Chemistry and Processing of Sugarbeet and Sugarcane, edited by M.A. Clarke and M.A.

Godshall
Elsevier Science Publishers B.V., Amsterdam, 1988 — Printed in the Netherlands

208

Chapter 14

POLYSACCHARIDES OF SUGARCANE AND THEIR EFFECTS ON SUGAR MANUFACTURE

R. A. KITCHEN

SUMMARY

The major proportion of polysaccharides entering the mill or the

refinery are generated by the sugarcane plant. The remaining
polysaccharides are formed by microbiological contamination, which can occur
either in the field or during processing. Recycling of these
polysaccharides occurs during processing, and in refineries can result in a
15 fold increase in content from the raw sugar to the final molasses. All
of these polysaccharides have a detrimental effect on sugar manufacture, and
this effect is not easily diminished as very few of the processing steps
remove polysaccharides.

INTRODUCTION

A comprehensive review in 1972 by Imrie and Tilbury (ref. 1) discussed

the polysaccharides in, and associated with, sugarcane. This current
review, therefore, will be largely concerned with the literature after that
date, although some of the more interesting earlier material will be
discussed.
Many different kinds of polysaccharides are found in the sugarcane
plant. These polysaccharides are all long chain molecules made up of simple
carbohydrate units; the linkages between the units and the structure of the
molecules, straight or branched, can vary. In this article polysaccharides
are considered to contain more than ten carbohydrate units.
Cellulose and hemicellulose, which are components of the cell wall,
give structural strength to the standing cane plant. They are not
considered in this review, however, as they are not soluble in water and
consequently are not likely to affect sugar manufacture. Starch, which is
involved in the metabolic activity of the growing plant, largely occurs in
sugarcane as insoluble granules. Because these granules can be solubilized
during processing, starch has an effect on the manufacturing process and
will therefore be discussed. Other soluble polysaccharides, such as
sarkaran, indigenous sugarcane polysaccharide, Roberts' glucan ,
galactomannan CP, molasses polysaccharide and dextran will also be
discussed. A recent article reviewed these same sugarcane polysaccharides
(with the exception of starch and dextran), but did not examine in detail
their chemistry in, and effects on, sugar manufacturing (ref. 2).

POLYSACCHARIDES OF SUGARCANE AND SUGARCANE PRODUCTS

Starch
Starch in sugarcane is largely in the form of insoluble, nearly
spherical granules varying widely in size, but averaging about 5 μπι. The
distribution of the starch granules in mature sugarcane stalks occurs
largely in the cane top, and in the nodal regions, where it disappears
rapidly once growth processes reach their peak. The quantity of starch
between varieties and within any one variety of cane varies widely. Some
poor varieties contain as much as 2,000 ppm starch, while a normal sugarcane
juice usually contains 50 ppm starch. Other than climate, the starch level
in sugarcane has been found to be affected by soil type, soil pH and the
potash levels in the soil (refs. 1,3).
During milling the starch granules are normally separated from the
plant tissue and carried into the cane juice. The effects of heat and lime
gelatinize the granules, and the solubilized starch passes into the
clarified juice. During subsequent boiling, starch and other high molecular
weight polysaccharides have a tendency to be incorporated into the raw sugar
crystals, which are then transferred to the refinery. The refinery thus
becomes the recipient of any problems associated with starch (ref. 3).
A recent investigation (ref. 4) on non-USA raw sugars found insoluble
starch that occurred in two size ranges. The larger granules were 5 μπι in
average size, whereas the smaller granules were 1 Jim average size, and were
attached to plant material. These latter granules did not gelatinize in
water or sucrose solution up to the boiling point of the solution, whereas
the larger granules did. Both granules were believed to have come from the
sugarcane plant.
Once the starch granules have been solubilized, two different
polysaccharides, amylose and amylopectin, are released. Amylose is
essentially an a-(1,4) linked, linear glucan having a helical structure, one
complete turn containing six glucose units. Amylopectin, as well, contains
a-(1,4) linkages, but it is a highly branched glucan with the branches
attached by a-(l,6) linkages (Figure 1). The considerable difference in
210

structures between the two glucans results in different chemical and

physical properties, as are shown in Table 1.
The ratio of amylose to amylopectin varies with the sugarcane variety,
and can also change as the starch passes through the manufacturing process
(refs. 1, 3). Part of the changes occurring during manufacture can be
attributed to the rétrogradation of amylose (ref. 5 ) ,

- OH CLÜC > - 0 - {> GLUC V 0 - ( s GLUC " " V o -s m S T ^ - O - f V CLÜC V O -

4 1 4 Ί 4 Ί 4 Ί 4 \

-0-j GLUC ^ - { " I Î L Û C " " " ^

0
I·
T- 0~C GLUC ">-0-( s GLUC V 0 - ( GLUC ) - 0 - { GLUC }
4 1 4 Ί C \ 4 "--—11
0

- 0 - ^ GLUC j-Q-^C GLUC > 0 H GLUC > < K GLUC

I·
^Q-^U^V-Q-

AMYLOPECTIN

CH.0H

G L U C : Of-D-GLUCOSE A( ^-
HO
3 Y0M
OM

Fig. 1. Representation of amylose and amylopectin.

 211

TABLE 1
Chemical and physical properties of amylose and amylopectin.

Property Amylose Amylopectin

Iodine reaction Intense blue Red -violet

x max of iodine complex About 650 nm About 540 nm
Molecular weight (daltons) 10" - lo6 107-10*
Chain length* More than 2,000 19-28
Solubility in water Variable Soluble
Stability of aqueous solution Retrogrades Stable

* Average number of glucose units per non-reducing end group.

Reproduced from Imrie and Tilbury (ref. 1). with thanks.

Sarkaran
Sugarcane which is not processed immediately after harvesting undergoes
deterioration and is classified as stale cane. A polysaccharide was
detected in such cane in South Africa, and its structure was determined.
The preliminary investigation involved the detection of various
compounds found in deteriorated cane versus fresh cane as a means of
monitoring the condition of harvested cane. Volatile acids, alcohols,
non-volatile organic acids, amino acids, starch and polysaccharide contents
were determined over a period of days. The starch decreased and the
polysaccharides increased with time, while the other analyses were
ineffective as indicators of deterioration. The analysis for soluble
polysaccharides was therefore judged to be the best indicator (ref. 6).
The polysaccharide was assumed to be a dextran, which along with lactic
acid, is produced from sucrose by bacteria. However, no lactic acid was
found (ref. 6). Large quantities of stale cane were milled; the
polysaccharide was isolated by alcohol precipitation and dialysis, and was
then compared to a starch sample, and to a dextran produced by a pure
culture of Leuconostoc mesenteroides. The composition and structure were
determined by periodate oxidation, acid hydrolysis followed by paper
chromatography, exhaustive methylation followed by hydrolysis and GLC
analysis, and by infrared spectroscopy. The polysaccharide was shown to be
a straight chain D-glucan having 25% a-(1,6)and 75% a-(1,4)linkages
(Figure 2 ) , a specific rotation of t160" and a molecular weight of
212

approximately 20,000 daltons. The results showed clearly that the

polysaccharide was not a starch or a dextran (ref. 7).

j» ,
C GLUC > < ^ GLUC ><K CLUC > Q < GLUC Λ
0
0
C GLUC ffi GLUC *><K GLOC Λ
<K
0

Fig. 2. Representation of sarkaran.

The stale cane polysaccharide showed some structural similarities to

pullulan, a glucan produced by the mold Aureobasidium pullulans. Samples of
the polysaccharide and pullulan were therefore hydrolyzed by pullulanase, an
enzyme specific for a-(1,6) glucan linkages. Paper Chromatographie
investigations indicated that, after the hydrolysis, pullulan yielded only
maltotriose, whereas the cane polysaccharide yielded 49Z maltotriose, 38Z
maltotetraose and 13Z other a-(l,4) linked glucose oligosaccharides.
Pullulan was clearly different from the cane polysaccharide, which,
therefore, was considered a new a-glucan and was named sarkaran (ref. 8).
In Queensland, Australia, sugarcane is normally grown and harvested
annually. Occasionally cane is left in the field, i.e. stand-over cane, and
is processed in the next milling season. Stand-over cane is quite often
difficult to process, a problem which has been attributed to the presence of
a sugarcane polysaccharide. Later, a polysaccharide was isolated from such
cane, and its structure was determined.
Stand-over cane samples were shredded and crushed, and the
polysaccharide was isolated from the juice by alcohol precipitation. The
composition and structure of the polysaccharide were determined by the
methods previously used in the South African investigation, but by newer
instrumental techniques as well. These included the use of reflective
densitometry to detect the oligosaccharides on paper chromatograms after
enzymatic hydrolysis of the polysaccharide, combined gas chromatography-mass
spectrometry to identify the alditol acetates after permethylation and
 213

13
hydrolysis of the polysaccharide, and C and ^H nuclear magnetic resonance
spectra of the stand-over cane polysaccharide, pullulan and South African
sarkaran. The results from this investigation indicated that the stand-over
cane polysaccharide was sarkaran, with a specific rotation of +167° and a
27Z a-(1,6) linkage content. Sarkaran, therefore, was much more widely
spread in cane than had been indicated by the stale cane work (ref. 9).
Molasses samples obtained from mills which had experienced difficulties
in processing stand-over cane were found to contain an impure glucan.
Purification of this glucan proved difficult because of the high
concentration of colorants. Structural determinations on the material
indicated that the polysaccharide was sarkaran (ref. 10).
A procedure for monitoring the concentration of sarkaran in cane
billets was developed using the enzyme pullulanase. Standard graphs, made
by plotting the concentration of pure sarkaran versus the reducing sugars
produced by the enzymatic hydrolysis, showed linearity and precision. The
application of the method to stand-over cane juice was time-consuming,
however, as the sarkaran had first to be isolated by alcohol precipitation.
The use of high performance liquid chromatography to monitor the formation
of oligosaccharides was ineffective, as sarkaran samples showed considerable
variation in their constituent maltodextrins with different conditions of
storage (ref. 11).
A survey of stand-over cane showed one area with high concentrations of
sarkaran, up to 0.13Z on cane. The cane in this area was in poor condition
with excessive stalk splitting and a color different from healthy cane. The
randomness with which sarkaran occurred in this area of similar climatic
conditions, and the relatively long development period before the glucan's
appearance, indicated that sarkaran was not a plant product. It was
suggested that the glucan could be formed by a microorganism, possibly a
yeast (ref, 12).
Gel permeation chromatography was used, with standard dextrans as
references, to determine the molecular weight of sarkaran. Values of
185,000 and 200,000 daltons were obtained; the difference in values from
those of South Africa were attributed to different isolation and
purification procedures, or to different conditions of biosynthesis (ref.
12).
21Λ

Indigenous sugarcane polysaccharide (I.S.P.)

In 1964, a polysaccharide was isolated from fresh cane juice in
Louisiana under conditions which prevented inclusion of starch or the
formation of dextran. After hydrolysis, the material was found to contain
arabinose, galactose, glucose, mannose, xylose and small amounts of rhamnose
(ref. 13). In later years, the composition of this material was further
investigated, galactose being found to be the major component, followed by
arabinose, with glucose, mannose and xylose in trace quantities. This
heterogeneous polysaccharide, which was termed I.S.P., was found to vary
with cane variety, cane age and the method of purification. It was not
completely removed during processing, and could be detected in all sugarcane
products (ref. 14). It had a negative specific rotation of -46° to -50°,
and a molecular weight ranging from 100,000 to 300,000 daltons. Glucuronic
acid was also found as a component of I.S.P. (ref. 15); its concentration
was in the 11 to 8Z range when freshly extracted (ref. 2). It was the
presence of this acid which was probably responsible for the early
literature reporting that pectin, composed of galacturonic acid, had been
found in sugarcane. Currently, no galacturonic acid has been found in any
polysaccharide isolated from a sugarcane product, which suggests that the
glucuronic acid had been misidentified and pectin does not exist in
sugarcane (ref. 15).

Indigenous sugarcane polysaccharide was also isolated from fresh cane

juice in Queensland, Australia. Purification of the I.S.P. was performed by
a combination of alcohol precipitations, gel permeation and ion exchange
chromatography. Gas chromatography was used to identify the constituent
carbohydrates, with arabinose and galactose being in highest concentrations.
Gel permeation chromatography employing standard dextrans as references
indicated a molecular weight of approximately 70,000 daltons; this value was
not substantiated by high performance liquid chromatography which indicated
two components of molecular weight 1-2 million and 20-25 thousand daltons.
Permethylation of the gel purified material, followed by hydrolysis and gas
chromatography of the methylated products indicated that the arabinogalactan
had a most unusual structure. The backbone consisted of a chain of
ß-(l,3)-D-galactose units to which every two out of three had attached (via
the primary hydroxyl) a D-galactosyl or L-arabinosyl side chain (Figure 3 ) .
A specific rotation of -56° was attributed to a ß-configuration in the
D-galactose and an a-configuration in the L-arabinose (ref. 16).
The Queensland group also investigated one of two fractions isolated
from a sample of the Louisiana I.S.P. They found essentially the same
structure as before, a backbone of D-galactose units with attached galactose
and arabinose side chains. The other low concentration monosaccharides,
rhamnose, xylose, mannose, glucose and glucuronic acid, were thought to be
attached to the arabinose and galactose side chains through the primary
hydroxyl groups of the latter. It was noted that variations in the
arabinose : galactose ratio had occurred, and that the glucuronic acid
concentration was higher in the Louisiana sample. Gel permeation
chromatography indicated that the I.S.P. sample had a molecular weight of
110,000 daltons (ref. 17).

OM

OH

GAL: 0 - 0 - G A L A C T O S E ARAB f : Of-L-ARABINOSE

#COOM

£7
ARAB p : a-L-ARABINOSC
G A:0-O-GLUCURONXC A C I D

Fig. 3. Generalized structure of indigenous sugarcane polysaccharide.

216

Roberts* glucan

During purification of I.S.P. by gel permeation chromatography, several

investigators have reported the appearance of two peaks (refs. 16,17).
These peaks indicated fractions of different molecular weight, but the
composition of both fractions had not been identified.
In Louisiana, therefore, juice from freshly cut sugarcane was treated
to isolate the I.S.P., and the purified product was then fractionated by a
hollow fiber dialyzer with a 50,000 molecular weight cut-off. The
polysaccharide isolated by this technique represented 401 of the original
I.S.P. weight.
The composition of this polysaccharide was established by
permethylation followed by gas chromatography, periodate oxidation,
treatment by the debranching enzymes pullulanase and isoamylase [specific
for a-(1,6) linkages], thin layer chromatography of the hydrolyzate, and
a-amylase treatment of the material which remained at the origin of the thin
layer plate.
The polysaccharide had a specific rotation of +120°, a molecular weight
of 15,000 - 50,000 daltons and, by acid hydrolysis, contained 98Z glucose,
with traces of arabinose, galactose and mannose. The proposed structure for
the D-glucan consisted of a straight chain backbone of a-(1,4) linked units,
with a-(1,4) linked side chains ranging in length from glucose to
maltooctaose. The side chains were attached to the backbone by a-(1,6)
linkages (Figure 4). The structure was highly branched, similar to
amylopectin and glycogen, but was of lower molecular weight (ref. 18).
Pending determination of the structure, the compound has been named
"Roberts' glucan" after the scientist who first isolated it.
C CLOC ^ CLÜC ^

0
I·
-O^CLÜC J^GUJC J(,

-Onf CLUC )>0Η[ GLOC

I· ^OjT^LüC ^

GUK CL0C
"°^ ì*$ ^ΐ C ™χ \
A k Λ k J: k A k ± k I; k
-O^f CLUC >0< GLUC y*< CLUC > Q - T c U « " > » < CU« > ^ CLOC ^

Fig. 4. Proposed structure of Roberts' glucan.

 217

Polysaccharide C.P.

Raw sugar shipped from Mackay, Australia, was refined in Japan, and
some of this sugar was used for the preparation of carbonated beverages.
Considerable amounts of floe were found in these beverages. Therefore, a
study was initiated in Japan to determine the materials responsible. The
flocculent material was precipitated out of raw or refined sugar by storage
in carbonated water. Purified material was analyzed for polysaccharides,
protein and inorganics. Raw sugar gave floe samples containing nearly equal
quantities of polysaccharides and protein, whereas refined sugar floe was
largely polysaccharide in nature. Acid hydrolysis, followed by paper and
gas-liquid chromatography, indicated the flocculent contained rhamnose,
arabinose, xylose, mannose, glucose and galactose (réf. 19).
Samples of Australian, Philippine, Cuban and South African raw sugars
each produced a floe in the Japanese carbonated beverage test. The floes
were isolated, purified and acid hydrolyzed; the component carbohydrates
were found to be mannose, glucose, galactose, arabinose, xylose and
rhamnose, the first three being in highest concentration. One of the
Australian floes was also fractionated on DEAE cellulose, and each of the
fractions acid hydrolyzed, and analyzed. The ratio of mannose to glucose to
galactose varied with each fraction, and the floe was classified as a
galactoglucomannan, or a mixture of glucomannan and galactomannan (ref. 20).
Subsequent work on a polysaccharide designated CP involved removal of
trace amounts of starch and dextran by enzymes, alcohol precipitation of the
polysaccharide, followed by dialysis. Structural analysis of the purified
polysaccharide involved gel filtration, permethylation followed by
gas-liquid chromatography-mass spectrometry, periodate oxidation, enzymatic
analysis, and acid hydrolysis followed by thin layer chromatography.
Gel filtration produced two fractions, fraction one being a
galactomannan with a D-mannose to D-galactose ratio of 2.3 : 1.0, a specific
rotation value of +97.3° and a molecular weight of 3,500,000 daltons. This
fraction was structurally analyzed; fraction two was mainly
glucose-containing with traces of galactose, arabinose and xylose.
218

Ç MAN Ì1 I

KAN : a-D-MANNOSE

GAI. : a-0-GALACTOSE

Fig. 5. Proposed structure A of galactomannan CP.

Two possible structures A and B were proposed for the galactomannan:

(A) The main chain consisted of a-(1,6) and a-(1,2) linked mannose
units. Single galactose-mannose residues in the ratio of 3 : 1 were attached
as side chains to 861 of the a-(1,6) linked mannose units by way of a-(1,2)
linkages (Figure 5 ) .
(B) The main chain consisted of only a -(1,6) linked mannose units, 86Z
of which were branched at 0-2 (Figure 6). Mannose residu.es were a-(l,2)
linked in the side chains, which were terminated by non-reducing mannose or
galactose groups (ref. 21).
 219

i Œ*

Fig. 6. Proposed structure B of galactomannan CP.

Molasses polysaccharide

A polysaccharide was isolated from a high viscosity molasses sample by

separation with cetyl trimethylammoniurn bromide, and purification by alcohol
precipitations and gel filtration. Analysis by " C nuclear magnetic
resonance spectroscopy and by gas-liquid chromatography-mass spectrometry
indicated the polysaccharide was composed of glucose-galactose-arabinose in
the ratio of 3 : 1 : 1, with trace amounts of mannose and xylose. The
backbone of the polysaccharide consisted of a-(1,3) linked glucose units,
with galactose branch chains attached by a-(1,6) linkages to the glucose,
220

and terminal arabinose units linked a-(1,6) to the galactose (Figure 7 ) . No

specific rotation, molecular weight or proposed source of the polysaccharide
was reported (ref. 22).

CH20H

QSSli GAL : Cr-D-GALACTOSE

OH
QÇLÛÇ),

ARAB : L-ARABINOSE
0 OH

C•L
GAL ]1 HOCHJ"

C biucli
5 l

Fig. 7. Proposed structure of molasses polysaccharide.

Dextrans

Dextrans are polysaccharides which, although associated with sugarcane,

are not considered to be present in healthy, sound cane. They are, however,
readily produced in damaged sugarcane, or during sugar manufacture under
conditions of poor housekeeping. An excellent review by Imrie and Tilbury
deals specifically with the dextrans arising from deteriorated cane or cane
juice, the effects of these dextrans on processing, and how to minimize the
effects (ref. 1 ) . A very detailed review by Sidebotham discusses the origin
and the structures of dextrans bacterially produced on a sucrose substrate,
and includes those produced in the sugar industry (ref. 23). A further
review outlines the bacterial production and structural determination of
dextrans; the review also considers the commercial uses of dextrans, which
represents areas of usage normally avoided by the sugar manufacturer (ref.
24).
Dextrans are glucose-containing polysaccharides in which the main chain
residues are a-(1,6) linked, with a-(1,4) and a-(1,3) linkages at the branch
points (ref. 24), A dextran (Figure 8) is defined as a glucan which has at
least 50-60Z of a-(1,6) linkages (refs. 25, 26). Most dextrans have high
 221

molecular weights, the range being 100,000 to 10,000,000 daltons. They are
normally soluble in water, insoluble in alcohol, and are highly
dextrorotatory with specific rotations of +200° and greater (ref. 1).
Dextrans are produced by bacteria which grow almost exclusively on
sucrose-containing media; these bacteria are confined to the genera
Lactobacillus, Leuconostoc and Streptococcus (ref. 23). Two of the
most common species of bacteria involved in the formation of dextran are
Leuconostoc mesenteroides and Leuconostoc dextranicum. Both of these
microorganisms have been identified in deteriorated mill juices, but so far
only the former has been found in contaminated refinery products (ref. 27).
Leuconostoc mesenteroides is a species of bacteria which contains many
different strains. Jeanes et al. (ref. 28), who characterized and
classified the dextrans produced from ninety-six different strains of
bacteria, found that dextrans with unlike properties were produced from
approximately eighty different strains of Leuconostoc mesenteroides. The
strain of bacteria that produced any particular dextran was found to affect
the percentage of a-(1,6) linkages, the type and percentage of branch
points, the molecular weight, and the specific rotation value. Even the
solubility varied with the strain type, greater contents of a-(1,6) linkages
increasing the water solubility, greater contents of a-(1,3) linkages
decreasing the water solubility (refs. 23, 28, 29).
Leuconostoc mesenteroides is found in most soils, is airborne, and thus
is also on the sugarcane plant (ref. 25). Contamination of the plant is
therefore possible, but generally requires prior damage to the rind of the
cane stalk by storm, burning (refs. 30, 31), insect problems or freezing
(refs. 32, 33). Any delays which occur between burning and harvesting, or
between harvesting and processing (refs. 34-37), can also create conditions
which are favorable for the growth of Leuconostoc (ref. 38). Contamination
by this microorganism represents a decrease in sucrose yield and, therefore,
an economic loss (ref. 26), but the accompanying formation of dextrans has
even more far-reaching effects on the manufacture of raw sugar and on the
refining processes (ref. 39).
222

( Uuc jj

1 >, o

Λ Uwe ii J GÜ^tf

0 (UOl
3 0
0
Γ c^ i
It 3 Ò
tGLUC

GLUC It
0
I

Fig. 8. Representation of dextran (Leuconostoc mesenteroides strain

B512).

Summary
Although the sugarcane plant is known as a highly efficient producer of
sucrose, the plant is also host to a wide variety of polysaccharides. These
materials differ considerably in their structure, their constituent
monosaccharides, their molecular weights and other properties, and in their
ability to affect the isolation and purificaton of sucrose. It is this last
category which is the subject of the second half of this review.

EFFECTS OF SUGARCANE POLYSACCHARIDES ON SUGAR MANUFACTURE

In the early days of sugar manufacture, many processing problems were

attributed to the presence of starch. The early investigations were
hindered by the lack of an accurate starch analysis method, and by
 223

disagreement as to what starch content caused a problem. There was also

disagreement whether the problems were caused solely by starch, or by a
combination of starch and other non-sugar impurities. It is now believed
that the presence of starch in cane juice and in raw sugar has its greatest
effect on the filterability of those materials.
As well as starch, other cane polysaccharides have a deleterious effect
on processing, usually by affecting viscosities, polarization values and
evaporation processes. The polysaccharides which are produced by
microbiological contamination, whether in the field, factory or refinery,
also cause difficulties in sugar production. The formation of dextrans,
primarily by the bacteria Leuconostoc mesenteroides. not only affects every
stage in sugar manufacture, but also represents a loss of sucrose.
The effects of all of these polysaccharides on sugar processing have
been thoroughly reviewed by Imrie and Tilbury (ref. 1 ) . Reviews dealing
specifically with dextrans include a paper discussing their formation and
their effects on processing in Australia over a thirty year period (ref.
39), a detailed account by Sidebotham of their effects in mills and
refineries (ref. 23), a discussion of the problems in sugar production (ref.
25), and a paper dealing solely with the effects on refinery processes (ref.
27). Other articles deal with the laboratory evaluation of dextran in
various refining processes (ref. 40), or on the passage of raw sugar dextran
through the refinery (refs. 41, 42).

Polarization values
Excluding the dextrans, the specific rotation values of most of the
polysaccharides associated with sugarcane are not overly dextrorotatory or
overly levorotatory. They should not, therefore, be expected to affect the
polarization of sugar samples unless present in very high concentrations.
The dextrans, however, are highly dextrorotatory, with specific
rotation values of +200°, and higher (refs. 1, 28). This value is at least
three times that of sucrose (+66.54°), which suggests that dextran-
containing raw sugar samples should show an enhanced polarization value.
Such an effect was observed when refined and raw sugar samples, which were
known to contain dextran, were dialyzed to remove the sucrose, and the
specific rotation/weight dextran determined (ref. 40). The enhancement in
polarization was about 0.3°/l,000 ppm dextran (refs. 40, 42).
22^

Polarization of dextran-containing cane juice or raw sugar samples,

after clarification by basic lead nitrate, did not show enhanced values,
while polarization after clarification with basic lead acetate did (ref.
43). In further studies, clarification by basic lead acetate prior to
polarization determination was found to co-precipitate some of the dextran
(ref. 44); in other studies, basic lead acetate clarification was found to
preferentially remove the higher molecular weight dextrans (> 40,000
daltons) leaving lower molecular weight dextrans (10,000 daltons) to affect
the polarization value (ref. 45). Thus, polarization values are elevated by
the presence of dextrans, but prior clarification by basic lead acetate
drastically decreases the effect.

Viscosity increases
With the exception of Roberts' glucan which showed little effect on
viscosity, the solubilization of sugarcane polysaccharides in juices and
liquors results in viscosity increases. Sarkaran (ref. 10) and molasses
polysaccharide (ref. 22) were both isolated from highly viscous products,
the high viscosity values being attributed to their presence. Starch
solubilized during milling also results in increases in viscosity (ref. 46).
The polysaccharides most thoroughly examined, however, are the
dextrans; their presence in juices and liquors increases the viscosity to
such an extent that many manufacturing processes are affected (ref. 47).
Furthermore, after the initial viscosity increase, the effect can be
worsened by the recycling and further dextran build-up via low purity
streams (ref. 41). Thus, viscosity increases can occur in the magma (ref.
42), massecuites (refs. 25, 48) and molasses (refs. 25, 48).
In laboratory studies, mixtures of cane dextran (molecular weight
5,000,000 daltons) and sucrose showed that the viscosity increased at a
slightly faster rate than the concentration of dextran increased (ref. 49).
This effect was found to be temperature independent (ref. 50). An increase
in viscosity also occurred with an increasing molecular weight of the
dextran added (ref. 51); furthermore, the viscosity was affected by the
structure of the dextran; the higher the degree of branching, the weaker was
the connection between molecular weight and viscosity (ref. 50). In 65Z
sucrose solutions at 80°C, the presence of 1Z dextran increased the
viscosity by 100-130Z, while 3Z dextran gave a 250-3502 increase (ref. 46).
 225

Dextrans in mill juices often resulted in poor clarifications of those

juices (refs. 35, 52). In refineries, where the dextran levels were much
lower, it was expected that the polysaccharides would be removed by the
clarification procedures. It was reported, however, that both carbonatation
and phosphatation (with and without cationic surfactants) were ineffective.
The increased viscosities due to dextran particularly influenced
phosphatation clarification, as the rates of flocculation, coagulum
flotation and scum compression were all adversely affected (ref. 40).
Decolorizations of feed liquor by bone char, granular or powdered
carbon, and ion exchange resins also did not affect the dextran
concentrations. Their presence in the feed liquors, and the accompanying
viscosity increases, adversely affected the decolorization processes, as
viscosity influences the rate of adsorption and the diffusion process (ref.
40). A recent publication described the complete blocking of bone char
adsorbents by a white gel-like material, presumably a dextran of unusual
structure (ref. 53).
The high viscosities produced in cane juices and liquors by the
presence of dextrans result in a decrease in sucrose crystallization rate
(refs. 37, 47, 48), the decrease being most pronounced in low-grade boilings
(ref. 54). The effects of these high viscosities are decreased heat
transfer in the evaporators, crystallizers and pans, increased in-boiling, a
decrease in both sucrose yield and quality, and increased energy costs due
to longer processing times (refs. 25, 40).

Filterability

Press filtration is used in sugar manufacture as a direct filtration

process or as a liquor polishing step. As these filtrations are carried out
throughout the manufacturing process, any decrease in filterability will
decrease throughput and increase energy and handling costs.
Starch is known to adversely affect filterability. In the milling
process, starch is released into the extracted juice as insoluble granules.
Clarification gelatinizes most of these granules; the soluble starch passes
into the clarified juice, and during crystallization is occluded in the raw
sugar. Dissolving of the raw sugar in the refinery releases the starch,
which in clarification by carbonatation causes severe filtration problems.
The amylopectin portion of starch, being negatively charged, interacts with
226

anionic sites on the growing crystal, and is immobilized in the crystal

matrix. The amylose, being neutral, accumulates on the surface of the
growing calcium carbonate crystal. This prevents the formation of
agglomerates, which normally provide a loose packing arrangement and faster
filtrations. Amylose, therefore, was considered one of the main filtration
impeding impurities in raw sugar (refs. 3, 55-57).
Other workers confirmed that the filtration rate after carbonatation
clarification was severely retarded by even small amounts of amylose.
Laboratory prepared samples of cane and potato amylopectins also retarded
filtrations, and this effect was attributed to blockage of the filter medium
due to their molecular size. No difference in size was noted for
agglomerated calcium carbonate crystals formed with, and without, the
addition of amylopectin (ref. 58). Amylopectin was also found to retard
liquor polishing rates in refinery-type phosphatation clarification, by
upsetting the coagulation of the scums (ref. 59).
The effect of starch on carbonatation filterability was found to be a
function of molecular weight and the degree of starch hydrolysis. The
molecular weights were expected to cover a wide range in raw sugars due to
the action of natural and added enzymes on the cane starch (ref. 60).
Dextrans with molecular weights no larger than 2 x 10 6 daltons had no
significant effect on carbonatated filterability, whereas a dextran of
molecular weight 5-40 x 10 6 daltons had very serious effects. The impedance
was markedly reduced by treatment of the polysaccharide by dextranase (ref.
60). Samples of different molecular weight dextrans (i.e. from 10,000 to
40,000,000 daltons) added to refined sugar showed that an increase in
dextran concentration gave a decrease in filterability, the effect being
most pronounced with the higher molecular weight dextrans. The
filterability was almost unaffected by low molecular weight dextran (ref.
49).
Dextran from deteriorated cane was also found to decrease the
filterability of raw sugar liquors. Plotting of the dextran content versus
the filterability for a number of samples gave graphs which showed an
inverse relationship: as the dextran concentration increased, the
filterability decreased, and vice versa (ref. 61).
Filterability variations with raw sugar were attributed to minor
constituents in the sugar, dextran and starch being the most undesirable.
 227

The principal effects on filterability were filter plugging and increased

viscosity. Starch, as ungelatinized granules, caused plugging, but in
solution, after gelatinization, increased the viscosity. The presence of
dextran in raw sugar often doubled or tripled the normal viscosity of the
syrup (ref. 46). In cases where the dextran concentrations did not affect
the viscosity, filter impedance was attributed to a surface tension effect
due to the dissolved dextran. Ultracentrifugation to remove insolubles gave
sugar solutions which still filtered more slowly than a pure sugar solution,
and it was concluded that filtration could be impeded by soluble as well as
insoluble components (ref. 62).
Filtration, therefore, appeared to be affected by viscosity and by
total solids (ie. dissolved and suspended). The viscosity due to dextrans
was subsequently found to have very little effect on the filtration
impedance of washed raw sugars at 25°C, the major contribution being as
dissolved solids. The total soluble sugarcane polysaccharides had less
effect on filtration impedance than dextran alone, again as dissolved solids
rather than through viscosity. The molecular weight of the dextrans was
also important, as increased molecular weight resulted in increased filter
impedance. Although the impedance was lower with the lower weights, there
was still considerable filter impedance at the lowest molecular weight
(70,000 daltons), and therefore a potential problem for the refiner. The
suspended solids, isolated by centrifugation, were found to cause severe
filtration impedance. They were either polysaccharides (75-90Z acid
hydrolyzable) or soil particles (non-hydrolyzable), with the major fraction
of particles under 10 μια. in size (ref. 63).
The filter impedance of washed raw sugars was also examined at 70°C and
80°C. As with the room temperature experiments, the suspended solids showed
the greatest filter impedance. In the dissolved solids fraction, the effect
of total soluble sugarcane polysaccharides increased as the temperature
increased, but dextran remained the most significant polysaccharide to
affect filtration. The low molecular weight dextrans still showed
considerable filtration impedance, with very little difference being found
between the 10,000 and 40,000 dalton molecular weights. With starch, the
filterability decreased with gelatinization of the starch granules, the
soluble starch effect being already evident at 70°C. The solutions
228

containing ungelatinized starch showed extremely high filtration impedance,

the starch granules still being intact (ref. 64).
A similar study discussed the various filter impeding impurities in raw
sugar, and concluded that although a particular impurity may decrease the
filterability in one raw sugar, another raw sugar with the same impurity may
be unaffected. It was concluded that filterability studies involved complex
mechanisms and interpretations, and the results may not even be applicable
to different raw sugar samples from the same country (ref. 65).

Sucrose crystal shape

During crystal growth, the shape of sucrose crystals can be influenced
by the presence of impurities. Polysaccharides are one of several
impurities which are preferentially adsorbed on a crystal face, causing that
face to grow more slowly. The dextrans are the only polysaccharides
associated with sugarcane which are believed to undergo such an adsorption,
the result being crystals elongated in a specific direction.
When dextran was added to pure sucrose solutions, and boiled, the
sucrose crystals showed c-axis elongation. This elongation was increased
when the dextran was added to a good quality syrup, and further increased
when a refractory syrup was used. Removal of the high molecular weight
material from the refractory syrup, followed by boiling, gave sucrose
crystals in which the c-axis elongation had been eliminated. The addition
of this high molecular weight material to standard sugar, and subsequent
boiling, gave elongated crystals identical to those produced by the addition
of dextran (ref. 66).
The c-axis elongations were enhanced by increasing the concentration
and the molecular weight of the added dextran, and by increasing the
temperature. The effect was not particularly strong with pure sugar
solutions, which required high levels of dextran to produce significant
elongations. Dextran produced much greater elongations in factory syrups,
which suggested that materials in the syrup interacted with dextran and
increased its effect as a habit modifier (ref. 67). Other workers found
similar effects, limited elongation in solutions of sucrose and dextran, and
extensive elongations in solutions with dextran and liquor impurities. They
suggested that dextran and the liquor impurities exerted a synergistic
effect, leading to the extensively elongated crystals found in needle grain
 229

(refs. 68, 69). This joint "dextran-syrup component" elongation was thought
to occur by a preferential adsorption onto the faces which hindered b-axis
elongation (ref. 66), thereby ensuring that growth occurred more rapidly
along the c-axis (ref. 70).
The structure of the dextran was also important, c-axis elongations
occurring only with dextrans having 83Z and higher a-(1,6) linkages (refs.
67, 71). Polysaccharides with low percentages of a-(l,6) linkages [ie. high
a-(1,4) linkages] did not cause c-axis elongation (refs. 67, 72).
There is some literature which questions the degree of influence that
dextran, oligosaccharides and polysaccharides have on sucrose crystal shape,
as will be briefly described. Syrups prepared from deteriorated cane were
fractionated into oligo- and polysaccharides. Each of three
polysaccharides, two being glucans, was found to cause c-axis elongation in
sucrose-polysaccharide crystallizations. The oligosaccharides did not, and
therefore, were not considered to be a primary cause of crystal elongation
(ref. 73). The mono- and oligosaccharides produced by partial or extensive
acid hydrolysis of dextrans were found to decrease the elongation effects as
the molecular weight decreased, suggesting that the oligosaccharides were
less significant than the polysaccharides (ref. 74). Other workers found
that a variety of oligosaccharides did not affect the axial ratios of
sucrose, while dextran did (ref. 75).
An oligosaccharide and a polysaccharide isolated from refinery molasses
were tested in sugar crystallization experiments, and the oligosaccharide
was found to cause elongation (ref. 76). Further experiments concluded that
the oligosaccharides had more influence on the elongation of sucrose
crystals than the polysaccharides, and that microorganisms present in juices
produce oligosaccharides which can cause c-axis elongations (ref. 77).
Recent publications reported that oligosaccharides caused c-axis elongation
in raw sugar factories and refineries, while polysaccharides at higher
concentrations also contributed to some of the elongation in the factories.
The treatment of the oligosaccharides by invertase removed their elongating
properties; tentative identification of the oligosaccharides indicated at
least two fructosyl-sucroses and at least two glucosyl-sucroses (refs. 78,
79).
230

A study with raffinose- and dextran-modified sucrose crystals found the

b-axis elongated by the former, and the c-axis elongated by the latter. The
b-axis elongated crystals were needle-shaped, while the c-axis elongated
crystals were square shaped (ref. 80), such as are normally produced in
massecuites. These square-shaped crystals were already elongated in the c-
direction, as pure sucrose crystals grown in water are approximately twice
as long in the b-direction as in the c-direction. The observations that
only limited elongations occurred with dextrans in pure sucrose solutions
can probably be attributed to workers accepting the square-shaped crystals
in massecuites as being the proper sucrose crystal shape (ref. 78).
The extensive c-axis elongation which occurs in needle grain makes
sucrose recovery by centrifuging very difficult. Firstly, the crystal shape
affects both the packing of the crystals in the fugai basket and their
subsequent washing, elongated crystals being less densely packed and less
easily washed (ref. 81). Elongated crystals are also more fragile and may
break during centrifuging (ref. 70). Massecuites with elongated crystals
are usually poorly purged, with the crystals either passing through the
fugai screens or plugging the screen holes (ref. 82). Low grade massecuites
are even more difficult to centrifuge. Soft massecuites with these crystals
are also difficult to purge, and the resulting sticky (gummy) soft sugars
are troublesome and time-consuming to package (refs. 40-42).

Melassigenic effect
Dextran has a melassigenic effect which decreases the yield of sucrose
(ref. 25). Furthermore, high concentrations of dextran in the final white
syrups and in the affination syrup ultimately end up in the soft sugars and
blackstrap molasses (ref. 42). The entry of any large quantities of dextran
into a refinery, therefore, can lead to elongated crystals, poor centrifugal
separations and, coupled with the melassigenic effect, will produce molasses
of higher than normal purity (refs. 40, 41). The other polysaccharides of
sugarcane are not known to cause a melassigenic effect.

Acknowledgements
The author is grateful to the senior management of B.C. Sugar for the
opportunity to prepare this chapter, to Mrs. Anne Kitchen for her excellent
diagrams and enthusiastic proof-reading, to Sandra Daly for her diligent
 231

typing and retyping, and to Mr. Dan O'Connell for his usual perfection in
slide preparation.

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