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Food Chemistry 114 (2009) 81–86

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Preparation and properties of octenyl succinic anhydride modified potato starch


Ruan Hui, Chen Qi-he *, Fu Ming-liang, Xu Qiong, He Guo-qing *
Department of Food Science and Nutrition, Zhejiang University, Kaixuan Road 268, Hangzhou 310029, PR China

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

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.

1. Introduction hydroxide is used to enhance the nucleophilicity of the hydroxyl


group and to swell the starch particles. But sodium hydroxide also
Among carbohydrate polymers, starch is currently enjoying in- plays a role in undesired side reactions (Rutenberg & Solarek,
creased attention owing to its usefulness in different food prod- 1984). After OSA modification, starch is an effective emulsifier,
ucts. Native starch is a good texture stabilizer and regulator in due to the addition of bifunctional groups that are both hydrophilic
food systems (Cousidine, 1982), but constraints, such as low shear and hydrophobic (Tesch, Gerhards, & Schubert, 2002). OSA starch
resistance, thermal resistance, thermal decomposition and high has been used in food products such as sauces, puddings, and baby
tendency towards retrogradation, limit its use in some industrial foods for more than 30 years. Recently, OSA starch was reported to
food applications. Starch modification, which involves the alter- have special nutritional value. Heacock, Hertzler, and Wolf (2004)
ation of the physical and chemical characteristics of the native found that esterification of starch with OSA might impair the bind-
starch to improve its functional characteristics, can be used to tai- ing of a-amylase, thus decreasing the extent of starch digestion.
lor starch to specific food applications (Hermansson & Svegmark, Their study indicated that OSA starch appeared to be a resistant
1996). Starch modification is generally achieved through derivati- starch, which could be used as a functional fibre for the treatment
zation, e.g., by etherification, esterification, cross-linking and graft- of certain human diseases.
ing of starch, decomposition (acid or enzymatic hydrolysis and Although many studies on the esterification of starches have
oxidization of starch) or physical treatment of starch using heat been conducted (Billmers & Mackewicz, 1997; Jeon, Viswanathan,
or moisture. & Gross, 1999; Jyothi, Rajasekharan, Moorthy, & Sreekumard, 2005;
The chemical and functional properties achieved, upon modify- Park, Chung, & Yoo, 2004; Song, He, Ruan, & Chen, 2006), little
ing starch by chemical substitution, depend, inter alia, on starch work has been reported on the preparation conditions and proper-
source, reaction conditions (reactant concentration, reaction time, ties of OSA starch from potato. Potato ranks fourth after wheat,
pH and the presence of catalyst), type of substituent, extent of sub- maize and rice in global production. In developing countries, such
stitution (DS), and the distribution of the substituent in the starch as India, with an average annual production of 25 million tons of
molecule (Hirsch & Kokini, 2002; Kavitha & BeMiller, 1998). OSA potato (FAO, 2005), the cold storage facilities available in the coun-
starch is synthesized in aqueous slurry systems. The different reac- tries are insufficient to accommodate the surplus produce during a
tions occurring during the synthesis are shown in Fig. 1. Sodium glut season, whereby the value addition to potato becomes inevita-
ble (Ezekiel, Verma, Sukumaran, & Shekhawat, 1999). Potato is
* Corresponding authors. largely produced in northern China; in considering this, potato
E-mail addresses: chenqh@zju.edu.cn (C. Qi-he), gqhe@zju.edu.cn (H. Guo-qing).

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

2.4. Determination of the degree of substitution

The degree of substitution (DS) is the average number of hydro-


xyl groups substituted per glucose unit. The DS of OSA starch was
determined by titration (Kweon, Choi, Kim, & Lim, 2001). An OSA
starch sample (5 g, dry weight) was accurately weighed and dis-
persed by stirring for 30 min in 25 ml of 2.5 M HCl isopropyl alco-
hol solution. 100 ml of 90% (v/v) aqueous isopropyl alcohol
solution were added and the slurry stirred for an additional
10 min. The suspension was filtered through a glass filter and the
residue was washed with 90% isopropyl alcohol solution until no
Cl could be detected any longer (using 0.1 M AgNO3 solution).
The starch was re-dispersed in 300 ml of distilled water, and then
the dispersion was cooked in a boiling water-bath for 20 min. The
starch solution was titrated with 0.1 M standard NaOH solution,
using phenolphthalein as an indicator. A blank was simultaneously
titrated with native starch as a sample. The DS was calculated by
the following equation:
0:162  ðA  MÞ=W
Fig. 1. Chemical reactions during OSA modification.
DS ¼
1  ½0:210  ðA  MÞ=W
where A is the titration volume of NaOH solution (ml), M is the
could be a cheap alternative source for various starch products and molarity of NaOH solution, and W is the dry weight (g) of the OSA
modified starch products in China. starch.
In the current study, OSA starches were prepared from potato The reaction efficiency (RE) was calculated as follows:
starch in aqueous slurry systems. The major factors affecting the
esterification process, including starch concentration, reaction Actual DS
RE ¼  100%
time, pH of reaction system, reaction temperature and OSA concen- Theoretical DS
tration, were systematically investigated. The physico-chemical The theoretical DS was calculated by assuming that all of the
properties of the products were determined by means of Fourier added anhydride reacted with starch to form the ester derivative.
transform infrared (FT-IR) spectroscopy, scanning electron micros-
copy (SEM), X-ray diffraction and the visco analyser (RVA). The re- 2.5. Fourier transform infrared (FT-IR) spectroscopy
sult may give a complete insight into the factors that affect the
esterification process, and allow determination of the optimum The change in chemical structure of the starch was qualitatively
operating conditions to achieve OSA potato starch with a high de- analyzed by using FT-IR (Nexus 670, Nicolet, Madison, WI, USA).
gree of substitution (DS) and reaction efficiency (RE). Samples were prepared by grinding the finely powdered starch
with KBr. The spectrum was recorded over the wave number range
2. Materials and methods between 400 and 4000 cm1. The starch samples were dried at
105 °C for 12 h before analysis to avoid interference by moisture.
2.1. Materials
2.6. Scanning electron microscopy (SEM)
The potato starch used for this study was from Gansu Jindadi
Starch Co. Ltd., (China), having the following approximate composi- The surface topography of starch granules was examined using
tion: amylopectin content 75.5 ± 2.5%, amylose content 19.5 ± 0.2%, SEM (XL-30-ESEM, Philips, Eindhoven, Netherlands). Before test-
crude protein content 0.22 ± 0.02%, crude fat content 0.18 ± 0.03%, ing, the samples were fixed onto metallic sample holders with con-
and moisture content 9.00 ± 0.16%. High-purity OSA was purchased ducting silver glue and then sputtered with a layer of gold.
from Sigma-Aldrich Chemical Co. (St. Louis, MO, USA). The other Magnifications of 500 and 3000 were used.
chemicals used in the study were of analytical grade.
2.7. X-ray diffraction
2.2. Preparation of OSA potato starch
The X-ray patterns of starches were obtained by using an X-ray
Potato starch (20 g, dry weight) was suspended in distilled diffractometer (D/max-Ra, Rigaku, Tokyo, Japan) operated at
water (20–40%, w/w) with agitation. The pH of the suspension 80 mA and 40 kV. The scanning region of the diffraction angle
was adjusted with a pH meter by adding 3% NaOH solution. A (2h) was from 5° to 50°, at 0.02° step size, with a count time of
weighed quantity of OSA was added (diluted five times with abso- 2 s. The starch samples were equilibrated at 40 °C for 24 h prior
lute alcohol, v/v) slowly over 2 h. The reaction was continued for to the analysis.
the required time. After reaction, the pH was adjusted to 6.5 with
3% HCl solution, the mixture was centrifuged, washed twice with 2.8. Pasting properties
distilled water and twice with 70% aqueous alcohol, and the solid
oven-dried at 45 °C for 24 h, then passed through a 120 mesh nylon The pasting properties were determined with a rapid rotating
sieve (60 mm opening). visco analyser (RVA) (Newport Scientific Instruments, Warrie-
wood, Australia). The analysis was based on the AACC standard
2.3. Moisture content programme for RVA analysis (AACC, 1995). Samples were prepared
by mixing starch (2.0 g) and 25 ml of distilled water. The mixture
Moisture content of the samples was determined by a moisture was stirred manually for 1 min to facilitate dispersion before test-
analyser, model No. MX-50 (A & D Co. Ltd., Tokyo). ing (Shih & Daigle, 2003). The initial speed of sample stirring in the
R. Hui et al. / Food Chemistry 114 (2009) 81–86 83

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)).

3.2.5. Effect of OSA concentration on esterification of potato starch


Fig. 6 shows the effect of OSA concentration on esterification of troscopy, differential scanning calorimetry (DSC), scanning elec-
potato starch. When the OSA concentration was increased from tron microscopy (SEM) and the visco analyser (RVA), respectively.
1.5% to 10%, DS increased but RE decreased. This may result from
insufficient mixing between the water-insoluble OSA and starch 3.3.2. Fourier transform infrared (FT-IR) spectroscopy
phases. In addition, the RE was decreased by dilution when using Succinylation leads to the substitution of hydroxyl groups in
higher amounts of anhydride and alkaline reagents. Hence, OSA the starch molecules with carbonyl groups of OSA. The introduc-
concentrations of 3–5% (based on dry starch) are preferred for tion of carbonyl groups could be confirmed by FT-IR spectroscopy
the preparation of low DS starch esters in water. If a higher conver- (Marcazzan, Vianello, Scarpa, & Rigo, 1999).
sion is needed, filtering unreacted starch from the reaction mixture The IR spectra of native and OSA modified starch showed that
and re-suspending it in a smaller but defined amount of water can native and OSA potato starch have similar profiles. In the finger-
offset the dilution effect. The esterification can be repeated using a print region, there are several discernible absorbancies at 1155,
second portion of anhydride (Billmers & Tessler, 1994). 1080, 1021 and 930 cm1, which were attributed to C–O bond
stretching (Fang, Fowler, Sayers, & Williams, 2004). Another char-
3.2.6. Effect of OSA dilution on esterification of potato starch acteristic peak occurred at 1638 cm1, which presumably origi-
The effect of OSA dilution on esterification was also investi- nates from tightly bound water present in the starch granule.
gated. Fig. 7 shows that a five times OSA dilution was the most The band at 2928 cm1 is characteristic of the C–H stretching
favourable for the esterification reaction. More or less dilution is vibration. An extremely broad band, resulting from vibration of
not suitable for esterification of potato starch. In addition, OSA is the hydroxyl groups (O–H), appeared at 3390 cm1. Compared
expensive. with native starch, the spectrum of OSA potato starch shows a
new peak at 1724 cm1, which suggests the formation of ester car-
3.3. Properties of OSA starch bonyl groups (Fang et al., 2004; Marcazzan et al., 1999; Thygesen,
Løkke, Micklander, & Engelsen, 2003). In the alkaline systems, OSA
3.3.1. General starch was synthesized in the form of starch sodium octenyl succi-
The effects of chemical modifications on thermal, morphologi- nate (Fig. 1); thus a peak at 1572 cm1 occurred, which is ascribed
cal and pasting behaviour of starches may be quantified using to the asymmetric stretching vibration of carboxylate RCOO
instrumentation such as Fourier transform infrared (FT-IR) spec- (Nagaoka, Tobata, & Takiguchi, 2005; Zhang, Jin, Zhang, et al.,
2004).

3.3.3. X-ray diffraction


0.045 90
In order to investigate the effect of OSA modification on the
0.040
DS crystal structure, the native and OSA potato starch were examined
80
RE (%) by powder X-ray diffraction. X-ray results indicated that both na-
0.035
70
tive and OSA potato starches showed typical B-type diffraction pat-
0.030 terns with strong reflection (Zobel, 1964, 1988). This result
RE (%)

suggested that esterification did not change the crystalline pattern


DS

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)

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
modification of a range of starches under aqueous reaction conditions.
source are the critical factors that govern the pasting behaviour of
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,
major RVA parameters such as PKV listed in Fig. 9, indicate that the 547–554.
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in the range of designed concentration. The peak apparent viscos- starch. Starch, 54, 148–154.
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of the starches. The intact starch had lower rise in the pasting curve agents (POCl3, STMP, and EPI) through swelling behavior and pasting
and a longer peak time compared with OSA starch. This result re- properties of cross-linked waxy maize starches. Cereal Chemistry, 79,
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Nagaoka, S., Tobata, H., Takiguchi, Y., & Satoh, T. (2005). Characterization of
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