Food Hydrocolloids 23 (2009) 2394–2402

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Rheological study of gum arabic solutions: Interpretation based on

molecular self-association
Xiaobei Li a, Yapeng Fang b, Saphwan Al-Assaf b, Glyn O. Phillips b,
Katsuyoshi Nishinari a, b, c, Hongbin Zhang a, *
a
Advanced Rheology Institute, Department of Polymer Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b
Glyn O. Phillips Hydrocolloid Research Center, Glyndwr University, Wrexham, Wales, UK
c
Graduate School of Human Life Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan

a r t i c l e i n f o a b s t r a c t

Article history: This study deals with the rheological properties of aqueous solutions of gum arabic, the complex arabi-
Received 2 December 2008 nogalactan polysaccharide containing about 2% protein. The flow behavior of control gum and a matured
Accepted 25 June 2009 gum (EM2), which have different molecular associations, was investigated at different concentrations in
water and added urea (6M) by rheological and dynamic light scattering methods. The influence of
Keywords: molecular association on rheological behavior of gum arabic solutions was studied. It was found that
Gum arabic
though Newtonian behavior was observed across a wide range of concentrations and at high shear rates,
Shear thinning
gum arabic solutions showed a pronounced shear thinning in low shear rate ranges. The maximum
Molecular association
Microstructure difference in viscosity between shear rate increasing and decreasing processes was observed at 6% for both
Aggregates control gum and EM2 in water, and at 3% for control gum and 9% for EM2 in urea solutions. The results
demonstrated macromolecular association of gum arabic occurring in the solutions, and the observed
time-dependent flow behavior reflected microstructural breakdown and re-building in the systems. This
phenomenon was understood in view of the relationship between rheological properties and micro-
structural characteristics. A model was presented to interpret the rheological behavior, which is attributed
to the occurrence of shear-induced breakdown and re-formation of gum arabic aggregates.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction exclusion chromatography, namely arabinogalactan (AG), arabinoga-

Gum arabic is a complex arabinogalactan polysaccharide, con-
taining about 2% protein, obtained as sticky exudates from the stems
and branches of Acacia trees when subjected to stress (Idris, Williams,
& Phillips, 1998). These trees grow widely across the Sahelian belt of
Africa situated north of the equator up to the Sahara desert and from
Senegal in the west to Somalia in the east (Williams & Phillips, 2000).
As a heteropolysaccharide containing a small amount of protein-
aceous material (w2%) (Williams and Phillips, 2000), the carbohy-
drate part of gum arabic has a highly branched structure consisting of
a 1,3-linked b-D-galactose core with extensive branching through 3-
and 6-linked galactose and 3-linked arabinose. Constituent units
include galactopyranose, arabinopyranose, arabinofuranose, rham-
nopyranose, glucuropyranosyl uronic acid, and 4-O-methyl glucur-
opyranosyl uronic acid (Idris et al., 1998). Three major constituents
have been separated from gum arabic by hydrophobic affinity and size
* Corresponding author.
E-mail address: hbzhang@sjtu.edu.cn (H. Zhang).
lactan protein (AGP), and glycoprotein (GP) (Randall, Phillips, & Wil-
liams, 1989; Renard, Lavenant, Ralet, & Sanchez, 2006). The main
component of gum arabic is AG, which represents w90% of the total
gum. Recent research suggests that the molecule of AG fraction is
a thin oblate ellipsoid (Sanchez et al., 2008). It is consistent with
previous hypothesis and explanation that the highly branched mole-
cules of AG were spherical with Newtonian behavior in aqueous
solution. The AGP component represents w10% of the total gum and
contains w12% protein, and it has been shown to have a ‘wattle
blossom-type’ structure, in which carbohydrate blocks are linked to
a common polypeptide chain (Fincher, Stone, & Clark, 1983). The AGP
component has been shown to be responsible for the emulsifying
characteristic of gum arabic. Hydrophilic sugar residues and hydro-
phobic amino acids in the AGP contribute to the interfacial activity of
gum arabic. And the steady viscosity and moduli of gum arabic solu-
tions can also be influenced by changing the proportion of AGP frac-
tion in whole gum (Al-Assaf, Phillips, Aoki, & Sasaki, 2007). Gum arabic
has been extensively studied (Al-Assaf, Phillips & Williams, 2005; Al-
Assaf et al., 2007; Elmanan, Al-Assaf, Phillips, & Williams, 2008; Ikeda,
Funami, & Zhang, 2005; Weinbreck, de Vries, Schrooyen, & de Kruif,

0268-005X/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodhyd.2009.06.018
 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402
2003; Weinbreck & Wientjes, 2004) and widely used for its nutritional
and surface properties in food, pharmaceutics, cosmetics or inks, etc.
(Kim, & Morr, 1996a, 1996b; McNamee, O’Riordan, & O’Sullivan, 1998;
Nishi, & Jayakrishnan, 2004; Weinbreck et al., 2003; Weinbreck,
Rollema, Tromp, & de Kruif, 2004)
With regard to the rheological properties of gum arabic in water,
a preconception dominates current thinking that it behaves only as
a Newtonian fluid. This, however, is not true. A few studies have
demonstrated that gum arabic solution is as complex as, or even
more complex than most of the non-Newtonian fluids. Newtonian
behavior was indeed observed across a wide range of gum arabic
concentrations and at high shear rates of 50–100 s1. However,
a pronounced shear thinning has been observed in the low shear rate
ranges (Mothè, & Rao, 1999; Sanchez, Renard, Robert, Schmitt, &
Lefebvre, 2002). This flow behavior of gum arabic solutions is not
common among many water soluble polysaccharides. The shear
thinning of gum arabic solutions shows two major features: (1) the
viscosity measured during increasing shear from a quiescent state is
lower than that measured during the subsequent ramp-down
decreasing shear process; and (2) this phenomenon becomes more
evident in the dilute/semi-dilute regime than in the concentrated
regime. The first feature has been suggested to be attributed to the
dehydration of the samples, the inertia effect, or the development of
shear-induced structures (Sanchez et al., 2002). No further explana-
tion has been offered especially for the second practical observation.
The shear-thinning behavior has hitherto received little attention,
which could be the reason why misunderstandings have occurred
about gum arabic rheology. Only a tentative explanation based on the
mechanical destruction of micro-aggregates has been advanced to
account for the shear thinning (Mothè & Rao, 1999). The rheological
complexity of gum arabic is also evident from the increase of
viscosity/elasticity with time, which has been attributed to the
interfacial activity of gum arabic, gradually developing an elastic
interfacial film between sample and measuring geometry (Sanchez
et al., 2002). In addition, it has been found that the air bubbles formed
in concentrated aqueous gum arabic solutions (30%) seem to also
have significant effect on the rheological behavior especially in the
low shear rate range (Tanaka, Fang, & Nishinari, 2006). Recently
Wang, Burchard, Cui, Huang, & Phillips (2008) observed the molec-
ular association of control gum and matured gum in dilute concen-
tration by static light scattering, which is helpful to understand the
microstructure of gum arabic in aqueous solutions.
In view of these uncertainties and misconceptions the present
work was undertaken via rheological and light scattering measure-
ments to study the rheological phenomenon and to understand the
relationship between rheological behavior and molecular self-asso-
ciation of gum arabic.
2. Materials and methods
2.1. Materials
To compare the effect of molecular aggregations on rheological
behavior of gum arabic solutions, two commercial gum arabic samples
have been used: a conventional commercial gum arabic (control gum,
lot No.: 051221) and a matured gum Acacia (sen) SUPERGUMÔ (EM2
lot No.: 050311) in spray dried forms. Both were kindly provided by
San-Ei Gen F.F.I., Inc, Japan. The moisture contents of control gum and
EM2 are 9.72% and 6.42%, respectively. The EM2 is a matured product
of the control gum by heat treatment. Maturation was done according
to the method described previously (Al-Assaf et al., 2007; Aoki,
Al-Assf, Katayama, & Phillips, 2007). The maturation process results in
an increased fraction of AGP via aggregations of AG and GP by physical
method, and hence an increased weight average molecular weight.
Molecular parameters of the two gums were measured by using gel
2395
permeation chromatography online coupled with multi-angle laser
light scattering system (GPC–MALLS), and the results were shown in
Table 1. A Superose 6 10/300GL GPC column and a DAWN EOS multi-
angle light scattering detector (Wyatt Technology Corporation,
USA) were employed in the GPC–MALLS measurements at 25  C;
0.2 M NaCl aqueous solutions were used both as a solvent and eluent.
The definition of the three fractions followed a previously reported
method (Al-Assaf et al., 2005). According to Table 1, the molecular
mass of matured gum EM2 is higher than control gum with increasing
the proportion of AGP fraction and decreasing the proportion of AG
and GP fractions in whole gum. The Rg of EM2 is also increased with
increasing the molecular mass, which is attributed to the increase in
the proportion of AGP fraction (Aoki et al., 2007).
2.2. Preparation of gum arabic solutions
Gum arabic solutions were prepared by dispersing a weighed
amount of gum arabic powders either in distilled water or 6 M urea
solutions. The solutions were left to hydrate on a roller mixer at
room temperature overnight. To avoid the presence of air bubbles,
all the solutions were subjected to a centrifugation at 2500g for
2 min before measurements.
2.3. Rheological measurements
Rheological measurements were carried out on an AR-550 or AR-
G2 rheometer (TA Instruments, USA). A double concentric cylinder
geometry (outer radius/inner radius ratio ¼ 1.08; stator inner radi-
us ¼ 20 mm) with a gap of 0.5 mm, or a cone-plate geometry of
60 mm diameter, 210800 cone angle, and 58 mm gap was employed
in all measurements. The temperature was maintained at
25  0.1  C. The exposed surfaces of samples were covered with
a thin layer of Poly (dimethylsiloxane) to avoid dehydration.
Steady shear viscosity curves were measured for gum arabic
solutions ranging from 1 to 30 wt% both upon shear rate ramp-up
(from 0.1 to 1000 s1) and subsequent shear rate ramp-down (from
1000 back to 0.1 s1). Steady state is assumed to be attained only
when the variation of torque is less than 5% throughout three
consecutive sampling periods (30 s). To investigate the effect of pre-
shearing, gum arabic solutions were treated with different shear
rates for 10 min and then followed by observation of the storage
modulus (G0 ) and loss modulus (G00 ) as a function of time. The applied
shear rates were 0, 100, 500, and 1000 s1, respectively. The time
dependence of moduli was measured at a constant frequency of
1 rad/s and a stress of 0.01 Pa after pre-shearing.
2.4. Dynamic light scattering
Molecular size measurement of gum arabic in different condi-
tions was made using a Zetasizer Nano-ZS apparatus (Malvern, UK).
The hydrodynamic diameter d was estimated according to the
following Stokes-Einstein equation:
d ¼ KB T=3phD (1)
where KB is the Boltzmann constant, T is the absolute temperature,
Table 1
Weight average molecular weight, radius of gyration (Rg), and mass recovery of
control gum arabic and EM2 as determined by GPC–MALLS.
Control gum EM2
AGP AG þ GP whole gum AGP AG þ GP whole gum
Mw (103) 2600 438 634 8250 445 1890
Rg (nm) 37 26 28 72 66 68
Mass recovery (%) 9 91 101 18 82 106
2396 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402
h is the viscosity of solvent (either water or 6 M urea), and D is the
diffusion constant. The concentration dependence of d of gum
arabic was measured over a wide range of concentration from 0.1 to
20 wt% at 25  C. Each sample was measured with and without
filtration (0.45 mm), respectively. d was also measured immediately
following gum arabic solutions being pre-sheared on the rheom-
eter at different shear rates for 10 min. As described by Eq. (1), the
viscosity of solvent is corrected to calculate the sphere equivalent
hydrodynamic diameter. All the measurements were repeated
6 times and were done using back scattering model to eliminate
multiply scattering. The mean values with standard deviation were
recorded.
3. Results
3.1. Rheological results
3.1.1. Steady shear flow
Fig. 1 shows the steady shear flow curves of control gum in water
and 6 M urea spanning the concentration range of 1–30 wt%. Each of
the flow curves show a shear thinning at lower shear rates, and
a viscosity plateau (Newtonian behavior) at higher shear rates.
Similar rheological observations have also been reported (Mothè and
Rao, 1999; Sanchez et al., 2002). The extent of the shear thinning
seems to be reduced at higher concentrations. For example, the 30
wt% control gum solution shows least shear thinning. Moreover,
there is a clear viscosity difference between shear rate ramp-up and
ramp-down processes, with the latter being larger than the former.
This difference in viscosity between shear rate ramp-up and ramp-
down processes reaches a maximum (i.e. maximum difference in
viscosity) at an intermediate gum concentration of w6 wt% in water,
and decreases with further increasing concentration.
The steady shear flow of control gum dissolved in 6 M urea
shows similar features. The presence of urea mainly leads to two
changes: (1) the difference in viscosity becomes more pronounced,
and (2) the concentration at which maximum difference in
viscosity is observed shifts to a lower concentration (i.e. w3 wt%).
Fig. 2 displays the steady shear rheological results for matured
gum EM2 in water and 6 M urea solution, respectively. Similar to
1000
a=+3
30%
a=+2
10 20%
a=+1
12%
(Pa.s)
0.1 a=0
a=-1 9%
1E-3
6%
a=-2
3%
1E-5 a=-3
1%
1E-7
0.1 1 10 100 1000
. diameter of control gum in water decreased markedly with filtra-
(s-1)
Fig. 1. Steady shear viscosity of control gum in water (solid line) and 6 M urea (dot
line) as a function of shear rate upon increasing shear rate (solid symbols) and
decreasing shear rate (open symbols) measured at different wt% concentrations as
indicated beside each curve. The data have been vertically shifted by a factor of 10a
with given a to avoid overlapping.
1000
a=+3
30%
a=+2
10 20%
a=+1
12%
(Pa.s)
0.1 a=0
a=-1
9%
1E-3
6%
a=-2
3%
1E-5 a=-3
1%
1E-7
0.1 1 10 100 1000
.
(s-1)
Fig. 2. Steady shear flow curves of EM2 in water (solid line) and 6 M urea (dot line)
upon increasing shear rate (solid symbols) and decreasing shear rate (open symbols)
measured at different wt% concentrations as indicated beside each curve. The data
have been vertically shifted by a factor of 10a with given a to avoid overlapping.
control gum, EM2 also exhibits shear thinning and a difference in
viscosity in low shear rate range. The maximum occurs at 6 and 9
wt% in water and 6 M urea solutions, respectively. The presence of
urea hence shifts the concentration at which the maximum
difference in viscosity is shown to higher values, which differs from
the observation for control gum where the presence of urea leads to
a lower value of concentration for maximum difference in viscosity.
This may be attributed to occurrence of the stronger molecular
associations of EM2, which decrease the urea influences.
3.1.2. Influence of pre-shear treatment
Gum arabic solutions were also pre-sheared at different shear
rates for 10 min followed by measuring the moduli of G0 and G00 at
a fixed angular frequency of 1 rad/s as a function of time. Fig. 3(a)
and (b) shows the time sweep results for 6% gum arabic solution.
Once the pre-shearing is stopped, G0 and G00 sharply increase with
time. This clearly indicates a structural re-building process for
dispersed gum arabic molecules and highly dispersed gum arabic
molecules induced by higher pre-shear rate facilitating formation
of more rigid structures with higher moduli.
3.2. Dynamic light scattering results
3.2.1. Concentration dependence of hydrodynamic diameter (d)
The concentration dependence of the hydrodynamic diameter
of control gum molecules in water and urea (6 M) is shown in Fig. 4,
respectively. The standard deviations of the results with and
without filtration treatment were also given. The results indicate
two distinct regions. For concentrations below 3%, the hydrody-
namic diameter almost maintains a constant value, whereas
above 3% it increases sharply, showing remarkable concentration
dependence. This inflexion might indicate a change in molecular
architecture. Filtration treatment has a significant effect on the
hydrodynamic diameter. It was found that the hydrodynamic
tion treatment. Similar behavior was also observed in 6 M urea
solutions, but the influence of filtration treatment is relatively
smaller. Fig. 5 illustrates the concentration dependence of hydro-
dynamic diameter for matured gum EM2 in water and 6 M urea
solutions, respectively. Similar to that of control gum, the
 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402 2397

a 2 pre-shear 10000
0 s-1
100s-1
500s-1
1000s-1
1000

d (nm)
G' (Pa)

100

10
0.1 1 10
0
Concentration (%)
0 500 1000 1500 2000 2500 3000
Time (s) Fig. 5. The concentration dependence of hydrodynamic diameter of EM2 solution in
water (solid) and 6 M urea (open) solution with (square) and without filtration (circle).

b 1
hydrodynamic diameter of EM2 also increases with concentration
pre-shear
-1 but the values in water and 6 M urea solutions are not significantly
0s
different. And it is notable that hydrodynamic diameters for EM2 in
100s-1
both water and 6 M urea are almost the same with and without
500s-1
filtration, and the pronounced influence of filtration for control
1000s-1
gum is not observed. This fact indicates that the decrease in the
G" (Pa)

hydrodynamic diameter in Fig. 4 after filtration treatment is not

mainly due to the removal of some bigger particles of impurity, but
due to a physical effect of filtration. The filtration treatments seem
to be equivalent to shearing applied on the samples. This
phenomenon may be related to the different intensity of molecular
associations in control gum and in EM2.
The hydrodynamic diameter of matured gum EM2 at 6 wt% as
a function of pre-shear rate in water is shown in Fig. 6. The hydro-
dynamic diameter increases from 422 nm on standing to 458 nm after
0
0 500 1000 1500 2000 2500 3000 pre-shearing at 1000 s1, indicating that shear-induced molecular
Time (s) association is occurring, which is consistent with rheological results.

Fig. 3. G0 and G00 as a function of time for 6% gum arabic solutions after pre-shearing at
different shear rates (control stress 0.01 Pa, 1 rad/s). The curves for G0 and G00 were
shown in both panel of (a) and (b), respectively.
4. Discussion
Two parameters are introduced to characterize the rheological
behavior of gum arabic which have been described in Figs. 1 and 2.

470
10000
460

1000 450
d (nm)

d (nm)

440
100
430

10 420

0.1 1 10 410
0 200 400 600 800 1000
Concentration (%)
Pre-shear rate (s-1)
Fig. 4. The concentration dependence of hydrodynamic diameter of control gum
solutions in water (solid) and 6 M urea (open) solution with (square) and without Fig. 6. The hydrodynamic diameter as a function of pre-shear rate for 6% EM2 solution. The
filtration (circle). samples on each concentration were pre-sheared at 0, 100, 500 and 1000 s1 respectively.
2398 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402

These are the normalized viscosity (hn) and critical shear rate ðg_ c Þ.
a 1.5
hn can be used to characterize the variation of steady shear viscosity
as a function of shear rate upon increasing shear rate (hup) and
decreasing shear rate (hdown) (Eq. (2)). 6%
3%
hn ¼ hdown =hup  1 (2) 1.0

down/ up-1
g_ c , is the value where the viscosity difference starts to appear, 9%
and provides a measure of the stability of the new structure formed
upon decreasing shear rate. 0.5
The normalized viscosity of control gum and EM2 in water and
urea (6 M) solution is illustrated in Figs. 7 and 8, respectively. Fig. 9 12%
shows the concentration dependence of the critical shear rate of 20%
control gum and EM2 in water and 6 M urea, respectively. The 1%
0.0 30%
maximum normalized viscosity and critical shear rate of control
gum in water occur at 6 wt% (Figs. 7 (a) and 9(a)) and in urea
solution at 3 wt% (Figs. 7 (b) and 9(b)) and are near the inflexion
0.1 1 10 100 1000
concentration in Fig. 4. The hn value in water increases to 6 wt% and .
(s-1)
then decreases at higher concentrations. Urea produces two effects,
namely increased normalized viscosity and a shift in the normal-
ized viscosity to lower concentration (w3 wt%). These changes in b 2.0
normalized viscosity parallel the changes of shear thinning and are
the same for EM2 solutions. The maximum hn values for EM2 in
9%
1.5 12%

a 6%
up/ up-1

1.0 1%
3
6%
20%
0.5
3%
2
down/ up-1

3%
1% 30%
12% 0.0
9%
1
20% 0.1 1 10 100 1000
.
(s-1)
30%
0 Fig. 8. Normalized viscosity of EM2 as a function of shear rate in water (a) and in urea
(6 M) solution (b). Concentration was indicated beside each curve.

0.1 1 10 100 1000

.
(s-1) water and 6 M urea are 6 and 9 wt%, respectively, which are also in
the inflexion concentration range (Fig. 5). However, the normalized
viscosity for EM2 solutions is smaller than control gum solutions at
b 3% the same concentration. It indicates a weak shear thinning for
5
matured gum EM2 compared with control gum. Furthermore, at
the same concentration, all of the critical shear rates of control gum
4 are higher than EM2 as shown in Fig. 9. This may imply a stronger
molecular association of EM2 than control gum. A higher critical
6%
shear rate needed reflects that the system is of a looser micro-
down/ up-1

3 9%
12% structure. As for the influence of urea, a hydrogen bond breaker,
on the molecular associations of gum arabic, the present results
2 1% indicate that the molecular association may be due to hydrogen
bonding. Upon addition of urea, associated gum arabic molecules
20%
will disassociate. Thus the hydrodynamic diameter decreases and
1
the difference in viscosity becomes large as shown in Figs. 4 and 7,
especially for control gum.
30%
0 Based on the observation described, it is suggested that the
unusual rheological behavior of gum arabic solution is due to
0.1 1 10 100 1000 molecular association of gum arabic molecules. Wang et al. (2008)
. using static light scattering recently found that control gum and
(s-1)
matured gum have almost the same ‘true’ radius of gyration and
Fig. 7. Normalized viscosity of control gum as a function of shear rate in water (a) and molar mass (i.e. unchanged molecular entities during maturation),
in urea (6 M) solution (b). Concentration was indicated beside each curve. and that maturation process in fact only enhances associating
 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402
a 300
Critical shear rate (s-1)
200
100
0
0 5 10 15 20
Concentration (%)
b 80
Critical shear rate (s-1)
60
40
20
0 shear rate is a serial processes of dissociation of aggregates and thus
0 5 10 15 20
Concentration (%)
Fig. 9. Critical shear rate of control gum (a) and EM2 (b) as a function of concentration
in water (,) and in urea (6 M) solution (B), respectively.
abilities of gum arabic molecules as described also by Aoki et al.
(2007). We demonstrate here that the rheological results obtained
in the present work are in accordance with these findings and can
be well described by the concept of molecular associations.
The shear-thinning behavior of gum arabic solutions has previ-
ously been reported (Goycoolea, Morris, Richardson, & Bell, 1995;
Mothè & Rao, 1999; Sanchez et al., 2002). Mothè and Rao (1999)
observed the shear-thinning behavior and attributed it to the
presence of micro-aggregates in the gum arabic solutions, just as the
aggregation for high-methoxyl pectin in dispersion. Our proposal is
that the shear-thinning behavior of gum arabic can be attributed to
the presence of equilibrium association of gum arabic molecules as
shown in Fig. 10. A model based on the association equilibrium of
gum arabic molecules has been constructed to interpret how
molecular association can affect the rheological behavior of gum
arabic solutions.
Solutions of many highly branched polymers such as poly
(etherimide) and poly(propylenimine) show a Newtonian behavior
within a wide range of shear rate (Sendijarevic & McHugh, 2000;
Sendijarevic, Liberatore, McHugh, Markoski, & Moore, 2001;
Markoski, Moore, Sendijarevic, & McHugh, 2001). Due to their high
degree of branching and steric hindrance, highly branched macro-
molecules are far less capable of forming entanglements than their
linear counterparts, thus generally showing Newtonian behavior.
2399
equilibrium association
granue-shaped molecules particulate aggregates
Fig. 10. Proposal model of equilibrium association of gum arabic molecules.
The rheological properties of branched polymers can be greatly
affected by the degree of branching (DB) (Thompson, Markoski,
Moore, Sendijarevic, Lee, & McHugh, 2000). However, shear-thin-
ning behavior also can be observed for some branched polymers
with lower DB or more linear fractions (Thompson et al., 2000;
25 30 Sendijarevic et al., 2001). Molecules with low DB are capable of
having a high degree of coil overlap and entanglement coupling.
With increasing DB, the range of shear rate of Newtonian behavior
becomes wider, and the shear-thinning behavior gradually dis-
appeared (Nunez, Chiou, Andrady, & Khan, 2000). The bulk of the
carbohydrate structure of gum arabic is highly branched, and can be
considered as granule-shaped molecules. When dissolved, the
molecules form particulate aggregates and this has been particularly
pronounced when the aqueous solutions are spray dried (Al-Assaf &
Phillips, 2006). An equilibrium association as shown in Fig. 10 would
account for the shear-thinning behavior and departure from New-
tonian behavior. When shearing is applied the aggregates formed
by association would be disassociated into smaller entities. And
when shearing is stopped, the association equilibrium shifts in the
opposite direction to form looser aggregates, as shown in Fig. 11. If
allowed sufficient rest time, the loose aggregates would again
compact themselves by draining effect. These to and fro changes in
the association equilibrium would lead to change in the architecture
of the aggregates. Therefore, the shearing process from low to high
25 30 the viscosity decreases synchronously with dissociation. For the
shear rates higher than the critical shear rate, the final association
equilibrium is established by intense shear, therefore showing
Newtonian behavior. When decreasing the shear rate to low values,
the association equilibrium would shift to aggregation again, during
which new architecture of the aggregates are rebuilt, inducing the
viscosity of shear rate ramp-up to be higher than ramp-down stage.
Fig. 12 describes this change in architecture of the aggregates during
shear rate ramp-up and ramp-down.
shearing
compact aggregates small pieces
r
ea
sh
ng
re
pi
dr
st
ai
op
in
st
nn
in
g
ef
fe
ct
loose aggregates
Fig. 11. State of gum arabic molecules with and without shear.
2400 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402

The dynamic light scattering (Figs. 4 and 5) data provide further

. gates can already be present as clusters and new shear-induced
Fig. 12. Architectural change of the aggregates during shear upon increasing shear rate
and decreasing shear rate.
evidence for this explanation. The hydrodynamic diameter sharply
increases at concentration higher than the overlap concentration,
showing that the molecular density decreases. These and the rheo-
logical data suggest that at the overlapping concentration a transition
occurs from a dense, globular structure to one that is increasingly
loose with larger associations with a tri-dimensionally spatial network
structure, therefore higher viscosity and the enhancement of shear
thinning. Thus three different concentration regimes can be distin-
guished from rheological and dynamic light scattering results, namely
the dilute regime, the overlapping regime and the (semi)-concen-
trated regime (Fig. 13). In the dilute regime, the gum arabic molecules
are aggregated as clusters and when these are broken by shearing they
cannot rebuild into larger clusters because the concentration is too
low. In the overlapping regime, the molecules of gum arabic aggre-
associations via network structures are capable of rebuilding. The
dimension of the molecular aggregates can increase as shown in Fig. 6
and the structure of molecular associations can change from clusters
to networks. The difference in viscosity is most pronounced at overlap
concentrations when the architecture of molecular associations
markedly changes. As concentration is increased in the semi-
concentrated region, only the extent of molecular association changes
rather than any significant structural change. However, with increase
in concentration, the association equilibrium shifts to the greater

initial state under shear rebuilding

in dilute regime particulate aggregated clusters

in overlapping regime particulate aggregated network

in (semi)-concentrated regime particulate aggregated network

Fig. 13. Particulate aggregates of gum arabic in solutions of different concentration regime.
 X. Li et al. / Food Hydrocolloids 23 (2009) 2394–2402
weak shear
strong shear
Fig. 14. Molecular association of gum arabic after pre-shear at different pre-shear rates.
association side, such that the critical shear rate moves to lower shear
rate. Therefore, gum arabic solutions show a Newtonian behavior over
a wider range of shear rate (Figs. 1 and 2).
The dependence of G0 and G00 on pre-shear rate is also affected by
the association equilibrium, as shown in Fig. 14. When different
pre-shear rates were applied to gum arabic solutions at the same
concentration, the association equilibrium at lower shear rates
shifts to the dissociation direction and at higher pre-shear rates
to more effective dissociation. Higher pre-shear rate will break
the aggregate into smaller particles, which re-associate to form
aggregate with a larger size and more loose structure, resulting in
a recovery process with a higher modulus.
5. Conclusion
Rheologic and dynamic light scattering results from control gum
arabic and matured gum arabic (EM2) samples showed that gum
arabic solution is not simply a Newtonian fluid, showing unique
shear thinning in low shear rate range. The shear thinning reflects
the presence of equilibrium association of gum arabic molecules
rather than disentanglement and orientation of linear polymers in
solution, and therefore the rheology of gum arabic solution is closely
related to the states of aggregates. The shear thinning of the system
is much more sensitive to shear rate. The breakdown of micro-
structures can be enhanced with increasing the applied shear rate
while the relevant rebuildup occurs with the decrease of shear rate
or after pre-shear treatment. The rheological behavior of gum arabic
solution is dependent on the concentration, pre-shear rate and
history as well. All these were reasonably interpreted in a model
based on the framework of molecular association of gum arabic.
Acknowledgements
H. Zhang thanks for the support from Shanghai Leading Academic
Discipline Project (No. B202). The authors acknowledge the Phillips
Hydrocolloids Research Ltd., UK for the financial support to X. Li to
undertake the research fellowship at Glyn O Phillips Hydrocolloid
Research Centre at Glyndwr University, Wrexham.
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