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Physicochemical, Thermal, And Rheological Properties of Acid-hydrolyzed Sago (Metroxylonsagu) Starch

Physicochemical, Thermal, And Rheological Properties of Acid-hydrolyzed Sago (Metroxylonsagu) Starch

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Physicochemical, Thermal, And Rheological Properties of Acid-hydrolyzed Sago (Metroxylonsagu) Starch
Physicochemical, Thermal, And Rheological Properties of Acid-hydrolyzed Sago (Metroxylonsagu) Starch

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Physicochemical, thermal, and rheological properties of acid-hydrolyzed sago(
Metroxylon sagu
) starch
, M. Robal
, L.H. Cheng
, A.Y. Tajul
, A.A. Karim
Food Biopolymer Research Group, Food Technology Division, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia
Institute of Mathematics and Natural Sciences, Tallinn University, Narva mnt 25, 10120 Tallinn, Estonia
a r t i c l e i n f o
 Article history:
Received 3 May 2011Received in revised form26 August 2011Accepted 20 October 2011
StarchSagoHydrolysisSolubilityRheological properties
a b s t r a c t
The effects of acid hydrolysis on physicochemical and rheological properties of sago starch wereinvestigated. Sago starch was hydrolyzed in hydrochloric acid at 50
C for 6, 12, 18, and 24 h. Themolecular weight distribution, physicochemical, thermal, and rheological properties of acid-hydrolyzedsago starch (AHS) were determined. After 24 h of hydrolysis, molecular weight of amylopectin andamylose were decreased to 3.57
and 6.5
g/mol, respectively. Differential scanning calo-rimetry studies showed that the gelatinization temperature and enthalpy of AHS increased withincreasing degree of hydrolysis. Hydrolyzed sago starch containing low molecular weight fractionsexhibited cold water solubility up to 100%. Setting temperature of AHS decreased with increasinghydrolysis time but amylose content and gel strength increased in the
rst 12 h of acid hydrolysis butdecreased with extended hydrolysis time. Hydrolyzed sago starch in concentrations lower than 8 g starchper 100 g water was cold water soluble and could be used to modify properties of starch for speci
capplications such as yogurt and concentrated milk processing.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Starch can be modi
ed by chemical, physical, genetic or enzy-matic mean. Acid modi
cation is a chemical method in used toprepare thin boiling starches for food and non-food industryapplications (BeMiller & Whistler, 2009). Acid-thinned modi
ca-tion is a type of hydrolysis using mineral acids at lowconcentrationand at a temperature below gelatinization. Typically, concentratedstarch slurry (36
40 g starch per 100 g water) is treated withhydrochloric acid at temperatures between 40
C and 60
C(Amaya-Llano, Martínez-Alegría, Zazueta-Morales, & Martínez-Bustos, 2008). The acid is neutralized when the desired conversionis obtained and the starch is recovered (Wurzburg, 2006). Time,temperature and acid concentration control the acid-thinninghydrolysis process.Hoover (2000)comprehensively reviewed theeffects and mechanism of acid hydrolysis on starch.Buttrose (1963)reported that the amylopectin content of thestarch is very important in acid hydrolysis and increasing theamylopectin levels leads toincreases in hydrolysis of starch. Duringthe acid modi
cation the rate of hydrolysis is not constant amongstarches. At temperature below gelatinization temperature theamylopectin (amorphous region) is hydrolyzed faster than amylose(crystalline region) (Kerr, 1952). Acid hydrolysis causes the loss of starch due to conversion to glucose. After 2 days of acid-thinnedhydrolysis of potato or corn starch with 0.5 mol/L sulphuric acid,the recovery percentage were reported as 95.0% and 97.4%,respectively. This difference is related to the higher amylopectincontent in potato starch than in corn starch (Komiya & Nara,1986;Komiya, Yamada, & Nara, 1987).Physicochemical properties of starch in acid-thinned hydrolysischange without destroying granular structure. The gelatinizationparameters (gelatinization temperature and enthalpy) increaseupon hydrolysis (Shi & Seib,1992). The tendency to retrogradationof acid-thinned starch also increases due to an increase in theconcentration of the linear chains. The viscosity and averagemolecularweightofhydrolyzedstarchdecrease,whereas solubilityand gel strength of acid-thinned starch are increased relative totheuntreated starch (Wang & Wang, 2001). Acid hydrolysis also affectsviscoelastic properties of starches. Acid modi
ed starches showNewtonian behaviour (Chamberlain & Rao, 1999). Storage and lossmoduli (G
, G
) decrease upon acid hydrolysis (Wang, Truong, &Wang, 2003).Sago starch is one of the important socioeconomic crops inSoutheast Asia. Starch from sago is the only example of an indus-trial starch derived from the trunk of the sago palm (
Rottb.). Although some of the physicochemical properties of 
Corresponding author. Tel.:
604 653 2268; fax:
604 657 3678.
E-mail address:
akarim@usm.my(A.A. Karim).
Contents lists available atSciVerse ScienceDirect
LWT - Food Science and Technology
journal homepage:www.elsevier.com/locate/lwt
see front matter
2011 Elsevier Ltd. All rights reserved.doi:10.1016/j.lwt.2011.10.015
sago starch are quite similar to those of common starches (potato,tapioca), it also has unique characteristics. Forexample, sagostarchgranules range in size from 10 to 50
m, and they generally havea smooth surface, although some pitting has been reported. Inaddition, gelatinization temperature of sago starches varies from69.5 to 70.2
c study on the effect of acid hydrolysis on sago starch isvery scarce. We hypothesized that acid hydrolysis at temperaturesbelowgelatinizationwould increase the solubility of sago starch bydepolymerization of amylopectin. Therefore the aim of this studywas to characterise acid-hydrolyzed sago starch to provide someinsight on the effect of hydrolysis on the physicochemical, thermal,and rheological properties.
2. Materials and methods
 2.1. Materials
Sagostarch(10 g watercontentper 100 g starch) waspurchasedfrom SIM Company Sdn. Bhd (Penang, Malaysia) and was usedwithout any further treatment. All chemicals were of analyticalgrade. All chemicals were of analytical grade.
 2.2. Preparation of acid-thinned sago starch and recovery yieldmeasurement 
Sago starch slurries (40 g starch per 100 g water) were preparedby adding 0.14 mol/L hydrochloric acid (HCl) solution to 400 gstarchtoa
nalweightof1000gaccordingtothemethoddescribedbyWang and Wang (2001). Preliminary experiments showed thathydrolysis time
6 h have no signi
cant effect on the molecularweight of sago starch. On the other hand, when hydrolysis wasextended to
24 h the molecular weight of starch was reducedextensively. The recovery ratio was calculated as dried starchweight after hydrolysis per initial dried weight (Shujun, Jinglin, Jiugao, Haixia, & Jiping, 2007).
 2.3. Molecular weight distribution
High Pressure Size Exclusion Chromatography (HPSEC)measurements were performed on a chromatograph equippedwith a Perkin Elmer Series 200 pump, a Knauer Smartline 2300refractive index detector, a Knauer Smartline column thermostat,a Shodex OHpak SB-G guard column and a Shodex OHpak SB-806MHQ column. Elution was carried out using a 5 mM LiBr inDMSO/DMF (respectively 75/25) solution as the mobile phase ata
ow rate of 0.3 mL/min. The temperature of the columns wasmaintained at 60.0
C. Acalibration curvewas constructed using 12pullulan standards (2560, 1660, 788, 404, 212, 112, 47.3, 22.8, 11.8,5.9,1.32, 0.342
g/mol).Thestarchconcentrationusedwas0.25gstarchper100gwater,and the sampling volume 100
L. To obtain more reliable results,the starch samples were dissolved in the same solvent used as aneluent in the HPSEC system. For better solubilization, the sols wereheated in an oil-bath at 120
C for 10 min. The warm (
C)solution was
ltered through a 0.45
m membrane (Whatman25 mm GD/X, GMF), allowed to cool down, and then injected intothe HPSEC system.
 2.4. Amylose content 
Total amylose content was measured by a modi
 2.5. Swelling power and solubility
The method described byLiu, Ramsden, and Corke (1999)wasused to determine the solubility and swelling power of the starch.To measure the maximum solubility in cold water, differentconcentrations of modi
ed sago starch (1
10 g starch per 100 gwater) were prepared by deionized water. The dispersions wereheatedupto90
Cfor30minandthencooledtoroomtemperature.The maximum concentration that, after cooling, still shows theliquidity was considered as maximum solubility in cold water.
 2.6. Pasting properties
A Rapid Visco
Analyser (Model RVA-4, Newport Scienti
c Pvt.Ltd., Warriewood NSW, Australia) was used to determine thepasting properties of the samples. In an RVA sample cup, 2.5 g of nativestarchor3.5gofhydrolyzedsagostarchwasaddedto25gof distilled water. The starch slurry was analyzed using the proceduredescribed byHuijbrechts et al. (2008).
 2.7. Gelatinization parameters and evaluation of tendency toretrogradation
The thermal characteristics of native and modi
ed sago starchwere studied using a differential scanning calorimeter (DSC-Q100,TA Instruments, New Castle, DE, USA) equipped with ThermalAnalyst 2000 software. Starch slurries (
10 mg) were prepared at1:2 dry starch/water ratios. An empty pan was used as a referenceand DSC was performed from 10
C to 100
C at a heating rate of 10
C/min. After completion of the DSC run, the gelatinized starchsamples were stored at 4
C in the original sealed pans for retro-gradation studies after 7 days following the method of Morikawaand Nishinari (2000).
 2.8. Intrinsic viscosity
Intrinsic viscosity was determined based on the methoddescribed byChan, Bhat, and Karim (2009).
 2.9. Gel hardness
Gel hardness of the samples was measured by a methoddescribed byTakahashi, Maningat, and Seib (1989).
 2.10. Dynamic rheological measurement 
Dynamic rheological measurements were conducted followingmethod described byWang et al. (2003)with some modi
cations.Acid-thinnedsagostarchesweredispersedindeionizedwater(10gstarch per 100 g water) and were heated to 95
C while stirring at700 rpm on the hotplate (indirect heating). The samples aftercompletion of gelatinization were immediately transferred to therheometer AR 1000 (TA Instrument, New Castel, USA) set at 85
mgap).Flowpropertieswere measured in stepped
ow by applying shear rates in linearmode from 0 to 100 rad/s. The oscillatory tests were conductedusing the following protocol: (a) cooling ramp from 85 to 5
C ata rate of 1.5
C/min, and (b) frequency sweep from 0.01 to 20 Hz at5
C.In another approach to study the effect of hydrolysis on gelati-nization, according toAhmed and Auras
s (2011)method, starchsamples (15 g starch per 85 g water) were placed in a 500
m gapbetween two stainless steel parallel plates with solvent trap. Thesampleswereequilibratedat40
by linear increment at 4
M.N. Abdorreza et al. / LWT - Food Science and Technology 46 (2012) 135
Storage modulus (G
), loss modulus (G
), and complex viscositywere monitored during oscillatory tests at 1 Hz and 1% strain,which was in the linear viscoelastic region (LVR).
 2.11. Statistical analysis
Analysisofvariancewas performed usingthe ANOVA procedureof the SPSS 17.0 statistical software for Windows (SPSS, Inc., Chi-cago, IL, USA). Tukey
s least signi
cant test was used to comparemeans at the 5% signi
cance level.
3. Results and discussion
 3.1. Structural characteristics of acid-thinned sago starches
The carbohydrate distributions of modi
ed sago starch atdifferent reaction times as analyzed by HPSEC are shown inFig. 1.Fraction I consists of high molecular weight carbohydrates (mainlyamylopectin), and fraction II consists of shorter chain carbohy-drates(mainlyamylose)(Wangetal.,2003).Increasingthereactiontime shifted the peak of Fraction I of acid-thinned starches toa longer retention time. A longer retention time indicates that theamylopectin molecular size was decreased relative to earlier timepoints. The average molecular weight of amylopectin was3.36
, 1.05
, 3.83
, and 3.57
g/mol while theaverage molecular weight of amylose was 6.5
, 6.6
, and 1.95
g/mol after 6,12,18, and 24 h hydrolysis.Six hours of hydrolysis (AH6) had little effect on sago starchmolecular weight as compared to the average molecular weight of amyloseandamylopectinreportedfornativesagostarches(Takeda,Takeda, Suzuki, & Hizukuri, 1989). Extended hydrolysis of starchcaused a signi
cant decrease in amylopectin molecular weight. TheFraction II peak also shifted to a longer retention time at 12 hcompared to the 6-h time point.
 3.2. Effects of acid modi
cation on recovery yield and amylosecontent of sago starch
Table 1shows the recovery yield and the amylose content of native and acid-thinned sago starch. The recovery yield decreasedfrom
100% for untreated starch to 94% after hydrolysis for 24 h.Shujun et al. (2007)exposed Rhizoma
starch to acidhydrolysis and reported similar yield of recovery.The native sago starch amylose content was around 30 gamylose per 100 g starch. Hydrolysis for 6 h decreased the amylosecontent but not signi
cantly. After 12 h, hydrolysis of someamylopectin branches and production of linear chains fromamylopectin resulted in a slight increase in amylose content.Furtherincreaseinthetimeofacidhydrolysisresultedinhydrolysisof theamylosechains into smallerbranches thatcouldnotcomplexwith iodine, and at 24 h the amylose content had decreased toaround 24 g amylose per 100 g starch. These results were consis-tence with the theory of Kerr (1952)that amylopectin is moresusceptible to acid than is amylose. This explains why amylosecontent was increased at early time points because hydrolysis
rstseparates some chains from amylopection; only after 12 h isamylose hydrolyzed to a signi
cant degree. The decrease inamylose content upon extended hydrolysis was reported by otherresearchers (Komiya etal.,1987; Singh, Sodhi,& Singh, 2009;Wanget al., 2003).
 3.3. Swelling power and solubility of acid-thinned sago starch
Fig. 2(a) and (b) show swelling power and solubility of nativeand acid-thinned sagostarches at temperaturesranging fromroomtemperature to above gelatinization temperatures. Swelling power
Fig. 1.
Gel permeation chromatograms of acid hydrolysis sago starches (
: 6 hhydrolysis.
: 12 h hydrolysis. - - - -: 18 h hydrolysis.
: 24 h hydrolysis).
 Table 1
Amylose content and starch recovery yield of native and acid-thinned sago starch.Time of hydrolysis Amylose content(g amylose/100 g starch)
Recoveryyield (%)
Native sago starch 30.6
0.4b 99.9
0.1a6 h (AH06) 30.5
0.8b 99.2
0.3b12 h (AH12) 32.5
0.4a 97.4
0.2c18 h (AH18) 26.4
0.3c 96.7
0.5d24 h (AH24) 24.7
0.3c 94.3
Values are mean
standard deviation (
3), and different letters representssigni
cant difference in 95% level of probability.
Fig. 2.
(a) Swelling power and (b) solubility of native and acid-thinned sago starch atdifferent temperatures ( : Native sago starch. : 6 h hydrolysis. : 12 hhydrolysis. : 18 h hydrolysis. : 24 h hydrolysis).
M.N. Abdorreza et al. / LWT - Food Science and Technology 46 (2012) 135

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