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Starch/Stärke 55 (2003) 287–296 287

Solomon Abera, Comparison of Physicochemical and Functional


Sudip Kumar Rakshit
Properties of Cassava Starch Extracted from
Fresh Root and Dry Chips
Processing Technology
Program, School of Environ- Starch was extracted from dry chips of three varieties of cassava using wet milling and
ment, Resources and dry milling methods. The physicochemical and functional properties were compared
Development (SERD), with those from fresh root. The starch obtained exhibited lower peak viscosities, break-
Asian Institute of Technology,
downs and setbacks, and higher pasting and peak temperatures than that from fresh
Pathumthani, Thailand
root. Most thermal properties (onset and peak temperatures of gelatinization and ret-
rogradation; conclusion temperatures, enthalpies and peak height indices of retrogra-
dation; and degree of retrogradation) were found to be higher than those of fresh-root
starch. Moreover, swelling power, paste clarity and freeze-thaw stability of the former
were inferior to those of the latter. Both types of starches exhibited increased rate of
syneresis with increase in freeze-thaw cycles. Differences observed in properties of
starches derived from dry chips by wet and dry millings were very minimal. No indica-
tion of major change in granule structure was noted for dry-chip starch that would alter
the properties relative to fresh root starch. Higher fiber content and annealing due to
exposure to heat and moisture of the former accounted for most of the variations of
properties as compared to the latter. With the advanced technology used in starch
manufacturing industry today it would be possible to obtain starch from dry chips with
similar quality from fresh root. This would enable the industry to overcome the cycle of
glut and low season, and allow them to remain open for longer period of time in a year.

Keywords: Cassava starch; Cassava chips; Physicochemical properties; Functional


properties

1 Introduction the supply of fresh root to starch factories fluctuates sea-


sonally. During peak harvest supply exceeds the produc-
In many tropical countries cassava (Manihot esculenta tion capacity of the factories resulting in low prices and
Crantz) is an economically important crop as a source of consequent reduced return to the growers. During slack
starch and in form chip and pellet as important ingredient

Research Paper
harvest the supply dwindles forcing the factories to oper-
of animal feed. Conventionally starch is extracted from ate under capacity and in some cases to temporary clo-
fresh root and numerous studies had been done on ex- sure of the plant for three to four months in a year.
traction, properties, modification and other aspects of the
starch. The idea of extracting starch from dry cassava chips is an
attempt to solve this problem. The surplus root during
Cassava, however, has one major drawback. The root
peak harvest could be dried and stored. When supply of
starts to spoil after 48 h of harvest due to physiological
fresh root drops below demand the dry chip from storage
changes and microbial activity, unless kept under special
could be used to run the starch factories in full swing. Fur-
storage condition [1, 2]. Some investigators reported an
ther, this can also alleviate a problem of lack of market for
even shorter period before the tuber become unusable
dry chips caused mainly due to European Union quota re-
[2]. So far there is no economically feasible technique of
strictions and trade barriers. This way all the parties in-
storing harvested cassava root for long period at a large
volved in cassava business in countries like Thailand
scale except in the form of dry chips. Compelled by this
would benefit considerably by managing the surplus root
fact starch factories are usually located close to the culti-
during peak harvest on the one hand and the shortage of
vation site to ensure supply of fresh root. As large-scale
raw material for the starch factories during slack harvest
cultivation of cassava is by and large climate dependent
on the other, while at the same time ensuring a market for
the chip factories.
Correspondence: Sudip Kumar Rakshit, Processing Techno-
logy Program, School of Environment, Resources and Devel-
An earlier study had been conducted to assess the possi-
opment (SERD), Asian Institute of Technology, Pathumthani, bility of extracting starch from dry chips and pellets [3].
12120, Thailand. Fax: 662-02524-6200, e-mail: rakshit@ait.ac.th. The starches obtained were of low quality suitable only for

© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0038-9056/2003/0707-0287 $17.50+.50/0
288 Abera et al. Starch/Stärke 55 (2003) 287–296

limited applications. It was felt that the process followed in In dry-milling the chips were first ground to powder by a
that work could easily be improved to produce starch of steel roller rice mill and then washed with water and sifted
acceptable quality. through a 200 mesh sieve. The slurry was left for 1 h to let
the starch settle before decanting the supernatant The
This study aimed at finding a strategy for obtaining good starch was suspended three times to remove impurities
quality starch from dry chips and comparing its quality in and then dried. The resulting dry cake was then crushed
terms of physicochemical and functional properties with and stored.
that of starch extracted from fresh roots.

2.4 Pasting property


2 Materials and Methods
A Rapid Visco Analyser (Model: RVA-4, Newport Scientif-
2.1 Commercial starch and fresh root ic, Warriewood, Australia) was used for the evaluation of
the pasting properties of various samples of starch.
Commercially processed native cassava starch was ob-
Starch (2.50 g, dry basis, d. b.) was suspended in
tained from Siam Modified Starch Co. Ltd. Thailand.
25.0 mL of distilled water. Test runs were conducted fol-
Fresh cassava root of three varieties namely Kasetsart 50
lowing standard profile 1 which included 1 min of mixing,
(KU50), Rayong 5 (R5) and CMR35-22-196 (CMR) was
stirring, and warming up to 50 °C, 3 min and 42 s of heat-
obtained from Rayong Field Crop Research Center in
ing at 12 °C /min up to 95 °C, 2.5 min of holding at 95 °C,
Thailand. The varieties were planted in December 1999
3 min and 48 s of cooling down to 50 °C at same the rate
and harvested in June 2001.
as the heating and 2 min holding at 50 °C.

2.2 Dry chip production


2.5 Thermal properties
The fresh root with a moisture content of around 61% (wet
basis, w. b.) was cleaned, washed and peeled. It was then Differential scanning calorimetry (DSC) analysis was per-
hand chopped into rectangular shape of dimensions 50 × formed using a Perkin Elmer system (Model DSC7; Nor-
24 × 6 mm, placed on drying trays and left in the sun for walk, CT, USA). Gelatinization properties were evaluated
drying. The rate of chip loading on to the trays was using 5 mg (d. b.) starch suspended in distilled water at a
6.56 kg/m2 [4] and it was stirred every 2 h. After 24 h of starch-water ratio of 1:3 (w/w). Scanning was done from
drying the moisture content dropped to 12% (w. b.). The 40 to 110 °C at a rate of 10 °C/min. Distilled water was
chips were then placed in polyethylene bags of 0.1 mm used in the reference pan. To evaluate retrogradation
thickness and stored at room temperature until required properties pastes obtained from gelatinization test were
for starch extraction. cooled and stored at 4 °C for 7 days after which they were
rescanned for the same range of temperature at same
heating and cooling rates as for gelatinization. Onset,
2.3 Starch extraction peak and conclusion temperatures (To, Tp and Tc, respec-
About 333 g of freshly chopped root was blended (Model tively) and enthalpy (∆Η) of gelatinization were deter-
Masterchef 65, Moulinex France) with 0.4 L water for 5 mined automatically. Gelatinization range (R), peak
min and sifted through a 200 mesh screen. The residue height index (PHI) and retrogradation (R%) were comput-
was rinsed twice with 300 mL of water each time to re- ed as described by Yamin et al. [5].
move remnants of starch. The slurry was left for 1 h be-
fore decanting the liquor. The starch was suspended 2.6 Swelling power, paste clarity and freeze-
three times in 3 L water (the last suspension in distilled thaw stability
water) and non-starch materials removed by decanting
the supernatant. The starch was then dried in a hot air A sample of 0.5 g (d. b.) starch suspended in 15 mL of dis-
oven at 45 °C for 18 h to attain 11 – 12% moisture content tilled water was heated in a hot water bath at 85 °C for
(w. b.), sifted with 200 mesh sieve, placed in a polyethyl- 30 min with vigorous shaking every 5 min. The cool paste
ene bag and stored at room temperature until required. was centrifuged at 2200 × g for 15 min. The supernatant
was decanted and the swelling power was determined as
Extraction of starch from dry chip was conducted in two the ratio of weight of sediment to dry weight of starch so-
ways, wet-milling (blending) and dry-milling. In wet- lidified by swelling (g/g) [6].
milling, the prepared dry chip was steeped in water at
room temperature for 24 h, changing the water every 6 h. Paste clarity was determined following the procedure by
Starch extraction from the re-hydrated chip was carried Craig et al. [7], using a spectrophotometer (Model Unicam
out the same way as described for the fresh root. 8675, Spectronic, Leeds, UK).
Starch/Stärke 55 (2003) 287–296 Physicochemical and Functional Properties of Cassava Starches 289

Freeze-thaw stability was evaluated using 5% starch rated from the starch by decanting. Three rounds of
pastes as described by Bello-Pérez et al. [8]. Each sam- washing the starch cake were needed to obtain a clean
ple was subjected to 1 – 5 cycles of 18 h freezing at and white starch sample.
–20 °C followed by 6 h thawing at room temperature.
During the process of starch extraction from dry chips by
wet milling greater disintegration of cell content occurred
2.7 Amylose content and proximate resulting in large proportion of fine fiber as compared to
composition
fresh root processing. Some of the fine fiber, which man-
The apparent amylose contents were determined by a aged to pass through the sieve with the starch, remained
simplified blue amylose-iodine complex procedure [9] us- loose on the surface of a tightly packed starch cake. This
ing a spectrophotometer (Model Unicam 8675). Starch fine fiber was easily washed off with water.
content was assayed as glucose colorimetrically after en-
Dry milling of the chips to 200 mesh size (80%) resulted in
zymatic conversion and subsequent reaction with glucose
flour with highly varying particle size comprising of very
oxidase-peroxidase [10]. Protein (N × 6.25) was deter-
fine and coarse materials. Upon washing the flour to re-
mined with a semi-micro Kjeldahl unit following AOAC
trieve the starch the apertures of the sieve were frequent-
standard method 2055 [11]. Lipids were analyzed using
ly clogged making it difficult for the starch slurry to pass
the Soxhlet method according to AOAC official procedure
through. Use of excess water was necessary to force the
[11]. Ash content was determined by weight of samples
material through the sieve. Large amount of fine fiber thus
after incineration in a muffle furnace at 550 °C for 3 h.
managed to pass through the sieve with the starch slurry
Crude fiber was determined according to AOAC official
but remained isolated on the top of the tightly packed
method [12].
starch cake. A minute fraction of the starch presumably of
smaller particle size remained trapped in the fiber forming
2.8 Statistical analysis small aggregates randomly spread throughout the same.
Analytical determination of data was performed in tripli- Decanting the water and subsequent washing of the cake
cate. Analysis of variance and Duncan multiple range test surface with water enabled to remove the mixture of fine
were done using SPSS (Version 9.0). starch and fiber. The starch yield per kilogram of net
peeled root is presented in Tab. 1. The quantity of starch
obtained from fresh root and that from dry chip by wet
3 Results and Discussion milling was almost equal for all the three varieties. How-
ever, dry milling resulted in high loss of starch ranging
3.1 Starch isolation and yield
from 13% to 20% of that obtained from fresh root. The
In fresh root processing the blended constituents of the loss is attributed to the small size starch particles re-
cell easily passed through the sieve leaving behind larger moved together with the fine fiber particles during clean-
fiber materials. The starch in the slurry quickly settled at ing of the starch cake and due mainly to that lost in form
the bottom forming a tightly packed layer while other cell of unreleased starch embodied in the large pieces of flour
contents and fine fiber materials remained dissolved particles which were not able to pass through the sieve
and/or suspended in the water. These were easily sepa- during wet sifting.

Tab. 1. Yield and composition of cassava starches processed from fresh root and dry chip.
Variety Process method Starch yield Composition [%]
[g/kg] Starch Fiber Lipid Protein Ash
CMR Fresh root 278±3.2a 98.1±0.6a 0.17±0.02a 0.08±0.03 0.30±0.02a 0.08±0.01
Dry chip (wet-milled) 278±3.4a 97.4±0.3ab 0.21±0.02ab 0.11±0.08 0.32±0.03a 0.13±0.01
Dry chip (dry-milled) 221±3.3b 97.2±0.4b 0.22±0.02b 0.04±0.01 0.30±0.02a 0.14±0.01
KU50 Fresh root 247±4.8a 98.1±0.2a 0.19±0.03a 0.12±0.01 0.25±0.03a 0.09±0.01
Dry chip (wet-milled) 249±4.2a 97.3±0.2b 0.31±0.04b 0.03±0.01 0.28±0.02a 0.09±0.02
Dry chip (dry-milled) 207±7.8b 97.1±0.2b 0.42±0.15c 0.05±0.02 0.36±0.05b 0.16±0.02
R5 Fresh root 246±7.5a 98.3±0.2a 0.16±0.02a 0.06±0.04 0.27±0.01a 0.10±0.01
Dry chip (wet-milled) 242±3.5a 97.4±0.5b 0.26±0.01b 0.15±0.05 0.26±0.03a 0.07±0.01
Dry chip (dry-milled) 214±9.9b 96.8±0.2b 0.28±0.03b 0.05±0.02 0.25±0.07a 0.12±0.01
All data are averages of triplicates and expressed in dry basis.
Means of each component within a variety followed by same letter are not significantly different (p < 0.05).
290 Abera et al. Starch/Stärke 55 (2003) 287–296

3.2 Pasting properties

84.8±0.8a
85.9±0.4b
85.9±0.4b
85.4±0.4a
86.3±0.0b
86.9±0.5b

84.5±0.0b
84.7±0.1b
83.4±1.0a
temp.[°C]

84.5±1.0
The viscosity profiles of the starch produced from fresh

Peak
roots, wet and dry milled chips are presented in Fig. 1.
They are typical of what has been reported previously of
cassava native starch [13, 14]; including a sharp rise in
viscosity shortly after pasting temperature, reaching the
peak viscosity followed by a drop until it reached the

71.8±0.0a
73.6±0.1b
73.7±0.0b
72.2±0.5a
76.0±0.0b
75.7±0.5b
70.0±0.5a
72.6±0.0b
72.4±0.5b
temp.[°C]

68.6±0.0
Pasting
trough viscosity (TV) before rising again gradually to a
moderately higher final viscosity (FV). The profiles of the
two groups of starches are the same except for the varia-
tions in values of main properties. Tab. 2 shows the val-
ues of the measured pasting properties.

69±12.7b
91±5.5a
63±2.6b
60±3.6b
80±5.8a
70±6.7b
65±6.9b
86±8.5a

65±3.6b
56±3.9
Setback
[RVU]
Peak viscosities (PV) of fresh-root starches were higher
than those of dry-chip starches. Even though the differ-

Tab. 2. Pasting properties of cassava starches extracted from fresh root and dry-chip obtained from RVA viscograms.
ences were statistically significant (p < 0.05) they were
not appreciable. Besides, the former had considerably
higher breakdowns (BD). These were because granules

208±13.3b

231±11.9a
226±3.7a
203±6.2b

229±4.5a
218±9.3b
228±8.5a
228±4.8a

212±3.7b
Final visco.
of fresh root starches had undergone a higher degree of

173±5.3
[RVU]
swelling and subsequent disintegration than those of dry-
chip starches, as evidenced by the higher swelling power
of the former (Tab. 5). The relatively higher fiber content in

Means of each property within a variety followed by same letter are not significantly different (p < 0.05).
156±5.4b
220±5.0a
194±0.8b
187±3.6b
234±0.9a
169±5.2b
171±5.3b
Breakdown

196±1.3a
160±1.9b

172±4.5
[RVU]

140±3.9ab
148±10.2b
Trough visco.

134±4.6a

148±3.8a

141±3.9a
162±6.9b
146±0.6a
150±1.2a

163±1.8b

117±2.1
[RVU]
Peak visco.

331±5.7a
300±5.6b
304±8.5b
370±3.9a
342±4.3b
350±5.0b
375±3.9a
332±3.7b
318±4.9c
289±2.9
[RVU]

All values are averages of triplicates.


Dry chip (wet-milled)

Dry chip (wet-milled)

Dry chip (wet-milled)


Dry chip (dry-milled)

Dry chip (dry-milled)

Dry chip (dry-milled)


Process method

Native commercial starch


Fresh root

Fresh root

Fresh root

Fig. 1. Pasting profiles of cassava starches: fresh root


Variety

KU50
CMR

( ), wet-milled chip ( ) and dry-milled chip ( )


R5

as determined by Rapid Visco Analyser.


Starch/Stärke 55 (2003) 287–296 Physicochemical and Functional Properties of Cassava Starches 291

dry-chip starches (Tab. 1) may have acted as a barrier to Pasting and peak temperatures of fresh root starches
heat transmission to and expansion of the starch granules were more or less the same as those reported elsewhere
resulting in delayed gelatinization, lower swelling and less [21] taking into account minor differences that may prevail
disintegration. Moorthy et al. [15] noted that fiber content due to varietal differences and environmental factors.
plays an important role in determining the characteristics Both pasting temperatures of the fresh root starches were
and functional properties of cassava starches. Further- found significantly (p < 0.05) lower than those of dry-chip
more, the drying of the high moisture content (61% w. b.) starches (Tab. 2). The differences varied between
chips at elevated temperature is likely to anneal the 2 – 3 °C. The higher pasting and peak temperatures of the
starches. Annealing of granular starches, which involves dry-chip starches indicated the impact of the fiber [15] and
incubation in excess water, for a certain period of time, at of annealing of the starches [16] in delaying gelatinization
a temperature above the glass transition temperature but of the granules.
below the gelatinization temperature, changes the amor-
phous part of the starch granules structure [16]. Accord- All aspects that have been discussed above on the past-
ing to Jacobs et al. [16] annealing of native starches leads ing properties of starches processed from fresh root and
to higher pasting temperature and more stable viscosity in dry chips have also been observed in case of six other va-
potato starches. Atichokudomchai et al. [17] found that rieties considered under the same study (data not pre-
annealing resulted in a shift of gelatinization endotherms sented).
to a higher temperature, a narrowing of the endotherms
and an unchanged or higher gelatinization enthalpy. They
concluded that the changes resulted from the ordering of 3.3 Gelatinization
double helices in the crystalline regions. Moreover, inter-
action between amylose and amylopectin [18], growth of Gelatinization of starch in water is the collapse of the
crystallites [19], and changes of the coupling forces be- crystalline structure in the granules accompanied by in-
tween crystallites and the amorphous matrix [20] were crease in volume, due to swelling, and leaching of soluble
forwarded as possible explanations. No consistent trend amylose and amylopectin into the surrounding aqueous
has been noted as regards FV. However, setbacks (SB) media as a result of heating [22]. The gelatinization prop-
were consistently and significantly (p < 0.05) higher for erties of starches extracted from fresh root and dry chip
fresh root starches than for dry chip starches. Observa- are summarized in Tab. 3 and the thermograms shown in
tion of the cooked starch obtained after the viscosity test Fig. 2. The temperatures agreed with those reported by
showed that pastes of dry-chip starches were less clear Moorthy et al. [23]. Gelatinization temperatures are re-
(translucent) and of shorter texture. On the other hand flection of the crystallite perfection [24]. The high gela-
PV, BD and SB of starches processed from dry chips by tinization temperatures of the starches indicate that the
wet and dry millings showed statistically not significant granules have a high level of crystallinity as evidenced by
difference between them. their high amylopectin content.

Tab. 3. Gelatinization properties of cassava starches extracted from fresh root and dry-chip as obtained from DSC ther-
mograms.
Variety Starch Process Onset temp. Peak temp. Conclusion Enthalpy Gelatinization Peak Height
[°C] [°C] temp. [°C] [J/g] range [°C] Index
CMR Fresh root 66.4±0.2a 70.0±0.3a 82.6±0.6a 15.3±0.3a 7.4 4.2
Dry chip (wet-milled) 67.1±0.2b 71.0±0.3b 81.1±0.3b 15.3±0.1a 7.9 3.9
Dry chip (dry-milled) 67.4±0.4b 71.6±0.2c 82.7±1.1a 14.6±0.3b 8.5 3.5
KU50 Fresh root 66.1±0.2a 72.2±0.5a 83.0±0.6a 15.5±0.1a 12.3 2.5
Dry chip (wet-milled) 69.1±0.4b 75.3±0.5b 84.6±0.7b 16.2±0.1b 12.3 2.6
Dry chip (dry-milled) 68.6±0.3b 75.5±0.2b 85.6±0.0b 15.1±0.1c 13.7 2.2
R5 Fresh root 63.9±0.2a 68.9±0.2a 80.3±1.2a 14.9±0.1a 10.2 2.9
Dry chip (wet-milled) 66.0±0.1b 71.4±0.4b 80.9±0.3a 14.7±0.6a 10.7 2.7
Dry chip (dry-milled) 66.6±0.2c 71.3±0.4b 81.3±0.9a 14.2±0.1b 9.4 3.0
Native commercial starch 65.0±0.1 69.8±0.4 81.1±0.5 15.1±0.1 9.6 3.2
All values are averages of triplicates.
Means of each property within a variety followed by same letter are not significantly different (p < 0.05).
292 Abera et al. Starch/Stärke 55 (2003) 287–296

dation [%]
Retrogra-

9.1a
12.5b

10.4a
12.3b

7.8a
10.5c

9.1c
11.7b

11.3b

13.9
Peak Height
Index
0.26
0.30
0.29
0.27
0.26
0.26
0.19
0.23
0.22
0.27
Tab. 4. Retrogradation properties of cassava starches extracted from fresh root and dry-chip obtained from DSC thermograms.
Gelatinization
range [°C]
10.5
12.6
10.5

15.1
13.6
12.3
14.2

15.5
11.9

11.7
1.8±0.4ab
1.4±0.4a
1.9±0.1b
1.5±0.1a
1.6±0.3a
2.0±0.0b

1.2±0.1a
1.7±0.2b
1.3±0.0a
2.1±0.02
Enthalpy
[J/g]
Fig. 2. DSC thermographs of gelatinization of starches

Means of each property within a variety followed by same letter are not significantly different (p < 0.05).
from fresh root ( ), wet-milled chip ( ) and dry-
65.1±0.4b
64.7±0.3b
63.6±0.6a
67.6±2.4b
67.3±0.2b

63.0±0.8b
Conclusion

62.9±1.2a

61.6±1.4a

63.8±1.3b
temp. [°C]

62.8±0.1
milled chip ( ). The thermograph of commercial
starch is shown for comparison.

Cooke and Gidley [25] indicated that enthalpy of gela-


tinization was a result of both the level of crystallinity and
54.7±2.0a
55.7±0.4b
55.7±0.5b

59.7±2.4b

55.1±0.2a
56.3±0.7b
Peak temp.

58.5±2.3c
56.7±1.1a

56.3±1.3b
56.3±0.6
level of the double-helical order of amylopectin. Gela-
[°C]

tinization of wet milled dry-chip starches exhibited smooth


and relatively sharp endotherms similar to those of the
fresh root starches. Neither narrowing nor broadening of
bases and peaks of endotherms were noted relative to
50.3±0.8ab
Onset temp.

their counterparts. Melting enthalpies, gelatinization


49.5±2.3a
49.4±0.2a
50.5±0.2b
50.8±0.6a

51.7±0.2b

50.5±0.3b
52.1±1.5b

48.9±1.1a

48.5±1.2

ranges and peak height indices of both group of starches


[°C]

showed little difference except dry-chip starch of KU50


which exhibited a slight increase in enthalpy value. How-
ever, the endotherms of dry-chip starches shifted to high-
er temperatures by few degrees as can be seen from To,
Tp and Tc (Tab. 3). This is in line with the result of RVA
All values are averages of triplicates.

analysis that showed higher pasting and peak temper-


Dry chip (wet-milled)

Dry chip (wet-milled)

Dry chip (wet-milled)


Dry chip (dry-milled)

Dry chip (dry-milled)

Dry chip (dry-milled)

atures for dry chip starches (Tab. 2). These changes are
Starch process

attributed to the same causes, brought forward earlier to


Native commercial starch

explain the changes in pasting property of dry-chip


Fresh root

Fresh root

Fresh root
Condition

starches, namely high fiber content and annealing of the


starches. The maximum differential gelatinization tem-
perature (in both To and Tp) was about 3 °C in the case of
KU50, which was also found to have the highest differ-
ence of about 4 °C in pasting temperatures. This can be
Variety

KU50
CMR

explained by the fact that KU50 starches processed from


R5

dry chip had the highest fiber content of all three varieties
Starch/Stärke 55 (2003) 287–296 Physicochemical and Functional Properties of Cassava Starches 293

(Tab. 1) and also exhibited an increase in gelatinization


enthalpy implying some change in the granules structure
as compared to the other starches.

Dry-chip starches processed by wet- and dry-milling


methods showed little difference in almost all gelatiniza-
tion properties between themselves with nearly identical
endotherms. However, the latter exhibited relatively lower
enthalpies that may be due to some degree of mechanical
damage inflicted to the granules during milling. The ex-
pected effect of lowering gelatinization temperatures due
to the starch damage was not observed probably be-
cause of low intensity of damage and/or counter effects of
the fiber and annealing.

3.4 Retrogradation

Retrogradation is a result of re-association of starch mol-


ecules in an ordered structure [22]. It is a situation where
the dissolved amylose chains associate to form helices
and insoluble double helices when starch paste cools.
Further retrogradation involves formation of inter- and in-
tra-molecular double helices of amylopectin resulting in a
Fig. 3. DSC thermographs of retrogradation of starches
gel. Tab. 4 presents the summary of retrogradation prop-
from fresh root ( ), wet-milled chip ( ) and dry-
erties of starches processed from fresh roots and dry
milled chip ( ). The thermograph of commercial
chips. Onset, peak and conclusion temperatures of the starch is shown for comparison.
retrograded starch were very much lower than those of
the native (fresh) starch. This is understandable as the
level of crystallinity restored by retrogradation was ex-
pected to have a different kind of order than the original. DSC traces of retrograded starches are shown in Fig. 3.
Both groups of starches had distinctly noticeable but
small endotherms for all the three varieties indicating low
Little difference was found in To and in Tp between starch- level of retrogradation. Dry milled starches had lower en-
es from fresh root and dry-chip for varieties CMR and R5. thalpies and retrogradation than wet milled ones for the
However, KU50 showed 3 to 4 °C difference in Tp and Tc same reason mentioned earlier in Section 3.3.
between the two groups. Enthalpy, peak height indices
and percentage of retrogradation of starches of all the
three varieties were higher for dry-chip starches than for
3.5 Swelling power
their counterparts which is a reflection of the higher de- Tab. 5 presents values of swelling power of starches.
gree of retrogradation of the former. This may seem in Tester and Morrison [24] had suggested that swelling of
contradiction with the results of RVA tests where the set- starch was attributed to amylopectin. Furthermore,
back values of fresh-root starches were higher than those swelling has a high negative correlation with amylose
of dry-chip starches. But this could be explained by the [28]. As the ratios of amylose/amylopectin fractions of the
fact that the breakdown values of the fresh root starches three varieties were not much different from one another
were so large that proportionally the setback would natu- so were the swelling powers of the starches from fresh
rally be high despite having a relatively lower percentage roots. Swelling is inhibited by lipid content of starch [22].
of retrogradation. Various starches retrograde differently The starches being of low lipid content (Tab. 1) no appre-
depending on the ratio of the amylose and amylopectin ciable influence was expected from lipid. However, as the
components of the starch, the molecular weight of amy- amylose contents (22.5% for R5, 22.9% for CMR and
lose and the chain length of amylopectin [26, 27]. Little 23.8% for KU50) were slightly higher than that reported
difference was exhibited in the retrogradation rate of (17%) elsewhere [14] the values of the swelling power
starches from the three varieties as there is between their were also less. Cassava varieties with amylose contents
amylose contents (22.5% for R5, 22.9% for CMR and exceeding 20% [29-31] are likely to have lower swelling
23.8% for KU50). power [28].
294 Abera et al. Starch/Stärke 55 (2003) 287–296

Fresh-root starches were found to have higher swelling

45.8±2.8a
46.8±4.1a
45.8±2.2a
46.1±0.3a
44.8±2.3a
44.1±0.9a
49.6±4.5a
47.6±4.5a
47.9±0.3a
Cycle 5
power (p < 0.01) than dry-chip starches for all the vari-
eties. This goes in agreement with the result of the RVA
where the peak viscosity values of the former were
greater than those of the latter. Values of swelling power
of dry-chip-starches processed by wet and dry milling

42.3±4.7a
46.1±2.1a
45.5±2.2a
45.7±0.5a
40.7±0.8b
41.8±0.5b
38.0±3.2a
39.5±4.0a
37.5±0.4a
methods have little difference between them except for

Cycle 4
KU50 where a profound difference was observed. How-
ever, this was not reflected by the RVA results.

In general the swelling power of the starches from both


fresh root and dry chip was not as high as reported in

Syneresis [%]

37.4±2.6b
39.1±3.0b
38.6±0.3a
33.6±0.5b

30.7±2.3a
31.5±1.1a

34.5±1.2b

30.8±1.4a
27.5±1.2a
some references [14]. This may be explained by varietal

Cycle 3
differences and environmental factors [13, 32].

3.6 Paste clarity

9.4±0.3a
19.6±2.1b
20.2±0.9b
17.3±0.6a

9.8±0.7a
26.1±0.9b
Tab. 5 shows summary of light transmittance values of

26.3±0.5c

22.6±0.7c
23.8±1.2b
Cycle 2
pastes produced from fresh root and dry chip starches.
The values are in agreement with other findings on cas-
sava starch [7]. Pastes of fresh root starches were found
to have a much higher light transmitting capacity than
those of dry-chip starches. The difference could be due to

Means of each property within a variety followed by same letter are not significantly different (p < 0.05).
3.8±0.0a

2.9±0.4a

18.9±0.3b
0.1±0.0a
4.7±0.2b
4.3±0.4b
8.0±1.3b
10.1±1.4b

17.5±1.5b
the presence of a higher level of fiber in pastes of dry-chip
Tab. 5. Functional properties of cassava starches processed from fresh root and dry chip.

Cycle 1
starches that would have a double effect in reducing clar-
ity. Firstly light would reflect on the surface of the fiber
particles resulting in diffused scattered light and also be
absorbed by the particles. Thus the intensity of light pass-
ing through the paste would be reduced [7]. Secondly in-
terference of the fibers inhibiting the expansion of the
Transmittance

68±0.8a
62.3±0.1b

63.5±0.6a
56.7±0.8b

67±0.4a
54.1±0.9b
53.9±0.8b
49.7±0.6c

35.2±1.6c
granules [15] may have resulted in retarded and distorted
swelling of single and aggregates of granules causing
[%]

non-uniform bending and inhomogeneous reflection of


light. Little difference in paste clarity was found between
wet-milled and dry-milled starches of dry chips for R5 and
CMR varieties. However, a significant difference was
Swelling power

25.5±0.4a

22.5±0.2b
25.7±0.3a

26±0.9a
19.9±0.6b
18.6±0.6c
23.6±1.4b

22.4±1.7b

20.2±1.8b

found for variety KU50 attributed to the large difference in


[g/g]

fiber content between the two differently milled starches.

3.7 Freeze-thaw stability


All values are of averages of triplicates.

The results of the syneresis test of the starches are


shown in Tab. 5. Gel of fresh root starch resulted in very
Dry chip (wet-milled)

Dry chip (wet-milled)

Dry chip (wet-milled)


Dry chip (dry-milled)

Dry chip (dry-milled)

Dry chip (dry-milled)

low syneresis value for the first two freeze-thaw cycles


Process method

and increased abruptly and steadily in the subsequent


ones for all the three varieties. The gel did not show no-
Fresh root

Fresh root

Fresh root

ticeable change in its texture for the first two cycles. It re-
mained as soft and loose as it initially was (before freez-
ing) with a tendency to flow when subjected to gravity
force. The gel became more compact and relatively firmer
with increase in the number of cycles. But it still had a
Variety

KU50
CMR

smooth surface. In general the extent of syneresis in-


R5

creased with the number of freeze-thaw cycles.


Starch/Stärke 55 (2003) 287–296 Physicochemical and Functional Properties of Cassava Starches 295

Starches from dry chips showed a considerably higher retrogradation properties including percentage of ret-
rate of syneresis than those from fresh roots in the first rogradation were also higher for dry-chip starches. How-
two cycles. This is related to the higher degree of ret- ever, the endotherms of the two groups of starches were
rogradation displayed by the former group (Tab. 4). These almost identical except a shift by few degrees to a higher
starches must have retrograded faster than their counter- temperature for those of dry-chip starches. This suggest-
part in the first two cycles such that more water separated ed occurrence of no major structural changes in the gran-
from the gels. However, in the subsequent cycles the rate ules of dry-chip starches due to chip drying and starch ex-
of increase in syneresis value was not much different. As traction. Moreover, dry-chip starches showed lower
freezing and thawing continued the gels of all the starch- swelling power, paste clarity, and freeze-thaw stability
es had enough time for more retrogradation hence in- than their counterpart. Percentage of syneresis increased
creased syneresis. Furthermore, rate of syneresis in both with the number of cycles for all the three types of starch-
groups of starches was highest for variety KU50, particu- es and cassava varieties. These differences in properties
larly in the first two cycles, followed by CMR and R5. This may have resulted largely from differences in the fiber
may be the influence of the amylose content on degree of content and also from annealing due to exposure to ex-
retrogradation hence on freeze-thaw stability of starches. cess heat and moisture during processing. The differ-
The syneresis of starches processed from dry chip ences are without severe drawback for the suitability of
showed little difference between those wet milled and dry dry-chip starches in many applications. Furthermore, the
milled ones for all the three varieties. high stability and resistance against heat and shear could
be beneficial in many respects. Processing of starch from
The gel texture of dry-chip starches after thawing during dry cassava chips resulted in more fine fiber particles in
the first cycle was relatively loose although not as loose the starches and required a more efficient method of sep-
as that of the fresh root starch. Gels in the subsequent cy- aration than processing from fresh root. It is felt that the
cles were more compact and firmer than their counter- problems indicated by earlier workers [3] in the prepara-
parts of the fresh root starches and capable of withstand- tion of good quality starch can easily be overcome taking
ing a certain level of tensile force. When subjected to light into account that they had started with pellets and chips
pressure, even after centrifuging, a considerable quantity prepared for animal feed containing sand, high fiber and
(about 0.5 mL) of water oozed out, unlike in the fresh root other impurities.
starch gels, indicating that greater separation of water
had occurred in the system although was not fully re- It is the opinion of the present authors that with little or no
trieved due to re-adsorption. This showed that the gel had modification to the modern processing equipment cur-
a porous texture. Rate of syneresis consistently in- rently in use it may be possible to extract starch of higher
creased up to the fifth cycle for all the three types of purity and desirable functional characteristics from dry
starches and all varieties. cassava chips which have been appropriately prepared
on a commercial scale.
In general the gels of starches extracted from fresh root
were found to have a better freeze-thaw stability than
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