Calorimetric Determination of the Arnylose Content of Starches Based on
Formation and Melting of the Amylose-Lysolecithin Complex
MASAYUKI KUGIMIYA
ABSTRACT
Amylose-lysolecithin complexes, formed in an exothermic reaction
when amylose or starches are heated with water and lysolecithin,
melt at temperatures near 107C. With excess lysolecithin present,
formation of the maximum amount of amylose complex requires
cooling after the first heating (during which gelatinization of starch
takes place), and then reheating. An amylose with chain length of
300 glucose units took up 14% lysolecithin; the enthalpy of melting
of this complex, observed by differential scanning calorimetry, was
5.9 Cal/g amylose. Amylose content of a starch was calculated from
the enthalpy of melting of its lysolecithin complex. Amylose con-
tents for potato, tapioca, lima bean, wrinkled pea, amylomaize and
waxy maize starches agreed with values obtained by iodine binding.
Amylose contents of maize and wheat starches were larger than ob-
tained by iodine binding, and in better agreementwith amylosecon-
tents obtained by fractionation.
INTRODUCTION
STARCH GRANULES are composed mainly of two com-
ponents: amylose, a linear polymer of some thousand
D-glucose units, with perhaps a small amount of branching
(Peat et al., 1952), and amylopectin, a hiply branched
glucose polymer with molecular weight -10 (Banks and
Greenwood, 1975). Amylose forms strong complexes with
molecules such as iodine, alcohols and fatty acids, but amy-
lopectin forms these complexes only weakly or not at all.
In the complexes, these molecules are located within
amylose helices (Bear, 1944; Mikus et al., 1946). The
capacity of amylose to bind iodine is now commonly used
to determine the amylose content of starches (Bates et al.,
1943; McCready and Hassid, 1943; Larson et al., 1953;
Banks et al., 1970). The capacity of amylose to form water-
insoluble complexes with n-butanol or other organic mole-
cules has been used to separate amylose and amylopectin
(Schoch, 1942b; Whistler and Hilbert, 1945; Haworth
et al., 1946). However, the presence of intermediate
components in starches does not always allow a clearcut
classification of starch components as either amylose or
amylopectin (Lansky et al., 1949. Whistler and Doane,
196 1; Adkins and Greenwood, 1969).
The phase transitions which starches undergo on heating
in the presence of water have been studied in recent years
by the technique of differential scanning calorimetry (Stev-
ens and Elton, 197 1; Donovan, 1979; Wooton and Bamunu-
arachchi, 1979; Donovan and Mapes, 1980). Transitions
which occur at temperatures above the gelatinization transi-
tion and which were observed on heating maize and wheat
starches in the presence of water, arise from the melting
or disordering of starch-lipid complexes (Kugimiya et al.,
1980).
When potato starch, which contains practically no lipid,
is heated in the presence of water and lysolecithin, a major
lipid of wheat starch (Acker and Schmitz, 1967), an endo-
Author Donovan is affiliated with the USDA-SEA,
gional Research Center, Berkeley, CA 94710. Author
is with the Dept. of Food & Nutrition, Hiroshima Womens Univ.,
Ujina-higashi, Hiroshima 734, Japan,
I
and JOHN W. DONOVAN
therm characteristic of the melting of an amylose-lyso-
lecithin complex is observed. We hypothesized that enthal-
pies of melting of the complex formed when starches are
heated with water and excesslysolecithin were proportional
to. amylose contents (Kugimiya et al., 1980). Accordingly,
we now present a new calorimetric method of determining
the amylose content of starches. Some interesting discrep-
ancies in amylose contents obtained by this new method
and by the conventional iodine-binding method are noted.
EXPERIMENTAL ----
-.. __----
POTATO STARCH was obtained from Matheson. Coleman and
Bell, tapioca starch from National Starch Products, and maize starch
from National Cooperatives, Inc. Wheat starch was General Mills
Aytex-P. Liia bean starch, variety Ventura, was provided by
Dr. Louis B. Rockland, and wrinkled pea starchby ProfessorClar-
ence Sterling. Amylomaize (Amylon VII, 70% amylose) and waxy
maize starches were provided by Professor Dexter French. Potato
amylose, of molecular weight >150,000, was Aldrich Chem. Co.
Lot No. KB 081777. Amylose, of about 300 glucose units chain
length, was ICN Pharmaceuticals Lot No. 8332. The former is
referred to as high molecular weight amylose (HMW amylose) and
the latter as low molecular weight amylose (LMW amylose). Potato
amylopectin was obtained from Calbiochem. Lysolecithin (L-o-
lysophosphatidyl choline) from egg yolk and lysolecithin (L-o-
lysophosphatidyl choline, pahnitoyl, synthetic) were obtained
from Sigma Chemical Co. The former is referred to as egg lyso-
lecithin. Other chemicals were reagent grade. Moisture contents
of starches, starch components and lysolecithins were calculated
from loss in weight after heating at 130C for 1 hr. To remove
lipids, maize and wheat starches were extracted with methanol
in a Soxhlet extractor (Schoch, 1942a; Kugimiya et al., 1980).
The differential scanning calorimeter, a Du Pont Model 990,
was calibrated and used as previously described (Donovan and
Ross, 1973; Donovan, 1977, 1979). Thermograms (plots of heat
flow as a function of temperature) were obtained at a heating
rate of lOC/min. Both first and second heatings were carried out to
127C. Samples, which usually contained l-2 mg of starch or
starch component with or without lysolecithin, and 12 ~1 of water,
were weighed directly into aluminum hermetic pans and sealed in a
press. Weights of starch and starch components are ail dry weights.
The ratios of lysolecithin to starch or starch components are based
on dry weight. EnthaIpies of melting were obtained from the areas
of the endotherms (peaks of heat flow). To obtain the area, a
baseline was constructed as a smooth line from beginning to end of
the endotherm, approximating the thermogram if the endotherm
were not present. The area between the baseline and the endotherm
was measured with a planimeter. The precision of the method de-
pends on how well baselines can be drawn under the experimentally
observed endotherms. For these experiments, a precision (S.D. of
mean) of 3-4% of the mean was usually obtained. X-ray diffraction
patterns of the dry amyloses were measured as described previously
(Kugimiya et al., 1980).
RESULTS
Basis of the method
To use the enthaipy of melting of amylose-lipid com-
plexes as a means of determining the amylose content of a
starch, it is necessary to: (1) choose a suitable lipid to form
the complex with the amylose when starches undergo gela-
Western Re-
tinization; (2) determine the enthalpy of melting for a
Kugimiya
pure amylose-lipid complex, or equivalently, qf the com-
plex formed upon fully saturating amylose with lipid; (3)
establish that complex formed by the lipid with starches is
Volume 46 (198l)-JOURNAL OF FOOD SCIENCE-765
stoichiometric-in c ther words, establish that the amylose
in the starch has been fully saturated with lipid under the
experimental conditions of formation of the complex.
Choice of a lipid
The choice of a lipid for formation of a complex with
amylose requires w:&er solubility of the lipid together with
strong binding of lipid in the complex. Lysolecithin meets
both of these criteria. In addition, its positive charge, to
which much of its water solubility can be attributed, is
probably helpful ir formation of complexes with starches
which have negatively-charged phosphate groups (Samotus
and Schwimmer, 1>62). Lysolecithin is known to be par-
ticularly difficult lo extract from some starches, such as
wheat starch.
Enthalpy of melting: of the amylose-lysolecithin complex
When HMW an1 LMW anyloses and amylopectin are
heated with an exe :ss of egg lysolecithin in the presence of
water, thermograms such as those shown in Figure 1 are
obtained. Figure 1 also shows thermograms obtained on re-
heating after coolirg to room temperature. In the presence
of lysolecithin, the amylose gives endotherms near 107C,
but amylopectin dies not. The amyloses and amylopectin
without lysolecithin give no endotherm characteristic of
this melting transition near 107C. Therefore, the endo-
therms obtained with amyloses and lysolecithin are due to
the melting transition of the amylose-lysolecithin com-
I I I I I I
HMW AMYLC6t
plex. The first heating gives a single endotherm with a
peak temperature at 104.7 + 0.4C or 104.4 + O.lC for
HMW or LMW amylose, respectively, regardless of amount
of lysolecithin added. Reheating gives an endotherm at
106.7 * 0.2C or 106.9 + 0.2C for HMW or LMW amylose,
respectively (with a shoulder at about 103C), regardless
of amount of lysolecithin added- These results show that
the peak temperature of the endotherm is not affected by
the molecular weight of the amylose. The biphasic charac-
ter of the amylose-lipid endotherms obtained on second
heating is not produced by alteration or hydrolysis of lyso-
lecithin on heating. When lysolecithin and water were
heated in the calorimeter to 150C, cooled and subsequent-
ly added to LMW amylose, the endotherm obtained on fist
heating was the same as that obtained with a fresh sample
of lysolecithin.
The enthalpies of melting of the amylose-lysolecithin
complexes are plotted against the weight ratio of lysoleci-
thin to amylose in Figure 2. The enthalpies increase with
increasing ratio of lysolecithin to amylose up to a ratio of
about 0.2, and remain constant thereafter. Enthalpies
obtained on reheating the amyloses with lysolecithin are
about twice those obtained on the first heating. Both
heating and reheating the LMW amylqse with lysolecithin
give larger enthalpies of melting than for HMW amylose.
A third heating did not further change the enthalpies. This
difference in enthalpies may result from: (1) a difference in
structure between the HMW and LMW amyloses, perhaps
from a low degree of branching in the HMW amylose
(Peat et al., 1952); (2) the inability to fully denature
some organized regions of the HMW amylose at the tem-
I I peratures of these experiments. If some regions of the HMW
amylose chains could not be fully dispersed into the sol-
I

7-ol-----l
LMW
-Tr=
AMYLOIE \ I

I I
1 I I VI I
0 0.11 0.4 0.6 0.8 1.0 1.2
I
r--- 60 80 100 120 Lysolecithin/Amylose (w/w)
1EMPERATURE ( o C)
Fig. 2-Enthelpies of melting of amylose-lysolecithin complexes as
Fig. l-Thermogran,s .of HMW and LMW amyloses and amylopec- a function of lysolecithin:amylose. LMW amylose with egg lysoleci-
fin with egg lysolel:ithin, obtained on first heating (I) and after thin: first heating, 0; second heating, 0; third heating, 0. LMWamy-
cooling and reheatir 0 (IN. Weight of amylose or amylopectin lmgl lose with synthetic iysolecithin: first heating, a; second heating, X.
and weight ratio of lysolecithin to amylose or amylopectin: HMW HMW amylose with egg lysolecithin: first heating, A; second heating
amylose, 0.86 and 0 51; LMWamylose, 1.01 and 0.38;amylopectin. A; third heating 4 HMW amylosa with synthetic lysolecithin: first
1.35 and 0.08. heating. q ; second heating, n .

766-JOURNAL DF FOOD SCIENCE-Volume 46 179811

 AMYLOSE CONTENT OF STARCHES. ..

vent, either because of crystallinity or branching, then com- lysolecithm gives the same enthalpy as with egg lysolecithii.
plex formation with Lipid might be restricted. The X-ray A third heating did not change the enthalpy. Therefore,
diffraction measurements of the dry amyloses showed a the enthslpy obtained on reheating represents maximum
clear pattern for the HMW amylose and a diffuse pattern incorporation of lysolecithin into the starch. This enthalpy
for the LMW amylose. This indicates that the HMW amy- was used to estimate the amylose content of the starch.
lose has a higher degree of crystallinity than the LMW
amylose. Since the LMW amylose appears to be fully dis- Calculation of amylose content
persible in the solvent, and since the chain length of 300 To determine amylose content, the following formula
glucose units is not so short that end effects in formation was used:
of the complex with lipid would be significant, the en- enthalpy (Cal/g) for starch
thalpy of melting the LMW amylose-lysolecithm complex % amylose = 100 x
was selected as the standard enthalpy for maximum incor- 5.9 d/g
poration of lysolecithin into amylose. This enthalpy change,
5.87 f 0.1 Cal/g of amylose, was then used to estimate the
amylose content of starches.
When synthetic lysolecithin was added to amyloses in
place of egg lysolecithin, endotherms similar to those ob-
tained with egg lysolecithin were obtained. The peak tem-
peratures for the first heating were 103.6 and 103.3C,
and those for the second heating, 105.4 and 105.9C, for
HMW and LMW amyloses, respectively. Synthetic lysoleci-
thin gives a peak temperature about lC lower than that for
egg lysolecithin. However, the enthalpies of melting ob-
tained with synthetic lysolecithin were the same as those
obtained with egg lysolecithin.
Stoichiometry of the complex
The plot of enthalpy of melting of the amylose-lysoleci-
thin complex as a function of lysolecithin/amylose ratio,
Figure 2, shows a characteristic saturation plateau for bmd-
ing. For the re-heating data, the rising portion of the plot
(at low lysolecithin/amylose ratios), when extended linearly
to the plateau, indicates that binding equivalence is attained
at a lysolecithin/amylose ratio of 0.14, with an estimated
error of kO.02. This suggeststhat amylose can bind at most 0.1 0.2 0.3 0.4 0.5
about l/7 of its weight of lysolecithin.
The enthalpy of melting of the amylose-lysolecithin Lysolecithin/Potato starch (w/w)
complex of potato starch was determined as a function of
lysolecithin/starch ratio (Fig. 3). As with amylose, the Fig. 3-Enthalpies of melting of potato starch-lysolecithin complex,
enthalpy obtained on reheating was higher than that on as a function of lysolecithin:starch. Egg lysolecithin: first heating,
first heating. The enthalpies were constant at lysolecithin/ o; second heating, a; third heating, Q. Synthetic lysolecithin: first
starch ratios above about 0.05. The starch with synthetic heating A; second heating, 4

I I I , 1 I I , -r I I I , , , , ,
MIZE (N)
A 8
OlAlO

APIOCA
\

EAN

-xl

lAXY MAIZE 1

Fig. 4-Thermograms o f,starches. Weights

of starches (mgl: A, potato, 1.36;
tapioca, 1.90; lima bean, 1.31; wrinkled
Pea, 1.02; amylomeize. 1.03; waxy
maize, 1.22. B, nondefatted IN) maize,
1.39; defatted (D) maize, 1.39; N-wheat,
II l I Ill I l I III I I III 1.19; D-wheat, 1.57.
40 60 80 100 120 40 C, 80 100 120
TEMPERATURE(

Volume 46 (1981)-JOURNAL OF FOOD SCIENCE-767

 I I , I I I , ,
POTATO

rAPlO> r\

.IMA BEAN 1 \/ /

VRINKLEO PEA 1 IE\/ ,

LMVLOMAIZE

Fig. 5-Thermogram3 of starches with

egg lysolecithin obtai,ied on first heating
(AI and after cooling and reheating IS).
Weight of starch (mo1 and weight ratio
of lysolecithin to st(?rch: potato, 1.47
and 0.24; tapioca, 1.32 and 0.29: lima
bean, 1.14 and 0.~16; wrinkled pea,
0.81 and 0.38; amylomaize. 1.13 and
0.53; waxy maize, 1.5 8 and 0.17. I , I I , 1 I I I
4 10 60 100 120 40 60 80 100 120
TEMPERATURE ( oC)

In this formula, tl!e 5.9 Cal/g is the best estimate we have I I I I

for the enthalpy c.f melting of the pure amylose-lysoleci- MAIZE

thin complex. When this formula was applied to the potato OJ)
starch data discus;ed above, an amylose content of 24%
was obtained. Literature values for the amylose content of
potato starch rangl: from 19-24%, with about half of these 3s
giving 22-24% as the amylose content. Accordingly, the
calorimetric method appears to give a reasonable estimate
of amylose contem for potato starch.
Application to starches
To estimate ti.e amylose content of starches calori-
metrically, egg 1y:;olecithin was added to the starches at
a weight ratio of lysolecithin to amylose in excess of 0.2.
Starches used were potato, tapioca, maize, wheat, lima
bean, wrinkled peq amylomaize, and waxy maize. Control
experiments withcut lysolecithin were carried out. Typical
thermograms of starches without lysolecithin are shown in
Figure 4. Thermcgrams of starches with lysolecithin, on \I
heating and on rr:heating, are shown in Figures 5 and 6.
The enthalpies of melting of the starch-lysolecithin com-
plex are given in Table 1. The enthalpies of gelatinization of
starches with and without lysolecithin are given in Table 2,
and reveal that formation of the starch-lysolecithin com-
plex is exothermic (see below).

Maize and wheat starches

It is important to examine whether defatting starches in-
fluences the calorinetric determination of amylose content. jxal/ C
It is known that the presence of fatty acids depressesthe $
iodine-binding power of starches, so that defatting is neces-
sary for the iodinletric determination of amylose (Schoch, I I I I. I I I I
1964). Maize and wheat starches show endotherms of melt- B 60 120
ing of starch-lipiC complexes (Kugimiya et al., 1980, and
Fig. 4). Extraction of these starches with methanol results TEMPEEuRE yk)
in elimination of i:he starch-lipid endotherm of maize starch Fig. 6-Thermograms of maize and wheat starches with egg lysc
and a reduction ii1 the size of the starch-lipid endotherm of lecithin on first heating (I1 and after cooling and reheating (II,
wheat starch (Fil;. 4). The endotherms for the amylose- Weight of starch (mg) and weight ratio of lysolecithin to starch
lysolecithin transitions of the nondefatted and defatted non-dafattad (NJ maize, 0.97 and 0.66; dafattad (0) maize, 1.31
starches (Fig. 8) are not different from those for other and 0.30; N-wheat, 1.66and 0.32; D-wheat, 1.35and 0.37.

768-JOURNAL (IF FOOD SCIENCE-Volume 46 (1981)

 AMYLOSE CONTENT OF STARCHES. ..

starches (Fig. 5). Defatting did not affect the amylose con- is formed exothermically during gelatinization (Kugimiya
tent of these starches, as determined calorimetrically et al., 1980). Quantitative calculations can be made by
(Table 1). comparing the enthalpy of melting of the complex
The amylose content of maize and wheat starches, as [AHi,,( Table 11 with the difference between the
calculated from the size of the endotherms of the lysoleci- enthalpies of gelatinization without [AH(G)] and with
thin-amylose complex, were significantly higher than amy- [AH,,(G)] lysolecithin (Table 2). Such calculations show
lose contents previously reported (Table 3), which are that within experimental error, for the first heating, the
based on iodine affinity. The reasons why these starches magnitude of the exotherm for formation of the complex
showed higher amylose contents is not clear. It is possible equals the magnitude of the endotherm for melting of the
that these starches contain an intermediate component or complex.
an amylopectin which is able to bind some lysolecithin A second heating of the starch-lysolecithin samples does
but is not able to bind iodine. Alternatively, and we think not give a gelatinization endotherm, but only an endotherm
this is less likely, the enthalpy of melting of the amylose- for melting of the amylose-lysolecithin complex. While the
lysolecithin complex formed by these starches may be
abnormally high.
Fractionation of maize and wheat starches gives a higher Table 1-Enthalpies of melting of starch-lysolecithin complexes and
content of amylose than obtained by iodine affinity. Whist- estimation of amylose contents
ler and Hilbert (1945) reported a 29-31% yield of crude
amylose from maize starch when 2-nitropropane was used Sequence Peak AHlysffNb Amylose
to form the complex with amylose. The yield from wheat of Temperatureb content
starch, using 1-nitropropane, was 31-32%. Lansky et al. Starch heatinga CC) (call91 (96)
(1949) reported that Pentasol gave a 28-29% yield of a
Potato I 104.9 f 0.2 1.22 f 0.03
linear component from maize starch, although n-butyl II 106.9 f 0.2 1.42 f 0.06 24
alcohol gave 22-23%. The amylose contents obtained by III 106.7 f 0.0 1.47 + 0.00
precipitating water-insoluble complexes thus seem higher
than those obtained by iodine affinity. Purely on entropy Tapioca I 103.6 f 0.1 0.79 f 0.15
considerations, the stability of complexes formed between II 106.8 f 0.1 1.14 i 0.06 19
short chains and the relatively large lipids or similar or-
ganic molecules could be significantly greater than the sta- Maize If 103.5 +_0.4 1 A4 i 0.02
bility of short-chain complexes with the smaller iodine (nondefatted) I 107.4 + 0.6 1.94 f 0.07 33
molecules. Accordingly, the discrepancy in the amylose Maize I 103.4 f 0.2 1.51 f 0.00
content of maize and wheat starches may be due to the fdefatted) II 107.2 f 0.3 1.96 f 0.05 33
presence of a fraction with properties intermediate between
amylose and amylopectin, or of an amylose fraction of Wheat I 103.4 + 0.2 1.36 + 0.04
short chain length. If so, these fractions must form com- (nondefatted) II 107.1 f 0.3 2.16 f 0.02 37
plexes with lysolecithin to a greater extent than with iodine.
The present results, and the fractionation experiments Wheat I 103.4 5 0.2 1.37 f 0.10
referred to above, suggest that maize and wheat starches (defatted) II 107.3 f 0.3 2.16 f 0.03 37
may have a considerable amount of such intermediate frac-
tions. It has been recommended that the amylose con- Lima bean I 104.0 1.39
II 107.2 2.01 34
tent of starches be expressed merely in terms of iodine
affinity, with no reference to percentage of amylose present Wrinkled pea I 104.8 f 0.2 2.32 + 0.03
(Lansky et al., 1949). II 107.5 + 0.6 3.80 * 0.06 65
Other starches
Amylomaize I 106.0 +_0.3 2.30 f 0.12
The amylose contents of most of the other starches, as II 107.0 f 0.1 3.83 f 0.08 66
determined by this calorimetric method, are in good agree-
ment with the reported amylose contents (Table 1 and 3). Waxy maize I 103.3 f 0.0 0.03 f 0.00
Amylomaize was found to be 66% amylose by the calori- II 107.8 f 0.3 0.04 f 0.00 0.6
metric method. Banks et al. (1974) have reported that E I, II, and III designate first, second and third heatlng.
iodine-binding measurements yield a higher estimate of the Mean and standard deviation for triplicates, except for lima bean.
amount of amylose present in amylomaize starches (79%)
than does butanol-complex formation (63%) and that the
discrepancy between these independent measurements of Table 2-Enthalpies of starch gelatinization with and without
amylose content represents material, abnormal amylopec- lysolecithin
tin, which is neither amylose nor amylopectin, in the con-
Without Lysolecithin With Lysolecithin
ventional sense, Their explanation for this is that amylo-
maize amylopectin is heterogeneous, and is composed of a TQa AH(GIa AHI (G)
high molecular weight material indistinguishable from Starch (C) (cal/g) (2, kaVd
normal amylopectin and a low molecular weight composed,
Potato 64.8 f 0.1 4.43 f 0.11 64.7 f 0.0 2.97 f 0.13
at least partially, of amylose of relatively short (<lOO
glucose units) chain length. If the discrepancy in amylose Tapioca 71.1 f 0.1 3.14 f 0.06 70.6 f 0.0 2.01 f 0.16
content obtained by the different methods arises from the
presence of intermediate material, the intermediate material Maize
of maize and wheat starches must be different from that of (defatted) 70.0 f 0.4 2.89 * 0.17 69.8 f 0.2 1.59 f 0.26
amylomaize starch.
Lima bean 80.6 4.26 79.9 2.91
DISCUSSION
THE ENTHALPIES of the gelatinization transition of Waxy maize 73.0 f 0.2 3.82 + 0.09 73.0 f 0.0 3.51 f 0.17
starches with added lysolecithin are smaller than without a Mean and standard devlatlon for triplicate determinations, except
lysolecithin. This suggests that all or most of the complex for lima bean.

Volume 46 1198lkJOURNAL OF FOOD SCIENCE-769

Table 3-Am ylose con1 ents of starches

Starch Amylose content (%I and reference

Potato 22e, 19b, 22.9C. 20.4-21 .O, 20-24. 23f

Tapioca 17e, 1 8.5c, 16.7. 18-lge. 18.gg

Maize 21e, 23.8, 24.0, 23.99, 22.2-28.4h, 27l

Wheat 24a, 25.0d, 21 -27e, 26f, 24.3-25.1g, 23.4-27.6]

Lima Bean 30-35e

Wrinkled Pea 66f, 64.7g 60-6gk, 66.0

Amylomaize 79. 7om

Waxy Maize Oa, 1.44 <lf

t Bates et al. (1943) : Whlstler and Weatherwax (1948)

McCreadY and Hassltl (1943) Banks et al. (1974)
z Doremus et al. (1951) j Medcalf and Gilles (1965)
Anderson and Greenwood (1955) : Hllbert and MacMasters (1946)
4 Deatherage et al. (1955) mPotter et al. (1953)
Greenwood and Thomson (1962) D. French, personal communication, 1978.
g Larson at al. (1953)

high temperature endotherm obtained on first heating has a method is still to be explained. However, high amylose
single, broad peak, the endotherm obtained on reheating is contents, in themselves, do not present a difficulty if the
a peak with a le;.ding shoulder. The asymmetry of the calorimetric method is used to compare one variety of
endotherm obtained on reheating appears to be related to wheat or maize starch with another. For the other starches,
the state of subdivision of the amylose-lipid complex. The the amylose content obtained by the calorimetric method
sharp peak at 107C appears to result from melting of crys- agrees well with the amylose content obtained by the io-
talline complex. The leading shoulder, and the endotherm dine-binding method, so that there should be no difficulty
obtained at 104-l 05C on first heating, appears to result in using the calorimetric method for these starches.
from melting of ei:her noncrystalline complex, or complex
with a much 1ow:r degree of order. The proportion of REFERENCES
shoulder to sharp peak can be altered by cooling the sam- Acker. L. and Schmitz. H.J. 1967. Uber die Lipide der Weizen-
ple slowly or rapii.ly after the first, or subsequent, heating. stiirke. 3. Mitt. Die iibrigen Lipide der Weizenstiirke sowie die
The total enthalpy of melting is not altered thereby. Lipide anderer StZrkearten. St.&k6 19: 275.
Adkins. G.K. and Greenwood, C.T. 1969. Studies on starches of
The enthalpy elf melting of the complex obtained on high amylose-content. Part 10. An improved method for the frac-
reheating was always greater than that obtained on fit tionation of maize and amylomaize starches by complex forma-
tion from aqueous dispersion after pretreatment with methyl
heating, regardless of starch studied. This suggests that a sulphoxide. Carbohyd. Res. 11: 217.
greater amount of complex is formed by heating to 13OC Anderson, D.M.W. and Greenwood, C.T. 1955. Physicochemical
studies on starches. Part 3. The interaction of starches and branched
and cooling. This rlay be due to the greater dispersibility of a-1:4-glucosans with iodine. J. Chem. Sot. (London) 3016.
amylose in water a i highei temperatures. Since the enthalpy Banks. W. and Greenwood. C.T. 1975. Fractionation of the starch
of melting of the ( omplex obtained on reheating appears to grade and the fine stru&ures of its components. In Starch and
its Components, p. 5. Halsted Press, N.Y.
show maximum incorporation of lysolecithin into amylose, Banks. W.. Greenwood. C.T., and Muir, D.D. 1970. The characteri-
the ratio of the ellthalpy obtained on first heating to that zation of starch and its components. Part 3. The technique of semi-
micro, differential. potentiometric. iodine titration, and the fac-
obtained on reheating is a measure of the relative amount tors affecting it. Staike 22: 105.
of complex formed during gelatinization. This ratio, when Banks, W., Greenwood, C.T.. and Muir, D.D. 1974. Studies on
calculated, shower! that 60-85s of amylose, depending on starches of high amylose content. Part 17. A review of current
concepts. St.&se 26: 289.
the starch, forms a complex with lysolecithin during gela- Bates, F.L., French, D., and Rundle, R.E. 1943. Amylose and amy-
tinization. This 1a:k of full reaction between amylose and lopectin content of starches determined by their iodine complex
formation. J. Am. Chem. Sot. 65: 142.
lysolecithin may be due to limitations on 8CCessibtity of Bear, R.S. 1944. Complex formation between starch and organic
reactants during t1.e first heating period. molecules. J. Am. Chem. Sot. 66: 2122.
Deatherage. W.L., MacMasters. M.M.. and Rist. C.E. 1955. A partial
The present calorimetric determination of amylose is a survey of amylose content in starch from domestic and foreign
simpler and fastel procedure than conventional iodimetric varieties of corn, wheat, and sorghum and from some other starch-
bearing plants. Transact. Amer. Assoc. Cereal Chem. 13: 31.
determination, which requires defatting of most starches. Donovan, J.W. 1977. A study of the baking process by differential
For the scanning calorimetric determination of amylose, scanning calorimetry. J. Sci. Fd. Agr. 28: 671.
the starch, lysolec:ithin, and water are weighed into a her- Donovan, J.W. 1979. Phase transitions of the starch-water system.
Biopolymers 18: 263.
metic pan, the pan sealed, and the sample heated twice in Donovan, J.W. and Mapes, C.J. 1980. Multiple phase transitions of
the calorimeter. (The first heating step probably could be starches and NXgeli amylodextis. St*Xrke 32: 190.
Donovan, J.W. and Ross, K.D. 1973. Increase in the stability of avi-
carried out in holing water or in an oven.) The observed din produced by binding of biotin. Biochemistry 12: 512.
enthalpy of the amylose-lysolecithin complex, divided by Doremus. G.L.. Crenshaw. F.A.. and Thurber, F.H. 1951. Amylose
content of sweetpotato starch. Cereal Chem. 28: 308.
the enthalpy of melting of pure amylose-lysolecithin com- Greenwood, C.T. and Thomson, J. 1962. Physicochemical studies
plex, gives the fraction of amylose present in the starch. on starches. Part 24. The fractionation end characterization of
The fact that unusually large amounts of amylose are ob- starches of various plant origins. J. Chem. Sac. (London) 222.
Haworth. W.N.. Peat, S.. and Sagrott, P.E. 1946. A new method for
tained for maize and wheat starches by the calorimetric the separation of the amylose and amylopectin components of
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770-JOURNAL OF FOOD SCIENCE-Volume 46 (7981)