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Article history: Potato starch was esterified with octenyl succinic anhydride (OSA) in aqueous slurry systems and the
Received 10 October 2007 major factors affecting the esterification were systematically investigated. The physico-chemical proper-
Received in revised form 19 July 2008 ties of the products were determined by means of Fourier transform infrared (FT-IR) spectroscopy, scan-
Accepted 4 September 2008
ning electron microscopy (SEM), X-ray diffraction and a viscosity analyser (VA). The results indicated that
suitable parameters for the preparation of OSA starch from potato in aqueous slurry systems were as fol-
lows: concentration of starch slurry, 35% (in proportion to water, w/w), reaction period, 3 h, pH of reac-
Keywords:
tion system, 8.0, reaction temperature, 35 °C, amount of OSA, 3% (in proportion to starch, w/w), OSA
Potato starch
OSA starch
dilution-fold, 5. The degree of substitution (DS) was 0.017 and the reaction efficiency (RE) was
Esterification 72 ± 1.8%. FT-IR spectroscopy showed characteristic absorption of the ester carbonyl groups in the OSA
Preparation condition starch at 1724 cm1. SEM and X-ray diffraction revealed that OSA groups acted by first attacking the sur-
Physico-chemical properties face and some pores formed, but OSA modification caused little change in the crystalline pattern of potato
starch (DS 0.045). Apparent pastiness measurement indicated that the starch derivatives gelatinized
within a shorter time to achieve higher viscosities over the range of designed concentration of OSA potato
starch.
Ó 2008 Elsevier Ltd. All rights reserved.
0308-8146/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2008.09.019
82 R. Hui et al. / Food Chemistry 114 (2009) 81–86
analyser was 60 rpm for the test. The peak viscosity (PKV) was 0.0145 64
recorded.
62
0.0140
2.9. Statistical methods DS
60
RE (%)
0.0135
RE (%) 58
DS
All tests were performed in triplicate. Analysis of variance (AN-
OVA) was performed using the Duncan’s multiple range tests to 56
0.0130
compare treatment means. Significance was defined at P < 0.05. 54
0.0125
52
3. Results and discussion 0.0120 50
1 2 3 4 5 6 7
3.1. Preparation of OSA potato starch Reaction time (h)
The rate and efficiency of the chemical modification process de- Fig. 3. Effect of reaction time on DS and RE. Reaction temperature was 35 °C; pH,
pend on the reagent type, botanical origin of the starch and on the 8.5; OSA concentration, 3%; starch concentration, 35% (pooled data from three
experiments are presented as means ± standard deviation of the mean (n = 3)).
size and structure of its granules (Huber & BeMiller, 2001). This
also includes the surface structure of the starch granules, which
encompasses the outer and inner surface, depending on the pores 0.0150 65
and channels, and leads to the development of the so-called spe- 0.0145 63
cific surface (Juszczak, 2003). Consequently, the preparation condi- 0.0140 61
tions were fully investigated in this part. 0.0135 59
RE (%)
0.0130 57
3.2. Effects on esterification
DS
0.0125 55
0.0120 DS 53
3.2.1. Effect of starch concentration on esterification of potato starch
0.0115 RE (%) 51
The first reaction parameter studied was the starch concentra-
0.0110 49
tion in aqueous slurry systems. Fig. 2 shows that increase in the
concentration of starch from 20% to 35% (in proportion to water, 0.0105 47
w/w) gave a steady increase of DS and RE. Further increase in the 0.0100 45
20 25 30 35 40 45 50
starch concentration, up to 40%, decreased DS and RE. Starch and Reaction temperature (°C)
OSA are insoluble in water; the esterification in aqueous slurry sys-
tems is a heterogeneous reaction. The chance that starch comes Fig. 4. Effect of reaction temperature on DS and RE. OSA concentration was 3%; pH,
8.5; reaction time, 3 h; starch concentration, 35% (pooled data from three
into contact with OSA increases with the increase in starch concen-
experiments are presented as means ± standard deviation of the mean (n = 3)).
tration; thus DS and RE increase correspondingly. However, as the
starch concentration is above 40%, it becomes difficult to agitate Fig. 1 became dominant. Thus, the optimum reaction time was
the reaction system; thus DS and RE decrease. Consequently, 35% 3 h when OSA concentration was 3%.
starch slurry was the best (p < 0.01) concentration for OSA synthe-
sis from potato starch. 3.2.3. Effect of reaction temperature on esterification
Fig. 4 shows the positive and negative effects of temperature on
3.2.2. Effect of reaction time on esterification of potato starch DS and RE. Increase in the reaction temperature from 25 to 35 °C
The effects of reaction time on DS and RE were studied (Fig. 3). resulted in large increases in DS and RE. Further increase in the
Increasing the reaction time from 2 to 3 h resulted in higher DS and reaction temperature, from 35 to 45 °C decreased DS and RE. This
RE. Prolonging the reaction time beyond 4 h resulted in a decrease is because an increase in temperature will enhance OSA diffusion
in DS and RE. An explanation was that, as the reaction progressed, into the starch granules, as well as the swelling of the starch gran-
the concentration of anhydride was depleted, due to esterification ules, that will increase the esterification rate. However, high tem-
and hydrolysis reactions. As a result, the side reactions shown in perature will result in enhanced solubility of OSA in the aqueous
phase, which will increase hydrolysis rate. Thirty five degree cel-
sius was found to be the most appropriate temperature for OSA
modification of potato starch in aqueous slurry systems. The reac-
0.018 80 tion temperature was higher than that used by Bao, Xing, Phillips,
0.016 75 and Corke (2003), but the reaction time was shortened to obtain
0.014 OSA starches with similar DS.
70
0.012
65 3.2.4. Effect of pH on esterification of potato starch
RE (%)
0.010
The pH of the aqueous slurry is important for esterification of
DS
60
0.008
DS 55
starch. As a catalyst, NaOH starts the reaction by the formation
0.006
RE (%) of alcoholate ions along the starch polymer (Funke & Lindhauer,
0.004 50
2001; Rutenberg & Solarek, 1984). In order to study the influence
0.002 45 of pH, the other reaction parameters were identical to the above
0.000 40 except that the reaction time was fixed at 3 h. Fig. 5 indicates that
15 20 25 30 35 40 45
DS and RE decreased strongly as pH was <7.5 or >8. This may be
Starch concentration (%) explained by the fact that pH values >8 favour side reactions
Fig. 2. Effect of starch concentration on DS and RE. Reaction temperature was
(Fig. 1) whereas, at pH <7.5, the hydroxyl groups of starch are
35 °C; pH, 8.5; OSA concentration, 3%; reaction time, 3 h. (pooled data from three not sufficiently activated for nucleophilic attack of the anhydride
experiments are presented as means ± standard deviation of the mean (n = 3)). moieties. Thus, pH 8.0 was used in the following experiments.
84 R. Hui et al. / Food Chemistry 114 (2009) 81–86
0.016 70 0.015 64
0.015
DS 62
0.015 65 0.014
RE (%)
0.014 60
0.014 60
RE (%)
0.013
RE (%)
58
DS
DS
0.013 55 0.013
56
0.012
0.012 DS 50
0.012 54
RE (%)
0.011 45 0.011
52
0.011
0.010 40
6 6.5 7 7.5 8 8.5 9 9.5 10 0.010 50
0 2 4 6 8 10
pH
OSA dilution times
Fig. 5. Effect of reaction pH on DS and RE. Reaction temperature was 35 °C; OSA
concentration 3%; reaction time 3 h; starch concentration 35% (pooled data from Fig. 7. Effect of OSA dilution times on DS and RE of potato starch. Reaction
three experiments are presented as means ± standard deviation of the mean temperature was 35 °C; pH, 8.0; reaction time, 3 h; starch concentration, 35%; OSA
(n = 3)). concentration, 3%. (pooled data from three experiments are presented as
means ± standard deviation of the mean (n = 3)).
0.025 60
of OSA potato starches up to DS 0.045, although the granules of
0.020
50 OSA potato starches have been damaged to some extent by the
0.015 modification processes. This observation agreed with the findings
40 of Wang and Wang (2002) and Song et al. (2006), who mentioned
0.010
that the esterification occurred primarily in the amorphous regions
0.005 30 and did not change the crystalline pattern of starches.
0 2 4 6 8 10 12
OSA concentration (%) 3.4. Scanning electron microscopy (SEM)
Fig. 6. Effect of OSA concentration on DS and RE. Reaction temperature was 35 °C;
pH 8.0; reaction time, 3 h; starch concentration, 35% (pooled data from three Starch modification involves physical, chemical and biochemi-
experiments are presented as means ± standard deviation of the mean (n = 3)). cal phenomena on the surface of contacting phases. Microscopy
R. Hui et al. / Food Chemistry 114 (2009) 81–86 85
Fig. 8. SEM photomicrographs of native potato starch granules and OSA potato starch granules. (a) Native potato starch; (b) OSA potato starch, DS = 0.025 (micrographs of
each starch sample were taken at 500 and 3000 magnifications, respectively).
is an important tool for understanding granular structure of mod- are presented in Fig. 8. SEM investigations showed that the OSA
ified starches. SEM has been used to detect structural changes treatment caused some changes in the structure of starch granules
caused by chemical modifications. Most of the structural changes compared with those of native starch. OSA starch granules exhib-
upon hydroxypropylation take place at the relatively less orga- ited slightly rough surfaces and their edges lost some definition.
nized central core region of the starch granule, i.e., where the The sides of these granules were porous and many cavities were
hydroxypropyl groups are most densely deposited (Kaur, 2004; observed. SEM photomicrographs indicated that OSA modification
Kim, Hermansson, & Eriksson, 1992). in aqueous slurry systems moderately altered the granular struc-
Potato starch granules are relatively larger than other starch ture of potato starch.
granules, in addition to having more phosphorus in the amylopec-
tin (Noda et al., 2004a; Noda et al., 2004b). Potato starch displays a 3.5. Pasting properties
normal distribution in granule size (most in the range of
20 70 lm), but the range of the size distribution is wide. Scan- Starch paste viscosity can be increased or reduced by applying a
ning electron photomicrographs of native and OSA potato starches suitable chemical modification (Agboola, Akingbala, & Oguntimein,
a 2500 b 5000
6r/min
2000 6r/min 4000 12r/min
Apparent viscosity (mPa.s)
12r/min
30r/min
30r/min
60r/min
1500 60r/min 3000
1000 2000
500 1000
0 0
0.5 1 1.5 2 0.5 1 1.5 2
concentration (%) concentration (%)
Fig. 9. The relationships between starch concentration, shaking speed and apparent viscosity. (a) Native potato starch; (b) OSA potato starch (DS = 0.017).
86 R. Hui et al. / Food Chemistry 114 (2009) 81–86
1991). Again, modification method, reaction conditions and starch Fang, J. M., Fowler, P. A., Sayers, C., & Williams, P. A. (2004). The chemical
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Carbohydrate Polymers, 55, 283–289.
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native and OSA modified potato starches are given in Fig. 9 at dif- of potato crop stat. data 2005. Rome, Italy: FAO http://www.fao.org.
ferent shaking speeds and different OSA starch concentrations. The Funke, U., & Lindhauer, M. G. (2001). Effect of reaction conditions and alkyl chain
lengths on the properties of hydroxyalkyl starch ethers. Starch/Stärke, 53,
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