0-1 g).
The mixtures were covered with toluene and
maintained at 37° C for 72 h after which they
were boiled to destroy enzymic activity.
Sugars not degraded to glucose were separated
and estimated by the methods described
above.
Worts and beers.—The green malt was
ground in a disc mill and mashed in the
development brewery8 whilst the kilned
malts were ground in the normal Seek mill
Vol. 78, 1972] MACWILL1AM: EFFECT OF KILNING ON MALT STARCH
and mashed in the conventional brewery7
for 2 h at 65-6° C. Subsequent boiling,
fermentation, conditioning and bottling were
carried out by methods already described.
The worts had pH values between 6-1 and 5-4
and the beers between 3-9 and 4-1.
Non-fermentable and non-dialysable dex-
trins were estimated by the chromatographic
method described above. Bound fructose
preserit in the dextrins was measured using
acidified resorcinol.1
Acknowledgement.—The author thanks Dr.
I. D. Fleming, Glaxo Research Ltd., Green-
ford, for the sample of purified amyloglucosi-
dase used in these investigations.
References
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the Chemical Society, 1061. 1822.
2. Bathgate, G. N., & Brennan. H., Proceedings of
the American Society of Brewing Chemists,
1971, in the press.
3. Caesar, G. V., In Starch and its Derivatives, Ed.
Radley, J. A., London: Chapman & Hall.
3rd Edition 1968, p. 282.
81
4. Christensen, G. M.. & Smith, F., Journal of the
American Chemical Society, 1967, 79, 4492.
6. Geerdes. J. D., Lewis, B. A., & Smith, F.,
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6. Hall, R. D., Journal of the Institute of Brewing,
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7. Hall, R. D.. Harris, G., & MacWiUiam, I. C.
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8. Hudson, J. R., & Button, A. H., Proceedings of
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0. Krauss, G., Monatsschrift fiir Brauerei, 1970,
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10. Lucre, H., & Nishimura, S.. Zeitschrift fiir
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11. Marshall, J. J., & Wholan, W. J., FEBS Letters,
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12. McFarlane, W. D.. & Held, H. R., Proceedings
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13. Meyer. K. H., Fischer. E. H., Staub, A., &
Bcrnfeld, P., Helvetica Chimica Ada, 1948,
31,2168.
14. Recommended methods of Analysis of the
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15. Thompson, A., & Wolfrom. M. L., Journal of the
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