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Starch Gelatinization Phenomena Studied by Differential Scanning Calorimetry

Article in Journal of Food Science · August 2006

DOI: 10.1111/j.1365-2621.1980.tb07586.x

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 STARCH GELATINIZATION PHENOMENA STUDIED BY
DIFFERENTIAL SCANNING CALORIMETRY

C. G. BILIADERIS, T. J. MAURICE, and J. R. VOSE

ABSTRACT 1978; Donovan, 1979) to study starch phase transitions

Differential Scanning Calorimetry (DSC) was used to study gelatini- from a physicochemical approach.
zation phenomena of corn, potato, acid-modified corn and smooth We have attempted, therefore, to study the gelatiniza-
pea, and various legume starches. Two endothermic transitions were tion of various legume starches using DSC. Corn and potato
observed for starches heated in the presence of limited amounts of starches were also used for comparison. The significance of
water (starch/water = 46-48% w/w). The effect of starch concentra- the amount of water on the mechanism of starch gelatiniza-
tion on the shape of these two endotherms was studied for three
legume starches. Considering the starch granule as a spherulite, the tion was further investigated.
experimental data were treated thermodynamically by applying
equations describing phase transitions of semi-crystalline polymers. MATERIALS & METHODS
Experimental evidence suggested that a solvation-assisted melting of
starch crystaIIites took place during gelatinization and that the pro- Starch
cess was facilitated by the presence of the amorphous parts of the
Corn, high-amylose corn and potato starches were obtained from
granule. The enthalpy change, AH, associated with the gelatinization a commercial source (A.E. Staley Inc. Decatur, Ill.). Corn starch was
varied among these starches within a range of 2.6-4.4 Cal/g. A com- also prepared according to Adkins and Greenwood (1966). The fol-
parison between DSC transition temperatures and characteristic
ge!atinization temperatures obtained by other methods was also lowing legume starches were prepared from their seeds by a wet-
made. milling process (Biliaderis et al., 1979): smooth pea (Pisurn SQfiUUfn
L. cv. Trapper), adzuki bean (Phaseolus chrysunthos), garbanzo bean
(Cicer arierinum), mung bean (Vigna radiata), green lentil (Lens culi-
nuns), red kidney bean (Ph. vulgaris), navy bean (Ph. vulgaris) and
INTRODUCTION faba bean (Viciu fuba equina L. cv. Diana).
STARCH gelatinization is an important phenomenon occur- Acid-modified (lintnerized) corn and smooth pea starches were
prepared by immersing granules in 2.2N HCl at 35°C for 10, 24, and
ring in various food processing operations. Processes such as 48 hr. The acid-treated granules were recovered on a sintered glass
baking of bread and cakes, extrusion of cereal based prod- filter and then washed repeatedly with deionized water. The extent
ucts, thickening, and gelling of sauces and pie fillings are all of lintnerization was then determined by measuring the total carbo-
dependent on proper starch gelatinization. It is not surpris- hydrates in the filtrate (Dubois et al., 1956) and expressing that as
ing, therefore, that considerable attention has been paid to percent of the initial starch. Smooth pea amylopectin was isolated
the technological implications of starch gelatinization, according to Banks and Greenwood (1967).
especially from the rheological point of view. Various meth- Chemical analysis
ods, which are based on the properties of granular starches, Standard AACC (1976) methods were used for proximate analy-
have been used to study starch gelatinization. These include sis. Protein was estimated as %N x 6.25. Starch was assayedaccord-
viscosity measurements, microscopic examinations of ing to Banks et al. (1970). Amylose contents were determined by
granule swelling and loss of birefringence, and light trans- measuring the iodine affinities of the defatted (hot extraction in
mittance (Collison, 1968). These methods, however, are 85% aqueous methanol for 48 hr) starches according to Schoch
limited by certain parameters such as starch/water ratio and (1964) and assuming that pure amylose has an iodine affinity of
temperature range over which the gelatinization process can 20.0%. For phosphorus analysis, the samples were successively di-
be studied. gested with cone H, SO, and H,O,; phosphorus in digests was
measured using Murphy and Riley’s method (1962).
Differential Scanning Calorimetry (DSC) is particularly
well suited to investigate the phase transitions of starch/wa- Starch gelatinization temperatures
ter systems because it allows: (1) study of starch gelatiniza- Gelatinization temperatures were determined according to
tion over a wide range of starch/water ratio; (2) determina- Schoch and Maywald (1956). The recorded temperatures cor-
tion of gelatinization temperatures above 1 OO’C; and (3) es- respond to loss of birefringence by 5, 50, and 95% of the granules.
To obtain initial pasting temperatures amylograms were prepared on
timation of transition enthalpies. Although earlier DSC a Brabender Visco-Amylograph with a 700 cm/g sensitivity cartridge
work on starch gelatinization is reported on native and at 75 rpm using 8% w/w slurries. Recorded temperatures were those
modified cereal and tuber starches (Stevens and Elton, at which an initial increase of 10 Brabender units (BU) in viscosity
1971; Donovan, 1979; Wada et al., 1979; Wootton and was reached (Medcalf and Gilles, 1966).
Bamunuarachchi, 1979a, b), there are no comparable stud- Differential scanning calorimetry
ies on legume starches. Furthermore, very little research has Starch of known moisture content was mixed with the appropri-
been carried out (Lelievre, 1973; Marchant and Blanshard, ate amount of distilled water and allowed to stand for 1 hr at room
temperature before heating. Samples of 10 I 2 mg were heated in
Du Font coated alumin&hermetically sealed pans using a Du Pont
990 thermal analyzer and a 910 DSC cell base. A known weight of
sand (SiO,) was used in the reference pan to balance the heat capac-
Author Biliaderis is with the Biotechnology Section, National
ity of the sample pan. Samples were heated from 25” to 150°C at a
Research Council of Canada, Prairie Regional Laboratory, Sas-
rate of S”C/min. The instrumental sensitivity was 0.02 meal/s/in;
katoon, Saskatchewan, Canada S7N OW9, Author Maurice is
analyses were performed in a nitrogen atmosphere (54 psi). The cali-
currently with General Foods Lrd., Coburg, Ontario. Author
bration coefficient, E, of the cell was determined from thermograms
Vose is now with rhe National Research Council of Canada, of weighed amounts of materials with known enthalpies of fusion.
Orrawa, Canada.
Transition temperatures were obtained from a temperature plot
which was calibrated from the baseline in mvolt/in. The conversion
0022-l 147/80/0006-1669$02.25/O to “C was made by using thermocouple tables. Heats of transition,
01980 Institute of Food Technologists AH, were calculated by measuring the areas by means of a plani-
meter and using the equation: -Continued on next page

Volume 45 (1980)-JOURNAL OF FOOD SCIENCE- 1669

 AH = A.60.B.E.Aqs and Greenwood. 1975). The V. was then calculated as the ratio of
M-C the volume of water divided bk the total volume of starch plus wa-
ter.
where A = area (in.2), AH = transition enthalpy (mcal/mg); M =
sample mass (mg); C = sample concentration (% w/w); B = time base RESU&TS&DISCUSSION
setting (min/in.); E = cell calibration coefficient (no units); and Aqs
= Y-axis range (mcal/sec/in.). The obtained AH values had an aver- PROXIMATE ANALYSIS of the native starches indicated
age standard deviation of to.25 Cal/g for repeated analyses (n = that all samples had protein, lipid, fiber and ash contents
S-10) of the same sample. The gelatinization characteristics of’ less than 0.49%, 0.23%, 0.51% and 0.18%, respectively.
starch in a DSC thermogram can be presented by various tempera- Their starch assay showed starch contents greater than
tures: the onset temperature (To); the peak temperature(s) (Tp); 93.5% in all cases.
and the melting point (Tm) of the most perfect crystallites at the The DSC thermograms of the starches are illustrated in
upper temperature limit of the thermogram. These temperatures and Figures 1 and 2. Amylose and phosphorus contents, charac-
the areastaken for calculating AH are shown in Figure 1. For calcula- teristic endothermal temperatures, transition enthalpies, ini-
tions of~the volume fraction of water, V, , the density of water was tial pasting temperatures and gelatinization temperatures
taken as 1.00 and that of starch an averagevalue of 1.5 g/ml (Banks
are given in Table 1. Two endothermic transitions were ex-
hibited by all native starches when heated under similar

._
intermediate water contents (45.6-48.2% w/w>. The influ-
I I I I I I I I
ence of water content on the appearance of these two endo-
I
therms was studied for smooth pea, adzuki bean and lentil
starches.
Tm
I

> ___-

TP,
--
%
___4---
2

- . I lfW3 i
-

--*_
--__
--__
s5
\--

I 1 I I I 1 I I 1 I , I , I, I I I I I

40 60 80 100 120 40 60 60 100 120 140

TEMPERATURE (“Cl TEMPERATURE (“C)
Fig. 2-DSC thermograms of starches: 1 Lab.-isolated corn, 2 High-
Fig. I-DSC thermograms of starches: 7 Potato, 2 Lentil. 3 Gar- amytose corn (commercial), 3 Smooth pea amylopectin, 4 Gelatin-
banzo bean, 4 Red kidney bean, 5 Mung bean, 6 Navy bean, 7 Faba ized smooth pea, 5 Smooth pea, 6 Adzuki bean, 7 Acid-modified
bean: To = onset temperature; Tp, , Tp, = peak temperatures; Tm = smooth pea (5.1% lin tnerizedl, 8 Acid-modified smooth pea (9.6%
melting point. Thermograms 2 and 5 indicate areas taken for AH lin tnerizedl, 9 Acid-modified smooth pea (20.2% lin tnerizedl. Per-
calculations. Percent concentrations of starch (w/w) for these ex- cent concentrations of starch (w/w) for these experiments, from top
perimen ts. from top to bottom, were: 46.3, 47.5, 45.6, 46.3, 47.5, to bottom, were: 47.3, 48.2, 48.2, 48.0, 47.5, 47.7, 47.8, 47.9,
46. 1. 46.6. 47.6.

1670-JOURNAL OF FOOD SCIENCE-Volume 45 (1980)

 STARCH GELATINIZATION BY DSC.. .

Table I-DSC characteristics and other physicochemical properties of the studied starches
Initial
Phosphorus Amy lose pasting Gelatinization Starch cone
content content temp temp for DSC exp. TP, TP, AH
Starch (%l (%I (“CI cc1 (%, wlw~ (“Cl CC) (cat/g)
-
Adzuki bean 0.013 34.9 78 83-(851-89 47.7 69 75 89 112 4.4
Smooth pea 0.006 33.1 73 65-(67 j-69 47.5 56 64 87 101 3.5
Acid-modified, 5.la - 26.8 - - 47.8 60 73 95 103 2.4
Acid-modified, 9.6a - 23.0 - - 47.9 60 72 96 109 2.2
Garbanzo bean 0.010 34.1 75 65-(68)-71 45.6 68 72 96 108 3.1
Red kidney bean 0.016 35.0 73 64-(661-68 46.3 61 68 86 100 2.6
Lentil 0.008 45.5 66 58-(59)-61 47.5 48 56 80 95 2.6
Navy bean 0.011 36.0 75 68-(71)-74 46.1 59 67 83 99 3.5
Mung bean 0.016 34.9 73 63-(65)-69 47.5 57 65 83 99 3.9
Faba bean 0.010 32.5 72 61-(631-66 46.6 56 65 83 97 3.3
Potato, commercial 0.075 20.1 51 64- (65)-67 46.3 55 60 68 85 4.4
Corn, commercial 0.019 22.6 74 63-(651-68 46.4 60 67 78 89 3.3b
Corn, lab prepared 0.012 22.4 73 62-1651-67 47.3 53 63 75c 86 2.7
Acid-modified, 6.5a 22.6 - 47.9 54 73 99C 89 2.4
High-amylose corn comm. 0.029 50.3 96 82-(86)-99 48.2 71 82 105 114 4.2b
Waxy corn, commercial 0.002 00.0 72 64-(68)-JO 47.6 64 71 88 97 4.ob
a Numbers represent percent lintnerization
b For calculations of AH values only P, and P, were used
c Shoulder

When smooth pea starch was heated at high water con-

centrations, a single endothermic transition, PI, was ob-
served (Fig. 3) at about 64’C (Tpr ). As the ratio of starch/
water increased the second endotherm, PZ, started to de-
velop at higher temperatures (Tpa) and became predomin-
ant at low water contents. Although the PI endotherm oc-
curred essentially at constant temperature (63-65’C), it
was of interest to observe a progressive shift of the P, endo-
therm as vr was decreased. Similar results were also exhib-
ited by both adzuki bean and lentil starches (Table 2). This
concentration dependent shift of both Tp, and melting
point, Tm, suggested a thermodynamic treatment of these
results by employing equations that characterize other
polymer systems. Similar theoretical treatments of starch
gelatinization data have also been used by Lelievre (1973)
and Donovan (1979). The former measured the loss of bire-

Table 2-DSC characteristics of three legume starches heated at dif-

feren t water concentrations
Volume Melting
fraction temp
of water, To Tpl Tp, Tm range AH
.49 Starch “1 (“Cl (“CI (“CI (“C) (Tm-To) (Cal/g)
Adzuki bean 0.87 JO 76 - 87 17 5.2
0.80 JO 76 - 93 23 3.7
0.73 JO 76 - 98 4.0
0.62 69 75 89 112 4.4
0.50 69 76 102 128 4.5
0.43 66 75 115 138 2.8
Smooth pea 0.86 55 64 - 80 25 3.5
-b .42 0.80 55 64 - 85 30 3.8
0.72 54 65 81 93 3.6
0.64 56 64 87 101 3.5
0.49 52 63 107 122 3.1
I 1 I , , , , , , I 0.42 50 65a 116 130 2.7
40 80 80 100 120 140
Lentil 0.86 47 57 - 77 30 3.4
TEMPERATURE (“C) 0.79 47 56 71 82 35 2.9
0.68 46 56 73 89 3.0
Fig. 3-DSC thermograms of smooth pea starch heated at different 0.62 48 56 80 95 2.6
I water concentrations; numbers represent volume fraction of water. 0.50 47 55 93 111 3.0
Percent concentrations of starch (w/w) for these experiments from 0.43 45 55 94 116 1.4
top to bottom, were: 19.0, 26.6, 37.0, 45.6, 60.8 and 67.5. a Shoulder
I
Volume 45 (1980)-JOURNAL Of FOOD SCIENCE- 1671
 I I I

- LENTIL

<
- SMOOTH PEA
t
- E l .
bl-
I
0.0
c l l T

..il
E
I-
R‘ -1:
0
IQ
0-

3. ADZUKI BEAN $

0.0-.--L.-ii-
t
2.01 0.61
0 0.2 0.4 0.6 0.0 1.0 0 1.0 2.0
VI 103u, /Tm

Fig. 4-The reciprocal melting point, h PKI, plotted against the Fig. 5-Plot ofexperimental data according to Eq. (21. Each line is a
volume fraction of water, v,, for three legume starchesEach line is a linear least-square fit of the experimental data.
linear least-square fit of the experimental data.

fringence in wheat starch granules as a function of tempera-
ture and water content, while the later employed DSC to
study the gelatinization of potato starch in the presence of
different amounts of water. According to the Flory equa-
tion (Flory, 1953) the following relation holds between
melting point of a polymer and diluent concentration:
where AHu is the change in enthalpy of fusion per repeat-
ing unit (glucose), Vu/V1 is the ratio of the molar volume
of the repeating unit (glucose) in the chain to that of the
diluent (water), R is the gas constant, Tm (“K) is the melt-
ing point of the diluent-polymer mixture, Tm’ (OK) is the
true melting point of the undiluted polymer, vr is the vol-
ume fraction of the diluent, and Xr , is the Flory interac-
tion parameter. The melting point, Tm, of the heated
starch/water mixtures was taken as the melting point of the
most perfect crystallites at the upper temperature limit of
the endotherm, according to Flory (I 953). For an ideal so-
lution, X1 = 0; hence Eq (1) gives a linear relation between
vr and l/Tm. The intercept at vr = 0, therefore, gives the
reciprocal of the melting point of the most perfect crystal-
lites of the undiluted polymer, l/Tm’. A plot of l/Tm
against v, for the three starches is given in Figure 4. Linear
regression analysis of the experimental data gave significant
correlations (rten, = 0.993, P = 0.01; rs.Pea = 0.998, P =
0.01; radz = 0.997, P =. 0.01). The obtained Tm’ values by
extrapolation at u1 = 0 were 439’K (166’C) for lentil, 467’K
(194’C) for smooth pea and 476°K (203°C) for adzuki
starch. Corresponding values of 2 10°C for wheat (Lelievre,
1973) and 168’C for potato (Dovonan, 1979) starches have
been reported previously. These values are significantly
lower than the temperature range of 260-330°C, where
extensive thermal decomposition of starch occurs (Green-
wood and Muirhead, 1967). Differences in the Tm” values
among the three legume starches may be related to various
factors, in which the granular organization and its inherent
crystallinity are probably the most important. In order to
develop this hypothesis, the structural characteristics of the
amylopectins (the principle component of the starch crystal-
lites) of these starches were determined by enzymic meth-
ods (Biliaderis, 1980). Indeed, some differences in the degree
of branching among these amylopectins were detected. The
order of increasing degree of branching was adzuki bean<
smooth pea<lentil. Considering that branching is detrimental
to crystallization and, therefore, broadens the melting tem-
perature range (Tm-To) and lowers the Tm’, as found in the
field of synthetic polymers (Cowie, 1973), one would ex-
pect that the higher the degree of branching, the wider the
melting temperature range and the less resistant the starch
is to gelatinization. The obtained values for Tm-To (Ta-
ble 2), gelatinization temperature, initial pasting tempera-
ture (Table I) and Tm’ were indeed in accord with this
concept.
An alternative plot of Eq (1) has also been suggested by
Flory to estimate the AHu values. Considering X1 to be in-
versely proportional to temperature (XI = BV,/RT, where
B is the energy of polymer-diluant interaction), the Eq (1)
can be written in the form:
(2)
A plot of the left-hand side of Eq (2) against v,/Tm is
shown in Figure 5 for the three legume starches. From the
intercepts the AHu values were calculated to be 18.9 for
lentil, 15.8 fro smooth pea, and 16.2 Kcal/mole D-glucose
unit for adzuki bean starch. Donovan (1979) reported a
value of 13.5 Kcal/mole D-glucose unit in the case of po-
tato starch. From the slopes, the energy of interaction, B,

1672-JOURNAL OF FOOD SCIENCE-Volume 45 (1980)


was computed to be 1.03 for lentil, 0.30 for smooth pea,
and 0.60 Cal/ml for adzuki bean starch; the positive values
of B suggest that the water is a poor solvent for starch
(Flory, 1953). The accuracy of the above calculated ther-
modynamic parameters depends first on the validity of the
extrapolations used in Figure 4 and, second, on various
experimental limitations. However, one must emphasize the
qualitative aspect of the above treatment which demon-
strated that the starch granule may indeed be treated as a
polymer spherulite; relations analogous to the Flory equa-
tion may be also used to predict starch gelatinization behav-
ior in heated food systems of different water activities.
To investigate the reversibility of the heat effects on the
starch samples the following experiments were carried out.
Samples (corn and smooth pea starches) were heated at
both high and intermediate water concentrations, until the
complete thermogram was obtained. Cooling to 40°C and
immediately reheating showed no transition endotherms.
This suggested that complete gelatinization was achieved
during the first heat treatment and that no significant re-
crystallization (annealing) in the gels took place over the
time of the experiment. In other experiments, the heating
process was stopped after the completion of the first endo-
therm and the starch samples were cooled quickly. Upon
reheating the thermogram obtained was still biphasic with
the Tp,, however, shifted to higher temperatures. The
second thermogram represents that portion of the sample
that did not gelatinize during the first heating and, there-
fore, exhibited a higher Tp, upon reheating. The shift of
Tp, must, therefore, be due to the heterogeneity of the
starch granules and was observed in all cases regardless of
the amount of water present. Gough and Pybus (1971) have
also reported that although gelatinization of individual
granules occurs over a range 0.5-1.5’C, the overall re-
sponse of the population, because of its heterogeneity, ex-
tends over lo-15’C. In conclusion, then, two suggestions
can be made. First, it seems unlikely that the observed
biphasic endothermic transition, occurring at intermediate
water levels, emmergcs from two discrete granule or crystal-
lite populations. A normal distribution of granules and
crystallites, in terms of their energy characteristics, would
rather be expected. Second, a partial heat treatment (i.e.,
process stopped between Pi and PZ) does not induce signi-
ficant changes in the system, which will eventually termi-
nate the gelatinization process, without any further increase
in temperature.
The thermograms of acid-modified smooth pea starch
(starch/water:47.6-47.9% w/w) at three different levels of
lintnerization, are shown in Figure 2 (Thermograms 7, 8,
9). It has been recognized that lintnerization selectively
hydrolyzes the amorphous parts of the granule (Kainuma
and French, 1971; Robin et al., 1974). It was of interest to
observe that progressive lintnerization resulted in obtaining
themograms quite similar to those of the native smooth pea
starch heated at low water concentrations. It appears, there-
fore, that the amorphous parts destabilize the system dur-
ing heating and cause a large part of the starch crystallites
to melt at low temperatures (first endotherm, P,). We sug-
gest that this effect, exercised by the amorphous regions, is
due to their swelling upon hydration, and increased chain
mobility upon heating to finally cause a solvation-assisted
melting of the starch crystallites.
It is necessary at this stage, to give a brief description of
the structure of the starch granule which will alow a subse-
quent discussion on the mechanism of gelatinization from a
theoretical approach. Treatment of the starch granule as a
semi-crystalline entity (spherulite) which contains both
crystalline and amorphous regions, is widely accepted
among starch chemists (Banks and Greenwood, 1975). It
has been suggested (French, 1972; Robin et al., 1974) that
STARCH GELATINIZATION BY DSC.. .
starch crystallinity is due to the presence of parallel clusters
of short chains (-50-60 A) packed side by side. These
chains could be either the external amylopectin chains (the
principle crystalline component) or parts of the amylose
molecules (less important) which can give analogous parallel
chain structures by chain folding. Double helical structures
have been poroposed in both cases (French, 1972). It is the
presence of such regularly oriented crystallites that makes
the starch granules birefringent and have distinct x-ray dif-
fraction patterns. On the other hand, the amorphous re-
gions are those where chain folding or multiple branching
occur and prevents the formation of ordered polymer struc-
tures. Recent experimental evidence suggests that water ab-
sorbed by the granule is associated only with its amorphous
parts (Kainuma and French, 1972). When starch granules
are heated in the presence of water, gelatinization takes
place. This phenomenon is associated with: (a) loss of
crystallinity as indicated by the disappearance of both bire-
fringence and x-ray pattern: (b) extensive swelling of the
granule, predominantly after the loss of birefringence.
From the above considerations and data, we suggest the
following, concepts as possible explanations of the overall
gelatinization process. If a large amount of water is present,
extensive hydration and swelling of the amorphous regions
facilitate melting of the starch crystallites upon heating.
This occurs over a very narrow temperature range, and
therefore results in a single endothermic transition, Pi. The
melting of the crystallites may involve a solvation assisted
helix-coil transition of their chains, which is an analogous
phenomenon to that found in heated solutions of other
biopolymers. It is the large gain in entropy, in going from
the ordered to the random conformation, that offsets the
attractive stabilization forces (hydrogen bonding) occurring
in the crystallites. Extensive swelling must also be associ-
ated with such crystallite disruption, to account for the
observed increase in viscosity following the loss of bire-
fringence in the granule. In more concentrated starch solu-
tions, however, the destabilizing effect of the amorphous
regions decreases and, because of the limited amounts of
water present, only partial melting of crystallites occurs
according to the previous mechanism (first endotherm).
Subsequent redistribution of the water, however, around
the unmelted crystallites will assist their melting upon fur-
ther heating at higher temperatures (second endotherm).
Jaska (197 1) found a rapid drop in NMR line width, after
the onset of gelatinization (an analogous state to Tp,) in
40% (w/w) wheat starch solutions. This was interpreted as a
sudden increase in mobilization of water and starch
molecules. Our calorimetric data and those reported by
Donovan (1979) further suggest that water mobilization
may take place toward the unmelted crystallites; this is
supported by the fact that the Tm values appeared to
smoothly fit the plot of l/Tm vs vi over the entire range of
water activities studied. Finally, under extreme conditions,
where no moisture is present in the system, and the only
denaturant is heat, melting of the starch crystallites would
be expected to occur at temperatures close to the estimated
Tm’ (“true-melting” of crystallites). The above suggested
mechanism is schematically summarized in Figure 6. It is
obvious therefore, that water plays an important role in the
overall process by assisting the melting of the starch crystal-
lites.
The transition enthalpies for the legume starches varied
over the range 2.6-4.4 Cal/g. The AH values for corn and
potato starches were in good agreement with those reported
by Stevens and Elton (1971), but significantly lower than
those obtained by Wootton and Bamunuarachchi (1979a). I
Differences may reflect variations between starch samples.
Moreover, the AH values are significantly affected by the
heating rate, amount of water and starch damage (Stevens
Volume 45 (1980)-JOURNAL OF FOOD SCIENCE-1673
 evidence that recrystallization of this polysaccharide may
MOLECULAR STRUCTURE possibly occur.
8 GRANULAR ORGANIZATION I The observation that the first endotherm (Pi ) appeared
at a constant temperature, regardless of the amount of wa-
ter present, suggested that Tpi can be used as an index to
heat
characterize the resistance to gelatinization of a particular
starch sample. The obtained Tpi values, although not di-
/ rectly correlated, were’ close to the average gelatinization
temperatures, i.e. 5 0 % loss of birefringence, and distinctly
lower than the initial pasting temperatures (Table 1). Ap-
parently, it is difficult to make direct comparisons between
these values because of their dependence on various experi-
mental parameters (heating rate, thermal lags in the equip-
ment, etc.)
In conclusion, the thermodynamic treatment of the DSC
solvotion-zsisted “true melting”
melting of crystollites of crystollitas
data indicated that the gelatinization process can be ex-
plained in terms of the theory of polymer spherulites. Al-
though quantitation of the thermodynamic parameters is
Fig. 6-Schematic representation of the possible interrelationships
subject to several potential sources of error, one must em-
among the various parameters involved in phase transition pheno-
phasize the versatility of the DSC technique to measure the
mena of granular starch. extent of gelatinization over a wide range of temperatures.
The influence of the amount of water and various food
ingredients on starch gelatinization can also be studied un-
der conditions resembling those employed in the prepara-
and Elton, 1971; Wootton and Bamunuarachchi, 1979b; tion of various heat-processed foods.
Donovan, 1979). Our data (Table 2), as well those of Woot-
ton and Bamunuarachchi (1979b) and Donovan (1979) REFERENCES
have indicated a pronounced decrease in the gelatinization
enthalpies in the presence of limited amounts of water. A American Association of Cereal Chemists. 1976. Approved methods
lower degree of disorder achieved by the starch during gela- of the AACC. Method 08-17, revised 1976. Method 32-15, ap-
proved 1961. Method 46-10, revised 1976. Method30-26. revised
tinization of concentrated starch/water systems was pro- 1976. The association: St. Paul, Minn.
posed as the reason for the decreased AH values (Stevens Adkins, G.K. and Greenwood, C.T. 1966. The isolation of cereal
starches in the laboratory. St&ke 18: 213.
and Elton, 1971). Donovan (1979) has further suggested Banks, W. and Greenwood..C.T. 1967. The fractionation of labora-
that thermodynamic quantities from different processes are tory-isolated cereal starches using dimethyl sulfoxide. StXrke 19:
measured by the calorimeter, at different amounts of water 394.
Banks, W. and Greenwood, C.T. 1975. “Starch and Its Compon-
present in the system. At low water content, the AH value ents.” H&ted Press, Wiley & Sons. New York.
mainly represents the enthalpy of melting of the starch Banks, W., Greenwood, C.T., and Muir, D.D. 1970. The characteri-
zation of starch and its components. Part 2. The semi-micro
crystallites; at high water levels, however, the AH value can estimation of the starch content of cereal grains and related
account for granule swelling, crystallite melting and exten- materials. St!irke 22: 105.
sive hydration of starch molecules. More detailed thermo- Biliaderis, C.G., Grant. D.R., and Vase, J.R. 1979. Molecular weight
distributions of legume starches by gel chromatography. Cereal
dynamic measurements, however, are required to provide Chem. 56: 475.
an adequate understanding of the processes contributing to Bihaderis, C.G. 1980. Ph.D. thesis, Univ. Saskatchewan (In prepara-
the enthalpy factor of the gelatinization process. Finally, it tion).
ColIison, R. 1968. Swelling and gelation of starch. In “Starch and
is of interest to note that similar effects of water content Its Derivatives.” p. 168. Ed. Radley, J.A. Chapman and Hall.
on both the magnitude and temperature shift of the “melt- London.
Cowie, J.M.C. 1973. “Polymers: Chemistry and Physics of Modem
ing endotherm? of other crystalline biopolymers have been Materials.” Intertext Books.
also reported (Morita, 1966). Donovan. J.W. 1979. Phase transitions of the starch-water system.
Biopoiymers 18: 263.
All commercial corn starches showed additional endo- Dubois. M.. GiIIes, K.A., Hamilton, J.K., Rebers, P.A.. and Smith. F.
thermic peaks (Fig. 2, thermogram 2) at temperatures over 1956. Calorimetric method for determination of sugars and re-
1 O O ’C. Since the laboratory isolated corn starch gave the lated substances. Anal. Chem. 28: 350.
Flory, P.J. 1953. “Principles of Polymer Chemistry.” Cornell Uni-
normal biphasic endothermic transition (Fig. 2, thermo- versity Press, Ithaca.
gram l), it is suggested that these additional peaks might French, D. 1972. Fine structure of starch and its relationship to the
organization of starch granules. J. Jap. Sot. Starch Sci. 19: 8.
reflect granular changes introduced during the isolation of GiBes. K.A.. Geddes, W.F.. and Smith, F. 1961. The carbohydrates
these commercial starches, of Graminae. 11. The constitution of the water-soluble polysac-
charides derived from bread crumb. Cereal Chem. 38: 229.
All AH values of the acid-modified corn and smooth pea Gough, B.M. and Pybus, J.N. 1971. Effect on the gelatinization
starches were lower than those of their native starches (Ta- temperature of wheat starch granules of prolonged treatment
ble l), in agreement with similar results reported for wheat with water at 5O’C. StXrke 23: 210.
Greenwood, C.T. and Muirhead. H.E. 1967. The thermal degrada-
starch by Wootton and Bamunuarachchi (1979a). tion of starch. Differential thermal an&Iysis of maltodextrins and
Smooth pea amylose and gelatinized smooth pea starch of starch and its components. Stffrke 19: 281.
Jaska, E. 1971. Starch gelatinization as detected by proton magnetic
showed no endothermic transitions. Smooth pea amylopec- resonance. Cereal Chem. 48: 437,
tin, however, gave a small endothermic transition, AH: 0.9 Kainuma, K. and French, D. 1971.. Nageli Amylodextrin and its
relationship to starch grqmle structure. 1. Preparation and prop-
Cal/g (Fig. 2, thermogram 3), suggesting a partial crystalline erties of amylodextrins from various starch types. Biopolymers
ordering of the isolated polysaccharide. In a poor solvent, 10: 1673.
such as water, the requirement for a minimum energy state Kainuma, K. and French, D. 1972. Naegeli amylodextrin and its
relationship to startih granule structure. 2. Role of water in
will favor such compact conformations. This is further sup- crystaIIization of B-starch. Biopolymers 11: 2241.
ported if one considers that the extensive branching of Lelievre, J. 1973. Starch gelatinization. J. APP~. Polym. Sci. 18: 293.
Marchant. J.L. and Blanshard. J.M.V. 1978. Studies of the dynamics
amylopectin facilitates an ordered conformation, by re- of the gelatinization of starch granules employing a small angle
stricting the rotation about individual glucosidic bonds light scattering system. St8rke 30: 257.
Medcalf, D.G. and GiIles. K.A. 1966. Effect of a lyotropic ion series
(Banks and Greenwood, 1975). Retrogradation of the amy- on the pasting characteristics of wheat and corn starches. Stgrke
lopectin during bread staling (Gilles et al., 1961) is further 4: 101.
-Continued on page 7680

1674-JOURNAL OF FOOD SCIENCE-Volume 45 (19801

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