Food Sci. Biotechnol.

23(2): 381-388 (2014)

DOI 10.1007/s10068-014-0053-0

RESEARCH ARTICLE

Physicochemical Properties of Thermal Alkaline Treated Pigeonpea

(Cajanus cajan L.) Flour
Piyanuch Roskhrua, Thierry Tran, Saiwarun Chaiwanichsiri, Sasikan Kupongsak, and Pasawadee Pradipasena

Received June 1, 2013; revised September 30, 2013; accepted October 3, 2013; published online April 30, 2014
KoSFoST and Springer 2014

Abstract Thermal alkaline treatment, normally used for

corn, was applied to pigeonpea grains. Starch granules
were isolated using wet milling and alkaline treatments.
Effects of the calcium hydroxide [Ca(OH)2] concentration
in the range of 0-1% (w/v) on granule structure, crystalline
structure, chemical composition, and physicochemical,
thermal, and pasting properties of isolated starch granules
were determined. Compared to native samples, thermal
alkaline treated samples had higher protein, lipid, calcium,
and phosphorus contents, but lower starch and amylose
contents. Thermal alkaline treatment increased starch granular
size and gelatinization temperatures, but decreased relative
crystallinity, gelatinization enthalpy, swelling power, solubility,
amylose leaching, and the pasting viscosity. Amylose-lipid
complexes were not found in thermal alkaline treated
flours. As the Ca(OH)2 concentration increased, the amylose
content, relative crystallinity, gelatinization temperature,
and enthalpy also increased, but the swelling power,
solubility, amylose leaching, and paste viscosity decreased.
A higher Ca(OH)2 concentration produced more stable
starch granules that resisted re-gelatinization.
Keywords: thermal alkaline treatment, calcium hydroxide,
physicochemical property, pigeonpea flour, structure

Piyanuch Roskhrua, Saiwarun Chaiwanichsiri, Sasikan Kupongsak,

Pasawadee Pradipasena (
)
Department of Food Technology, Faculty of Science, Chulalongkorn
University, Bangkok 10330, Thailand
Tel: +66-2-218-5515; Fax: +66-2-254-4314
E-mail: pasawadee.p@chula.ac.th
Thierry Tran
Centre de Coopration Internationale en Recherche Agronomique pour le
Dveloppement (CIRAD), Unit Mixte de recherche Qualisud, Montpellier,
Cedex 5, France

Introduction
Thermal alkaline treatment, also called alkaline cooking or
nixtamalization, is an ancient process in which grains are
cooked and then soaked in an alkaline solution of either
calcium hydroxide [Ca(OH)2] or sodium hydroxide (NaOH)
prior to being dehulled (1-3). The process has been used to
produce corn tortillas, a staple food for people in Mexico
and Central America (4). Research has shown that
consumption of corn tortilla chips has increased worldwide
because consumers like the unique crispy and crunchy
texture that is developed using a heterogeneous matrix of
thermal alkaline treated flour. During treatment, hydroxyl
ions (OH-) and charged ions of either calcium (Ca2+) or
sodium (Na+) diffuse into grains causing partial starch
gelatinization, protein denaturation, and lipid saponification.
Calcium complexes with amylose, protein, phytate, and
amylose-lipids are formed when Ca(OH)2 is used (3,5-7).
Therefore, the flour microstructure is modified with alteration
of the functional properties (8). Ca(OH)2 concentration
affects the water and Ca2+ ions diffuse into grains, affecting
starch gelatinization during the thermal alkaline process
and incorporation of calcium into grains and the final
product. At higher Ca(OH)2 concentrations water uptake
increases, indicating that Ca2+ ions participate in the water
diffusion process (9). Compared to native flour, treated
corn flour has a higher water absorption capacity and
gelatinization temperature, but a lower swelling power,
viscosity, storage modulus, gelatinization enthalpy, and less
tendency to retrogradation. Changes in these properties
probably result from interactions of Ca2+ ions with starch.
Therefore, the Ca(OH)2 concentration used in this process
affects the starch granule structure and the physicochemical
properties of the treated flour. Many reports on thermal
alkaline treatments for corn in a Ca(OH)2 concentration
range of 0-1% (w/w) have shown that a value of 0.2% is

382

the critical Ca(OH)2 concentration that produces a maximum

peak temperature, enthalpy of gelatinization, crystallinity,
swelling power, and solubility of treated corn flour
(7,10,11). This concentration was also reported to produce
the maximum crystallinity and thermal diffusivity for corn
tortillas (10).
This ancient process has been used and studied mainly
for corn and sorghum (5,12). Legume grains are cheap protein
sources that contain vitamins and minerals commonly used
in food products (13). Pigeonpea grains, such as those
found in mung bean, are low in fat and high in starch and
protein contents (14). Pigeonpea grains contain 3% fat,
19% protein, and 45-53% starch (14) and have a low
concentration of fat, a moderate amount of fiber, adequate
amounts of proteins and starches, and a balanced range of
all dietary essential minerals (15). Products similar to
tortillas can be made using thermal alkaline treated
pigeonpea flour. The focus of this research was on the
effects of calcium hydroxide concentrations on chemical
compositions, structures, and functional properties of
thermal alkaline treated pigeonpea flours. Results will
provide useful information for use of these flours as high
protein food products.

Materials and Methods

Thermal alkaline treatment Pigeonpea grains (obtained
from the Nan Province Land Development Department,
Ministry of Agricultural and Cooperatives, Thailand) were
boiled in Ca(OH)2 (124; Ajax Finechem, Auckland, New
Zealand) solutions (0, 0.2, 0.4, 0.6, 0.8, and 1.0% w/v) at
a ratio of solution:grain=5:1 for 30 min, then steeped in
the cooking solution for 15.5 h (3). The pH values of the 0,
0.2, 0.4, 0.6, 0.8, and 1.0% (w/v) Ca(OH)2 solutions were
6.86, 7.98, 8.56, 9.27, 10.01, and 10.42, respectively. After
steeping, the thermal alkaline treated grains were washed
twice with tap water to remove excess lime, and dried at
501oC for 14 h.
Starch granule isolation The modified procedure of
Lawal and Adebowale (16) was used for starch isolation
and purification. Native and thermal alkaline treated grains
(SB-4; Hull Miller, Sombupan Company, Pisanulok,
Thailand) were dehulled prior to wet milling. The weight
ratio of water to either dry dehulled grain or wet cake was
5:1. The suspension pH was adjusted to 8.5 before the
protein removal step. A hot air oven (HA-100S; Yeoheng
Co., Ltd., Bangkok, Thailand) was used to dry the cake at
501oC for 14 h. Dried samples were ground, sieved
through a 200-mesh sieve, packed in aluminum foil bags,
and stored at 51oC. Starch granules isolated from native
and thermal alkaline treated grains were called native

Roskhrua et al.

samples (NS) and modified samples (MS), respectively.

Microscopy studies The shape of starch granules was
determined using a scanning electron microscope (SEM,
JSM-5410 LV; JEOL Ltd., Tokyo, Japan) at magnifications
of 1,000 and 2,500. Birefringence was determined using
an optical microscope (BX 51TF; Olympus Co., Tokyo,
Japan) with polarized film (U-POT; Olympus Co.), and
images were captured at 40 magnification.
Granule size and size distribution Samples were
suspended in distilled water using a magnetic stirrer and
slowly mixed for 1 h at 282oC. The volume moment
mean diameter (D[4,3]) value and size distribution of the
starch granules were determined using a laser diffraction
particle size analyzer (Mastersizer 2000; Malvern Instruments
Ltd., Malvern, UK) with an RI value of 1.330 for water
and 1.529 for starch granules, and an absorption value of
0.1 for starch granules (17).
Proximate composition Moisture, crude protein, total
lipid, ash, and crude fiber contents were determined using
official methods of analysis of the Association of
Analytical Communities (AOAC) 925.10, 920.87, 920.39,
923.03, and 920.86, respectively (18). The total carbohydrate
content was then calculated from the difference between
100 and the sum of moisture, crude protein, total lipid,
crude fiber and ash contents.
Starch content The starch content was determined using
the enzymatic method (19). Samples were hydrolyzed
using -amylase (A3403 Starch Assay Kit; Sigma-Aldrich
Co., St. Louis, MO, USA) and amyloglucosidase (A7095;
Sigma-Aldrich Co.). The glucose content was determined
using the glucose oxidase/peroxidase method with 2,2'azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) (Thermo
Fisher Scientific Inc., Waltham, MA, USA) as the chromogen
and anhydrous D-glucose (G5400; Sigma-Aldrich Co.) as
the standard. The absorbance was measured at 560 nm
(JENWAY 6300 spectrophotometer; Barloworld Scientific
Ltd., Dunmow, UK). The starch content was calculated on
a dry matter basis according to the method described by
Holm et al. (19).
Amylose content Spectrophotometric assays of amyloseiodine complexes at 620 nm (Spectronic 200; Thermo
Fisher Scientific) were used to determine the amylose
content (20). Pure potato amylose (Fluka Chemie GmbH,
Buchs, Switzerland) was used as a standard.
Calcium and phosphorus contents To determine the
calcium content, samples were digested using AOAC
methods 975.03 and 984.27 (17) and analyzed using

383

Properties of Alkaline Cooked Pigeonpea Flour

inductively coupled plasma-optical emission spectroscopy

(Ultima 2C; HORIBA Jobin Yvon S.A.S., Longjumeau,
France). The phosphorus content was determined as
described by Heyns (21).
XRD Samples were kept in a vacuum desiccator (No.
2240; Ted Pella Inc., Redding, CA, USA) contained a
saturated sodium chloride (10478; Ajax Finechem) solution
(relative humidity approximately 75%) for 2 weeks.
Crystallinity was analyzed using XRD (D5005; Siemens
AXS, Karlsruhe, Germany) equipped with a copper source
operating at 40 kV and 50 mA and producing monochromatic copper K radiation (=0.154 nm) X-rays. Data
were collected from 5 to 30o (2) at 0.1o intervals with a
scanning rate of 1o/min. The relative crystallinity was
determined quantitatively from the ratio of the sharp peak
area to the total peak area using peak-fitting software
(Origin-version 8.0; Microcal Inc., Northampton, MA,
USA) (22).
Thermal properties Transition (gelatinization) temperatures
and enthalpy values were determined using a method
described by Mestres et al. (23). Samples (approximately
10 mg) were placed in pre-weighed stainless-steel pans
before addition of de-ionized water (50 L). Sample pans
were sealed, then kept at 251oC for one hour. Sealed
samples and empty reference pans were heated in a
differential scanning calorimeter (DSC-7; Perkin-Elmer
Corp., Norwalk, VA, USA) from 20 to 120oC at rate of
10oC/min.

percentage of amylose leaching (mg of amylose leached

per 100 mg of amylose content in a dry sample) was
calculated.
Pasting properties Using a Rapid Visco Analyzer (RVA
Series 4; Newport Scientific), starch granule suspensions
(25 g) of 10.4% (w/w) on dry basis were mixed at 960 rpm
for 10 s. The pasting properties were determined at 160
rpm. The temperature-time profile used was holding at
25oC for 1 min, heating to 95oC at 12oC/min, holding for
2.5 min, cooling to 50oC at 12oC/min, and holding for
2 min. The profile used for MS was holding at 25oC for
1 min, heating to 95oC at 12oC/min, holding for 30 min,
cooling to 50oC at 12oC/min, and holding for 2 min.
Statistical analysis All analyses were done using triplicate
data values. Analysis of variance and Duncans multiple
range tests were performed using SPSS software (version
17; SPSS Inc., Chicago, IL, USA).

Results and Discussion

Swelling power and solubility The swelling power and

solubility were determined as described by Ceballos et al.
(24) except for starch granule suspensions (1.5% dry
matter), which were heated from 35 to 90oC at 6oC/min
and kept at 90oC for 30 min, then analyzed using a Rapid
Visco Analyzer (RVA, Series 4; Newport Scientific,
Warriewood, Australia) before centrifugation (Sigma 3K10;
Fisher Bioblock Scientific, Illkirch, France) at 8,000g for
5 min. The supernatant was then removed using a pipette.
Sediments were weighed and the swelling power was
calculated (g/g).

Microscopy studies Images of NS and MS starch

granules are shown in Fig. 1. NS granules were not
damaged and had a smooth surface while MS granules
partially lost birefringence and had a rough surface. Most
MS granules were swollen, causing irregular shapes, and
granule aggregates were present. Loss of birefringence
increased with an increasing Ca(OH)2 concentration.
Hydroxide ions are reported to be a gelatinizing agent (26).
The rough surface of MS granules was the result of
gelatinization of surface starch and adhesion of denatured
proteins (27). Surface gelatinization formed granule
aggregates (6). In the presence of calcium, the MS granule
surface may also contain calcium deposits (7,11,28). The
presence of MS granules with birefringence indicated
incomplete starch gelatinization during grain boiling,
possibly because granules did not absorb enough water
during boiling (6). During boiling in the presence of
Ca(OH)2, hydroxyl ions disrupted the starch granules,
resulting in loss of birefringence (11).

Amylose leaching The same procedure was used to

determine both the swelling power and the solubility.
Starch granule suspensions were exposed to heat (90oC for
30 min) and centrifuged (Sigma 3K10; Fisher Bioblock
Scientific) at 8,000g for 5 min. The supernatant volume
was then measured. An amylose content in the supernatant
was determined using standard method of the International
Organization for Standardization (ISO) 6647-2 section 8.5
(25). A standard curve was prepared using pure potato
amylose. The absorbance was measured at 620 nm. The

Granule size and size distribution NS granules had a

unimodal size distribution while MS granules had a
bimodal size distribution (Fig. 2A). The D[4,3] value of
MS granules was 60% larger than the value of NS granules
(Fig. 2B). There was no specific trend in alteration of
D[4,3] values with respect to the Ca(OH)2 concentration
(Fig. 2B). Starch gelatinization occurred during the boiling
step of the thermal alkaline treatment process, which
caused irreversible swelling of the starch granules (29).
Aggregates of swollen gelatinized granules formed during

384

Roskhrua et al.

Fig. 1. Light, polarized light, and SEM images of native and

modified sample starch granules.

boiling as gelatinized starch has strong binding and

adhesive properties (6). Swollen granules and aggregates
observed in SEM images (Fig. 1) had larger D[4,3] values
than NS granules. The small particle fraction of MS
granules was smaller than the same fraction of NS granules
and contained fragments of swollen granules that were
broken during starch isolation. The particle size and the
size distribution of nixtamalized corn flour were reported
to be the most critical parameters to control the textures of
tortilla chips, taco shells, and soft tortillas (5,6). Small
particles had more water uptake and higher viscosity,
cohesiveness, plasticity, and smoothness values than large
particles (5). In contrast, large particles (>250 m) not only
disrupted the dough network, but also reduced blistering,
decreased oil uptake, and had increased crispiness. Large
particles are, therefore, more suitable for adjusting the
textural characteristics of fried products (6). Similarly, MS
from pigeonpea can be fractionated into specific size
ranges for different applications.
Chemical compositions The total yield for native grains
was lower than for treated grains, with an opposite trend
for the starch yield (Table 1) due to removal of non-starch
components from native samples. The lower starch content
in modified samples resulted from gelatinization, then
solvation in water. Interactions between starch and calcium
produced higher starch yields for Ca(OH)2 treatments than
for water treatments. Salt bridges between amylose chains
were formed between Ca2+ ions and amylose OH groups

Fig. 2. Effect of boiling pigeonpea grains in 0-1.0% (w/v)

Ca(OH)2 on granule size distribution (A) and volume moment
mean diameter, D[4,3] (B).

(12,28) and the resulting starch-calcium complexes were

not water soluble. All MS granules had higher crude
protein, crude fiber, lipid, ash, calcium, and phosphorus
contents, but lower carbohydrate, starch, and amylose contents
than NS granules (Table 1). An increasing Ca(OH)2
concentration increased the lipid, ash, amylose, calcium,
and phosphorus contents of MS granules. Boiling pigeonpea
grains causes protein denaturation, starch gelatinization,
and association of protein-protein, protein-amylose, proteinlipid, and amylose-lipid complexes (5,6,11). Denatured
protein, protein-amylose, and protein-lipid were not lost
from starch granules during the starch isolation process
since they did not dissolve in water (3,5). Boiling

6.230.03d

6.450.04

6.160.03e

6.620.04a

6.380.04c

38.960.21a

36.670.32

37.360.33b

38.930.28a

38.250.30a

0.2

0.4

0.6

0.8

1.0

2.810.02a

2.760.03a

2.290.09b

2.230.04

2.280.03b

0.710.02a

0.640.04b

0.720.02a

0.660.03

0.630.04b

0.720.02a

0.380.03c

Crude fiber

1.980.02a

1.950.06a

1.820.03b

1.780.04

1.040.03c

0.550.03d

0.320.03e

Ash

88.120.06g

88.030.06f

88.310.05e

88.890.10

89.820.10c

91.570.07b

98.490.05a

Carbohydrate

67.850.74b
a

58.110.50bc

0.8

1.0

76.110.48

76.900.31a

77.355.99a

73.192.71c

72.961.57cd

0.830.23

1.290.13b

1.300.13b

1.310.22b

1.360.12b

5.080.63a

H (J/g)

2)

For modified samples, values were determined from the second peak.
Mean of three replicationsSD. Different superscripts within a column are significantly different (p<0.05).

1)

67.790.75b

58.770.55b

0.6

68.690.46

67.080.73c

58.681.02b

0.4

59.750.66

65.110.98d

57.620.74c

0.2

Tc ( C)

72.320.29d

1st endotherm

60.910.79e

Tp ( C)

052.500.42d2)

To ( C)

0.0

Modified using
%(w/v) Ca(OH)2

Native

Sample

1)

Table 2. Thermal properties of native and modified samples

To ( C)

o
e

64.050.08e

65.320.01b

64.790.08c

63.880.08

64.580.04d

62.620.08g

96.520.05a

84.920.32

84.230.14b

83.550.46c

83.090.38c

80.640.14d

80.250.23d

23.420.12

93.000.22

90.210.29b

88.680.32c

87.910.22d

85.890.29e

84.580.36f

77.220.32

60942a

52581c

56661b

42691

19201e

12601f

4882g

Calcium
(ppm)

98.630.19

97.620.22b

97.020.29c

95.860.15d

93.800.26e

92.640.22f

82.620.14

Tc (oC)

25.100.16b

24.290.13c

23.590.14d

2nd endotherm
Tp ( C)

24.500.11b

25.430.12a

24.210.10b

22.750.17

22.040.19f

21.660.12g

31.150.12a

Amylose
content
(% starch
basis)

25.160.14a

22.960.11d

29.160.12e

% Yield
(dry grain
basis)

Starch
Content
(% dry basis)

72.690.13

Mean of three replicationsSD. Different superscripts within a column indicate significant differences (p<0.05).

1)

5.580.03f

36.660.32b

0.0

1.580.04c

Native

Modified using
%(w/v) Ca(OH)2

0.300.03d

30.210.24c1)

Sample

0.510.03g

Total lipid

% Total yield
(dry grain
Crude protein
basis)

Proximate composition (% dry basis)

Table 1. Effect of boiling pigeonpea grains in 0-1.0% (w/v) Ca(OH)2 on yield, proximate composition, starch, amylose, calcium, and phosphorus contents

5.180.13b

4.880.12c

4.090.11d

2.810.13e

2.280.12f

0.870.13g

17.350.32a

H (J/g)

59642a

55801b

53251c

40912d

2413 2e

1599 2f

1581g

Phosphorus
(ppm)

Properties of Alkaline Cooked Pigeonpea Flour

385

386

Roskhrua et al.

the crystalline organization of starch granules (6,7,29).

Recrystallization occurred during steeping and cooling of
the grains (10-11) and an increasing Ca(OH)2 concentration
probably enhanced cross-linking, leading to a higher
relative crystallinity (7).

Fig. 3. Effect of boiling pigeonpea grains in 0-1.0% (w/v)

Ca(OH)2 on crystalline pattern (A) and percentage relative
crystallinity (B).

pigeonpea grains in Ca(OH)2 results in lipid saponification

and chelation of phytic acid while forming calciumprotein, calcium phytate-protein, and calcium phytateamylose complexes (1,6,12,28). An increasing Ca(OH)2
concentration enhanced these reactions and, as a consequence,
more lipid, amylose, calcium, and phosphorus were retained
in gelatinized starch granules. The lower carbohydrate,
starch, and amylose contents in MS samples were linked to
loss of a fraction of the gelatinized starch from samples
during starch granule isolation (7). This also resulted in a
relative increase in the amounts of other components, such
as proteins and lipids.
XRD studies All samples showed large peaks at 17.2,
18.1, and 23.1o2 and small peaks at 5.54 and 15.18o2
(Fig. 3A), corresponding to a Ca-type diffraction pattern
(30). Thermal alkaline treatment did not alter the
amylopectin crystalline pattern of the starch granules. The
X-ray pattern of all MS samples did not show V polymorph
patterns, which sometimes appear after gelatinization when
amylose-lipid complexes are formed in a sufficient quantity.
The relative crystallinity of MS samples was lower than
NS samples (Fig. 3B), and increased linearly with an
increasing Ca(OH)2 concentration was possibly due to
gelatinization of starch that was partially destroyed during

Thermal properties A single phase transition (gelatinization)

endotherm with To, Tp, Tc, and H values of 72.69oC,
77.22oC, 82.62oC, and 17.35 J/g is shown in the NS
thermogram (Table 2). A differential scanning calorimeter
(DSC) was used to detect changes in heat flow, and a RVA
was used to detect changes in viscosity. Therefore, the
pasting temperature detected using the RVA was 85oC (Fig.
4A), which was higher than the Tc value. Two endotherms
were observed for MS samples (Table 2). The 1st endotherm
(To under 80C) was attributed to melting of retrograded
starch (specifically amylopectin) that was previously
gelatinized during grain boiling. The 2nd endotherm (To
above 80oC) corresponded to a phase transition of nongelatinized MS portions. Therefore, the To, Tp, Tc, and H
values for MS granules (Table 2) were measured using the
2nd endotherm. Identification of 2 MS sample endotherms
using the DSC confirmed the polarized light microscope
observations, which indicated partial gelatinization during
boiling. MS samples had higher phase transition temperatures
and lower H values than NS samples, in accordance with
the expected properties of partially gelatinized starch (31).
Phase transition temperatures and H values for MS samples
increased with an increasing Ca(OH)2 concentration. A
possible reason for the increase in the To value is that To
represents a distribution over a range of temperatures, not
a single temperature value. For partial gelatinization, starch
fractions with low To values gelatinize first. Therefore, the
remaining non-gelatinized fractions have a higher average
gelatinization temperature than the original sample. The
degree of gelatinization for MS samples increased with an
increasing Ca(OH)2 concentration and the average To value
of the remaining non-gelatinized fraction increased.
Heating starch granules disrupts some of the double helix
in crystalline and non-crystalline regions of granules.
Gelatinization caused starch granules to swell and probably
created wider channels, allowing calcium ions into these
starch granules. The presence of Ca(OH)2 created alkaline
conditions and polyhydroxyl compounds, such as starch
molecules, may have undergone ionization by release of
hydroxylic protons (32). Therefore, intermolecular interactions
between starch molecules, especially amylose, via calcium
salt bridges were possible (10). Higher Ca(OH)2 concentrations
promoted intermolecular interactions. This cross-linking
effect of calcium ions may have stabilized starch granules
against gelatinization (33). Mndez-Montealvo et al. (2)
reported that thermal alkaline treated maize flour had
higher gelatinization temperatures than the raw counterpart

387

Properties of Alkaline Cooked Pigeonpea Flour

Table 3. Swelling power, solubility, and amylose leaching of
native and modified samples
Sample

Swelling power
(g/g)

Solubility
(%)

Amylose leaching
(% total amylose)

Native

31.310.10a1)

16.500.07a

63.161.10a

Modified using
% w/v Ca(OH)2
0.0
26.350.25b
0.2
21.550.32c
0.4
18.200.25d
0.6
17.590.34e
0.8
16.100.20f
1.0
15.040.20g

15.720.09b
13.430.08c
12.830.06d
11.880.02e
10.700.08f
10.550.09g

26.610.99b
24.010.19c
22.020.72d
21.741.04d
18.631.27e
16.490.68f

1)

Mean of three replicationsSD. Different superscripts within a

column are significantly different (p<0.05).

because calcium ions stabilized the starch structure in

thermal alkaline treated flour. All MS thermograms
showed no melting of amylose-lipid complexes in the
range 90-120oC (34). This observation is supported by
absence of XRD V-type, suggesting that lipid was
saponified rather than interacting with amylose (1).
Swelling power, solubility, and amylose leaching At
90oC, the swelling power, solubility, and amylose leaching
values of MS samples were lower than for NS samples.
These 3 properties also decreased as the Ca(OH)2
concentration increased (Table 3). Calcium bridges between
starch molecules may also have contributed to stabilizing
thermal alkaline treated starch granules against swelling,
regelatinization, and leaching of amylose (11). In addition,
calcium deposited on the MS granule surface probably
inhibited diffusion of components into and out of granules.
Additionally, MS granules may have been already swollen,
compared to NS granules, due to partial gelatinization
during boiling, so that the measured swelling power was
smaller.
Pasting properties Viscosity values (peak and trough)
and breakdown and setback values for all MS samples
could not be determined using the standard RVA profile
due to low viscosity development (Fig. 4A). This is typical
of pre-gelatinized starch (2). To evaluate the effect of the
Ca(OH)2 concentration on the MS pasting properties, MS
suspensions were analyzed using a different temperaturetime RVA profile with a longer cooking step at 95oC (30
min). Both the viscosity at the end of the 95oC step and the
final viscosity decreased as the Ca(OH)2 concentration
increased (Fig. 4B), which could be related to less amylose
leaching. Mndez-Montealvo et al. (2) explained that,
depending on conditions, partial pre-gelatinization treatments,
such as thermal alkaline treatments, can reduce the capacity
of starch granules to form a compact paste, resulting in low

Fig. 4. RVA profiles for native (A) and modified (B) samples.

viscosity during and after cooking. Compared to native

granules, thermal alkaline treated pigeonpea starch granules
had a lower swelling power, less amylose leaching, and a
reduced pasting viscosity, similar to the heat-moisture
treated pigeonpea starch granules reported by Hoover et al.
(31).
In conclusion, thermal alkaline treated starch granules
were more resistant to heating and leaching of amylose
than native granules. An increasing Ca(OH)2 concentration
resulted in increasing phase transition temperatures for
thermal alkaline treated pigeonpea flour with a reduction in
the swelling power, solubility, amylose leaching, and paste
viscosity.
Acknowledgments The research was funded by a
Chulalongkorn University graduate school thesis grant
from Chulalongkorn University, Bangkok, Thailand. P.
Roskhruas scholarship was provided by Rajamangkala
University of Technology Lanna, Nan, Thailand.

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