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Production of Low Substituated Cassava

Starch Acetates and Citrates


S. 0. Agboola, J. 0. Akingbala, and
G. B. Oguntimein, Oyo State (Nigeria)

Starch acetates and citrates were prepared by treating starch with Herstellung von niedrig substiiuierten Cassava-Stlrkeacetaten
sodium hydroxide at room temperature with and without 1% concen- und -citraten. Durch die Behandlung von Starke mit Natriumhydro-
trated sulphuric acid (per dry weight of starch) as catalyst. Starch xid bei Raumtemperatur mit und ohne Zusatz von 1% konzentrierter
acetates were obtained by varying the reaction time (2 h, 4 h, 6 h and Schwefelsaure (bez. a. Starke-TS) als Katalysator wurden Starkeace-
8 h) while starch citrates were obtained using citric acid monohydrate tate und -citrate hergestellt. Die Starkeacetate wurden durch Variie-
conentrations of 5 , 10, 15 and 20% (per dry weight of starch). The ren der Reaktionszeit (2h, 4h, 6 h und 8h) und die Starkecitrate
yields of acetylated starches were greater than those of the starch unter Verwendung von Citronensaure-Monohydrat-Konzentrationen
citrates. Use of catalyst significantly increased the rate and extent of von 5 , 10, 15 und 20%, bez. a. Starke-TS. erhalten. Die Ausbeuten
acetylation. Also there were progressive increases in the acetyl values an acetylierten Starken waren haher als die an Starkecitraten. Die
of the catalysed reaction with time. Citrate substitution in catalysed Anwendung des Katalysators erhohte die Geschwindigkeit und das
and uncatalysed reactions were not significantly different at citric AusmaB der Acetylierung erheblich. Auch fanden zunehmende
acid concentrations higher than 10%. Erhohungen der Acetylwerte bei der katalysierten Reaktion mit
zunehmender Reaktionszeit statt. Die Citratsubstitution in kataly-
sierter oder unkatalysierter Reaktion unterschied sich bei hoheren
Citronensaurekonzentrationen als 10% nicht wesentlich.

1 Introduction 2 Materials and Methods


Native starches are often modified to improve their functional 2.1 Materials
properties. Many starches including corn, potato, wheat and
cassava have been modified although waxy corn starch is often Cassava starch extracted from "Odongbo", a low cyanide indigenous
prefered for commercial purposes [l].Cassava starch has been cassava variety was supplied by International Institute of Tropical
identified by Knight [l] as a good starch for modification Agriculture (IITA) Ibadan. Acetic anhydride, acetic acid, sodium
because of the high paste clarity, bland taste and comparable hydroxide and citric acid used were of analytical grade.
Brabender amylograph curves of cassava starch to waxy corn
starch. In Nigeria and other West African countries, cassava is 2.2 Preparation of substituted starches
the major source of starch. It is therefore logical that cassava
starch should be the focus for starch modification. O m a n [2] Figs. 1 and 2 show the flow charts for the preparation of the starch
acetates and citrates, respectively. For starch acetates, four samples
reported various means of starch modification including sub-
(150 g each) of the native starch were suspended in 200 ml of distilled
stitution. Substitution, even at low degree, improves paste water to form a slurry. To each sample, 10 ml of 1M NaOH was added
clarity, freeze-thaw stability, and ease and stability of cooking to bring the pH to about 9. 10 ml of acetic anhydride was also added,
[1,3,4,5].The substituted starches prepared in this study were and the contents were held for 30 min at 28 k 2C with occasional
acetates and citrates. stirring during the holding period. At the end of the holding period
Starch acetates have been prepared from cassava starch using 200 ml of glacial acetic acid was added to each sample. Another set of
various reagents. The starches are often modified at high
temperature above 100C, using very large amounts of reagents
and for very long periods [3-61. The volatile nature of some of
the reagents especially acetic anhydride usually necessitates
elaborate safety precautions. Starches prepared under these
conditions are partly or totally gelatinized and have off white
colour. Very little work has been done on starch citrate
preparation for food uses even though citric acid is one of the
widely recognized food additives. A dry reaction method has
Fig. 1. Flow chart for the preparation of starch acetates.
been used by Kluushofer et al. [3] to prepare starch citrate from
cassava starch and some other starches. The objectives of this
study are:
(i) To prepare starch acetates and citrates from cassava starch
at room temperature using minimum amounts of reagents and
(ii) to investigate the effects of 1%H2S04 catalysis, reagent
concentration and duration of reaction on the extent of modifi-
cation.

Fig. 2. Flow chart for the preparation of starch citrates.

starch/st*e 43 Nr. 1. S. 13-15 0 VCH Verlagsgesellschaft mbH,D-6940 Weinheim, 1991 0038-9056/91/0101-0013%03.50+.25/0 13


"'ab=e7 1.2 1

- 0
5 n 6 m
Y. CITRIC ACID CONCENTRATKN TIME. h

Fig. 3. Effect of HzS04on acetate substitution Fig. 4. Effect of citric acid concentration on citrate substitution.

four samples similar to the f i s t set, was prepared. 1%concentrated substitution for both catalysed and uncatalysed reactions. The
H2S04 (per dry weight of native starch) was added to each sample. levels of citrate substitution for starch in the uncatalysed
Samples in both sets were then held for 2, 4, 6 and 8 h before washing reaction were very low (0.18%) at 5% citric acid concentration,
each sample with about 600 ml of distilled water through a Whatman increasing appreciably to 0.88% citrate at 10% concentration,
No. 9 filter paper under vacuum. The modified starches were then dried 1.5 at 15% and 2.64 at 20%. For the catalysed reaction, the
at 50C in a Leec oven for 24 h before cooling at ambient temperature
and milling in a warring blender into powdery form.
citrate substitution at 5% citric acid concentration was 0.88%
For starch citrates, the slurry formation and alkalination were the same which increased to 1.23% at 10% citric acid concentration and
as for acetates. The alkalized slurry was held for 30 min with occasional 1.59% at 15% concentration. There was an increase in the per
stirring. At the end of this period, 5%, lo%, 15% and 20% citric acid cent citrate value to 2.82 for catalyzed and 2.6 for uncatalyzed
monohydrate (based on dry weight of native starch) made up to 100 ml reaction at 20% citric acid concentration. The effect of catalysis
with distilled water was added to each of the four samples, respectively. on the yield of citrate was significant at low citric acid concen-
The second set of treatments involved addition of 1%concentrated trations but decreased with increasing concentrations of citric
H2S04(based on dry weight of native starch) to the varying citric acid acid. At 15% citric acid concentration, the difference between
concentrations before adding to the alkalized starch slurry. The 2 sets citrate yields of the H2S04 catalysed and the uncatalysed
were held for 5 h at room temperature before each batch was washed
with about 600 ml of distilled water and filtered through a Whatman
substituted starches was not significant. As with acetates,
No. 9 filter paper under suction. Drying and milling were done as for increase in the concentration of protons with the increase in
starch acetates. citric acid concentration may be responsible for this observa-
tion. At low concentration of citric acid, the additional protons
2.3 Analytical from the catalyst (HzS04) may have been responsible for the
difference in citrate substitution levels between the catalysed
The yield on a dry matter basis was determined for the substituted and uncatalysed reactions. Thus acid catalysis of cassava starch
starch. The per cent acetyl and degree of substitution (DS) were for citrate ion uptake may not be necessary especially since
determined according to the method described by Smith [7] while the citrate substitution of starches for use in foods need not be to a
per cent citrate and corresponding DS were determined by the same high degree [4,91.
method taking into account the molecular weight of the citric acid
substituent .
3.2 Effects of processing conditions on the yield
3 Results and Discussion The yields of the acetylated starches (92-98%) were generally
greater than the yields of the starch citrates (85-92%). It
3.1 Effects of processing conditions on the rate appears that there is greater degradation and solubilization of
and extent of substitution starch in the citrate substitution reactions generally and in the
catalysed reactions for both acetates and citrate modification
Fig.3 shows the effect of catalysis on the amount of acetyl (Tables 1 and 2). Also, the yields of the substituted starches
substitution for starch at the different acetylation periods. obtained in this study (slurry method) were greater than the
Acetylation was considerably enhanced by the use of 1% HzSO4 yields obtained from the reflux method which were between
as catalyst. In the uncatalysed reaction, the maximum acetyl 39% and 53% [lo]. The smaller yields of substituted starch from
value obtained was 0.47% at 2 h, reducing gradually to 0.18% the reflux substitution method may be due to greater heat
for 6 h of reaction. The reduction in acetylation might be due to demage and solubilization of starch heated in acid for an
saponification of the acetylated starch reverting it to starch. appreciable length of time [6].
With catalysis, there was a general increase in the rate of acetyl
substitution with holding time. Starch degradation which 4 Conclusion
enhanced penetration and subsequent substitution by acetyl
groups has been reported to be the likely mechanism [6]. Substitution of cassava starch by the slurry method at room
However, it appears that protons from ionised HzSO4 pre- temperature under conditions of pretreatment with sodium
vented saponification of the starch acetyls resulting in increase hydroxide with and without catalyst using acetic acid and citric
in acetylation products [8]. acid is possible. Varying the reagent concentration and dura-
Kruger and Rutenberg [4]and Degering [6]reported a slow rate tion of the substitution reactions affected the extent of modifi-
of acetylation at room temperature. However, apart from the cation. While the use of catalyst improved the rate and extent of
rate, there appears to be an optimum reaction period after acetyl substitution, the levels of citrate formation was not
which acetylation decreases. The optimum reaction period for significantly increased by catalysis above 10% citric acid con-
the uncatalysed acetylation in this study appears to be 2 h. centration.
Fig. 4 shows the effect of citric acid concentration on citrate

14 starchhtike 43 Nr. 1, S. 13-15


Table 1. Table 2.
Yields and Degree of Substitution (DS) of Acetic Acid Modified Yields and Degree of Substitution (DS) of Citric Acid Modified
Cassava Starch. Cassava Starch.

Sample Yield (d. b.) (%) Acetyl (%) Degree of substitution (DS) Sample) Yield (d. b.) (%) Citrate (%) Degree of substitution (DS)

1 98 0.47 0.018 1 89 0.18 0.002


2 97 0.33 0.012 2 89 0.88 0.007
3 98 0.18 0.007 3 92 1.50 0.013
4 98 0.21 0.008 4 92 2.64 0.022
1A 92 0.58 0.022 IA 86 0.88 0.007
2A 93 0.85 0.032 2A 85 1.23 0.010
3A 93 0.96 0.037 3A 88 1.59 0.013
4A 93 1.06 0.040 4A 87 2.82 0.023

) Samples 1, 2, 3, 4 are modified starches from uncatalised reaction ) Samples 1, 2, 3, 4 are modified starches from uncatalised reaction,
while samples l A , 2A, 3A and 4A are from H2SO4cataIysedreaction. while samples 1A, 2A, 3A and 4A are from H2S04catalysed reaction.

Bibliography [7] Smith, R. J . : In: Starch: Chemistry and Technology. Vol. 11.
Industrial Aspects (Whistler, R. L., and E. F. Paschall, eds.),
[ l ] Knight, J . W.:In: Cassava Processing and Storage. Internatio- Academic Press, New York 1967,569.
nal Development Research Centre IORC. 1974, 76. [8] Jarowenko, W. :In: Modified Starches, Preparations and Uses
[2] Osmun. E. M.: In: Starch: Chemistry and Technology. Vol. 11. (Wurzbury, 0. B., ed.).
Industrial Aspects (Whistler R. L., and E. F. Paschall, eds.), [9] Roberts, H . J . : In: Starch: Chemistry and Technology Vol. 11.
Academic Press, New York 1961, 163. Industrial Aspects (Whistler, R. L., and E. F. Paschall, eds.),
Academic Press, New York, 1967, 293.
[3] Klaushofer. H . , E. Berghofer, and W. Steyner: StarcWStarke 30
[lo] Osunsami, A . T.: M. Sc. Dissertation, University of Ibadan,
(1978), 47.
Ibadan, Nigeria, 1987, 80.
141 Kriraer. L. H . . and M . M.Rutenbera: In: Starch: Chemistrv and
L ,

Techology. Vol. II. Industrial kpects (Whistler, R. L.-, and


E. F. Paschall, eds.), Academic Press, New York 1967, 369. Address Of authors: S. 0. Agboolu, J . 0. Akingbala, and G . B.
[S] Osumumi, A . T., J . 0.Akingbala, and G. B. Oguntimein: Starch/ OgUntimein*, Department of Food Technology, Faculty of Techno-
Starke 41 (1989), 54. logy. University of Ibadan. Oyo State (Nigeria).
(61 Degering, E. F.: In: Starch and Its Derivatives, Vol. I. (J. A. * Corresponding author.
Radley, ed.), Chapman and Hall Ltd.. London 1953, 298. (Received: June 14,1990).

Studies on Cross-linked A. paniculafas


(Rajgeera) Starch
Rekha S. Singhal and Pushpa R. Kulkarni,
Bombay (India)

Earlier studies from our laboratories on waxy A. paniculutas starch Untersuchungen an vernetzier Siarke aus A. paniculatas (Raj-
have shown it to be sensitive to mechanical shear and acidity. Cross- geera). Friihere Untersuchungen in unseren Laboratorien an wachsiger
linking of this starch with phosphorus oxychloride at room temperature A. paniculutus-St%ke haben gezeigt, d& diese empfindlich gegeniiber
for ten min using 5 ml p o C I 3 per 100 g starch improved the stability mechanischer Scherung und Aziditat ist. Die Vemetzung dieser Stiirke
under canning conditions, low pH and also mechanical shear. Its paste mittels Phosphoroxychlorid 10 min lang bei Raumtemperatur unter
clarity also improved distinctly. However, it had very poor freeze-thaw Verwendung von 5 ml POC13 je 100 g Stiirke verbesserte die Sta-
stability indicating it to be unsuitable for frozen foods. Evaluation of bilitat unter Konservierungsbedingungen,gegeniiber niedrigem PH-
this starch in canned tomato soup showed it to be a useful thickener Wert sowie auch mechanischer Scherung. Die Pastenklarheit verbes-
for foods processed under retort conditions. serte sich ebenfalls deutlich. Allerdings hatte die St;?rke eine geringe
Gefrier-Tau-Stabilitat,wodurch sie ftir gefrorene Lebensmittel unge-
eignet ist. Die Bewertung dieser Sttirke in Dosen-Tomatensuppezeigte
jedoch. daB sie unter harten Bedingungen bei der Lebensmittelherstel-
lung ein geeignetes Dickungsmittel ist.

1 Introduction
tries. Cross-bonding of granular starches with a wide variety
Native starches, both waxy and non-waxy are frequently required of polyfunctional agents introduces cross-links within molecules
to be tailored through modifications so as to meet the demands in micellar network, thus stabilising the granule mechanically
of product characterisation in food as well as in other indus- against excessive swelling and breakdown of viscosity by heat

starch/stiirke 43 Nr. 1, S. 15-18 0 VCH Verlagsgesellschafi mbH, D-6940 Weinheim, 1991 0038-9056/91/0101-0015$03.50+.25/0 15

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