202 STARCH/Analysis of Quality

The primary function of a starch in the food indus- Whistler RL and BeMiller JN (1997) Starch. Carbohydrate
try is to control viscosity. It is used to thicken, add Chemistry for Food Chemist, pp. 117
151. St. Paul,
texture and to control viscosity in a variety of pre- MN: Eagan Press.
pared foods ranging from canned foods and salad Whistler RL, BeMiller JN, and Paschall EF (eds.) (1984)
Starch Chemistry and Technology, 2nd edn. Orlando,
dressings to pie fillings and puddings. Starches used
FL: Academic Press.
during retort are fill viscosity starches designed to give
viscosity during the initial mixing and filling process
of canning. A viscosifying starch is used to retain Relevant Websites
viscosity during retort and as such cannot break
down at high temperatures and when shear is applied. http://www.corn.org
Corn Refiners.
For salad dressing, starch is needed for both texture http://www.starch.dk
International Starch Institute.
and viscosity control. High-amylose starches are used http://www.pulpandpaper-technology.com
Pulp
to provide the set (or spoonable nature) and mouth and Paper Technolgy.
feel, whereas a waxy starch would provide the viscos-
ity control. Pourable salad dressing uses starch to
modify the viscosity, shorten the texture, and add
creaminess to the dressing. Starch is used in fillings
to modify the viscosity, add stability, and to give
smooth short texture. The starch should also not
mask or alter the flavor of the filling. For fruit fillings,
it is important that the starch gives a clear gel. Analysis of Quality
A Gunaratne and H Corke, The University of
See also: Noodles: Starch Noodles. Starch: Analysis of Hong Kong, Hong Kong, People’s Republic of China
Quality; Chemistry; Modification; Synthesis.
ª 2004, Elsevier Ltd. All Rights Reserved.

Further Reading
Jarowenko W (1976) Starch based adhesives. In: Skeist I Introduction
(ed.) Handbook of Adhesives, pp. 192
211. New York:
Van Nostrand. Starch is the main polysaccharide produced in pho-
Kennedy HM (1989) Starch- and dextrin-based adhesives. tosynthetic tissues. Recently, there has been a grow-
In: Hemingway RW and Conner AH (eds.) Adhesives ing demand for starch in both food and nonfood
from Renewable Resources. Washington, DC: industries because of its wide array of applicability
American Chemical Society. in diverse systems. Functionality is the key for the
Maurer HW (2001) Manufacture and composition of industrial utilization of starch. Functional properties
unmodified starch. Starch and Starch Products in can be defined as the characteristics that govern the
Surface Sizing and Paper Coating, pp. 25
28. Atlanta, behavior of a food component during processing,
GA: TAPPI Press.
storage, and preparation. Factors such as botanical
Maurer HW and Kearney RL (1998) Opportunities and
source, structure and physicochemical properties,
challenges for starch in the paper industry. Starch 9:
396
402. and pretreatments of starch directly affect functional
Nordquist CE (ed.) (2001) Corrugated Adhesives Prepara- properties of starch. Analysis of starch-related func-
tion, 5th edn. Atlanta, GA: TAPPI Press. tionality should provide a clear picture of the relevant
Radley JA (ed.) (1976) Industrial Uses of Starch and its property that will allow better use of starch in food
Derivatives. London: Applied Science Publishers. and nonfood systems, for example, to maintain con-
Rapaille A and Van Hemelrijck J (1992) Modified starches. sistent quality and functionality of starch-based pro-
In: Imeson A (ed.) Thickening and Gelling Agents for ducts in every batch, otherwise the product will not
Foods, pp. 171
201. London: Blackie Academic and survive in the competitive market. Methods that are
Professional. implemented for the analysis of starch functional
Shogren RL (1998) Starch: properties and materials
properties should be simple and fast, technically fea-
applications. In: Kaplan DL (ed.) Biopolymers from
sible, nondestructive, and able to provide reproduc-
Renewable Resources, pp. 30
46. New York: Springer.
Stevens ES (2002) Green Plastics. Princeton, NJ: Princeton ible results with high accuracy. Although several
University Press. methods have been developed recently to monitor
Thomas DJ and Atwell WA (1999) Starches, Practical some of the functional properties, individual methods
Guides for the Food Industry. St. Paul, MN: Eagan are sometimes not capable of providing adequate
Press. data on all the dimensions of a functional property,
 STARCH/Analysis of Quality 203

especially in the determination of retrogradation and chloride solutions, it is a random coil with short,
gelatinization. Therefore, it is often worth applying at loose helical segments. Although helical conforma-
least two methods to get complementary data. This tion is common in amylose, double helices form
article aims to discuss some functional properties of when different helices are packed together. The heli-
starch from the perspective of the applicability of cal arrangement of amylose forms a hydrophobic core
methods that are currently employed to determine inside the amylose molecule, which permits complex-
those properties. ing with guest molecules such as lipids and iodine. The
amount and molecular characteristics of amylose
have a significant influence on starch functionality.
Properties, Functions, and Analysis of Higher amylose content decreases the granular swell-
Starch Macromolecules ing power, whereas increasing amylose concentration
Amylose decreases the gel stickiness but increases the gel firm-
ness. Reassociation of amylose chains on cooling of
The two major compounds of starch are amylose and a starch paste shrink the starch gel resulting in water
amylopectin. The two polymers are structurally dif- accumulation on an aging gel, which decreases the
ferent, the minor component, which is linear, consist- storage stability and usually the quality of an affected
ing mainly of a(1
4)-linked glucose. However, in starch-based food product.
some starches, amylose chains have shown a slight
degree of branching. Incomplete conversion to malt-
ose by b-amylase suggests the presence of branched Methods used in amylose estimation Conventional
points in the amylose polymer. The branched chains quantitative determination of amylose is based on its
can also act similar to unbranched chains. Amylose ability to form a deep blue color complex with iodine.
isolated from tuber and root starches such as potato Amylose content of starch therefore can be quantified
and cassava has a larger molecular weight than that either by spectrophotometric means or by potentio-
isolated from cereal starches such as maize and wheat. metric titration. Table 1 shows amylose content of
Although amylose is a linear molecule, its conforma- some common starches. However, interference from
tion tends to change due to the large number of hy- amylopectin and other intermediate materials in the
droxyl groups that can produce higher hydrogen blue color formation reaction biases the estimation of
bonding capability with strong internal forces. The actual content of amylose. Amylopectin
iodine com-
conformation of amylose has been the subject of con- plex is not stable due to shorter unit chain length of
troversy and has been shown to vary from helical to an amylopectin, but long chains of amylopectin, e.g.,
interrupted helix, to a random coil. In alkaline solu- long B chain of waxy maize amylopectin can bind
tions (KOH) and dimethyl sulfoxide (DMSO), amy- with iodine in a similar way to amylose. This
lose probably has an expanded coil conformation, would lead to an overestimation. Despite short-
while in water and neutral aqueous potassium comings such as this, and the time-consuming nature

Table 1 Some physical and chemical properties of common starches

Starch Granular size (m) Granular shape Amylose (%) Swelling power Solubility Taste
at 95 C at 95 C

Barley 2
35 Round, elliptical, lenticular 22 Low

Maize
Regular 5
25 Round, polygonal 26 24 25 Low
Waxy 5
25 Round, oval 1 64 23 Low
High amylose Round Up to 80 6 12 Low
Potato 15
100 Egg-like, oyster indentations 22 1000 82 Slight
Rice 3
8 Polygonal clusters 17 19 Low
Rye 2
35 Elliptical, lenticular 23 Low
Sago 20
60 Egg-like, some truncate forms 27 97 Low
Sorghum 5
25 Round, polygonal 26 22 22 Low
Tapioca 5
35 Round, oval, truncated on side 17 71 48 Fruity
Wheat 2
35 Round, elliptical, lenticular 25 21 41 Low
Oats 2
10 Polygonal, compound 27 Low

Adapted from Collado LS and Corke H (2003) Starch properties and functionalities. In: Kaletunc G and Breslauer KJ (eds.) Characterization of Cereals and
Flours, pp. 473
506. New York: Marcel Dekker.
204 STARCH/Analysis of Quality

of the assay, the amylose
iodine reaction is still the the conventional iodine
amylose complex forma-
basis of the most widely used method to determine tion, spectroscopic methods have been developed re-
amylose content of starch because of its accuracy, cently. These techniques provide advantages such
reproducibility, and easy operation. However, the ex- as ease of sample preparation, speed, and applicability
cessive time needed limits its use in quality control to online monitoring in the process control situation
applications. Instead of conventional thermal disso- compared with other techniques. Near-infrared
ciation of amylose in DMSO, low-temperature gela- (IR)-reflectance analysis has been successfully intro-
tinization in CaClB2B could be employed to reduce duced in determining the amylose content of
the time requirement. High performance size exclu- waxy, normal, and high amylose maize, unground
sion chromatography (HPSEC), that has shown brown or milled rice, and whole grain maize samples.
a good correlation with blue value measurements of Raman spectroscopy on the other hand is becoming
amylose content, can be employed to separate starch more popular as a quantitative analytical technique in
and de-branched starch. Ability to directly monitor the food industry and has shown potential applica-
the effect of de-branching on the molecular size dis- bility in the estimation of amylose content in maize
tribution of starch and high-molecular weight linear starches.
amylose content from this technique provides the
estimation of long-chain amylopectin chains that
Amylopectin
contribute to the apparent amylose content. Recently
another technique that is able to eliminate the effect Amylopectin, the highly branched molecule, is usually
of long-chain amylopectin in the estimation of amy- the major component in the starch granule with
lose content has been introduced. In this method, a(1
4)-linked glucose linear chains and a(1
6)-
starch completely dissolved in DMSO is subjected linked branch points. Crystalline domains of the
to de-fatting with ethanol. The precipitate after de- starch granules are due to the clustered branches of
fatting is dissolved in acetate/salt solution. A special amylopectin chains that are packed together, whereas
reaction mixture (concanavalin-A) is then added to the free amylose, amylose complexed with lipids, and
the solution to precipitate the amylopectin compo- branch points of the amylopectin are found in the
nent and the resulting supernatant after centrifuga- amorphous region. Alternative arrangement of crys-
tion contains only the amylose component. However, talline and amorphous region was proposed for the
a comparative study of size exclusion chromatogra- semicrystalline starch granule. However, there is no
phy (SEC), differential-scanning calorimetry, iodine- clear demarcation between amorphous and crystal-
binding capacity (IB), and concanavalin-A, where line regions. Crystalline region is less susceptible to
SEC was used as the reference method, has revealed enzymatic hydrolysis, water penetration, and other
that IB, differential-scanning calorimetry (DSC), and chemical reactions than amorphous region. Amylo-
concanavalin-A resulted in an overestimation in the pectin has a lesser tendency to gelation, retrograda-
determination of amylose content of mutant maize tion, and syneresis because of the branched structure.
starches (Table 2). As other alternative methods to The amount of amylopectin varies among different
starches. Waxy varieties contain almost 100% amy-
lopectin. The extent of functional characteristics of
starch (viscosity, gelatinization, solubility, texture,
Table 2 Amylose content in maize mutant starches as estimated
with size exclusion chromatography (SEC), Concanavalin (Con. gel stability, retrogradation, shear resistance) are
A), differential scanning calorimetry (DSC), and iodine binding directly affected by the amylose/amylopectin ratio.
capacity (IBC) Although amylopectin is the major component of
the starch granule, there is no convenient method
Starches Amylose (%)
developed for direct estimation of amylopectin and
SEC Con. A DSC IBC studies on amylopectin are dependent on develop-
ment of enzymatic and instrumental methods. Aver-
ae wx nd 7 nd 14
du 27 45 55 45 age structural properties of whole molecule and
su2 24 50 58 45 impact of internal structure of clusters on crystalliza-
du su2 34 58 66 60 tion have been studied by means of enzymatic
ae du 30 56 64 56 and SEC. It has been shown that the combined appli-
ae 54 63 60 63
cation of preparative and analytical size exclusion
nd: not detected. chromatography with multiple detection, precipi-
Source: Planchot V, Gerard C, Bertoft E, and Colonna P (2001) An tation techniques, and enzymatic de-branching
approach to structural analysis of granules using genetically modified
starches. In: Barsby TL, Donald AM, and Frazier PJ (eds.) Advances in provides the most detailed analytical insight on the
Structure and Function, pp. 104
128. UK: The Royal Society of Chemistry. microstructural properties of amylopectin.
 STARCH/Analysis of Quality 205

Function Related to Morphological (e.g., imparts texture on consumption) in a gelatinized

Characteristics of Starch Granules form. Several concepts have been proposed to explain
the gelatinization process. Granular swelling acts pri-
Granules are the basic physical structural unit of marily as a driver to destabilize the starch crystallites.
starch. The size, shape, and other morphological char- Recently, a model was proposed to explain the phe-
acters of starch granules are extremely diverse nomena involved in gelatinization and hydration of
(Table 1). The shape of the starch granule can be starch based on the side-chain liquid crystalline. In
spherical, disk, polygonal, or elongated. In general, this model, lamellae in starch are considered in terms
cereal starches have smaller granules compared to of three components
(1) backbone, (2) side-
tuber and root starches. Most tuber and root starch chain, and (3) double helices. The degree of mobility
granules have a simple size distribution. In some of these three components, coupled with the helix

starches, such as barley and wheat, two different gran- coil transition, give starch its distinctive properties
ular size populations exist, i.e., a bimodal distribu- in gelatinization. Gelatinization is influenced by
tion. Granular size and morphology have recently many factors such as, botanical source of starch,
received more attention, e.g., the size of granules is water content, and added solutes. Several methods
important in determining taste and mouth feel of have been proposed to study the effect of water
some starch-based fat mimetics. Some specific indus- content on thermal stability. Depending on the
trial applications of starch are related to size and the water content available during gelatinization, changes
size distribution of starch granules. For example, the in endothermic transition have been detected in terms
small size of rice starch granules makes it highly suit- of number and the position of the differential
able for laundry use. Most of the physicochemical scanning calorimetric endotherms. Only one
properties of native starch are highly correlated endotherm is detectable at higher levels of moisture
with the size of the starch granules. Larger size gran- content while two endothermic transitions are re-
ules tend to swell more than smaller granules, whereas ported at the low-moisture-content level for some
smaller size granules are more susceptible to enzy- starches where low temperature and higher tempera-
matic hydrolysis. The outer surface of starch granules ture endotherms are designated as G1 and M1 respec-
also plays a key role in many applications of starch. tively (Figure 1). In addition to two endothermic
Electron microscopic images have revealed that tuber transactions at lower moisture content, peaks are
and root starches show no sign of any pores on the shifted to higher temperature, indicating need for
granular surface. However, pores are present on the higher thermal energy to melt the starch crystallites
surface of maize, sorghum, and millet starch granules. at low moisture content. If there is sufficient water
Pores on granule surfaces increase accessibility of available in gelatinization, then crystallites melt co-
a-amylase to the granule interior resulting in increased operatively, resulting in a single endotherm. Two
enzymatic hydrolysis. Microscopic analysis provides endothermic transition peaks in insufficient water
information on surface features and size of starch could be attributed to the differences in the stability
granules. of starch crystallites, which melt over different tem-
peratures, less stable crystallites melt first and the

Characterization and Analysis of

Starch Thermal Properties Temperature (°C)

Gelatinization
To Tc
Gelatinization is one of the most important processes ∆Hcx
Endothermic heat flow

affecting starch. It occurs when starch is heated in M2

∆Hgel
excess water, when irreversible granular swelling, na- Tcx
tive crystallites melting, loss of granular order, loss of
G M1
birefringence, and starch solubilization take place.
The extent of these changes depends on type of starch,
starch concentration, temperature, presence of other Tm
solutes, and shear applied during the gelatinization
process. As a result of the above changes during gela-
Figure 1 Schematic representation of DSC thermograms
tinization, the starch paste develops viscosity, the
obtained for wheat starch heating. (Eliasson A-C (2003) Utilization
basis of most technological usefulness of starch as of thermal properties for understanding baking and salting
an ingredient in food and nonfood applications. In processes. In: Kaletunc G and Breslauer KJ (eds.) Characterization
the majority of food applications, starch functions of Cereals and Flours, pp. 65
115. New York: Marcel Dekker.)
206 STARCH/Analysis of Quality

others are next causing the second endotherm. Redis- Table 3 Gelatinization parameters of some starches measured
tribution of water between crystalline domain and by differential scanning calorimetry
gelatinized starch could also result in two endother- Starch Starch
To Tp Tc To
Tc DH
mic transitions, in which the first endotherm could be water ratio
attributed to melting of starch crystals in excess
water. Much research has been conducted to investi- Wheat 1:3 57.0 62.0 67.0 10.0 9.7
Maize normal 1:3 65.3 71.3 80.9 15.6 11.0
gate the influence of added solutes such as sugars, Maize waxy 1:3 62.9 72.8 84.3 21.4 13.6
emulsifiers, and electrolytes (such as sodium chlo- Potato 1:3 59.6 66.3 76.0 16.4 16.3
ride), which are widely applied in food industry on Cassava 1:3 63.0 71.5 81.5 18.7 12.3
starch behavior. Sugars have shown to increase the Sweet potato 1:3 60.0 69.0 82.5 22.5 7.1
gelatinization temperature but not to affect endother- Taro 1:3 76.8 83.0 95.2 18.4 14.5
True yam 1:3 75.0 80.0 90.2 16.5 17.8
mic heat absorption. Quality of various food pro- (Dioscorea)
ducts, bread and cakes, thickening and gelling of
sauce, pie filling, and extrusion of cereals are highly To onset temperature ( C); Tp peak temperature ( C); Tc conclusion tem-
perature ( C). DH enthalpy (J g
1).
dependent on starch
water interaction. Increased Sources:Gunaratne A and Hoover R (2002) Effectof heat-moisture treatment
gelatinization, when sugars are added to starch on the structure and physicochemical properties of tuber and root starches.
Carbohydrate Polymers 49: 425
437; and Hoover R, Vasanthan T,
paste could be due to decrease of water availability Senanayake NJ, and Martin AM (1994) The effects of defatting and heat-
for the gelatinization, binding water to sugar mole- moisture treatment on the retrogradation of starch gels from wheat, oat,
potato, and lentil. Carbohydrate Research 261: 13
24.
cules. However, it was reported that sugar acts as an
antiplasticizer rather than gelatinizer through the
effect on water-binding capability. Increased sugar Table 4 DSC parameters of amylose
lipid complex of some
concentration decreases the plasticization effect re- cereal starches
quiring more heat energy to achieve the gelatiniza- Starch Condition Tcx DHcx
tion. The extent of the influence of sugars on
gelatinization, swelling, and viscosity differs depen- Wheat 50% water 110.1 1.4
ding on the type of sugars and salts used when com- Rye 50% water 107.8 0.8
Barley 50% water 110.3 1.8
pared on a molar basis. Monosaccharides are less High-amylose barley 50% water 110.8 2.8
effective than disaccharides except maltose; among
disaccharides, sucrose is more effective. Tcx (peak temperature); DHcx (transition enthalpy).
Source: Fredriksson H, Silverio J, Andersson R, Eliasson A-C, and Aman P
(1998) The influence of amylose and amylopectin characteristics on gela-
Methods in the analysis of starch tinization and retrogradation properties of different starches. Carbohydrate
Polymers 35: 119
134.
gelatinization There are several methods to analyze
the gelatinization process, such as DSC, Kofler hot-
stage microscopy, light microscopy, electron micros- Gelatinization parameters measured by DSC can be
copy, X-ray crystallography, enzymatic analysis, affected by sample preparation, baseline application,
nuclear magnetic resonance (NMR), pulsed nuclear pan selection, method of adding water, sample mass,
magnetic resonance, small angle X-ray scattering, and heating rate, and moisture equilibration time. Ther-
small angle neutron scattering, Brabender visco- mal behavior of amylose
lipid complex as well as
amylography (BV), and Rapid Visco Analysis. DSC, formation of amylose
lipid inclusion with various
the most widely used method, measures the dissocia- molecules such as fatty acids and emulsifiers can
tion parameters, TBoB (onset), TBpB (peak), TBcB also be detected by DSC. Characterization of
(conclusion), and DH (endothermic heat absorption), amylose
lipid complex in cereal starches and influ-
of starch crystallites in gelatinization (Figure 1). DH is ence of amylose
lipid complex on starch properties
the area below the transition endotherm. Gelatiniza- are well documented. Some of the internal lipids in
tion parameters of starches from different botanical cereal starch is thought to be complexed with amylose
sources measured by DSC are presented in Table 3. In to form the amylose
lipid complex, which is disso-
addition, DSC can be used to study the glass trans- ciated at higher temperature (M2 endotherm in
ition temperatures of various starchy food products. Figure 1) than that of normal starch crystallites (Fig-
Gelatinization temperatures are influenced more ure 1 and Table 4). Although DSC is widely used to
by the granular architecture than the amylose
study gelatinization, the small sample size used can
amylopectin ratio and depend on the degree of starch limit its real applications. In a comparative study of
crystallite perfection, whereas endothermic heat ab- maize starch gelatinization with DSC and NMR, it
sorption reflects the quality and amount of starch was reported that NMR could provide much better
crystallites. Analysis of gelatinization parameters performance in the analysis of gelatinization for larger
of starch using DSC was first reported in 1971. samples than DSC. Gelatinization temperature of
 STARCH/Analysis of Quality 207

Table 5 Gelatinization temperature range of some starches as measured with different techniques: DSC, NMR, BV, and RVA

Starch Starch
water ratio Gelatinization temperature range

DSC NMR BV a RVAb

Maize 1:2 58.1
79.6 59
67

Waxy maize 1:2 56.4
81.3 60
67
Potato 1:2 49.2
73.9 53
60 76
86 75
86
Cocoyam 1:2 74
87 78
95 85
95
Peruvian carrot 1:2 56
73 62
95 68
95

a
Starch concentration (4%) except Peruvian carrot (6%).
b
Starch concentration (8%).
Sources: Perez EE, Breene WM, and Bahnassey YA (1998) Gelatinization profiles of cassava, sagu, and arrowroot native starches as measured with
different thermal and mechanical methods. Starch/Starke 50: 14
16 and Gonera A and Cornillon P (2002) Gelatinization of starch/gum/sugar systems
studied by using DSC, NMR, and CSLM. Starch/Starke 54: 508
516.

Peruvian carrot, potato, and maize starch measured

by Rapid Visco Analyzer (RVA) and BV, and DSC
have shown different values for different methods.
This indicates the need for multiple analytical tech-
niques for a meaningful understanding of gelatiniza-
tion along with careful specification (and preferably
Viscosity

standardization) of experimental conditions used.

Table 5 shows the differences in gelatinization param-
eters measured by different techniques for the same
starch.

Pasting properties
Starch heated in excess water undergoes various
Time/temperature
changes as a result of heat and moisture transfer.
Gelatinization and pasting occur in the same system Figure 2 Schematic representation of granular changes and
and have often been used to describe all the changes viscosity development during starch pasting (Daniel JR and
that occur. Gelatinization may be used to refer to Whistler RL (1985) Principal changes in starch during food
processing. In: Richardson TR and Finley JW (eds.) Chemical
early changes whereas pasting includes later changes.
Changes in Food During Processing, pp. 305
326. Westport,
Starch gelatinization is defined as the collapse of the CT: Avi Publishing Co.).
starch granule manifested in irreversible melting, loss
of birefringence, and starch solubilization. The point
of gelatinization, and the range over which it occurs is temperature at which viscosity begins to increase is
governed by starch concentration, method of obser- termed pasting temperature. With further heating,
vation, granular type, and heterogeneity. Pasting is granular swelling increases the viscosity to reach
defined as the phenomena following gelatinization a peak. Further heating at elevated temperature
in the dissolution of starch, involving granular swell- under shear force tends to disintegrate the swollen
ing, exudation of molecular components from the granules resulting in decrease of viscosity. Upon cool-
granule, and eventually total disruption of the gran- ing the starch paste in the next stage, there is
ules. The schematic representation of granular a tendency, mainly due to amylose chain reassocia-
changes and viscosity development that occurs during tion, to increase viscosity. Therefore, a typical pasting
pasting is shown in Figure 2. profile exhibits three distinct viscosity developments,
peak viscosity, hot paste viscosity, and cold paste vis-
cosity (Figure 3). Pasting curves vary according to
Measurement of pasting properties The BV is the botanical source of the starch, starch concentration,
most widely established method for determining past- and the programmed heating
cooling cycle chosen.
ing properties, although it has some methodological Among the native starches, potato shows the highest
and geometrical shortcomings. This apparatus mea- peak viscosity, and generally, low peak viscosity and
sures the development of viscosity when a starch
higher setbacks can be detected in normal cereal
water suspension is subjected to a programmed starches compared to tuber and root starches.
heating and cooling cycle under a shear force. The Waxy cereal starches, on the other hand, behave
208 STARCH/Analysis of Quality

more like the tuber and root starches (Figure 4). Ac- rate to 1.5 C min
1 in RVA provides similar results to
cording to the characteristics of pasting curves, starch those observed in the BV. Comparative study of past-
has been categorized into four groups as, high swell- ing properties of cassava, ‘‘sago’’ (sagu), and arrow-
ing starch (potato, cassava, waxy cereals, ionic starch root using Brabender and RVA has shown that both
derivatives), moderate swelling starch (normal cereal techniques provide similar pasting patterns (Table 6).
starch), restricted swelling starch (cross-linked Pasting curves of some of the starches determined by
starch), and highly restricted starch (starches BV and RVA is presented in Figures 4 and 5.
455% amylose). The above four different categories
of starch exhibit the following pasting properties re-
spectively: high peak followed by rapid and major
Swelling and Solubility
thinning during cooking; lower peak and much less
thinning; no peak but maintain high viscosity during Native starch granules are insoluble in water. Al-
cooking; and no swelling to gave a viscous paste at though small amounts of water can be absorbed at
normal concentration. room temperature, granular swelling is limited in in-
Because of some technical shortcomings with the tact granules. During heating in excess water, after
BV, such as large sample size requirement and inabil- the onset of gelatinization, granules begin to swell
ity to program the temperature profiles, a more recent rapidly, losing the polarization crosses. The extent
equipment, the RVA, has become popular for analyz- of the swelling power and solubility depends on the
ing pasting properties. The RVA differs from the magnitude of the starch chain interaction within the
Brabender instrument due to rapid heating rate and amorphous and crystalline domain, size of the starch
stronger mixing action. However, controlled heating granules, amylose content, bound lipids, starch

250 100 Time

Cool paste viscosity 0 30 60 90 120 150 180 min
Temperature
3000
profile
200 Peak viscosity 80
Peak time 2500
5% starch
Potato by weight
Setback
Temperature (°C)

2000
Viscosity (RVU)

Breakdown
150 60
1500
Tapioca Maize
Viscosity (BU)

100 40 1000
Hot paste viscosity
Waxy maize
500
50 20 Wheat
0
50 95 95 95 50 50 50°C
Heat Hold Cool Hold
0 0
0 3 6 9 12 15 Temperature
Time (min)
Figure 4 Brabender Viscoamylogram of starches from different
Figure 3 Characteristics of a typical pasting curve. botanical sources.

Table 6 Pasting properties of cassava, sago, and arrowroot as determined by BV and RVA

Starch Method GT PV FV at 95 C V at 50 C BD SB Consistency

a
Cassava BV 68
90 50 40 40 10
10 0
RVAb 73
90 23 9 17 14
6 8
Sago BV 68
90 300 460 660
160 360 200
RVA 73
95 60 22 37 38
23 15
Arrowroot BV 75
90 150 150 170 0 20 20
RVA 79
92 30 14 18 16
12 4

a
Starch concentration 4.3%.
b
Starch concentration 8%.
GT
gelatinization temperature range; PV
peak viscosity; FV
final viscosity; V
viscosity; BD
breakdown; SB
setback.
Source: Perez EE, Breene WM, and Bahnassey YA (1998) Gelatinization profiles of cassava, sagu, and arrowroot native starches as measured with
different thermal and mechanical methods. Starch/Starke 50: 14
16.
 STARCH/Analysis of Quality 209

100 blue dextran dye (molecular weight 2  10P6P) will

600
dissolve in supernatant and interstitial water. The
advantages of this method over the others are the
Potato ability to measure the true swelling and the high ac-
450 80
curacy.

Temperature (°C)
Viscosity (RVU)

Sweet potato

60
Retrogradation Reassociation of starch polymers
300 Maize via hydrogen bonding in gelatinized starch on cooling
is generally termed retrogradation, and is time- and
150
temperature-dependent. Starch gels tend to undergo
40
structural changes during storage as they are meta-
stable and nonequilibrium systems. Both amylose
Rice
0
Wheat and amylopectin are involved in retrogradation,
0 5 10 15 20 25
where rapid amylose aggregation causes a short-
Time (min) term development of starch gel providing initial
firmness. Branched amylopectin recrystallization,
Figure 5 Pasting curves obtained for different starches from particularly outer branches of amylopectin molecule,
Rapid Visco Analyzer. is correlated with long-term development of starch
gel. Several factors influence starch retrogradation,
damage, temperature, and molecular characteristics such as, starch concentration, storage temperature,
and the amount of amylose
amylopectin ratio. initial heating temperature, chain length distribution
Table 1 presents the swelling and solubility of some of amylopectin, molecular size of amylose, lipids,
starches at 95 C. High amylose content lowers the and physical and chemical modification of starch.
swelling whereas larger granules show greater swell-
ing. The swelling power and solubility provide infor- Effect of retrogradation on quality of starch-based
mation on the relative strength of bonding within the food products Retrogradation has desirable as well
granules. as undesirable effects on quality of starch-based food
products. Mostly it is undesirable. Bread staling is
Methods used to analyze starch swelling Swelling one of the main undesirable effects of retrogradation.
volume, swelling power or swelling factor, all mea- Although several factors contribute to bread staling,
sure the extent of granular swelling at a given tem- it has been found that retrogradation is the key phys-
perature, when starch is heated in excess water. ical change associated with bread staling. Retrogra-
However, swelling factor measures only the intergra- dation sometimes aids processing in some food
nular water content and hence reflects the true swell- products such as hardening of parboiled rice and to
ing of starch granules at a given temperature. Swelling improve textural characteristics of certain types of
power measures the weight of swollen starch sediment noodles.
relative to the initial starch dry weight, and is ex-
pressed as the ratio of the wet sediment to the initial Determination of starch retrogradation Several
weight of the dry starch. Measuring the soluble car- methods have been developed to determine starch
bohydrate that dissolved in the supernatant either by retrogradation, because of its great influence on in-
oven drying or colorimetric method enables solubil- dustry-based food and nonfood products, such as
ity, the ratio between the amount of soluble carbohy- DSC, X-ray analysis, rheological methods, and
drate to the initial weight of dry starch to be obtained. spectroscopic methods.
Swelling volume is a modified version in which pro-
grammed shaking of starch suspension is used instead Differential scanning calorimetry Several studies on
of stirring, and measurement is of the volume ex- retrogradation behavior have been examined using
panded due to granular swelling. Swelling factor is DSC techniques. DSC is probably the best thermal
the ratio of volume of swollen starch granule to the analysis method to study the starch-aging process
volume of the dry starch. Swelling factor measures for different systems. However, dissociation parame-
only the intragranular water content. Calculation of ters of stronger crystals that formed due to the asso-
the swelling factor is based on starch weight adjusted ciation of amylose are usually difficult to detect using
to 10% moisture assuming the density of 1.4 mg ml
1. DSC, since those crystals dissociate at higher temper-
The basic principle of this method is the measurement ature (4120 C). Therefore, DSC usually measures
of the volume of water absorbed by starch granules the melting of recrystallized amylopectin, that occurs
heated in excess water, based on the observation that at the same temperature interval as gelatinization
210 STARCH/Analysis of Quality

Heating steps
Bread crumb
1
2
Wheat starch
Endothermic heat flow

Endothermic heat flow

Amylopectin
4

Amylose
0.05 mcal s–1

40 60 80 100 60 100 140 180

Temperature (°C)
Temperature (°C)
Figure 6 Differential scanning calorimetric curves for different
retrograded food systems. (Eliasson A-C (2003) Utilization of ther- Figure 7 DSC curves obtained for amylose retrogradation.
mal properties for understanding baking and salting processes. In: (Eliasson A-C (2003) Utilization of thermal properties for under-
Kaletunc G and Breslauer KJ (eds.) Characterization of Cereals standing baking and salting processes. In: Kaletunc G and
and Flours, pp. 65
115. New York: Marcel Dekker.) Breslauer KJ (eds.) Characterization of Cereals and Flours,
pp. 65
115. New York: Marcel Dekker.)

Table 7 DSC characteristics of amylopectin retrogradation Table 8 X-ray pattern and crystallinity of different starches
of wheat and potato starch gel (1 : 1) under different storage
conditions Starch X-ray pattern Crystallinity

Starch Storage conditiona (To
Tc) DH (J g
1 AMP) Rice A 38

Oat A 33
Wheat 6/6 40.4
63.3 8.1 Wheat A 36
6/30 48.5
64.7 7.7 Rye A 34
6/306/30 49.3
65.4 9.4 Amylomaize B 15
22
6/40 58.0
68.5 4.5 Corn A 40
6/40/6/40 58.2
69.0 5.9 Waxy rice A 37
Potato A 30
Potato 6/6 35.2
78.2 13.3 Cassava C 37
6/30 48.8
78.3 11.7
True yam (Dioscorea) B 32
6/30/6/30 49.7
78.1 13.1 Taro A 31
6/40 59.2
78.3 9.9 Sweet potato C 38
6/40/6/40 60.7
79.5 10.6

a
Sources: Zobel (1988b) and Gunaratne A and Hoover R (2002) Effect of
Each number indicates the temperature for one day of storage; 6/40 heat-moisture treatment on the structure and physicochemical properties of
means one day at 60 C, followed by one day at 40 C. tuber and root starches. Carbohydrate Polymers 49: 425
437.
To
Tc
transition temperature range; DH
enthalpy; AMP
amylopectin.
Source: Silverio J, Fredriksson H, Andersson R, Eliasson A-C, and Aman P
(2000) The effect of temperature cycling on the amylopectin retrogradation
of starches with different amylopectin unit-chain length distribution. Carbo- Melting temperature indicates the perfection
hydrate Polymers 42: 175
184. of recrystallized amylopectin, the quality and
heterogeneity.
(Figure 6), when reheating of retrograded starch gel, Although DSC has some advantages especially that
in which heat absorption, the area under the it is not time consuming, has a wide range of
endotherm (DH), and transition temperatures can applications, and measures directly, it has some weak-
be detected (Table 7). Crystals formed by the associ- ness particularly its small sample size and inability to
ation of amylose chains would be possible to detect determine retrogradation in dilute starch paste. More
using DSC pans, that can withstand a higher temper- often DSC coupled with X-ray analysis provides
ature range (Figure 7). Characteristic smaller endo- better performance in characterizing retrogradation.
sperms were usually reported for the retrograded gel
compared with the gelatinization endotherm of their X-ray analysis X-ray analysis can be applied to
native counterpart. However, it was reported that detect the presence and nature of crystallinity in
retrograded starch crystals melt over a wide range native starch granules as well as crystals formed in
of temperature indicating the more heterogeneous aging starch gels. In native starch, the crystallinity is
crystal perfection than those of native starch crystals. due to the amylopectin components and the crystal
 STARCH/Analysis of Quality 211

Table 9 Gel textural properties of maize starches differing in amylose content

Sample Probe type Hardness (g) Adhesiveness Springiness Cohesiveness

Regular 5 (mm) 75 219 0.94 0.51

Waxy
High amylose 19 18 0.61 0.031
Waxy 20 (mm) 28 18 0.94 0.81
High amylose 128 160 0.85 0.35

Starch paste after RVA analysis kept at 25 C for 24 h.

Source: Liu H, Ramsden L, and Corke H (1999) Physical properties and enzymatic digestibility of hydroxypropylated ae, wx, and normal maize starch.
Carbohydrate Polymers 40: 175
182.

domains are constructed mainly of A chains and outer direct measurement, time saving, and technical feasi-
B chains of amylopectin. Native starches can be cat- bility of the texture analyzer increases its attractive-
egorized into three groups according to their X-ray ness among food technologists. The main issue which
diffraction pattern. The A type crystallinity is found requires continuing work is that of instrumental to
mainly in cereal starches. Most tuber and root sensory correspondence, i.e., whether the texture
starches exhibit typical B type X-ray pattern and C analysis profile is adequately predictive of the sensory
type is intermediate between A and B types, shown in traits important to the consumer.
legumes, cassava, and some varieties of sweet potato Many additional methods can be employed to de-
(Table 8). X-ray analysis of retrograded starch has tect retrogradation. No individual method is able to
shown that aging gels form B-type crystals irrespective fully characterize all the events of the starch-aging
of the native starch. Some research using wide range process. DSC measures only the transition of heat
and small angle X-ray diffraction, shows that crystal- energy in the melting of crystal aggregates, X-ray
line formation in starch paste occurred primarily due measures the presence and characteristics of retro-
to amylopectin aggregation, whereas amylose pro- graded starch crystals, and texture analysis provides
vides a template effect and highly ordered amylose textural parameters for the aged starch gel. Therefore,
aggregation does not necessarily possess a crystalline it is clear that a multiple analytical technique ap-
nature but accelerates the amylopectin reassociation. proach for the advance detection of retrogradation
Recently, more information on bread staling has been behavior is necessary. For example, a study of
revealed by X-ray analysis. Aggregation of starch bread staling with multiple techniques, DSC, FTIR,
polymers that formed crystals in bread staling was and NIR, led to greater understanding of the process
shown from X-ray analysis; however, NMR and than would be possible with each individual technique
FTIR techniques are better at detecting minor used alone.
differences of starch polymer aggregation than
X-ray analysis. See also: Noodles: Starch Noodles. Starch: Uses of
Native Starch; Chemistry; Modification; Synthesis.

Rheological methods Measurement of pasting pa-

rameters, analysis of textural properties of starch
paste using texture analyzer, and small deformation Further Reading
dynamic techniques oscillatory rheometry can be ap- Collado LS and Corke H (2003) Starch properties and
plied to the behavior of starch. Pasting behavior of functionalities. In: Kaletunc G and Breslauer KJ (eds.)
starch indicates the trend of starch retrogradation. In Characterization of Cereals and Flours, pp. 473
506.
a typical pasting profile, the magnitude of setback New York: Marcel Dekker.
reflects the tendency of mainly amylose polymer re- Daniel JR and Whistler RL (1985) Principal changes in
association in a starch paste. Several investigations starch during food processing. In: Richardson TR and
have been performed to study the properties of Finley JW (eds.) Chemical Changes in Food During
aging breads using viscometry and have observed Processing, pp. 305
326. Westport, CT: AVI
Publishing Co.
a tendency of decreased peak viscosity when bread
Eliasson A-C (2003) Utilization of thermal properties for
staling progresses. Recently there is a growing
understanding baking and salting processes. In: Kaletunc
interest, especially in industry, in use of texture ana- G and Breslauer KJ (eds.) Characterization of Cereals
lyzers that can directly and rapidly measure the tex- and Flours, pp. 65
115. New York: Marcel Dekker.
tural properties such as hardness, stickiness, Fredriksson H, Silverio J, Andersson R, Eliasson A-C,
cohesiveness, adhesiveness, fracturability of starch and Aman P (1998) The influence of amylose and
paste (Table 9). Long-term reliability and accuracy, amylopectin characteristics on gelatinization and
212 STARCH/Chemistry

retrogradation properties of different starches. Carbo- Chemistry

hydrate Polymers 35: 119
134.
Gonera A and Cornillon P (2002) Gelatinization of starch/ F L Stoddard, University of Wolverhampton,
gum/sugar systems studied by using DSC, NMR, and Wolverhampton, UK
CSLM. Starch/Starke 54: 508
516. ª 2004, Elsevier Ltd. All Rights Reserved.
Gunaratne A, and Hoover R (2002) Effect of heat-moisture
treatment on the structure and physicochemical proper-
ties of tuber and root starches. Carbohydrate Polymers Introduction
49: 425
437.
Hoover R, Vasanthan T, Senanayake NJ, and Martin AM Starch is the major energy reserve of higher plants.
(1994) The effects of defatting and heat-moisture This makes it a major energy source in the diet of
treatment on the retrogradation of starch gels from humans and many other animals, including livestock
wheat, oat, potato, and lentil. Carbohydrate Research animals grown for their meat and milk as well as pest
261: 13
24. animals which consume grains in storage. Starch com-
Jane J, Kasemsuwan T, Leas S, Zobel HF, and Robyt JF prises 70% of the dry matter of the endosperm of
(1994) Anthology of starch granules morphology by a mature cereal grain and 16% of the fresh matter of
scanning electron microscope. Starch/Starke 46: 121.
a mature potato tuber.
Karim AA, Norziah MH, and Seow CC (2000) Methods
for the study of starch retrogradation. Food Chemistry
Starch may be loosely defined as a polymer of glu-
71: 9
36. cose which is distinguished from other glucans by
Liu H, Ramsden L, and Corke H (1999) Physical proper- a number of key features.
ties and enzymatic digestibility of hydroxypropylated First, it is a-linked, unlike cellulose and other
ae, wx, and normal maize starch. Carbohydrate b-linked glucans. The majority of these links are
Polymers 40: 175
182. a-1,4 (also written as a-(1 ! 4)), leading to chains
Perez EE, Breene WM, and Bahnassey YA (1998) of varying lengths, and the chains are joined together
Gelatinization profiles of cassava, sagu, and arrowroot by a-1,6 linkages. These branching points occur in
native starches as measured with different thermal and a highly ordered fashion, leading to double-helix
mechanical methods. Starch/Starke 50: 14
16. formation and a type of crystallinity, minimizing
Phillips DL, Xing J, Liu H, Pan DH, and Corke H (1999)
water-holding capacity. This feature is in significant
Potential use of Raman spectroscopy for the determina-
contrast to glycogen, an a-(1!4), (1!6) mixed-link
tion of amylose content in maize starch. Cereal
Chemistry 76: 821
823. glucan found in animals and bacteria. Ordering in
Planchot V, Gerard C, Bertoft E, and Colonna P (2001) An glycogen is very limited, so it holds much more
approach to structural analysis of granules using geneti- water than an equivalent mass of starch. It is thus
cally modified starches. In: Barsby TL, Donald AM, and not as efficient an energy store where water availabil-
Frazier PJ (eds.) Advances in Structure and Function, ity is limited, such as in a dry, dormant seed.
pp. 104
128. UK: The Royal Society of Chemistry. Starch is deposited in granules between 1 and 100 mm
Praznik W, Huber A, Watzinger S, and Beck RHF (1994) in diameter within membrane-bound organelles. In the
Molecular characteristics of high amylose starches. actively photosynthetic parts of the plant, these organ-
Starch/Starke 46: 88
94. elles are the chloroplasts, and in storage organs, they are
Silverio J, Fredriksson H, Andersson R, Eliasson A-C, and
the modified chloroplasts called amyloplasts. Granule
Aman P (2000) The effect of temperature cycling on the
amylopectin retrogradation of starches with different
structure has a number of features which are consistent
amylopectin unit-chain length distribution. Carbohy- across species, while granule size, morphology, and
drate Polymers 42: 175
184. composition vary widely among species. These aspects
Tester RF and Morrison WR (1990) Swelling and as well as starch composition affect the processing
gelatinization of cereal starches 1. Effects of amylopec- properties of the starch.
tin, amylose and lipids. Cereal Chemistry 67: 551
557.
Yu L and Christie G (2001) Measurement of starch
thermal transitions using differential scanning calori- The Monomer and Linkages
metry. Carbohydrate Polymers 46: 179
184. The building block of starch is D-glucose, in its hex-
Zobel, HF (1988) Molecules to granules: a comprehensive agonal pyranose ring conformation (Figure 1). Car-
starch review. Starch/Stãrke 40: 44
50.
bon 1 of this ring is a highly reactive, aldehydic,
‘‘reducing’’ end. Most commonly, during polymer for-
Relevant Website mation in a plant, it attaches to carbon 4 of another
glucopyranose residue (Figure 2). When the mono-
http://www.starch.dk
Website of the International mers are a-D-glucopyranose, the resulting polymer
Starch Institute, Denmark, with useful links to other is a chain of starch, and when they are b-D-glucopyr-
starch-related sites. anose, it is a chain of cellulose.