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Materials Science and Engineering C 29 (2009) 651656

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Materials Science and Engineering C


j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m s e c

Chemical and rheological properties of a starch-rich fraction from the pulp of the fruit
cupuassu (Theobroma grandiorum)
Lcia C. Vriesmann, Joana L.M. Silveira, Carmen L. de O. Petkowicz
Universidade Federal do Paran, Departamento de Bioqumica e Biologia Molecular, CP 19046, CEP 81531-990, Curitiba-PR, Brazil

a r t i c l e

i n f o

Article history:
Received 8 May 2008
Received in revised form 28 November 2008
Accepted 9 December 2008
Available online 16 December 2008
Keywords:
Theobroma grandiorum
Cupuassu
Starch
Amylose
Gel
Rheology

a b s t r a c t
The pulp obtained from the fruit of cupuassu (Theobroma grandiorum) was extracted with hot aqueous 0.1%
citric acid to give fraction 0.1CA-2 in 15% yield. This was the predominant component polysaccharide, 91% of
which was composed of starch, by an iodine test and monosaccharide composition, and its 13C NMR
spectrum was consistent with that of a high amylose starch. The content of amylose found in fraction 0.1CA-2
was 71%. This value is higher than those of common starches of cereal grains, tubers, roots, and other fruits.
The fraction was submitted to rheological examination, gels being prepared on heating with concentrations
of 4 to 7% (w/w). A non-Newtonian behavior was observed, and gel viscosity and strength depended on the
concentration. The presence of starch, as well as the presence of previously investigated pectin, conferred the
high viscosity and gelling capability of the pulp.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Starch is the main reserve polysaccharide of many plants. It is an
important renewable and a low-cost polymer, occurring as granules,
which determine its physical properties. Due its thickening and
gelling properties, it is used in the food, pharmaceutical, and chemical
industry [13].
Cereal grains, legume seeds, tubers, and certain fruits contain from
30 to 85% starch on a dry-weight basis [3]. Commercial starches are
obtained mainly from yellow corn, although potato, wheat, tapioca,
rice and sorghum also are signicant sources [2,3].
Many reports have described the characterization of starch from
cereals, roots and tubers [47]. The fruit starches have also been
investigated, mainly those from banana [8,9], mango [8,10], apple [11],
squash [12], cherimoya [13] and Kamo Kamo [14].
Starch consists of a mixture of two polymers, amylose and
amylopectin. Whereas amylose is an essentially linear molecule,
consisting of (14)-linked -D-glucopyranosyl units, amylopectin is a
highly branched molecule with substitution of these at O-6 by -Dglucopyranosyl branches. These are composed of (14)-linked -Dglucopyranosyl units with various lengths [13].
It has been demonstrated that the pulp of the fruit of Theobroma
grandiorum, Schumann (family Sterculiaceae), growing in the
Brazilian Amazon, known locally as cupuassu, contains a considerable
amount of starch as well as pectin polysaccharides [15,16]. The pulp is
Corresponding author. Tel.: +55 41 3361 1661; fax: +55 41 3266 2042.
E-mail address: clop@ufpr.br (C.L.O. Petkowicz).
0928-4931/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2008.12.011

greatly appreciated for its pleasant acidic taste, being consumed fresh
or processed, mainly as juice, ice cream, candy and jellies [17]. It has an
intense fragrance [17], whose volatile compounds have been extensively analyzed [18], as well as its content of vitamin C [19].
As chemical and rheological characterization of native starch can
lead to improvements for predicting desirable functional properties of
starchy products, we now study some chemical and rheological
features of the native starch-rich fraction obtained from the pulp of
cupuassu fruit [15].
2. Experimental
2.1. Extraction of fraction 0.1CA-2
After enzyme-inactivation with methanolH2O (4:1, v/v) under
reux for 20 min, the grounded pulp fruit was defatted with ptoluene-ethanol (2:1, v/v) in a Soxhlet and dried. The residue was
submitted to sequential extractions with water (25 C and 60 C), citric
acid (0.1%, 0.5%, 1%, 2.5% and 5%, using temperatures of 50 C and
100 C at each concentration) and NaOH (2 mol L 1 and 4 mol L 1
NaOH; 25 C) [15,16]. Fraction 0.1CA-2 was obtained with 0.1% citric
acid at 100 C for 60 min. The extract was concentrated and treated
with ethanol (2:1 v/v) in order to obtain precipitated polysaccharide,
which was then washed three times with ethanol and dried under
vacuum.
The fraction was identied according to the conditions applied on
extraction: 0.1 displays the concentration of citric acid (CA) and 2
was used for the second hot extraction (100 C).

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L.C. Vriesmann et al. / Materials Science and Engineering C 29 (2009) 651656

2.2. Chemical characterization of fraction 0.1CA-2


Total carbohydrate was determined by the phenolsulfuric acid
colorimetric method [20], employing glucose as standard. Uronic acid
was estimated by the sulfamate/3-phenylphenol colorimetric method
[21], using galacturonic acid as standard. Protein was measured by the
Hartree method [22], with BSA as standard.
Amylose content was determined by the Chrastil method [23] with
a modication, using 80% amylose and waxy amylopectin (0%
amylose) (Sigma) as standards. Intermediate amylose proportions
were obtained by mixing appropriate amounts of each. A straight line
plot was used to determine the content of amylose in the sample.
Fraction 0.1CA-2 was solubilized in distilled water at 100 C during
10 min, then alkalinized with 1 mol L 1 NaOH and kept for 5 min at
100 C. After cooling at 25 C, it was submitted to the procedure for
amylose determination.
The monosaccharide composition was determined after total acid
hydrolysis with 2 mol L 1 triuoroacetic acid (5 h, 100 C). The
monosaccharides, obtained on evaporation to dryness, were reduced
with NaBH4 and then acetylated with pyridine-acetic anhydride
(1:1 v/v, 16 h, at 25 C). The resulting alditol acetates were analyzed by
gasliquid chromatography (GLC) using a model 5890 S II HewlettPackard gas chromatograph at 220 C (ame ionization detector and
injector temperature, 250 C) with a DB-210 capillary column
(0.25 mm internal diameter 30 m, lm thickness 0.25 m), the
carrier gas being nitrogen at 2.0 mL min 1 [16].
For high pressure size exclusion chromatography (HPSEC) analyses, suspension of the sample in 0.1 mol L 1 NaNO2 solution
containing NaN3 (0.5 g L 1) was heated to 80 C during 2 h under
magnetic stirring. HPSEC was carried out on polysaccharide solution at
25 C, using a multidetection equipment in with a Waters 2410
differential refractometer (RI) and a Wyatt Technology Dawn F multiangle laser light scattering (MALLS) detector were adapted on-line.
Four Waters Ultrahydrogel 2000/500/250/120 columns were connected in series and coupled to the multidetection equipment. The
mobile phase consisted of a 0.1 mol L 1 NaNO2 solution containing
0.5 g L 1 NaN3 (vacuum-ltered through a 0.22 m membrane lter)
at a ow rate of 0.6 mL min 1 and pressure 830 psi. The sample,
previously ltered (0.22 m; Millipore), was injected (100 L loop) at a
1.5 mg mL 1. HPSEC data were collected and analyzed by a Wyatt
Technology ASTRA program.
13
C NMR spectra of fraction 0.1CA-2 were obtained using a Bruker
DRX 400 Avance spectrometer incorporating Fourier transform (FT) on a
solution in D2O at 70 C. Chemical shifts are expressed as (ppm), using
the resonances of CH3 groups of acetone as internal standard ( 30.2).
2.3. Rheological analysis of fraction 0.1CA-2
Solutions of fraction 0.1CA-2 at concentrations of 4, 5, 6 and 7% (w/w)
were prepared by stirring in water for 16 h at 25 C. They were then
heated at 92 C with continuous stirring for 15 min and cooled at room
temperature. The samples were stored at 5 C prior to rheological
examination.
These were carried out using a model RS 75 Haake Rheometer,
coupled with a DC5 heating circulator, with a C60/2 (cone and plate
geometry) or PP20 sensor (plate and plate geometry). Mechanical
responses of the samples were determined by subjecting them to a
frequency sweep (0.110 Hz) at 25 C at tension () between 1 and
4 Pa. These values refer to the viscoelastic-linear region, where the gel
structure was preserved. The temperature sweeps, heating (595 C)
and subsequent cooling (955 C), were performed at a rate of 1 C
min 1, at a frequency of 1 Hz. Before starting the experiments, the
exposed sample edge was covered with a thin layer of low viscosity
mineral oil to minimize evaporation losses during measurements.
Continuous ow ramps in the CR mode (controlled rate) were
performed at 25 C. The sensor was programmed to increase the shear

rate from 0.1 to 100 s 1 (up curve) in 100 s followed immediately by a


reduction from 100 to 0.1 s 1 in 100 s (down curve). The shear stress
() was then measured as a function of shear rate. As done by
Techawipharat, Suphantharika and BeMiller (2008) [24], data from the
down curve of the shear cycle were used to characterize the ow
behavior of the cupuassu starch samples. The experimental data were
evaluated and tted according to the rheological models of Herschel
Bulkley ( = 0 + Kn), Power-law ( = Kn), and Bingham ( = 0 + p),
where is the shear stress (Pa), is the shear rate (s 1), K is the
consistency coefcient (Pa s n), n is the ow behavior index
(dimensionless), 0 is the yield stress (Pa), and p is the Bingham
plastic viscosity (Pa s). The software RheoWin 3 Data Manager was
employed to obtain the rheological and statistical parameters. The
temperature of all analyses was controlled with a Peltier system.
3. Results and discussion
The pulp of cupuassu, which sums 40% of the total weight of the
fresh fruit, was used to the isolation and characterization of its
polysaccharides [15,16]. Fraction 0.1CA-2, obtained by extraction with
hot 0.1% citric acid, was the main fraction, yielding 15% on an enzymeinactivated, defatted, dry-weight basis. Due to its high yield, it was
selected for detailed chemical and rheological analysis.
3.1. Characterization of fraction 0.1CA-2
3.1.1. Chemical composition
The monosaccharide composition of fraction 0.1CA-2 showed it to
contain 91% glucose (Table 1) and this and a blue coloration with
iodine test suggested the presence of starch. The glucose content was
close those reported by Freitas et al. [7] for starches of yam (Dioscorea
alata: 88%) and cassava (Manihot utilisssima: 87.4%). The monosaccharides Rha, Ara, Gal, and uronic acid were detected, typical of pectic
polysaccharides, in small quantities of 0.6, 0.4, 1, and 6.6%, respectively. The protein content of fraction 0.1CA-2 was negligible at 1%.
The amylose content of fraction 0.1CA-2 determined by colorimetric method [23] was 71% (R2 = 0.9993). According to Chrastil [23],
the same color intensity is obtained after sample solubilization in
NaOH, Me2SO, or urea-Me2SO, and the choice depends only on the
solubility of the sample. Fraction 0.1CA-2 was found to be more
soluble in aqueous NaOH than in urea-Me2SO or Me2SO. When only
Glc content of fraction 0.1CA-2 (Table 1) is take into account, the
content of amylose increases to 77%.
Thus, the amylose content of starch present in fraction 0.1CA-2
from cupuassu is larger than that reported for starch from roots and
tubers (1038%) [6,7,25] and also of normal corn (21.432.5%) [25,26],
wheat (1830%) and rice (528.4%) starches [26].
Comparing with other fruits, this fraction from cupuassu pulp
presented a native high amylose starch, differing of apple (26.029.3%
of amylose) [11], cherimoya (15.416.3%) [13], squash (12.918.2%)
[12] and Kamo Kamo fruit starches (17.2%) [14].
Amylose level greatly affects the properties of starch and highamylose starch has attracted attention because of their benecial
properties in many food and non-food applications [27]. It has been
reported that long-term intake of dietary amylose may be valuable in
decreasing insulin response while maintaining proper control of
glucose tolerance and low levels of blood lipids [28]. Therefore,

Table 1
Monosaccharidea composition of fraction 0.1CA-2 obtained from the pulp of cupuassu
Fraction

Rha

Ara

Xyl

Man

Gal

Glc

Uronic acidb

1.0

90.8

6.6

mol%
0.1CA-2
a
b

0.6

0.4

0.4

0.2

Determined by GLC of derived alditol acetates.


Determined by colorimetric method, Filisetti-Cozzi and Carpita [21].

L.C. Vriesmann et al. / Materials Science and Engineering C 29 (2009) 651656

653

Fig. 1. 13C NMR spectra of fraction 0.1CA-2 in D2O at 70 C (A) and DEPT-135 (B).

consumption of cupuassu pulp which contains high-amylose starch


could have some health advantages in relation to the other fruits
known to contain starch.
3.1.2. 13C-NMR analysis
As expected, the 13C-NMR spectrum of fraction 0.1CA-2 contained
6 main signals (Fig. 1A), typical of starch with a high proportion of
amylose and minor ones of amylopectin [29]. Present were signals of
(14)-linked units of glucopyranose (C-1; 99.5 ppm), O-substituted
C-4 (77.4 ppm). The resonance at 73.2, 71.5 and 71.2 ppm corresponded to C-3, C-2 and C-5 respectively. The signal at 60.6 ppm arose
from unsubstituted C-6, conrmed by a DEPT-135 spectrum (Fig. 1B),
which contained an inverted signal. Minor signals were present near
to the C-1, C-4 and C-5 signals, which should arise from amylopectin.
Similar 13C-NMR assignments for a starch fraction of mango pulp and
for a standard corn starch with a high amylose content have been
reported by Iagher et al. and Freitas, respectively [10,30].
3.1.3. HPSEC-MALLS analysis
Fraction 0.1CA-2 was analyzed by HPSEC using MALLS and RI
detectors (Fig. 2). The RI gives a signal proportional to concentration

Fig. 2. Elution prole of fraction 0.1CA-2 obtained by HPSEC-MALLS/RI.

whereas the MALLS response depends on both concentration and


molar mass.
Although the alkaline media (pH1314) has been considered good
solvent for amylose, according to the literature the unperturbed
dimensions are adopted at pH 7 and 25 C, whatever the ionic strength
[31]. Milles et al. [32] isolated amylose from starch and determined the
molecular weight by light scattering using aqueous solutions of
amylose. In the present work, for HPSEC analysis, fraction 0.1CA-2
(71% amylose) was solubilized in 0.1 mol L 1 NaNO2 solution
containing NaN3 (0.5 g L 1) at 80 C.
Fig. 2 showed fraction 0.1CA-2 to be heterogeneous. A broad RI
peak, representing the proportion of the molecules present, appeared
between 45 and 58 min and is characteristic of molecules with lower
molecular weight, with another being eluted at 38 min with higher
molecular weight. With MALLS, this appeared overlapping with a
minor RI peak of higher molecular weight.
The prole of fraction 0.1CA-2 with both detectors is similar to that
obtained by SEC-MALLS for a low molecular weight polydisperse
amylose sample [33]. Its RI response showed a small shoulder eluted
before a large peak and whose LS prole had a large peak eluted and
then with a shoulder. The authors interpreted these responses as
indicating that amylose solutions of low molecular weight are
heterogeneous with respect to molecular weight distribution, containing a high molecular weight population at a low elution volume and
the majority with lower molecular weight at higher elution volumes.
The RI prole of fraction 0.1CA-2 is similar as those of debranched
amylopectins of corn, sorghum, barley, wheat, and rice, measured by a
intermediate SEC pressure [34], or by ow eld-ow fractionation
analysis [35], exhibiting in the same way, a multi-modal chain
distribution and also it is close to that of the hot-water soluble starch
of Bolivar rice cultivar [36]. The authors suggest that the amylopectin
molecules of Bolivar are bigger, are more capable of inter- and intramolecular interactions, and may be more difcult to dissolve in hot
water, and thus the hot-water soluble fraction of Bolivar starch
predominantly consisted of amylose.
The results suggest that the peak eluted at 38 min could be a
high-molecular amylopectin, while the peaks eluted later correspond
to an intermediate-molecular weight and low-molecular weight
amylose fractions.

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L.C. Vriesmann et al. / Materials Science and Engineering C 29 (2009) 651656

Fig. 3. Frequency sweeps at 25 C of fraction 0.1CA-2 at 4, 5, 6 and 7% (w/w) at tensions


of 1.5, 4.0, 1.0 and 3.0 Pa, respectively.

According to Cheetam and Tao [37], the amylose content in corn


starches has a strong correlation with the molecular size of its
amylose, the molecular size of amylose decreasing with the increase in
amylose content. If that was true for other species, amylose from
cupuassu should be a low molecular weight polymer and consequently more soluble.
The general results are in agreement with reports that consider
starch to be a polymolecular and polydisperse polysaccharide [2,3].
3.2. Rheological analysis
Starch is a biopolymer largely employed by industry [3]. Highamylose starches have the ability to form strong gels and lms. In the
food industry, the high gelling strength of these starches makes them
especially useful for producing sweets. The lm-forming ability of
these starches prevents moisture loss in fried products crispy and
reduces their fat uptake upon cooking. High-amylose starches can be
processed into resistant starch, which has nutritional benets, and
also may be used for the creation of biodegradable packing materials
and adhesives [27,38].
As discussed by Prokopowich and Biliaderis [39], gelation of
amylose (concentration b 10%) involves rapid formation of double
helical structures from an amorphous sol upon cooling, which acts as
junction zones among polymer chains, leading to the establishment of
a three-dimensional hydrated gel network. On the other hand,
gelation of amylopectin (concentration b 10%) is a much slower
process involving recrystallization of the outer branches.
As fraction 0.1CA-2 was the main polysaccharide fraction obtained
from cupuassu pulp and was composed mainly by starch with a high
amylose content (71%), it was submitted to rheological analysis.
Solutions were prepared at concentrations of 4 to 7% (w/w).
3.2.1. Dynamic rheological properties of fraction 0.1CA-2 at different
concentrations
Frequency sweeps for gelatinized starch-rich fraction, at different
concentrations, are shown in Fig. 3. The elastic moduli (G) at all
concentrations were relatively frequency-independent, while viscous
moduli (G) were only slightly dependent on frequency. There was a
gradual increase of G with an increase of frequency for all tested
concentrations.

Rosalina and Bhattacharya [40] and Khondkar et al. [41] obtained


similar rheological characteristics for some corn and waxy corn
starches, respectively. They proposed that starch samples give rise to a
weak-gel behavior or a high viscosity gel respectively.
Dynamic oscillatory results showed a gel-like behavior for all
concentrations of fraction 0.1CA-2 with G being signicantly larger
than G over studied frequencies (0.110 Hz). These data, together
with G being independent of frequency, characterize the presence of
a network structure [42]. Furthermore, G of the sample with a higher
concentration (7%) was about ten times higher than G, characterizing
a stronger gel [43].
The G of fraction 0.1CA-2 gels as a function of concentration
measured at three different frequencies can be seen in Fig. 4. The
magnitude of G increased with increasing sample concentration. The
variation of the elastic modulus with concentration for 0.1CA-2 gels
followed the relation G C5.
Iturriaga et al. [44] evaluated starch gels from seven novel
argentine rice genotypes and the dependence of storage modulus on
concentration followed the Power-law, G Cn, with n = 2.93.2 for the
non-waxy genotypes and n = 1.1 for waxy starch. Other authors have
reported that G varies as C2.63.2 for non-waxy starches [45,46]. Ring
(1983) cited by Miles et al. [47] have reported that G C7 for amylose
gels in the concentration range 1.57%, which is similar to the results
for high-amylose starch from cupuassu (fraction 0.1CA-2). However, it
has been pointed out by the same author that the values of G are
sensitive to thermal history of the amylose sample. Also, the
differences in the origin, molecular weight of the samples of amylose
could affect the values of G as well as the methods of preparation of
the gels.
The value of C0 has been used as an estimate of the lowest
concentration where gelation is possible and it is obtained by the
extrapolation of the values of G to zero [31]. A C0 of 0.9% was
observed for amylose gels in 0.2 and 0.5 M KCl. Although we have not
enough data to determine C0, when the concentration of 0.9% was
used in the relation obtained for 0.1CA-2, the value determined for G
was 0.018 Pa.
Ortega-Ojeda et al. [48,49] reports that at the same concentration,
the moduli values for potato starch (20.4% amylose) were not as high
as for amylose. A lower minimum concentration (1.7%) was required
for amylose to observe solid-like behavior [48]. On the other hand,
potato starch showed G N G only when concentration was approximately higher than 4%.

Fig. 4. G as a function of concentration for 0.1CA-2 gels at different frequencies (25 C).

L.C. Vriesmann et al. / Materials Science and Engineering C 29 (2009) 651656

Fig. 5. Temperature dependence of elastic modulus (G) of fraction 0.1CA-2 from


cupuassu fruit pulp (47%, w/w) during heating trace at 1 Hz.

Samples of gelatinized fraction 0.1 CA-2 also were submitted to


temperature sweeps, by cooling and heating curves from 5 to 95 C
and 95 to 5 C, respectively. Fig. 5 shows the temperature dependence
of the elastic modulus (G) at a heating rate of 1 C min 1. Two-step
mechanisms were observed at all concentrations of the fraction,
namely a slow G decreases from 5 to 40 C, then a sharp decrease of
the G modulus between 65 to 70 C. The proles revealed losses in the
gel strength above this temperature suggesting that structural
changes occurred in the three dimensional network after the thermal
cycle of the sample. This is similar to those described for starches from
rice [50].
A temperature sweep of the 5% fraction 0.1CA-2 during the
complete thermal cycle (heating followed by cooling) is shown in
Fig. 6. The G underwent a decrease of about ten times during heating,
approximately twice that of G, and during cooling, both moduli
underwent a gradual increase, but more pronounced for G, so much
so that reaching 5 C, its value was greater than that of the start of the
analysis. Thus, after thermal variation, the sample had a lower solid
character than that of the start of the experiment. According to Yu and
Christie [51], the thermal behavior of starches is complex. Several
physicochemical changes may occur during heating, involving
gelatinization, crystallization, volume expansion, molecular degradation and motion of water, among others.
3.2.2. Flow behavior of fraction 0.1CA-2 at different concentrations
The viscosity of gelatinized starch is inuenced by the extent of
swelling of the granules prior to their rupture, as well as the expansion
and dispersion of resistant starch granules after the rupture of the

Fig. 6. Variation of G and G (1 Hz, 4 Pa) during initial heating from 5 to 95 C and
subsequent cooling from 95 to 5 C for a 5% (w/w) 0.1 CA-2 gel.

655

granular structure. When the viscosity of starch pastes is determined,


the volume of swollen granules and their inherent deformability are
important [52].
Fig. 7 shows viscosity curves for fraction 0.1CA-2 at different
concentrations (4 to 7 w/w %) at 25 C. A decrease in the viscosity with
shear rate increase was observed, characterizing a non-Newtonian
behavior under the examined conditions. The non-Newtonian
behavior of starch solution was reported by many other researches
[24,5355].
The viscosity value increased with the increase in the fraction
0.1CA-2 concentration, as expected for polysaccharides in solution. For
example, at concentrations of 4, 5, 6 and 7% the absolute viscosity
was 14120; 37230; 63960 and 90410 mPa s respectively, with all
measurements determined at 1.2 s 1 (low shear rate). These results
showed that the viscosity of fraction 0.1CA-2 in aqueous solution is
strongly dependent on starch concentration. A similar behavior was
observed by Chaudemanche and Budtova [56] for pregelatinized corn
starch (70% amylose) at concentrations higher than 1% at 60 C. Under
high shear, the gelatinized starch granule structure was broken down,
which caused a drop in paste viscosity [57].
The experimental data for the cupuassu starch (fraction 0.1CA-2)
were evaluated according to different rheological models. The
parameters of the HerschelBuckley, Power-law and Bingham models
obtained from regression analysis between the shear stress and the
shear rate from 4 to 7% (w/w) samples are summarized in Table 2.
The Bingham model is a special case of HerschelBulkley model
when n is equal to unity [53]. For the values of n in HerschelBulkley,
which were far from unity, the samples of this study can not be
appropriately described by the Bingham model. Considering the R2
values, HerschelBuckley (R2 0.98) was found to be the most
adequate model to describe the ow behavior of the sample in this
study.
Gelatinized starch dispersions are described as non-Newtonian
uids which may also exhibit a yield stress at low shear [53,58], which
seems the case of starch of this study at concentration of 47%.
According to Lagarrigue and Alvarez [58], the yield stress value
depends on concentration, mass fraction of swollen granules, granule
mean diameter and gelatinization procedure. Although other models
have been used, gelatinized starch dispersions are usually represented
by the Power-law or the HerschelBulkley model in the range 1
1500 s 1. The consistency index (K) and the ow behavior index (n)
depend on the kind of starch, its concentration and temperature [58].
As can be seem from Table 2, K increases with the increasing of
concentration of 0.1CA-2, showing increasing viscosities. Similar

Fig. 7. Inuence of shear rate on the absolute viscosity of gels of fraction 0.1CA-2 at
25 C.

656

L.C. Vriesmann et al. / Materials Science and Engineering C 29 (2009) 651656

Table 2
Comparison of different models for the ow behavior of fraction 0.1CA-2 samples
obtained from the pulp of cupuassu
Concentration
(%, w/w)

Model

K (Pa sn)

0 (Pa)

p (Pa s)

R2

HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham

1.52
5.22

10.22
21.94

11.52
23.66

12.16
24.72

10.34

15.08
38.40

107.1
40.43

117.8
44.45

120.1

0.70
0.51

0.55
0.45

0.55
0.45

0.55
0.44

0.2630

0.5416

0.5992

0.5998

0.980
0.946
0.951
0.989
0.985
0.960
0.996
0.993
0.964
0.997
0.992
0.960

observations were reported for cassava starch [53], sago starch pastes
[55] and corn starch [59].
4. Conclusions
For the rst time, a starch-rich fraction from the pulp of cupuassu
fruit (T. grandiorum) is described with a yield of 15% related to
defatted-dried material. The fraction was composed predominantly by
a high amylose (71%) starch, characterized by a blue coloration with
iodine solution, monosaccharide composition and 13C NMR spectroscopy. This fraction contained a minor proportion of pectin that may
contribute to its gel-like behavior. Analysis of the rheological properties of the fraction showed a non-Newtonian behavior at concentrations from 4 to 7% (w/w). Considering the R2 values, HerschelBuckley
was found to be the most adequate model to describe the rheological
comportment of the samples.
Dynamic oscillatory experiments indicated a highly elastic behavior with G signicantly larger than G, being independent of the
range of examined frequencies (0.110 Hz), conrming gel characters
for all concentrations. A gel-like behavior was demonstrated for
fraction 0.1CA-2, a native high amylose starch, suggesting a potential as
a gelling additive in pharmaceutical, cosmetic and food applications.
Acknowledgements
The authors thank the Brazilian agencies, CNPq and Fundao
Araucria-PRONEX for nancial support, and Dr. Philip A. J. Gorin for
help with the English language.
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