Вы находитесь на странице: 1из 22

ARTICLE IN PRESS

FOOD
HYDROCOLLOIDS
Food Hydrocolloids 21 (2007) 1–22
www.elsevier.com/locate/foodhyd

Review

Factors influencing the physico-chemical, morphological, thermal and


rheological properties of some chemically modified starches for food
applications—A review
Jaspreet Singha,, Lovedeep Kaurb, O.J. McCarthyb
a
Riddet Centre, Massey University, Palmerston North, New Zealand
b
Institute of Food, Nutrition and Human Health, Massey University, Palmerston North, New Zealand

Received 12 August 2005; accepted 20 February 2006

Abstract

Effect of some common chemical modifications such as acetylation, hydroxypropylation and cross-linking on the physico-chemical,
morphological, thermal and rheological properties of starches from different botanical sources have been reviewed. The distinguishing
factors that affect the efficiency of modification are the starch source, amylose to amylopectin ratio, granule morphology, and type and
concentration of the modifying reagent. The extent of alteration in the starch properties reflects the resistance or the susceptibility of a
starch towards different chemical modifications. Modified starches with desirable properties and degree of substitution can be prepared
by critically selecting a suitable modifying agent and a native starch source.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Starch; Potato; Maize; Wheat; Rice; Chemical modification; Cross-linking; Hydroxypropylation; Acetylation; Physico-chemical;
Morphological; Thermal; Rheological

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Common types of chemical starch modifications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Extent of chemical modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Physico-chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Morphological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6. Thermal properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
7. Rheological/pasting properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
8. Nutritional and toxicological aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
9. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Corresponding author. Tel.: +64 6 3505799 Ext. 2534.


E-mail address: j.x.singh@massey.ac.nz (J. Singh).

0268-005X/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodhyd.2006.02.006
ARTICLE IN PRESS
2 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

1. Introduction modification is generally achieved through derivatization


such as etherification, esterification, cross-linking and
Among carbohydrate polymers, starch is currently grafting of starch; decomposition (acid or enzymatic
enjoying increased attention owing to its usefulness in hydrolysis and oxidization of starch) or physical treatment
different food products. Starch contributes greatly to the of starch using heat or moisture, etc. (Table 1). Chemical
textural properties of many foods and is widely used in modification involves the introduction of functional groups
food and industrial applications as a thickener, colloidal into the starch molecule, resulting in markedly altered
stabilizer, gelling agent, bulking agent and water retention physico-chemical properties. Such modification of native
agent. The physico-chemical properties and functional granular starches profoundly alters their gelatinization,
characteristics of starch systems and their uniqueness in pasting and retrogradation behaviour (Choi & Kerr, 2003;
various food products vary with starch biological origin Kim, Muhrbeck, & Eliasson, 1993; Liu, Ramsden, &
(Svegmark & Hermansson, 1993). Starches from various Corke, 1999a, 1999b; Liu et al., 1999a, 1999b; Perera,
plant sources, such as wheat, maize, rice and potato have Hoover, & Martin, 1997; Seow & Thevamalar, 1993). The
received extensive attention in relation to structural and majority of the reviewed work has been focused on native
physico-chemical properties (Takeda & Priess, 1993). starch properties, with only few literature surveys covering
Native starch is a good texture stabilizer and regulator in the synthesis and physico-chemical properties of chemically
food systems (Cousidine, 1982), but limitations such as low modified starches (Hung & Morita, 2005; Kim, 1988;
shear resistance, thermal resistance, thermal decomposition Tharanathan, 2005; Tomasik & Schilling, 2004). In this
and high tendency towards retrogradation limit its use in review, we have re-examined the information on the
some industrial food applications. Starch modification, various factors that influence the extent of chemical
which involves the alteration of the physical and chemical modification of starches from different plant sources, with
characteristics of the native starch to improve its functional an emphasis on the post-modification changes in their
characteristics, can be used to tailor starch to specific food physico-chemical, morphological, thermal and rheological
applications (Hermansson & Svegmark, 1996). Starch properties.

Table 1
Different starch modification types and preparation techniques

Modification Types Preparation

Physical Heat/moisture Heat–moisture treatment—Heating starch at a temperature above its gelatinization point with
treatment insufficient moisture to cause gelatinization
Annealing—Heating a slurry of granular starch at a temperature below its gelatinization point for
prolonged periods of time
Pregelatinization Pregels/instant/cold-water swelling starches prepared using drum drying/spray cooking/extrusion/
solvent-based processing
Conversion Partial acid Treatment with hydrochloric acid or ortho-phosphoric acid or sulphuric acid
hydrolysis
Partial enzymatic Treatment in an aqueous solution at a temperature below the gelatinization point with one or more
hydrolysis food-grade amylolytic enzymes
Alkali treatment Treatment with sodium hydroxide or potassium hydroxide
Oxidation/bleaching Treatment with peracetic acid and/or hydrogen peroxide, or sodium hypochlorite or sodium
chlorite, or sulphur dioxide, or potassium permanganate or ammonium persulphate
Pyroconversion Pyrodextrins—Prepared by dry roasting acidified starch
(dextrinization)
Derivatization Etherification Hydroxypropyl starch—Esterification with propylene oxide
Esterification Starch acetate—Esterification with acetic anhydride or vinyl acetate
Acetylated distarch adipate—Esterification with acetic anhydride and adipic anhydride
Starch sodium octenylsuccinate—Esterification by octenylsuccinic anhydride
Cross-linking Monostarch phosphate—Esterification with ortho-phosphoric acid, or sodium or potassium ortho-
phosphate, or sodium tripolyphosphate
Distarch phosphate—Esterification with sodium trimetaphosphate or phosphorus oxychloride
Phosphated distarch phosphate—Combination of treatments for monostarch phosphate and
Distarch phosphate
Dual modification Acetylated distarch phosphate—Esterification by sodium trimetaphosphate or phosphorus
oxychloride combined with esterification by acetic anhydride or vinyl acetate
Hydroxypropyl distarch phosphate—Esterification by sodium trimetaphosphate or phosphorus
oxychloride combined with etherification by propylene oxide
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 3

Table 2
Some properties and applications of modified starches

Types Properties Applications

Pregelatinization Cold water dispersibility Useful in instant convenience foods


Partial acid or Reduced molecular weight polymers, exhibit reduced Useful in confectionery, Batters and food coatings
enzymatic hydrolysis viscosity, increased retrogradation and setback
Oxidation/bleaching Low viscosity, high clarity, and low temperature stability Used in batters and breading for coating various food
stuffs, in confectionery as binders and film formers, in
dairy as texturizers
Pyroconversion Low to high solubility depending on conversion, low Used as coating materials for various foods, good film
(dextrinization) viscosity, high reducing sugar content forming ability and as fat replacers in bakery and dairy
products
Etherification Improved clarity of starch paste, greater viscosity, reduced Used in wide range of food applications such as gravies,
syneresis and freeze-thaw stability dips, sauces, fruit pie fillings and puddings
Esterification Lower gelatinization temperature and retrogradation, Used in refrigerated and frozen foods, as emulsion
lower tendency to form gels and higher paste clarity stabilizers and for encapsulation
Cross-linking Higher stability of granules towards swelling, high Used as viscosifiers and texturizers in soups, sauces,
temperature, high shear and acidic conditions gravies, bakery and dairy products
Dual modification Stability against acid, thermal and mechanical degradation Used in canned foods, refrigerated and frozen foods, salad
and delayed retrogradation during storage dressings, puddings and gravies

2. Common types of chemical starch modifications hydroxypropylated starches are generally prepared by
etherification of native starch with propylene oxide in the
Food grade starches are chemically modified mainly to presence of an alkaline catalyst. The hydroxypropyl groups
increase paste consistency, smoothness and clarity, and to introduced into the starch chains are capable of disrupting
impart freeze-thaw and cold storage stabilities (Jane, 1997; the inter- and intra-molecular hydrogen bonds, thereby
Liu et al., 1999a, 1999b; Perera et al., 1997; Shi & BeMiller, weakening the granular structure of starch, leading to an
2000; Tuschhoff, 1986, Chapter 6; Wu & Seib, 1990; Xu & increase in motional freedom of starch chains in amor-
Seib, 1997). The properties of some modified starches and phous regions (Seow & Thevamalar, 1993; Wootton &
their applications are presented in Table 2. The chemical Manatsathit, 1983).
and functional properties achieved when modifying starch Cross-linking treatment is intended to add intra- and
by chemical substitution depend, inter alia, on starch inter-molecular bonds at random locations in the starch
source, reaction conditions (reactant concentration, reac- granule that stabilize and strengthen the granule (Acquar-
tion time, pH and the presence of catalyst), type of one & Rao, 2003). Starch pastes from cross-linked starches
substituent, extent of substitution (degree of substitution, are less likely to break down with extended cooking times,
DS1; or molar substitution, MS2), and the distribution of increased acidity or severe shear (Hirsch & Kokini, 2002;
the substitutent in the starch molecule (Hirsch & Kokini, Langan, 1986; Wurzburg, 1986a, 1986b). Cross-linking
2002; Kavitha & BeMiller, 1998; Lim & Seib, 1993; minimizes granule rupture, loss of viscosity and the
Richardson, Nilsson, Bergquist, Gorton, & Mischnick, formation of stringy paste during cooking (Woo & Seib,
2000; Rutenberg & Solarek, 1984; Steeneken & Woortman, 1997), yielding starch that is suitable for canned foods and
1994; Takahashi, Fujimoto, Miyamoto, & Inagaki, 1987; other food applications (Hirsch & Kokini, 2002; Rutenberg
Wang & Wang, 2002). Some chemical modification & Solarek, 1984). Nutritional benefits of cross-linked
reactions of starch are presented in Table 3. Acetylated starch as a new source of dietary fiber have also been
starch with a low DS is commonly obtained by the reported (Woo, 1999; Wurzburg, 1986a, 1986b). Cross-
esterification of native starch with acetic anhydride in the linking is generally performed by treatment of granular
presence of an alkaline catalyst, where as the food grade starch with multifunctional reagents capable of forming
either ether or ester inter-molecular linkages between
1
DS represents the average number of hydroxyl groups on each hydroxyl groups on starch molecules (Rutenberg &
anhydroglucose unit which are derivitised by substituent groups. DS is Solarek, 1984; Wurzburg, 1986a, 1986b). Sodium trimeta-
expressed as average number of moles of substituent per anhydroglucose
unit. As each anhydroglucose unit has three hydroxyl groups available for
phosphate (STMP), monosodium phosphate (SOP),
substitution the maximum possible DS is 3. sodium tripolyphosphate (STPP), epichlorohydrin (EPI),
2
The substituent moiety on some starch esters and ethers can react phosphoryl chloride (POCl3), a mixture of adipic acid and
further with the modifying reagent during the modification reaction, acetic anhydride, and vinyl chloride are the main agents
resulting in the formation of an oligomeric or possibly polymeric used to cross-link food grade starches (Wattanchant,
substituent. In these cases molar substitution is preferred, which represents
the level of substitution as moles of monomeric substituent per mole of
Muhammad, Hashim, & Rahman, 2003; Woo & Seib,
anhydroglucose unit. Thus, in contrast to degree of substitution, the value 1997; Wu & Seib, 1990; Yeh & Yeh, 1993; Yook, Pek, &
of MS can be greater than three. Park, 1993). POCl3 is an efficient cross-linking agent in
ARTICLE IN PRESS
4 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

Table 3
Some common starch chemical modification reactions

aqueous slurry at pH411 in the presence of a neutral salt than distarch phosphates (diesters) because even a very few
(Felton & Schopmeyer, 1943). STMP is reported to be an cross-links (in the case of diesters) can drastically alter the
efficient cross-linking agent at high temperature with semi- paste and gel properties of the starch. Starch phosphates
dry starch and at warm temperature with hydrated starch are conventionally prepared through the reaction of starch
in aqueous slurry (Kerr & Cleveland, 1962). EPI is poorly with salts of ortho-, meta-, pyro-, and tripolyphosphoric
soluble in water and partly decomposes to glycerol, thus acids and phosphorus oxychloride (Nierle, 1969; Paschall,
water-soluble cross-linking agents such as POCl3 and 1964).
STMP are preferred. Moreover, it has also been reported Dual modification, a combination of substitution and
that EPI cross-links are likely to be less uniformly cross-linking, has been demonstrated to provide stability
distributed than STMP ones (Shiftan, Ravanelle, Alex- against acid, thermal and mechanical degradation of starch
andre Mateescu, & Marchessault, 2000). So, the type of and to delay retrogradation during storage. Dual modified
cross-linking agent greatly determines the change in starches are used widely in salad dressings, canned foods,
functional properties of the treated starches. Starch frozen foods and puddings (Jane, 1997; Wurzburg, 1986a,
phosphates, which are conventionally prepared have been 1986b). The control of reaction conditions is important
reported to give clear pastes of high consistency with good during preparation of dual-modified cross-linked/hydro-
freeze-thaw stability and emulsifying properties, and may xypropylated starches using different cross-linking reagents
be grouped into two classes: monostarch phosphates and with different starch bases such as maize, tapioca, wheat,
distarch phosphates (cross-linked starches). In general, waxy maize, waxy barley, rice and sago (Tessler, 1975;
monostarch phosphates (monoesters) can have a higher DS Wattanchant et al., 2003; Wu & Seib, 1990; Yeh & Yeh,
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 5

1993; Yook et al., 1993). The quantity of cross-linking & BeMiller, 2001). This also includes the surface structure
reagent required to prepare a dual modified starch (with of the starch granules, which encompasses the outer and
desirable properties) vary with the source of starch, the inner surface, depending on the pores and channels, leads
type of cross-linking reagent, the efficiency of the cross- to the development of the so-called specific surface
linking reaction, the degree of substitution required and the (Juszczak, 2003). Channels that open to the granule
specified range of final modified-starch properties (Wattan- exterior provide a much larger surface area accessible by
chant et al., 2003). The effects of different reaction chemical reagents, and provide easier access by the
conditions such as starch base concentration, temperature, reagents to the granule interior. However, the reagent
pH and the concentration of the catalyst salt plays an may diffuse through the external surface to granule matrix
important role during preparation of duly modified in the absence of channels (BeMiller, 1997). Although
hydroxypropylated-crosslinked starch (Lim & Seib, 1993; starches from various sources exhibit fundamental struc-
Smolka & Alexander, 1985; Tessler, 1975; Wu & Seib, tural similarities, they differ in the specific details of their
1990; Yeh & Yeh, 1993). The effects of chemical modifica- microstructure and ultrastructure. These structural differ-
tions on thermal, morphological and pasting/rheological ences have the potential to affect the chemical modification
behaviour of starches may be quantified using instrumen- process (Huber & BeMiller, 2001).
tation such as differential scanning calorimetry (DSC), The DS and MS of some chemically modified starches
scanning electron microscopy (SEM), Viscoamylograph/ prepared from different sources are presented in Table 4.
Rapid Visco Analyser (RVA) and dynamic rheometer, Potato, maize and rice starches show significant variation
respectively (Kaur, Singh, & Singh, 2004; Kaur et al., in their DS when acetylated under similar reaction
2005a; Kim, Hermansson, & Eriksson, 1992; Liu et al., conditions (Singh, Kaur et al., 2004; Singh, Chawla et al.,
1999a, 1999b; Shi & BeMiller, 2000; Singh & Singh, 2003; 2004; Sodhi & Singh, 2005). Factors such as amylose to
Singh, Kaur, & Singh, 2004; Singh, Chawla, & Singh, 2004; amylopectin ratio, intragranule packing and the presence
Yeh & Yeh, 1993). of lipids mainly govern the degree of substitution during
acetylation of starches from different sources (Phillips, Liu,
3. Extent of chemical modification Pan, & Corke, 1999; Singh, Kaur et al., 2004; Singh,
Chawla et al., 2004). Starches with low amylose content
The rate and efficiency of the chemical modification have been observed to exhibit a higher degree of substitu-
process depends on the reagent type, botanical origin of the tion after acetylation. The CQO bond of the acetyl group
starch and on the size and structure of its granules (Huber experiences a different molecular environment depending

Table 4
DS* and MS** of some modified starches from different botanical sources

Starch source DS (acetylated) MS (hydroxypropylated) DS (Cross-linked)


a h
Normal potato 0.115–0.238 0.098–0.122 0.07–0.26l
Normal maize 0.104–0.184b 0.091–0.092i 0.09–0.25l
Normal maize ND*** 0.061–0.094j ND
Waxy maize 0.081c 0.067–0.127j ND
Hi amylose maize ND 0.078–0.119j ND
Hybrid normal maize 0.030–0.040d ND ND
Normal wheat 0.035–0.131e 0.117–0.123i 0.004–0.020m
Normal rice 0.087–0.118f 40.03k 0.025–0.035n
Normal rice 0.018g ND ND
Waxy rice 0.016g ND ND

*DS ¼ degree of substitution.


**MS ¼ molar substitution.
***ND ¼ Not detected.
a,b
Singh, Kaur et al. (2004); Singh, Chawla et al. (2004) (different levels of acetylation and starches from different potato cultivars).
c
Wang and Wang (2002).
d
Lawal (2004) (two levels of acetylation).
e
Phillips et al. (1999) (different levels of acetylation used).
f
Sodhi and Singh (2005) (starches from different rice cultivars).
g
Liu et al (1999b).
h
Kaur et al. (2004) (starches from different potato cultivars).
i
Stapley and BeMiller (2003) (low MS values from two populations of starch granules).
j
Liu et al. (1999a) (two levels of hydroxypropylation).
k
Yeh and Yeh (1993) (two levels of hydroxypropylation).
l
Sitohi and Ramadan (2001) (DS of starches phosphorylated using a mixture of monosodium and disodium phosphate).
m
Bertolini et al. (2003) (molar substitution values; three levels of cross-linking performed).
n
Yeh and Yeh (1993) (different levels of cross-linking).
ARTICLE IN PRESS
6 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

on whether it is a substitutent on amylose or on (Koch, Bommer, & Koppers, 1982). Studies on waxy maize
amylopectin (Phillips et al., 1999). It has been reported starches using different reagents (POCl3 and propylene
that during acetylation, the acetyl groups are introduced oxide) reported variations in the relative reaction patterns
exclusively in the outer lamellae of the granules and high (Huber & BeMiller, 2001). Due to the higher reactivity of
substitution occurs only in certain parts of the amylopectin POCl3, the cross-links predominate on the granule
fraction of starch (Biliaderis, 1982; Phillips et al., 1999). surfaces, when using highly reactive POCl3 (Gluck-Hirsch
However, Chen, Schols, and Voragen (2004) reported that & Kokini, 1997; Huber & BeMiller, 2001) while the less
acetylation occurs in all the amorphous regions and also at reactive propylene oxide generally diffuses into the granule
the outer lamellae of crystalline regions, rather than matrix prior to reaction (Huber & BeMiller, 2001; Kaur
throughout the crystalline regions of the whole starch et al., 2004).
granule. This has been suggested to be due to the poor Knowledge about the structural changes in starch
penetrating ability of acetic anhydride in starch granules granules caused by modification with chemical reagents
(Chen et al., 2004). Studies (Singh, Kaur et al., 2004) on can be of importance for understanding the altered
acetylated potato starches suggest that the small size functional properties, and for developing chemically
granule population with lower amylose content favours modified starches with desired properties (Kim et al.,
the introduction of acetyl groups and hence results in 1992). Shiftan et al. (2000) reported that EPI cross-linking
higher DS. The size and shape of potato starch granules of is not homogeneous and is concentrated in the non-
different cultivars have been found to be significantly co- crystalline domain of starch granules. Jane, Radosavljevic,
related with their amylose content (Kaur, Singh, & Sodhi, and Seib (1992) found that cross-linking of starch chains
2002; Singh, Singh, Kaur, Sodhi, & Gill, 2003; Singh & occurred mainly in amylopectin. Another factor that may
Singh, 2003; Singh & Kaur, 2004). influence the extent of cross-linking is the size distribution
During hydroxypropylation, the hydroxypropyl groups of starch granule population (Hung & Morita, 2005).
are primarily introduced into the starch chains in the During cross-linking small size granules have been reported
amorphous regions composed mainly of amylose (Blan- to be derivatized to a greater extent than the large size
shard, 1987; Hood & Mercier, 1978; Steeneken & Smith, granules (Bertolini, Souza, Nelson, & Huber, 2003).
1991). Kavitha and BeMiller (1998) and Shi and BeMiller Characterization of substitution upon modification is
(2000) have confirmed using acid/enzymatic hydrolysis that important at both monomer and polymer levels (Richard-
amylose is modified to a greater extent than amylopectin in son et al., 2003). The distribution of substituents at both
hydroxypropylated maize and potato starches, and that the monomeric and polymeric levels may be affected by the
modification of amylopectin occurs close to the branch presence of granule pores and channels; the proportions of
points, presumably because amorphous regions are more amylose and amylopectin and their arrangement; the
accessible to the modifying reagent. However, Richardson nature of the granule surface and granule swelling
and Lo Gorton (2001), after investigating the substituent (BeMiller, 1997; Kavitha & BeMiller, 1998). Techniques
distribution in hydroxypropylated potato amylopectin such as nuclear magnetic resonance (NMR) spectroscopy
starch (PAP) suggested that the hydroxypropyl groups (Heins, Kulicke, Kauper, & Thielking, 1998; Xu & Seib,
are homogeneously distributed on the amylopectin mole- 1997) or gas chromatography/mass spectrometry (Richard-
cule. The modification reaction conditions and starch son et al., 2000; Wilke & Mischnick, 1997) may be helpful
source may also affect the distribution of hydroxypropyl for the determination of the distribution of the substituent
groups along the starch chain (Kaur et al., 2004; Steeneken groups at the monomeric level. The methods used for the
& Woortman, 1994). Azemi and Wootton (1995) reported analysis of the substituent distribution along the polymer
that hydroxypropylated common maize, waxy maize, and chains and the homogeneity/heterogeneity of substitution
high-amylose maize starches differed with regard to the are based on partial degradation of the polymer by acid
distribution of substituent groups on the starch polymer hydrolysis (Arisz, Kauw, & Boon, 1995; Mischnick &
molecules. Investigations carried out on hydroxypropy- Kuhn, 1996) or by enzymatic degradation (Kavitha
lated PAP prepared in granular slurry or solution suggests & BeMiller, 1998; Wilke & Mischnick, 1997; Steeneken &
that more substituents were located in close vicinity to Woortman, 1994; van der Burgt et al., 1998).
branching points, which constitute the amorphous areas in
the semicrystalline granule, than elsewhere Starch hydro- 4. Physico-chemical properties
xypropylated in granule slurry had a more heterogeneous
substituent distribution compared with starch modified in a The physico-chemical properties of starches such as
polymer ‘solution’ of dissolved starch (Richardson & Lo swelling, solubility, and light transmittance have been
Gorton, 2001). The reactivity and concentration of reported to be affected significantly by chemical modifica-
reagents have been reported to influence the degree tion (Table 5). The change in these properties upon
of substitution of cross-linked starches. Also, the type of modification depends on the type of chemical modification.
reagent used and the reaction conditions determine the Chemical modifications such as acetylation and hydro-
ratio of mono- and di-type bonds (esters with phosphorus xypropylation increase, while cross-linking has been obser-
based agents, and glycerols with EPI) during cross-linking ved to decrease (depending on the type of cross-linking
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 7

agent and degree of cross-linking) the swelling power and higher MS. The decrease in associative forces within the
solubility of starches from various sources. The introduc- starch granule due to hydroxypropylation may result in an
tion of (bulky) acetyl groups into starch molecules by increased penetration of water during heating that leads to
acetylation leads to structural reorganization owing to the greater swelling (Kaur et al., 2004). Choi and Kerr
steric hindrance; this results in repulsion between starch (2003) studied the effects of hydroxypropylation on water
molecules, thus facilitating an increase in water percolation sorption isotherms and molecular mobility of both starch
within the amorphous regions of granules and a conse- and water molecules in wheat starch gels using pulsed
1
quent increase in swelling capacity (Lawal, 2004). Studies H NMR techniques. They reported that the water
conducted on acetylated maize, potato and rice starches absorption capacity of hydroxypropylated wheat starch
(Gonzalez & Perez, 2002; Singh, Kaur et al., 2004; Singh, increases with an increasing degree of MS in a specific
Chawla et al., 2004) suggest a significant increase in water activity range (aw 40:53). Choi and Kerr (2004) also
swelling power and solubility upon acetylation in all these reported that the cross-linked starch granules have higher
starch types. The extent of this increase was observed to be resistance towards temperature and heating time. Cross-
higher for potato starches. The degree of substitution linking strengthens the bonding between the starch chains,
introduced after acetylation mainly affects the intensity of causing an increase in the resistance of the granules to
change in the swelling power and solubility of starches. The swelling with increasing degree of cross-linking. Higher
differences in the granule size distribution, physico- concentrations of fast acting cross-linking reagents such as
chemical composition and granule rigidity among the POCI3 result in greater reductions in the swelling potential
starches may also be responsible for the alteration in as compared with slower acting agents such as EPI (Hirsch
swelling power and solubility after acetylation. The & Kokini, 2002). A large concentration of POCl3 cross-
structural disintegration probably weakens the starch links at the surface of the granule causes the formation of a
granules after acetylation, and this enhances amylose hard outer crust that restricts granule swelling (Gluck-
leaching from the granule, thus increasing starch solubility Hirsch & Kokini, 1997; Huber & BeMiller, 2001). Inagaki
(Lawal, 2004). The extent of the increase in swelling power and Seib (1992) also reported that the swelling power of
has been observed to be higher in starches with a low cross-linked waxy barley starch declined as the level of
amylose content and small size granule population (Singh, cross-linking increased. Cross-linked starches exhibit lower
Kaur et al., 2004; Sodhi & Singh, 2005). Liu et al. (1999b) solubility than their native equivalents, and solubility
reported that the waxy starches show an increased swelling decreases further with an increase in the concentration of
power upon acetylation because of the presence of mainly cross-linking reagent, which may be attributed to an
amylopectin with a more open structure than in non-waxy increase in cross-link density (Kaur et al., 2005a). Cross-
starch; this allows rapid water penetration, and increased linking at low levels, although having a substantial effect
swelling power and solubility. on starch properties such as granule swelling (Inagaki &
Kaur et al. (2004) studied the swelling power and Seib, 1992; Reddy & Seib, 1999; Rutenberg & Solarek,
solubility of hydroxypropylated potato starches and found 1984) contributes little to water sorption properties
higher swelling power and solubility in starches with a (Chilton & Collison, 1974). Starch modifications alter the

Table 5
Swelling power of some modified starches from different botanical sources

Starch source SP* (g/g) (acetylated) SP* (g/g) (hydroxypropylated) SP* (g/g) (cross-linked)

Normal potato 60–71 (native 58–70)y a 33–39 (native 28–31)e 20–25 (native 28–31)h
Normal potato ND** ND 23–27 (native 28–31)i
Normal maize 38 (native 36)b E20 (native E6)f ND
Waxy maize ND E42 (native E30)f ND
Normal wheat ND 9–16 (native E6–8)g ND
Normal rice 15–19 (native 14–18)c ND E9 (Native E18)d
Waxy rice E31 (native E41)d ND E14 (Native E41)d

*SP ¼ Swelling power (g/g).


** ¼ not detected.
y
¼ The properties of corresponding native (unmodified) starches are given in brackets.
a
Singh, Kaur et al. (2004).
b
Singh, Kaur et al. (2004) (starches from different potato cultivars).
c
Sodhi and Singh (2005) (starches from different rice cultivars).
d
Liu et al. (1999a, b).
e
Kaur et al. (2004) (starches from different potato cultivars).
f
Liu et al. (1999a) (two levels of hydroxypropylation)
g
Hung and Morita (2005) (two wheat starch granule populations)
h
Kaur et al. (2005a) (starches from different potato cultivars; cross-linking performed using POCl3).
i
Kaur et al. (2005a) (starches from different potato cultivars; cross-linking performed using EPI).
ARTICLE IN PRESS
8 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

light transmittance of starch pastes to a considerable 5. Morphological properties


extent. Modifications such as acetylation and hydroxypro-
pylation have been reported to increase the light transmit- Starch modification involves physical, chemical and
tance of various starches (Kaur et al., 2004; Lawal, 2004; biochemical phenomena on the surface of contacting
Singh, Kaur et al., 2004; Singh, Chawla et al., 2004). The phases. Microscopy (light and SEM) has played an
chemical substitution of the –OH groups on the starch important role in increasing understanding of granular
molecules by acetyl moieties hampers the formation of an structure of modified starches. It has been used to detect
ordered structure following gelatinization, and thus retards structural changes caused by chemical modifications and
retrogradation, resulting in a more fluid paste with the most substituted regions in starch granules (Kaur et al.,
improved long-term clarity (Lawal, 2004). The high 2004; Kim et al., 1992). Most of the structural changes
retention of water entering the starch granule results in a upon hydroxypropylation take place at the relatively less
greater swelling power and favours the clarity of pastes and organized central core region of the starch granule i.e.
gels. Starch source, granule size distribution, amylose where the hydroxypropyl groups are most densely depos-
content and degree of substitution introduced upon ited (Kim et al., 1992). The ‘pushing apart effect’ exerted by
modification have been found to be the important factors the bulky hydroxypropyl groups, especially in the central
affecting light transmittance of acetylated starches. Singh, region of the granule, might lead to an alteration in granule
Chawla et al. (2004) reported a higher light transmittance morphology upon hydroxypropylation. Another possible
of acetylated potato starches compared to acetylated maize explanation is that the starch granule itself is not
starches acetylated under similar reaction conditions. structurally homogeneous from a physical and chemical
Highly cross-linked starch pastes generally show lower point of view, since it has different physical natures
light transmittance than their counterpart native starches. (amorphous and crystalline regions) as well as different
Incomplete gelatinization and reduced swelling of cross- chemical compositions in each region (French, 1984). Kaur
linked starches is mainly responsible for their reduced paste et al. (2004) reported that the treatment of potato starch
clarity (Kaur et al., 2005a; Lim & Seib, 1993; Morikawa & granules with propylene oxide (10%, dwb) alters granule
Nishinari, 2000b; Reddy & Seib, 2000; Woo & Seib, 1997; morphology (Fig. 1A and B). Many of the less affected
Zheng, Han, & Bhatty, 1999). modified granules developed a depression that resulted
The solubility of native, cross-linked and hydroxypropy- later in slight fragmentation, indentation, and the forma-
lated starches in dimethyl sulphoxide (DMSO) varies to a tion of a deep groove in the central core region along the
significant extent (Table 6). Hydroxypropylation results in a longitudinal axis in highly affected granules (Fig. 2). These
significant increase in the solubility of starches in DMSO granules appeared as folded structures with their outer
(Kaur et al., 2004; Yeh & Yeh, 1993). Yeh and Yeh (1993) sides drawn inwards, giving the appearance of a doughnut
compared the solubilites (in DMSO) of hydroxypropylated (Fig. 2A and B). Moreover, these altered regions were
and cross-linked rice starches with the solubility of native rice observed to be apparently larger in large size granules
starch, and observed higher and lower solubilities for compared with small size granules in all the potato starches
hydroxypropylated and cross-linked rice starches, respec- examined; this may be attributed to differences in the
tively. Differences in granule morphology, amylose content native granule architecture and fragility. The peripheral
and degree of substitution of native and modified starches, regions and also the outer layer of the less affected starch
respectively, have been reported to affect the light transmit- granules remained unaltered, and the changes remained
tance in DMSO (Kaur et al., 2004). Sahai and Jackson confined to the central core regions. By contrast, highly
(1996) reported that the solubility of starch in methyl affected starch granules developed blister like appearances,
sulphoxide varies significantly with granule size, presumably cracks and small protuberances on their surfaces, and a
reflecting inherent structural hetrogeneity within granules. deep groove in the central core region; this suggests that the

Table 6
Solubility (%) in DMSO of some modified starches from different botanical sources

Starch source SB* (after 4 h) SB (after 8 h) SB (after 16 h) SB (after 24 h)

Normal potato (hydroxypropylated)a y


E76 (native E57)y E83 (native E60) E95 (native E65) E99 (native 75)
Normal rice (hydroxypropylated)b E35 (native E10) E80 (native E20) E95 (native E35) E98 (native E55)
Normal rice (cross-linked)c E08 (native E10) E10 (native E20) E20 (native E35) E26 (native E55)

*Solubility in DMSO (%).


y
¼ values reported as % transmittance in DMSO.
y
¼ The properties of corresponding native (unmodified) starches are given in brackets.
a
Kaur et al. (2004) (starches from different potato cultivars used).
b
Yeh and Yeh (1993) (two levels of hydroxypropylation used).
c
Yeh and Yeh (1993) (different levels of cross-linking used).
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 9

Fig. 1. Effects of hydroxypropylation on the granule morphology of potato starches I: (A) native potato starch granules, (B) potato starch granules after
hydroxypropylation (at 10% propylene oxide concentration), and (C) effect of increased concentration of propylene oxide (15%) on the starch granule
structure (Kaur et al., 2004).

Fig. 2. Effects of hydroxypropylation on the granule morphology of potato starches II: (A,B) formation of deep groove in the central core region, folding
of starch granules and formation of doughnut like appearance, and (C) formation of blister like appearance and cracks on the starch granules (Kaur,
2004).

granule peripheral regions may be the last to be modified boundaries and fused together to form a gelatinized mass
(Fig. 2C) (Kaur et al., 2004). (Fig. 1C). This effect was again more pronounced in larger
The granule structure is more substantially altered when granules as compared with smaller granules (Kaur et al.,
the reaction is carried out with a higher concentration of 2004). Huber and BeMiller (2001) also reported that the
propylene oxide (15% compared with 10%). Highly material within the inner regions of potato starch granules
affected granules appear as if gelatinized, having lost their was more susceptible to reaction (with propylene oxide)
ARTICLE IN PRESS
10 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

than that in the outer granule layers. Also, as potato starch


granules do not possess channels, the reagent diffuses
inwards through the exterior granule surface. Propylene
oxide, being less reactive than other modification reagents,
may diffuse into the granule matrix prior to reacting
(Huber & BeMiller, 2001). However, Biliaderis (1982) in a
study on chemically modified pea and waxy maize starches
found that hydroxypropylation occurred uniformly
throughout the starch granules. The structural changes in
hydroxypropylated starch granules become more evident
with increasing MS (Kaur et al., 2004; Kim et al., 1992).
Hydroxypropylation leads to alteration in the structure of
the gelatinized potato starch gels also, which may be
attributed to a weakened granule structure, leading to
increased granule disruption during gelatinization (Kaur
et al., 2004). Hydroxypropylated starch gels maintained
well the planar structure during storage at 4 1C for 10 days,
whereas stored gels of native starches showed extensive
aggregation of granule remnants. Similar observations
have been reported by Yeh and Yeh (1993) and Perera and
Hoover (1999) for hydroxypropylated potato and rice
starch gels respectively. Kaur et al. (2004) have also
reported the appearance of numerous rod-shaped fuzzy
clustered microfibrils in hydroxypropylated starch gels
(after 30 days storage at 4 1C) that could be easily
distinguished from the other starchy material (Fig. 3).
The extensive phase separation occurring during long-term
storage at 4 1C may be responsible for the formation of
these rod-shaped microfibrils. Slow cooling has also been
reported to enhance the formation of non-spherulitic
morphologies in starch gels (Nordmark & Ziegler, 2002).
Acetylation treatment has also been found to alter the
granule morphology, although to a lesser extent. Singh,
Kaur et al. (2004) carried out acetylation of maize and Fig. 3. (A,B) Rod-shaped microfibrils (showing longitudinal arrangement
potato starches using different concentrations of acetic of crystalline structures) formed during long term storage of hydro-
anhydride, and reported that the acetylation treatment xypropylated gelatinized starch pastes (Kaur et al., 2004).
caused granule fusion in both maize and potato starches
(Fig. 4). The granule fusion was also observed to be more
pronounced in potato starches with small size granules during acetic anhydride addition (Singh, Chawla et al.,
(Singh, Kaur et al., 2004; Singh, Chawla et al., 2004). 2004). Sitohi and Ramadan (2001) studied the granular
Maize starch granules show a higher resistance towards properties of phosphorylated normal maize, potato, rice,
acetylation treatment than potato starches. The addition of maize amylopectin and maize amylose starches, prepared
4% acetic anhydride resulted in the fusion of granules in using a mixture of mono- and disodium phosphate. They
potato starches while maize starch granules tended to fuse concluded that the starch granule size is very responsive to
at concentrations of acetic anhydride of 8% or higher the changes in the DS by phosphate groups, higher the DS,
(Singh, Kaur et al., 2004). The granule surface of maize larger the granule size. The average increase in granule size
and potato starch granules was observed to be slightly was observed to be higher for rice and maize starches than
rough upon acetylation (Singh, Chawla et al., 2004). The for potato starch for a given DS. They suggested that this
granule surface of rice starches becomes rough and the increase may be due to the substitution by phosphate
granules tend to form aggregates upon acetylation (Gon- groups inside the modified granules, building certain
zalez & Perez, 2002; Jeong, Bae, & Oh, 1993; Sodhi & repulsive forces that increase the sizes of inter- and intra
Singh, 2005). Jae, Jung, and Man (1994) reported the molecular spaces, allowing more water molecules to be
deformation of rice starch granules after acetylation. absorbed. Phosphorylation does not cause any detectable
However, some granule fusion and deformation, and the change in the general granule shape (Sitohi & Ramadan,
rough appearance of the granule surface in the acetylated 2001). After being cross-linked using EPI and POCl3,
starches might also be the result of surface gelatinization potato starch granules remain smooth and similar to native
upon addition of NaOH to maintain alkaline conditions starch granules in morphology when viewed under SEM,
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 11

Fig. 4. Effects of acetylation on the granule morphology of maize and potato starches: (A) native maize starch granules, (B) acetylated maize starch
granules, (C) native potato starch granules, and (D) acetylated potato starch granules (Singh et al., 2004b).

suggesting that the modification does not cause any common technique used for detecting both first order
detectable morphological change (Kaur et al., 2005a). (melting) and second order (glass) thermal transitions
Some chemical modifications of starch have been reported (Biliaderis, Page, Maurice, & Juliano, 1986; Huang, Chang,
to increase granule surface area and granule porosity Chang, & Lii, 1994; Nakazawa et al., 1984; Russel &
(Fortuna, Juszczak, & Palasinski, 1999). Oliver, 1989; Yook et al., 1993).
DSC studies have shown that modification alters thermal
6. Thermal properties transition temperatures (onset (To); peak (Tp); conclusion
(Tc) and the overall enthalpy (DHgel) associated with
Starch gelatinization is the collapse (disruption) of gelatinization (Tables 7 and 8). Upon hydroxypropylation,
molecular orders within the starch granule manifested in the reactive groups introduced into the starch chains are
irreversible changes in properties such as granular swelling, capable of disrupting the inter- and intra-molecular
native crystalline melting, loss of birefringence, and starch hydrogen bonds, leading to an increase in accessibility by
solubilization (Atwell, Hood, Lineback, Varriano-marston, water that lowers the temperature of gelatinization. Perera
& Zobel, 1988). It is an important starch functional et al. (1997) studied the effect of hydroxypropylation on
property that varies with respect to the composition the thermal properties of different potato starches. In all
(amylose to amylopectin ratio, phosphorus, lipids, proteins starches, increasing the level of MS resulted in decreases in
and enzymes, etc.), the molecular structure of amylopectin DHgel, To, Tp and Tc and a widening of the gelatinization
(unit chain length, extent of branching, molecular weight temperature range (TcTo). A progressive shift of the
and granule architecture (crystalline to amorphous ratio), biphasic gelatinization endotherms to lower temperatures
granule morphology and size distribution of starches (Kaur as well as a broadening and shortening of the gelatinization
et al., 2002, 2004, 2005a, 2005b; Krueger, Knutson, Inglett, endotherm with increasing MS have also been observed for
& Walker, 1987; Singh & Singh, 2001; Singh et al., 2003; hydroxypropylated rice starch, indicating increased inter-
Singh, Kaur et al., 2004; Singh, Chawla et al., 2004; Singh nal plasticization and destabilization of the amorphous
& Kaur, 2004; Tester, 1997). Gelatinization has been regions of the granules (Seow & Thevamalar, 1993). An
studied by various means such as thermal analysis increase in gelatinization temperature range upon hydro-
(Nakazawa, Noguchi, Takahashi, & Takeda, 1984; Shiot- xypropylation of different potato starches has also been
subo & Takahashi, 1984; Slade & Levine, 1987; Wada, reported by Kaur et al. (2004), which could be attributed to
Takahashi, Shirai, & Kawamura, 1979), X-ray diffraction increased inhomogeneity within both the amorphous and
(I’Anson, Miles, Morris, & Ring, 1988; Zobel, Young, & crystalline regions of the starch granules. Decreases have
Rocca, 1988) and nuclear magnetic resonance (NMR) been recorded in gelatinization temperatures and gelatini-
(Chinachoti, White, Lo, & Stengle, 1991). DSC is the most zation enthalpies of amylose extender (ae) mutant, waxy
ARTICLE IN PRESS
12 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

Table 7
Thermal properties of some modified starches from different botanical sources

Starch source T*, 1C (acetylated) T*, 1C (hydroxypropylated) T*, 1C (cross-linked)

Normal potato 48–67 (native 57–69)y a 51–62 (native 57–68)i 60–68 (native 57–68)o
Normal potato 55–64 (native 59–70)b ND 59–68 (native 57–68)p
Normal maize 65–77 (native 69–77)c 59–75 (native 65–81)j ND
Normal maize 66–75 (native 70–78)d ND ND
Waxy maize 64–69 (native 68–72)e 61–79 (native 63–84)j 65–75 (native 62–76)q
Waxy maize ND* ND 67–72 (native 68–73)r
Hybrid normal maize 71–84 (native 60–78)f ND ND
Hi-amylose maize ND 66–95 (native 67–105)j ND
Normal wheat ND 55–71 (native 63–84)k 63–76 (native 63–84)s
Normal wheat ND 46–55 (native 55–67)l 61–72 (native 57–58)t
Waxy wheat ND ND 62–66 (native 61–66)r
Normal rice 60–72 (native 66–78)g 64–83 (native 63–84)m 70–87 (native 71–87)u
Normal rice ND 57–92 (native 63–92)n ND
Waxy rice 60–78 (native 60–78)h ND 61–78 (native 60–78)v
Waxy rice ND ND 55–66 (native 53–67)q

T* ¼ Transition temperatures of different starches (1C).


ND* ¼ not detected, y ¼ The properties of corresponding native (unmodified) starches are given in brackets.
The properties of corresponding native (unmodified) starches are given in brackets.
a
Singh, Chawla et al. (2004) (different levels of acetylation).
b
Singh, Kaur et al. (2004) (starches from different potato cultivars).
c
Singh, Chawla et al.(2004) (different levels of acetylation).
d
Singh, Kaur et al. (2004) (starches from different potato cultivars).
e
Wang and Wang (2002).
f
Lawal (2004).
g
Sodhi and Singh (2005) (starches from different rice cultivars).
h
Liu et al. (1999b).
i
Kaur et al. (2004) (starches from different potato cultivars).
j
Liu et al. (1999a) (two levels of hydroxypropylation).
k
Choi and Kerr (2004) (three levels of hydroxypropylation).
l
Hung and Morita (2005) (two wheat starch granule populations).
m
Yeh and Yeh (1993) (two levels of hydroxypropylation).
n
Seow and Thevamalar (1993) (three levels of hydroxypropylation).
o
Kaur et al. (2005a) (starches from different potato cultivars used, cross-linking performed using POCl3).
p
Kaur et al. (2005a) (starches from different potato cultivars used, cross-linking performed using EPI).
q
Tsai et al. (1997) (cross-linking performed using EPI).
r
Reddy and Seib (2000) (cross-linking performed using POCl3).
s
Choi and Kerr (2004) (cross-linking performed using POCl3).
t
Bertolini et al. (2003) (three levels of cross-linking performed using POCl3; onset transition temperatures only).
u
Yeh and Yeh (1993) (different levels of cross-linking performed using POCl3).
v
Liu et al. (1999b).

mutant (wx) and normal maize starch upon hydroxypro- in unmodified starches (Perera et al., 1997). Similar DSC
pylation (Liu et al., 1999a). The decrease was observed to results have been reported for hydroxypropylated pea
be greater for high amylose maize starches (66% amylose) starch (Hoover, Hannouz, & Sosulski, 1988), hydroxypro-
as compared with waxy maize starch (3.3% amylose). The pylated rice starch (Seow & Thevamalar, 1993) and
peak transition temperature (Tp) gives a measure of hydroxypropylated potato starch (Kim & Eliasson, 1993).
crystallite quality (double helix length), whereas DHgel Substitution on granular starch occurs mainly in the
gives an overall measure of crystallinity (quantity and amorphous regions, which promotes swelling in these
quality) and is an indicator of the loss of molecular order regions and thus, disrupts the crystalline phase, which
within the granule on gelatinization (Cooke & Gidley, melts at a lower temperature than in the case of the
1992; Hoover & Vasanthan, 1994; Tester & Morrison, unmodified starch.
1990). The decrease in DHgel on hydroxypropylation Thermal studies of gelatinization of acetylated Mucuna
suggests that hydroxypropyl groups disrupt double helices bean (Mucuna pruriens) and Jack bean (Canavalia ensifor-
(owing to the rotation of these flexible groups) within the mis) starch revealed that acetylation reduced the To, Tp and
amorphous regions of the granules. Consequently, the Tc (Adebowale & Lawal, 2003; Betancur-Ancona, Chel-
number of double helices that unravel and melt during Guerrero, & Canizares-Hernandez, 1997). Starches with
gelatinization would be lower in hydroxypropylated than higher degrees of acetyl substitution have been observed to
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 13

Table 8
Thermal properties of some modified starches from different botanical sources

Starch source DHgel,* J/g (Acetylated) DHgel, J/g (Hydroxypropylated) DHgel, J/g (Cross-linked)

Normal potato 10.1–11.4 (native 12.1)y a 10–11 (native 11.7–12.9)g 12.7–14.7 (native 11.7–12.9)l
Normal potato 10.1–11.8 (native 12.8–13.2)b ND 12.7–14.4 (Native 11.7–12.9)m
Normal maize 08.52 (native 10.9)a ND ND
Normal maize 08.9–09.7 (native 10.6)b 07.1–8.4 (native 11)h ND
Hybrid normal maize 09.8–10.6 (native 14.3)c ND ND
Hi-amylose maize ND** 6.4–8.4 (native 13.7)h ND
Waxy maize 14.8 (native 15.6)d 08–8.7 (native 13.6)h 15.2 (native 15.3)n
Normal wheat ND 04.7–05 (native 6.8)i 6.6–7.4 (native 06.8)o
Normal wheat ND 02.2 (native 06.2)j —
Waxy wheat ND ND 12.8 (native 13.2)n
Normal rice 08.1–11.4 (native 08.1–11.9)e 08–09 (native 10.4)k 11–13 (native 10.4)p
Waxy rice 08.5 (native 09.8)f ND 10.3 (native 09.8)q

*DHgel ¼ enthalpy of gelatinization of different starches (J/g).


**ND ¼ Not detected.
y
¼ The properties of corresponding native (unmodified) starches are given in brackets.
a
Singh, Chawla et al. (2004) (different levels of acetylation).
b
Singh, Kaur et al. (2004) (starches from different potato cultivars).
c
Lawal (2004).
d
Wang and Wang (2002).
e
Sodhi and Singh (2005) (starches from different rice cultivars).
f
Liu et al. (1999b).
g
Kaur et al. (2004) (starches from different potato cultivars).
h
Liu et al. (1999a) (two levels of hydroxypropylation).
i
Choi and Kerr (2004) (three levels of hydroxypropylation).
j
Hung and Morita (2005) (two wheat starch granule populations).
k
Yeh and Yeh (1993) (two levels of hydroxypropylation).
l
Kaur et al. (2005a) (starches from different potato cultivars; cross-linking performed using POCl3).
m
Kaur et al. (2005a) (starches from different potato cultivars; cross-linking performed using EPI).
n
Reddy and Seib (2000) (cross-linking performed using POCl3).
o
Choi and Kerr (2004) (three levels of cross-linking performed using POCl3).
p
Yeh and Yeh (1993) (different levels of cross-linking performed using POCl3).
q
Liu et al. (1999b).

show greater decreases in the transition temperatures and these phenomena are related to the reduced mobility of
enthalpy of gelatinization. Weakening of the starch amorphous chains in the starch granule as a result of the
granules by acetylation leads to early rupture of the formation of intermolecular bridges. The level of phos-
amylopectin double helices, which accounts for the lower phate cross-links has a strong influence on the DSC
values of To, Tp and Tc (Adebowale & Lawal, 2003). properties of starches. Choi and Kerr (2004) reported that
Decreases in the thermal parameters are consistent with cross-linked starches prepared using a relatively low
fewer crystals being present after modification (owing to concentration of the POCl3 had gelatinization parameters
damage to the crystals during acetylation) and with a co- similar to those of native starches, while cross-linked
operative melting process enhanced by added swelling starches prepared using higher reagent concentrations
(Singh, Chawla et al., 2004). The extent of the lowering of showed considerably higher Tc and DHgel values. These
transition temperatures and DHgel on acetylation has been findings are consistent with those of Yeh and Yeh (1993)
observed to be different for starches from different sources. and Liu, Weber, Currie, and Yada (2003), who reported
Potato starches show a greater decrease in thermal that DHgel of starch increased with increasing levels of
parameters upon acetylation compared with maize and cross-linking; however, Tp was not affected significantly.
rice starches (Singh, Kaur et al., 2004; Singh, Chawla et al., Cross-linking at lower levels reduces the proportion of the
2004; Sodhi & Singh, 2005). The differences in granule starch that can be gelatinized, resulting in a lower value of
rigidity, presence/absence of lipids, degree of substitution DHgel (Yook et al., 1993). Yoneya, Ishibashi, Hironaka,
and amylose to amylopectin ratio between these starches and Yamamoto (2003) also reported that potato starches
affect the extent of changes in thermal parameters. Cross- treated with 100 ppm of POCl3 displayed significantly
linking also alters the thermal transition characteristics of lower gelatinization temperatures and lower DHgel than
starch, the effect depending on the concentration and type other treated samples (with 40–5000 ppm). Decreasing or
of cross-linking reagent, reaction conditions and the increasing the degree of phosphate cross-links caused a
botanical source of the starch. An increase in gelatinization gradual increase in To, Tp and DHgel of cross-linked
temperature has been observed for cross-linked starches; potato starch samples compared with the values of these
ARTICLE IN PRESS
14 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

properties for the 100 ppm-treated sample. Chatakanonda, plays a decrease proportional to the amount of cross-
Varavinit, and Chinachoti (2000a) conducted studies on linking agent used (Chung et al., 2004). This opposite trend
cross-linked rice starches (using as reagent a mixture of may be attributed to the internal plasticization by bulky
STMP and STPP) that showed deep and sharp en- and ionic mono-substituted phosphate groups that con-
dotherms, E30 1C wide. Also, the gelatinization tempera- tribute to a free volume increase for starch chains that
ture increased significantly (by up to 5 1C) with an increase reduces the glass transition temperature.
in the degree of cross-linking, while enthalpy showed no When a stored starch gel is reheated in a DSC, an
significant change (E15% decrease), suggesting complete endothermic transition occurs that is not present in the
melting of crystalline regions in spite of cross-linking. The DSC scan of the freshly gelatinized sample. Such a
introduction of phosphate cross-links into the starch by transition is generally attributed to the melting of
STMP alone tightened the molecular structure, leading to recrystallized amylopectin. The enthalpy change involved,
an increase in the gelatinization temperature (Chataka- the enthalpy of retrogradation is generally considered to
nonda et al., 2000a). The enthalpy of cross-linked normal correspond to order-disorder transitions of crystallites, i.e.
rice starch was observed to decrease while waxy rice starch double helices present in extended order arrays and regions
showed an increase in enthalpy after cross-linking (Liu et of lesser crystalline order. The retrogradation properties of
al., 1999b). These findings suggest that the type and starches are indirectly influenced by the structural arrange-
concentration of the reagent; amylose/amylopectin ratio of ment of starch chains within the amorphous and crystalline
starch during cross-linking significantly affects the extent regions of the un-gelatinized granule, which in turn,
of change in thermal properties. influence the extent of granule breakdown during gelatini-
Dual modified (substituted and cross-linked) normal zation and the interactions that occur between the starch
maize, waxy maize, tapioca, potato and normal wheat chains during gel storage (Perera & Hoover, 1999). The
starches are available commercially with varying degrees of crystallinity of starch granules is disrupted during chemical
hydroxypropylation and cross-linking. The temperatures modification (Saroja, Shamala, & Tharanathan, 2000), and
and enthalpies of gelatinization of the dual modified this leads to a greater degree of separation between the
(hydroxypropylated/cross-linked or acetylated/cross-lin- outer branches of adjacent amylopectin chain clusters in
ked) waxy wheat and maize starches are generally lower modified starches compared with those in native starches.
than those of the unmodified starches (Reddy & Seib, Consequently, double-helix formation (during storage)
2000). The gelatinization temperatures (To; Tp; Tc) of between adjacent amylopectin chains of the modified
cross-linked waxy wheat starch and its hydroxypropylated/ starches is much slower and less extensive owing to the
cross-linked and acetylated/cross-linked forms are 5–7 1C introduction of functional groups upon chemical modifica-
below than those of unmodified forms of waxy maize tion. Retrogradation of starch has been reported to be
starch when measured in excess water (Reddy & Seib, suppressed by cross-linking using STMP and STPP
2000). mixture, as indicated by their lower enthalpy of retro-
The majority of the reported work on thermal behaviour gradation after storage which may be because of the
of starch has been focused mainly on the melting behaviour restricted mobility of cross-linked amylopectin branches
of starch crystals, and information on the amorphous due to the presence of phosphate groups (Chung et al.,
phase is limited (Morikawa & Nishinari, 2000b; Tsai, Li, & 2004). DSC heating of stored native starch gels has also
Lii, 1997; Yeh & Yeh, 1993; Yook et al., 1993; Zheng et al., been reported to be more conspicuous than that of
1999). Glass transition of rice starch cross-linked using an hydroxypropylated phosphate cross-linked potato starch
STMP-STPP mixture has been studied by Chatakanonda, (HPS) dispersions as the retrogradation phenomenon of
Varavinit, and Chinachoti (2000b). They claimed that the HPS dispersions was barely observed by DSC measure-
glass transition temperature (Tg) of the starch was not ments even when a high concentration of starch (33%) was
significantly changed by cross-linking or by cold storage at used (Morikawa & Nishinari, 2000a). Moreover, it has
a moisture content of 67%. Chung, Woo, and Lim (2004) been reported that the effect of phosphate cross-linking on
reported an increase in the Tg of maize starch by nearly starch is more pronounced than that of hydroxypropyla-
1 1C by cross-linking using an STMP-STPP mixture, when tion with respect to retrogradation. Yook et al. (1993)
measured with excess water (67%). However, the increase concluded that the tendency towards retrogradation was
in the Tg by 1 1C may not be of significance because of the greatly reduced by both hydroxypropylation and cross-
difficulties observed in analysing the Tg of starches linking, and they showed a synergistic effect of these
(Biliaderis, 1991; Biliaderis et al., 1986; Blond & Simatos, treatments in retarding the retrogradation of gelatinized
1998; Liu & Lelievre, 1992). The Tg of starch under limited rice starch gels. Hydroxypropylated-crosslinked starch
water conditions (E15%) is usually measured after the exhibited significantly higher onset and peak gelatinization
starch has been transformed to an amorphous state temperatures, enthalpy of gelatinization and lower retro-
because Tg of granular starch containing crystals is difficult gradation than crosslinked-hydroxypropylated starch, con-
to measure due to the low heat capacity change at Tg firming the previous assumption that the locations of
(Chung et al., 2002; Zeleznak & Hoseney, 1987). The Tg of cross-links are different in the two kinds of modified starch
cross-linked starches under limited water conditions dis- (Yook et al., 1993). Hydroxypropylation followed by
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 15

Breakdown (RVU)
cross-linking provides starch with better storage stability in

104 (Native 140)b


55 (Native 136)b
food applications.

7. Rheological/pasting properties

ND
ND
ND
ND
ND
Rheological properties of a material reflect its structure.
During gelatinization, starch granules swell to several times
their initial volume. Swelling is accompanied by leaching of

Peak viscosity (RVU)


granule constituents, predominantly amylose, and the
formation of a three dimensional network (Eliasson,

229 (Native 233)b


346 (Native 226)b
1985; Hennig, Lechert, & Goemann, 1976; Steeneken,

Cross-linked
1989; Tester & Morrison, 1990). These changes are
responsible for the rheological characteristics exhibited by
starch suspensions during heating and shearing. Rheologi-

ND
ND
ND
ND
ND
cal/pasting behaviour of starch is governed by amylose
content, granule size distribution, granule volume fraction,
granule shape, granule-granule interaction and continuous

286–305 (Native 195)c

213–227 (Native 243)c


phase viscosity (Kaur et al., 2004; Morikawa & Nishinari,

Breakdown (RVU)
2002; Okechukwu & Rao, 1995; Singh & Kaur, 2004; Singh
et al., 2003). Starch exhibits unique viscosity behaviour
with change of temperature, concentration and shear rate

9–26 (-)c
(Nurul, Azemi, & Manan, 1999). This can be measured in

ND

ND
ND
terms of rheological/pasting curves (plots of viscosity


versus temperature) obtained with the Brabender Viscoa-
mylograph or the Rapid Viscosity Analyzer (RVA) and
rheometer. Information obtained from rheology/pasting

414–425 (Native 337)c

350–379 (Native 391)c


Peak viscosity (RVU)
curves is vital when considering a starch as a possible

** ¼ Not detected, y ¼ the properties of corresponding native (unmodified) starches are given in brackets.
Hydroxypropylated
component of a food product (Adebowale & Lawal, 2003).

139–144 (—)c
The maximum viscosity at a given concentration reflects
the ability of the granules to swell freely prior to their
physical breakdown. Starches that are capable of swelling ND
ND

ND
ND
to a high degree are also less resistant to breakdown on
cooking and hence exhibit significant viscosity decreases
after the maximum viscosity is reached (Adebowale &
Lawal, 2003). The increase in viscosity during the cooling
Pasting properties of some modified starches from different botanical sources

Breakdown (RVU)

136)b
140)b
175)a
387)a

period is indicative not of only the normal inverse


relationship between the viscosity and temperature of
252 (Native
352 (Native

146 (Native
143 (Native

suspensions but also of the tendency for various constitu-


ents present in the hot paste (swollen granules, fragments
ND

ND
ND

of swollen granules, and colloidally dispersed and dissolved


*RVU ¼ Rapid viscosity units, where 1 RVU ¼ E10 mPas.

starch molecules) to associate or retrograde as the


temperature of the paste decreases.
Chemical modification leads to a considerable change in
Peak viscosity (RVU*)

the rheological and pasting properties of starches (Table 9).


535)y a

233)b
226)b
627)a

Starch paste viscosity can be increased or reduced by


applying a suitable chemical modification (Agboola,
592 (Native
695 (Native

259 (Native
268 (Native
Acetylated

Akingbala, & Oguntimein, 1991). Again, modification


method, reaction conditions and starch source are the
ND**

ND
ND

critical factors that govern the rheological/pasting beha-


viour of starch pastes (Gonzalez & Perez, 2002; Kim et al.,
Wilkins et al. (2003).

1993; Reddy & Seib, 1999; Singh, Kaur et al., 2004; Singh,
Liu et al. (1999b).
Liu et al. (1999a).

Chawla et al., 2004; Woo & Seib, 1997; Yeh & Yeh, 1993).
Hi-amylose maize

A significant variation in rheological/pasting properties has


Normal maize
Starch source

been reported after acetylation of starch obtained from


Waxy maize

Waxy maize
Normal rice
Dent maize

Waxy rice

different sources. Betancur-Ancona et al. (1997) studied the


Table 9

rheological properties of acetylated Canavalia ensiformis


b
a

(jack bean) starches and reported a substantial increase in


ARTICLE IN PRESS
16 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

the apparent viscosity upon acetylation. Control of mechanisms: (1) by steric hindrance, which prevents the
reaction conditions such as pH during acetylation may close association of chains and restricts the formation of
allow reduction of secondary hydrolysis reactions and inter-chain hydrogen bonds; and (2) by changing the
facilitate the incorporation of acetyl groups. Such mod- hydrophilicity of the starch molecules and thus altering
ification enhances the water holding capacity of the starch bonding with water molecules. The observed effects of
matrix and the development of more organized structures, hydroxypropylation are consistent with an overall reduc-
leading to a higher resistance to deformation and thus a tion in bonding between starch chains and a consequent
higher peak viscosity can be achieved (Betancur-Ancona increase in the ease of hydration of the starch granule.
et al., 1997). A similar enhancement viscosity has been Gelatinization can thus commence at a lower temperature,
reported by Sathe and Salunkhe (1981) for acetylated and greater swelling of the granule will lead to an increased
Phaseolus vulgaris (haricot bean) starch. Differences in peak viscosity (Liu et al., 1999a). Kim et al. (1992) reported
relative reactivities are observed among native, partial that with increase in MS, the pasting temperature of potato
waxy and waxy starches during acetylation that may affect hydroxypropylated starches decreased and their peak
their rheological properties. The amylose/amylopectin Brabender viscosity increased. Hoover et al. (1988)
ratio was also considered to be the prime determinant of reported similar observations on hydroxypropylated pea
the change in the paste viscosity upon acetylation. Liu, starches. The peak viscosity of high amylose and normal
Ramsden, and Corke (1997) studied the pasting behaviour starches increased considerably while the waxy starches
of acetylated normal, waxy and high amylose maize show a little effect on the viscosity upon hydroxypropyla-
starches. They reported a considerable increase in paste tion. The higher increase in viscosities of high amylose and
viscosities of high amylose and waxy maize starches normal starches may be because of more hydroxyl groups
whereas the increase was not significant for normal maize at their amorphous regions, which are mainly composed of
starch, after acetylation. Unfortunately, no explanation in amylose. The extent of change in starch functional
this study is given for this odd order of increase in properties upon hydroxypropylation has also been ob-
viscosities of the three types of starches. Another study served to be influenced by the starch granule size
conducted by Gonzalez and Perez (2002) on commercial distribution. Studies carried out by Hung and Morita
rice starch, reported an increase in pasting viscosity after (2005) on the pasting properties of hydroxypropylated
acetylation that can be explained through increased water A- and B-type wheat starch granules showed that, on
absorption. Acetylation influences interactions between modification, considerable increases in the peak, final and
starch chains by steric hindrance, altering starch hydro- breakdown viscosities occurred. The large A-type wheat
philicity and hydrogen bonding and resulting in a lower granules showed higher peak, final and breakdown
gelatinization temperature and a greater swelling of viscosities than did small B-type starch granules.
granules, the latter resulting in an increased peak viscosity Cross-linking has been reported to increase the shear
(Liu et al., 1997; Singh, Kaur et al., 2004; Singh, Chawla stability, viscosity and pasting temperature of waxy rice
et al., 2004). Adebowale and Lawal (2003) reported that starch, and to decrease pasting temperature of normal rice
acetylation leads to a decrease in the RVA breakdown and starch (Liu et al., 1999b). The greater strength of the cross-
setback tendency of mucuna bean starch. The substituent linked granule limits the breakdown of viscosity under
groups restrict the tendency of the starch molecules to shear, giving a higher HPV, and persistence, or resistance
realign after cooling, thus facilitating lower setback values to breakdown, of the swollen granules and on cooling,
(Betancur-Ancona et al., 1997). Similar results have been results in a higher CPV. Cross-linked waxy maize starch
reported for acetylated rice and maize starches (Gonzalez pastes are more viscous and heavy bodied, and are less
& Perez, 2002; Liu et al., 1997). The hot paste viscosity likely to breakdown with extended cooking times, in-
(HPV) and cold paste viscosity (CPV) of the acetylated creased acidity or severe agitation than their unmodified
starches have also been observed to be higher than in the counterparts (Langan, 1986). Hirsch and Kokini (2002)
case of the unmodified starch. This may be attributed to studied the relative effects of different cross-linking agents
physical interaction between more swollen but weaker on the physical properties of starches and reported that
granules (Gonzalez & Perez, 2002). Maize hybrid, growth POCl3 has the ability to impart a greater viscosity than
conditions and milling have also been reported to influence other agents. POCl3-treated granules have a more rigid
the reaction efficiency and pasting properties of acetylated external surface than STMP- and EPI- treated granules
waxy maize starches (Wilkins et al., 2003). owing to the concentration of cross-links at the surface of
The changes in viscosity of starches upon hydroxypro- the granule. Cross-linking leads to a higher increase in the
pylation has been studied using the viscoamylograph and peak viscosity of waxy starches as more amylopectin than
RVA (Hsu, Lu, & Huang, 2000; Jeong et al., 1993; Kim et amylose molecules have been reported to become cross-
al., 1992; Liu et al., 1999a, 1999b; Reddy & Seib, 1999; Shi linked (Jane et al., 1992; Liu et al., 1999b).
& BeMiller, 2000; Tsai et al., 1997). All these studies have Dynamic rheometry allows continuous measurement of
suggested an increase in viscosity after hydroxypropyla- dynamic moduli during temperature and frequency sweep
tion. Hydroxypropylation can influence interaction be- testing of a starch suspension. The dynamic storage
tween the starch chains through different possible modulus (G0 ) is a measure of the energy stored in the
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 17

material and recovered from it per cycle of sinusoidal alteration in their dynamic rheological behaviour. Cross-
deformation while the loss modulus (G00 ) is a measure of linking leads to an increase in the peak viscosity of both
the energy dissipated or lost per cycle (Ferry, 1980). The normal and waxy starches (Acquarone & Rao, 2003; Liu
ratio of the energy lost to the energy stored (G00 /G0 ) for each et al., 1999a, 1999b). In non-waxy starch, molecules inside
cycle can be defined as tan d, the loss tangent d is the phase granules are more entangled owing to the presence of
difference between the applied sinusoidal strain and the unleached-out amylose and hot cross-linked waxy starch
resulting sinusoidal stress (Singh & Singh, 2001; Singh with adequate granular rigidity can form a gel network
et al., 2003). The G0 of starch progressively increases to a from swollen granules alone (Hoover & Hadziyev, 1981;
maximum (peak G0 ) at a certain temperature and then Tsai et al. (1997). Eliasson, Finstad, and Ljunger (1988)
drops with continued heating in a dynamic rheometer. The observed a more solid like behaviour, higher G0 , on the part
initial increase in G0 can be attributed to granule swelling. of cross-linked waxy maize starch as compared to their
Granules may swell to fill the entire available volume of the native counterparts. Cross-linked waxy starch pastes had
system (Eliasson, 1986), and intergranular contact might greater resistance to cooking shear, temperature, and low
then result in the formation of a three-dimensional network pH compared with native and cross-linked partially waxy
of swollen granules (Evans & Haisman, 1979; Wong & starches (Bertolini et al., 2003; Whistler & BeMiller, 1997).
Lelievre, 1981). With further increases in temperature, G0 A fairly high degree of cross-linking results in a lower peak
decreases, indicating that the gel structure is destroyed G0 , owing to the lower degree of swelling and consequent
(Tsai et al., 1997). This destruction is due to the melting of lower degree of intergranular interaction. Starches treated
crystalline regions remaining in the swollen granules, with a relatively low concentration of POCl3 showed a
allowing the granules to deform (Eliasson, 1986). higher maximum G0 , and lower tan d maximum, than their
The rheological properties of modified starches exhibit counterpart native starches, whereas those treated with
significant differences from those of native starches when higher concentrations showed an opposite effect (Kaur
subjected to temperature sweep testing using heating and et al., 2005a). Strengthening bonding between starch chains
cooling cycles on a dynamic rheometer (Kaur et al., 2004; by cross-linking will increase the resistance of the granule
Singh, Chawla et al., 2004). The parameters such as G0 and towards swelling, leading to lower paste viscosity, which
G00 of acetylated, hydroxypropylated and cross-linked suggests that the concentration of the cross-linking reagent
starches from different sources increase to a maximum affects the structure within the granule, perhaps by
and then drop during heating, confirming that these affecting the distribution of the introduced cross-links.
starches follow the same general rheological pattern as Cross-link location has also been reported to have varied
native starches. The temperature of maximum G0 drops effects on different properties of cross-linked starches
significantly on acetylation or hydroxypropylation, while it (Muhrbeck & Eliasson, 1991; Muhrbeck & Tellier, 1991;
increases after cross-linking (Kaur et al., 2004; Kaur et al., Yoneya et al., 2003). The extent of change in the
2005a; Singh, Chawla et al., 2004). Changes may be rheological properties upon cross-linking also varies
explained on the same basis as for the changes in thermal significantly for starches from different sources depending
and pasting properties caused by modification. Acetylation on the granule size distribution. Potato cultivars with a
of maize and potato starches results in increased G0 and G00 higher percentage of large size irregular starch granules
maxima and a decreased tan d maximum. Acetylated showed a higher susceptibility towards cross-linking and
starches with higher DS exhibit a correspondingly higher exhibited greater changes in their functional properties
increase in G0 and G00 maxima during heating. These upon cross-linking (Kaur et al., 2005a). These character-
changes occur for the same reasons that acetylation causes istics could also be explained on the basis of differences in
an increase in peak pasting viscosity (see above) (Betancur- the amylose to amylopectin ratio, amylopectin branch
Ancona et al., 1997; Singh, Kaur et al., 2004). chain length, degree of crystallinity between larger and
Acetylated maize and potato starch gels showed slightly smaller granules (Noda et al., 2005; Singh & Kaur, 2004).
lower G0 and G00 as compared with their native starch gels, Dual-modification results in starch pastes with higher
during cooling cycle of heated starch pastes on the peak viscosity and greater stability than those of native
rheometer. This confirms the lowered tendency of these starch pastes (Wu & Seib, 1990). However, the effect of
modified starches to retrograde (Betancur-Ancona et al., dual-modification depends upon the preparation proce-
1997; Singh, Kaur et al., 2004). Similarly, increases in the dure. Cross-linking followed by hydroxypropylation has
peak G0 and G00 of hydroxypropylated starches during been reported to yield starches that are more shear and
heating occurs, owing to the decrease in associative forces heat stable than the native starch. This may be due to the
within the starch granules caused by the introduction of structural change in the granules after the first modification
hydroxypropyl groups; this introduction results in greater (cross-linking). Cross-linking reduces the degree of sub-
water penetration and swelling and a consequent increase sequent hydroxypropylation, but prior hydroxypropyla-
in G0 . Hydroxypropylated potato starches with a higher tion increases the degree of subsequent cross-linking.
MS and large size granules exhibit higher peak G0 and G00 Moreover, the cross-linked and then hydroxypropylated
during heating than do the native starches (Kaur et al., (XL-HP) starch exhibited lower pasting temperature and
2004). Cross-linking of starches leads to a significant viscosity than the hydroxypropylated and then cross-linked
ARTICLE IN PRESS
18 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

(HP-XL) starch samples, suggesting the locations of the produce modified starches using different modification
cross-links in the two types of starch are different. The reagents and starch sources. Some factors such as starch
cross-links in XL-HP starch were also found to be more composition, concentration and type of reagent, and
resistant to attack by enzymes and chemicals (Reddy & reaction conditions may affect the reactivity of starch
Seib, 2000). The reactivity of the modifying agent during during chemical modifications like acetylation, hydroxy-
dual modification may vary towards different starch propylation and cross-linking. The heterogeneity of the
sources. The cross-linked hydroxypropylated waxy wheat granule population within a single starch source may also
starch gave pasting curves showing higher viscosities than affect the extent of modification. The changes observed in
those of cross-linked hydroxypropylated waxy corn starch the physico-chemical, morphological, thermal and rheolo-
(Reddy & Seib, 2000). Therefore, by appropriate choice of gical properties of the starches after modification may
the native starch source (potato, maize, wheat etc.) and of provide a crucial basis for understanding the efficiency of
the type of chemical modification, concentration of the the starch modification process at industrial scale.
modifying reagent, modified starches with very useful
rheological properties can be obtained (Dubois, Picton, Acknowledgements
Muller, Audibert-Hayet, & Doublier, 2001; Kaur et al.,
2004; Singh, Kaur et al., 2004; Singh, Chawla et al., 2004). This work was supported by the Foundation for
Research Science and Technology, New Zealand (Contract
8. Nutritional and toxicological aspects # MAUX 0402). The authors are greatly indebted to Prof.
Harjinder Singh, Director, Riddet Centre for useful
Many modified starches made for food use contain only discussions.
small amounts of substituent groups and have been used as
safe food ingredients. During acetylation and hydroxypro-
pylation of food grade starches, the level of monosubstitu- References
tion groups introduced is relatively low. The maximum
Acquarone, V. M., & Rao, M. A. (2003). Influence of sucrose on the
permitted levels of substitution for starch acetates, starch rheology and granule size of cross-linked waxy maize starch
phosphates and hydroxypropylated starches are 2.5, 0.4 dispersions heated at two temperatures. Carbohydate Polymers, 51,
and 10% respectively (FAC (Food additives and con- 451–458.
taminants committee report on modified starches), 1980). Adebowale, K. O., & Lawal, O. S. (2003). Functional properties and
Similarly, cross-linked food starches containing one sub- retrogradation behaviour of native and chemically modified starch of
mucuna bean (Mucuna pruriens). Journal of the Science of Food and
stituent cross-linking group per 1000 or more anhydroglu- Agriculture, 83, 1541–1546.
cose units are considered safe (Wurzburg, 1986a, 1986b). Agboola, S. O., Akingbala, J. O., & Oguntimein, G. B. (1991).
The legislative approval for the use of novel starch Physicochemical and functional properties of low DS cassava starch
derivatives in processed food formulations is still under acetates and citrates. Starch, 43, 62–66.
Arisz, P. W., Kauw, H. J. J., & Boon, J. J. (1995). Substituent distribution
debate, but several tailor-made starch derivatives with
along the cellulose backbone on O-methylcelluloses using GC and
multiple modifications are being prepared and character- FAB-MS for monomer and oligimer analysis. Carbohydrate Research,
ized (Tharanathan, 2005). Some of the starch derivatives 271, 1–14.
are being increasingly used as fat replacers or fat Atwell, W. A., Hood, L. F., Lineback, d. R., Varriano-marston, E., &
substitutes. These derivatives are either partially or totally Zobel, H. F. (1988). The terminology and methodology associated
undigested, therefore contributes zero calories to the food with basic starch phenomena. Cereal Foods World, 33, 306–311.
Azemi, B. M. N. M., & Wootton, M. (1995). Distribution of partial
on consumption (Tharanathan, 1995). Many studies have digestion products of hydroxypropyl derivatives of maize (NM), waxy
suggested that the physiological effects of chemically maize (WM) and high amylose (HA) maize starches. Starch, 47,
modified starches are affected by the type of modification 465–469.
(Ebihara, Shiraishi, & Okuma, 1998). The chemical Bemiller, J. N. (1997). Starch modification: Challenges and prospects.
Starch, 49, 127–131.
modification of starch by acetylation improves the satiat-
Bertolini, A. C., Souza, E., Nelson, J. E., & Huber, K. C. (2003).
ing, glycemic and insulinemic properties of the meal Composition and reactivity of A- and B-type starch granules of
(Raben, Andersen, Karberg, Holst, & Astrup, 1997). normal, partial waxy and waxy wheat. Cereal Chemistry, 80, 544–549.
Phosphorylated/cross-linked starches are slowly digestible Betancur-Ancona, D., Chel-Guerrero, L., & Canizares-Hernandez, E.
and are thought to provide nutritional benefits for humans (1997). Acetylation and characterization of Canavalia ensiformis
(Sang & Seib, 2006). Also the slowly digesting modified starch. Journal of Agricultural and Food Chemistry, 45, 378–382.
Biliaderis, C. G. (1991). Non-equilibrium phase transitions of aqueous
starches could be used for the treatment of certain medical starch systems. In H. Levine, & L. Slade (Eds.), Water relationships in
modalities (e.g. glycogen storage disease and diabetes food (pp. 251–273). New York: Plenum Press.
mellitus) (Wolf, Bauer, & Fahey, 1999). Biliaderis, C. G. (1982). Physical characteristics, enzymatic digestibility,
and structure of chemically modified smooth pea and waxy maize
9. Conclusion starches. Journal of Agricultural and Food Chemistry, 30, 925–930.
Biliaderis, C. G., Page, C. M., Maurice, T. J., & Juliano, B. O. (1986).
Thermal characterization of rice starches: A polymeric approach to
Progress in understanding the high value of chemically phase transitions of granular starch. Journal of Agricultural and Food
modified starches has encouraged the starch industry to Chemistry, 34, 6–14.
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 19

Blanshard, J. M. V. (1987). In T. Galliard (Ed.), In starch: Properties and Gluck-Hirsch, J., & Kokini, J. L. (1997). Determination of the molecular
potential. New York: Wiley p. 16. weight between cross-links of waxy maize starches using the theory of
Blond, G., & Simatos, D. (1998). Optimized thermal treatments to obtain rubber elasticity. Journal of Rheology, 41, 129–139.
reproducible DSC thermograms with sucrose+dextran frozen solu- Gonzalez, Z., & Perez, E. (2002). Effect of acetylation on some properties
tions. Food Hydrocolloids, 12, 133–139. of rice starch. Starch, 54, 148–154.
Chatakanonda, P., Varavinit, S., & Chinachoti, P. (2000a). Effect of cross- Heins, D., Kulicke, W.-M., Kauper, P., & Thielking, H. (1998).
linking on thermal and microscopic transitions of rice starch. Characterization of acetyl starch by means of NMR spectroscopy
Lebbensmittel–Wissenschaft und -Technologie, 33, 276–284. and SEC/MALLS in composition with hydroxyethyl starch. Starch,
Chatakanonda, P., Varavinit, S., & Chinachoti, P. (2000b). Relationship 50, 431–437.
of gelatinization and recrystallization of cross-linked rice to glass Hennig, V. H. J., Lechert, H., & Goemann, W. (1976). Examination of
transition temperature. Cereal Chemistry, 77, 315–319. swelling mechanism of starch by pulsed NMR method. Starch, 28,
Chen, Z., Schols, H. A., & Voragen, A. J. G. (2004). Differently sized 10–17.
granules from acetylated potato and sweet potato starches differ in the Hermansson, A. M., & Svegmark, K. (1996). Developments in the
acetyl substitution pattern of their amylose populations. Carbohydrate understanding of starch functionality. Trends in Food Science and
Polymers, 56, 219–226. Technology, 7, 345–353.
Chilton, W. G., & Collison, R. (1974). Hydration and gelation of modified Hirsch, J. B., & Kokini, J. L. (2002). Understanding the mechanism of
potato starches. Food Technology, 9, 87–93. cross-linking agents (POCl3, STMP, and EPI) through swelling
Chinachoti, P., White, V. A., Lo, L., & Stengle, T. R. (1991). Application behaviour and pasting properties of cross-linked waxy maize starches.
of high-resolution carbon-13, oxygen-17, and sodium-23 nuclear Cereal Chemistry, 79, 102–107.
magnetic resonance to study the influence of water, sucrose, and Hood, L. F., & Mercier, C. (1978). Molecular structure of unmodified and
sodium chloride on starch gelatinization. Cereal Chemistry, 68, chemically modified manioc starches. Carbohydrate Research, 61,
238–244. 53–66.
Choi, S.-G., & Kerr, W. L. (2003). Effects of chemical modification of Hoover, R., & Hadziyev, D. (1981). Characterization of potato starch and
wheat starch on molecular mobility as studied by pulsed 1H NMR. its monoglyceride complex. Starch, 33, 290–300.
Lebensmittel-Wissenchaft und -Technologie, 51, 1–8. Hoover, R., Hannouz, D., & Sosulski, F. W. (1988). Effect of
Choi, S.-G., & Kerr, W. L. (2004). Swelling characteristics of native and hydroxypropylation on thermal properties, starch digestibility and
chemically modified wheat starches as a function of heating freeze-thaw stability of field pea (Pisum sativum cv Trapper) starch.
Starch, 40, 383–387.
temperature and time. Starch, 56, 181–189.
Hoover, R., & Vasanthan, T. (1994). The effect of annealing on the
Chung, H.-J., Woo, K.-S., & Lim, S.-T. (2004). Glass transition and
physico-chemical properties of wheat, oat, potato and lentil starches.
enthalpy relaxation of cross-linked corn starches. Carbohydrate
Journal of Food Biochemistry, 17, 303–325.
Polymers, 55, 9–15.
Hsu, S., Lu, S., & Huang, C. (2000). Viscoelastic changes of rice starch
Cooke, D., & Gidley, M. J. (1992). Loss of crystalline and molecular order
suspensions during gelatinization. Journal of Food Science, 65,
during starch gelatinization: Origin of the enthalpic transition.
215–220.
Carbohydrate Research, 227, 103–112.
Huang, R.-M., Chang, W.-H., Chang, Y.-H., & Lii, C.-Y. (1994). Phase
Cousidine, D. M. (1982). Foods and food production encyclopedia. NY:
transitions of rice starch and flour gels. Cereal Chemistry, 71, 202–207.
John Wiley Inc. p. 142.
Huber, K. C., & BeMiller, J. N. (2001). Location of sites of reaction within
Dubois, I., Picton, L., Muller, G., Audibert-Hayet, A., & Doublier, J. L.
starch granules. Cereal Chemistry, 78, 173–180.
(2001). Structure/Rheological properties relations of cross-linked
Hung, P. V., & Morita, N. (2005). Physicochemical properties of
potato starch suspensions. Journal of Applied Polymer Science, 81,
hydroxypropylated and cross-linked starches from A-type and B-type
2480–2489.
wheat starch granules—Review. Carbohydrate Polymers, 59, 239–246.
Ebihara, K., Shiraishi, R., & Okuma, K. (1998). Hydroxypropyl-modified I’Anson, K. J., Miles, M. J., Morris, V. J., & Ring, S. G. (1988). A study
potato starch increases fecal bile acid excretion in rats. Journal of of amylose gelation using a synchrotron X-ray source. Carbohydrate
Nutrition, 128, 848–854. Polymers, 8, 45–53.
Eliasson, A. C. (1985). Retrogradation of starch as measured by Inagaki, T., & Seib, P. A. (1992). Firming of bread crumb with cross-
differential scanning calorimetery. In R. D. Hill, & L. Munck (Eds.), linked waxy barley starch substituted for wheat starch. Cereal
New approaches to research on cereal carbohydrates (pp. 93–98). Chemistry, 69, 321–325.
Amsterdam, Netherlands: Elsevier Science Publishers. Jae, H. J., Jung, S. B., & Man, J. O. (1994). Physico-chemical properties of
Eliasson, A. C. (1986). Viscoelastic behaviour during the gelatinization of acetylated rice starches. Korean Journal of Food Science and
starch. I. Comparison of wheat, maize, potato and waxy-barley Technology, 25, 123–129.
starches. Journal of Texture Studies, 17, 253–265. Jane, J. L. (1997). Starch functionality in food processing. In P. J. Frazier,
Eliasson, A.-C., Finstad, H., & Ljunger, G. (1988). A study of starch-lipid A. M. Donald, & P. Richmond (Eds.), Starch: Structure and
interactions of some native and modified starches. Starch, 40, 95–100. functionality (pp. 26–35). Cambridge: The Royal Society of Chemistry.
Evans, I. D., & Haisman, D. R. (1979). Rheology of gelatinized starch Jane, J., Radosavljevic, M., & Seib, P. A. (1992). Location of amylose in
suspensions. Journal of Texture Studies, 10, 347–370. normal starch granules. I. Susceptibility of amylose and amylopectin to
FAC (Food additives and contaminants committee report on modified cross-linking reagents. Cereal Chemistry, 69, 406–409.
starches). (1980). Report 31. Ministry of agriculture. London, UK: Jeong, J. H., Bae, J. S., & Oh, M. J. (1993). Physico-chemical properties of
Fishries and Food. rice starches. Korean Journal of Food Science and Technology, 25,
Felton, G. E., & Schopmeyer, H. H. (1943). Thick bodied starch and 123–129.
method of making. U.S. Patent 2, 328, 537. Juszczak, L. (2003). Surface of triticale starch granules—NC-AFM
Ferry, J. D. (1980). Viscoelastic properties of polymers (3rd ed.). observations. Electronic Journal of Polish Agricultural Universities,
New York: Wiley P. 641. Food Science and Technology, 6.
Fortuna, I., Juszczak, L., & Palasinski, M. (1999). Changes in granule Kaur, L. (2004). Physico-chemical properties of potatoes in relation to
porosity on modification of starch. Zywnosc Technologia Jakosc, 5, thermal and functional properties of their starches. Ph.D dissertation,
124–130. Guru Nanak Dev University, Amritsar (India).
French, D. (1984). Organization of starch granules. In R. L. Whistler, Kaur, L., Singh, J., & Singh, N. (2005a). Effect of cross-linking on some
et al. (Eds.), Starch chemistry and technology (pp. 183–247). New York: properties of potato starches. Journal of the Science of Food and
Academic Press. Agriculture accepted.
ARTICLE IN PRESS
20 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

Kaur, L., Singh, J., & Singh, N. (2005b). Effect of glycerol monostearate and chemically modified potato starch. Food Hydrocolloids, 14,
on the physico-chemical, thermal, rheological and noodle making 395–401.
properties of corn and potato starches. Food Hydrocolloids, 19, Morikawa, K., & Nishinari, K. (2000b). Rheological and DSC studies of
839–849. gelatinization of chemically modified starch heated at various
Kaur, L., Singh, N., & Singh, J. (2004). Factors influencing the properties temperatures. Carbohydrate Polymers, 43, 241–247.
of hydroxypropylated potato starches. Carbohydrate Polymers, 55, Muhrbeck, P., & Eliasson, A.-C. (1991). Influence of the naturally
211–223. occurring phosphate esters on the crystallinity of potato starch.
Kaur, L., Singh, N., & Sodhi, N. S. (2002). Some properties of potatoes Journal of the Science of Food and Agriculture, 55, 13–18.
and their starches II. Morphological, thermal and rheological proper- Muhrbeck, P., & Tellier, C. (1991). Determinationof the phosphorylation
ties of starches. Food Chemistry, 79, 183–192. of starch from native potato varieties by 31P NMR. Starch, 43, 25–27.
Kavitha, R., & BeMiller, J. N. (1998). Characterization of hydroxypro- Nakazawa, F., Noguchi, S., Takahashi, J., & Takeda, M. (1984).
pylated potato starch. Carbohydrate Polymers, 37, 115–121. Gelatinization and retrogradation of rice starch studied by differential
Kerr, R. W., & Cleveland Jr., F. C. (1962). Thickening agent and method scanning calorimetry. Agricultural and Biological Chemistry, 48,
of making the same. U.S. Patent 3,021,222. 201–203.
Kim, H. R. (1988). Chemically modified starches and their physicochem- Nierle, W. (1969). The influence of the manufacturing conditions on the
ical properties with emphasis on hydroxypropylated starch – A properties of phosphated corn starch and their applications. Starch,
literature review. Sik Rapport, 560. 21, 13–15.
Kim, H. R., & Eliasson, A. (1993). Changes in rheological properties of Noda, T., Takigawa, S., Matsuura-Endo, C., Kim, S. J., Hashimoto, N.,
hydroxypropyl potato starch pastes during freeze-thaw treatments. II. Yamauchi, H., et al. (2005). Physicochemical properties and amylo-
Effect of molar substitution and cross-linking. Journal of Texture pectin structures of large, small, and extremely small potato starch
Studies, 24, 199–213. granules. Carbohydrate Polymers, 60, 245–251.
Kim, H. R., Hermansson, A. M., & Eriksson, C. E. (1992). Structural Nordmark, T. S., & Ziegler, G. R. (2002). Spherulitic crystallization of
characteristics of hydroxypropyl potato starch granules depending on gelatinized maize starch and its fractions. Carbohydrate Polymers, 49,
their molar substitution. Starch, 44, 111–116. 439–448.
Kim, H. R., Muhrbeck, P., & Eliasson, A.-C. (1993). Changes in Nurul, I. M., Azemi, B. M. N. M., & Manan, D. M. A. (1999).
rheological properties of hydroxypropylated potato starch pastes Rheological behaviour of sago (Metroxylon sagu) starch paste. Food
during freeze-thaw treatments. III. Effect of cooking conditions and Chemistry, 64, 501–505.
concentration of the starch paste. Journal of the Science of Food and
Okechukwu, P. E., & Rao, M. A. (1995). Influence of granule size on
Agriculture, 61, 109–116.
viscosity of corn starch suspension. Journal of Texture Studies, 26,
Koch, V. H., Bommer, H. D., & Koppers, J. (1982). Analytical
501–516.
investigations on phosphate cross-linked starches. Starch, 34, 16–21.
Paschall, E. F. (1964). Phosphorylation with inorganic phosphate salts.
Krueger, B. R., Knutson, C. A., Inglett, G. E., & Walker, C. E. (1987). A
Methods in Carbohydrate Chemistry, 4, 296–298.
differential scanning calorimetry study on the effect of annealing on
Perera, C., & Hoover, R. (1999). Influence of hydroxypropylation on
gelatinization behaviour of corn starch. Journal of Food Science, 52,
retrogradation properties of native, defatted and heat–moisture treated
715–718.
potato starches. Food Chemistry, 64, 361–375.
Langan, R. E. (1986). Food industry. In O. B. Wurzburg (Ed.), Modified
Perera, C., Hoover, R., & Martin, A. M. (1997). The effect of
starches: Properties and uses (pp. 199–212). Boca Raton, FL: CRC
hydroxypropylation on the structure and physicochemical properties
Press.
of native, defatted and heat- moisture treated potato starches. Food
Lawal, O. S. (2004). Succinyl and acetyl starch derivatives of a hybrid
Research International, 30, 235–247.
maize: Physicochemical characteristics and retrogradation properties
Phillips, D. L., Liu, H. L., Pan, D., & Corke, H. (1999). General
monitored by differential scanning calorimetry. Carbohydrate Re-
search, 339, 2673–2682. application of Raman spectroscopy for the determination of level of
Lim, S. –T., & Seib, P. A. (1993). Location of phosphate esters in a wheat acetylation in modified starches. Cereal Chemistry, 76, 439–443.
starch phosphate by 31P-nuclear magnetic resonance spectroscopy. Raben, A., Andersen, K., Karberg, M. A., Holst, J. J., & Astrup, A.
Cereal Chemistry, 70, 145–152. (1997). Acetylation of or b-cyclodextrin addition to potato starch:
Liu, H., & Lelievre, J. (1992). Transitions in frozen gelatinized-starch Beneficial effect on glucose metabolism and appetite sensations.
systems studied by differential scanning calorimetry. Carbohydrate American Journal of Clinical Nutrition, 66, 304–314.
Polymers, 19, 179–183. Reddy, I., & Seib, P. A. (1999). Paste properties of modified starches from
Liu, H., Ramsden, L., & Corke, H. (1997). Physical properties and partial waxy wheats. Cereal Chemistry, 76, 341–349.
enzymatic digestibility of acetylated ae, wx, and normal maize starch. Reddy, I., & Seib, P. A. (2000). Modified waxy wheat starch compared to
Carbohydrate Polymers, 34, 283–289. modified waxy corn starch. Journal of Cereal Science, 31, 25–39.
Liu, H., Ramsden, L., & Corke, H. (1999b). Physical properties of cross- Richardson, S., & Lo Gorton, A. C. (2001). High-performance anion-
linked and acetylated normal and waxy rice starch. Starch, 51, exchange chromatography-electrospray mass spectrometry for inves-
249–252. tigation of the substituent distribution in hydroxypropylated potato
Liu, H., Ramsden, L., & Corke, H. (1999a). Physical properties and amylopectin starch. Journal of Chromatography A, 917, 111–121.
enzymatic digestibility of hydroxypropylated ae, wx and normal maize Richardson, S., Nilsson, G. S., Bergquist, K., Gorton, L., & Mischnick, P.
starch. Carbohydrate Polymers, 40, 175–182. (2000). Characterisation of the substituent distribution in hydroxy-
Liu, Q., Weber, E., Currie, V., & Yada, R. (2003). Physicochemical propylated potato amylopectin starch. Carbohydrate Research, 328,
properties of starches during potato growth. Carbohydrate Polymers, 365–373.
51, 213–221. Richardson, S., Nilsson, G., Cohen, A., Momcilovic, D., Brinkmalm, G.,
Mischnick, P., & Kuhn, G. (1996). Model studies on methyl amyloses: & Lo Gorton (2003). Enzyme-aided investigation of the substituent
Correlation between reaction conditions and primary structure. distribution in cationic potato amylopectin starch. Analytical Chem-
Carbohydrate Research, 290, 199–207. istry, 75, 6499–6508.
Morikawa, K., & Nishinari, K. (2002). Effects of granule size and size Russel, P. L., & Oliver, G. (1989). The effect of pH and Nacl content on
distribution on rheological behaviour of chemically modified potato starch gel ageing. A study by differential scanning calorimetery and
starch. Journal of Food Science, 67, 1388–1392. rheology. Journal of Cereal Science, 10, 123–138.
Morikawa, K., & Nishinari, K. (2000a). Effects of concentration Rutenberg, M. W., & Solarek, D. (1984). Starch derivatives: Production
dependence of retrogradation behaviour of dispersions for native and uses. In R. L. Whistler, J. N. BeMiller, & E. F. Paschall (Eds.),
ARTICLE IN PRESS
J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22 21

Starch: Chemistry and technology (pp. 312–388). London: Academic Takahashi, S. I., Fujimoto, T., Miyamoto, T., & Inagaki, H.
Press. (1987). Relationship between distribution of substituents and water
Sahai, D., & Jackson, D. S. (1996). Structural and chemical properties of solubility of O-methyl cellulose. Journal of Polymer Science, 25,
native corn starch granules. Starch, 48, 249–255. 987–994.
Sang, Y., & Seib, P. A. (2006). Resistant starches from amylose mutants of Takeda, Y., & Priess, J. (1993). Structures of B90 (sugary)
corn by simultaneous heat-moisture treatment and phosphorylation. and W64A (normal) maize starches. Carbohydrate Research, 240,
Carbohydrate Polymers, 63, 167–175. 265–275.
Saroja, N., Shamala, T. R., & Tharanathan (2000). Biodegration of Tessler, M. M. (1975). Hydroxypropylated, inhibited high amylose retort
starch-g-polyacrylonitrile, a packaging material, by Bacillus cereus. starches. US Patent. 3904601.
Process Biochemistry, 36, 119–125. Tester, R. F. (1997). Starch: The polysaccharide fractions. In P. J. Frazier,
Sathe, S. K., & Salunkhe, D. K. (1981). Isolation, partial characterization P. Richmond, & A. M. Donald (Eds.), Starch, structure and
and modification of the great northern bean starch. Journal of Food functionality (pp. 163–171). Royal Society of Chemistry.
Science, 46, 617–622. Tester, R. F., & Morrison, W. R. (1990). Swelling and gelatinization of
Seow, C. C., & Thevamalar, K. (1993). Internal plasticization of granular cereal starches. Cereal Chemistry, 67, 558–563.
rice starch by hydroxypropylation: Effects on phase transitions Tharanathan, R.N. (1995). Fat Substitutes–A new approach. (p. 63),
associated with gelatinization. Starch, 45, 85–88. CFTRI Annual Conference Proceedings.
Shi, X., & BeMiller, J. N. (2000). Effect of sulfate and citrate salts on Tharanathan, R. N. (2005). Starch-value addition by modification.
derivatization of amylose and amylopectin during hydroxypropylation Critical Reviews in Food Science and Nutrition, 45, 371–384.
of corn starch. Carbohydrate Polymers, 43, 333–336. Tomasik, P., & Schilling, C. H. (2004). Chemical modification
Shiftan, D., Ravanelle, F., Alexandre Mateescu, M., & Marchessault, R. of starch. Advances in Carbohydrate Chemistry and Biochemistry, 59,
H. (2000). Change in V/B polymorphratioand T1 relaxation of 175–403.
epichlorohydrin cross-liked high amylose starch excipient. Starch, 52, Tsai, M. L., Li, C. F., & Lii, C. Y. (1997). Effects of granular
186–195. structure on the pasting behavior of starches. Cereal Chemistry, 74,
Shiotsubo, T., & Takahashi, K. (1984). Differential thermal analysis of 750–757.
potato starch gelatinization. Agricultural and Biological Chemistry, 48, Tuschhoff, J. V. (1986). Hydroxypropylated starches. In O. B. Wurzburg
9–17. (Ed.), Modified starches: Properties and uses. Boca Raton, FL: CRC
Singh, J., & Singh, N. (2001). Studies on the morphological, thermal and Press.
rheological properties of starch from some Indian potato cultivars. van der Burgt, Y. E. M., Bergsma, J., Bleeker, I. P., Mijland, P. J. H., van
Food Chemistry, 75, 67–77. der Kerk-van Hoof, A., Kamerling, J. P., et al. (1998). Distribution of
Singh, J., & Singh, N. (2003). Studies on the morphological and methyl substituents over branched and linear regions in methylated
rheological properties of granular cold water soluble corn and potato starches. Carbohydrate Research, 312, 201–208.
starches. Food Hydrocolloids, 17, 63–72. Wada, K., Takahashi, K., Shirai, K., & Kawamura, A. (1979). Differential
Singh, N., Chawla, D., & Singh, J. (2004). Influence of acetic anhydride on thermal analysis (DTA) applied to examining gelatinization of starches
physicochemical, morphological and thermal properties of corn and in foods. Journal of Food Science, 44, 1366–1368.
potato starch. Food Chemistry, 86, 601–608. Wang, Y.-J., & Wang, L. (2002). Characterization of acetylated waxy
Singh, J., Kaur, L., & Singh, N. (2004). Effect of acetylation on some maize starches prepared under catalysis by different alkali and
properties of corn and potato starches. Starch, 56, 586–601. alkaline-earth hydroxides. Starch, 54, 25–30.
Singh, N., & Kaur, L. (2004). Morphological, thermal and rheological Wattanchant, S., Muhammad, K., Hashim, D., & Rahman, R. A.
properties of potato starch fractions varying in granule size. Journal of (2003). Effect of cross-linking reagents and hydroxypropylation
the Science of Food and Agriculture, 84, 1241–1252. levels on dual-modified sago starch properties. Food Chemistry, 80,
Singh, N., Singh, J., Kaur, L., Sodhi, N. S., & Gill, B. S. (2003). 463–471.
Morphological, thermal and rheological properties of starches from Whistler, R. L., & BeMiller, J. N. (1997). Starch. In Carbohydrate
different botanical sources: A review. Food Chemistry, 81, 219–231. chemistry for food scientists (pp. 63–89). Eagan Press: St. Paul, MN.
Sitohi, M. Z., & Ramadan, M. F. (2001). Granular properties of different Wilke, O., & Mischnick, P. (1997). Determination of the substitution
starch phosphate monoesters. Starch, 53, 27–34. pattern of cationic starch ethers. Starch, 49, 453–458.
Slade, L., & Levine, H. (1987). In S. S. Stivala, V. Crescenzi, & I. C. M. Wilkins, M. R., Wang, P., Xu, L., Niu, Y., Tumbleson, M. E., & Rausch,
Dea (Eds.), Recent developments in industrial polysaccharides (pp. K. D. (2003). Variability of reaction efficiencies and pasting properties
387–430). New York: Gorton and Breach Science. of acetylated dent corn starch from commercial hybrids. Cereal
Smolka, G. E., & Alexander, R. J. (1985). Modified starch, its method of Chemistry, 80, 72–75.
manufacture and the salad dressings produced therewith. US Patent Wolf, W. B., Bauer, L. L., & Fahey, G. C., Jr. (1999). Effects of chemical
4562086. modification in vitro rate and extent of food starch digestion: An
Sodhi, N. S., & Singh, N. (2005). Characteristics of acetylated starches attempt to discover a slowly digested starch. Journal of Food and
prepared using starches separated from different rice cultivars. Journal Agricultural Chemistry, 47, 4178–4183.
of Food Engineering, 70, 117–127. Wong, R. B. K., & Lelievre, J. (1981). Viscoelastic behaviour of wheat
Stapley, J. A., & BeMiller, J. N. (2003). Hydroxypropylated starch: starch pastes. Rheologica Acta, 20, 299–307.
Granule subpopulation reactivity. Cereal Chemistry, 80, 550–552. Woo, K. S. (1999). Cross-linked, RS4 type resistant starch: preparation
Steeneken, P. A. M. (1989). Rheological properties of aqueous suspen- and properties. Ph.D. Thesis. Kansas State: University Manhattan,
sions of swollen starch granules. Carbohydrate Polymers, 11, 23–42. KS.
Steeneken, P. A. M., & Smith, E. (1991). Topochemical effects in the Woo, K. S., & Seib, P. A. (1997). Cross-linking of wheat starch and
methylation of starch. Carbohydrate Research, 209, 239–249. hydroxypropylated wheat starch in alkaline slurry with sodium
Steeneken, P. A. M., & Woortman, A. J. J. (1994). Substitution pattern in trimetaphosphate. Carbohydrate Polymers, 33, 263–271.
methylated starch as studied by enzymic degradation. Carbohydrate Wootton, M., & Manatsathit, A. (1983). The influence of molar
Research, 258, 207–221. substitution on the water binding capacity of hydroxypropyl maize
Svegmark, K., & Hermansson, A. M. (1993). Microstructure and starches. Starch, 35, 92–94.
rheological properties of composites of potato starch granules and Wu, Y., & Seib, P. A. (1990). Acetylated and hydroxypropylated distarch
amylose: A comparison of observed and predicted structure. Food phosphates from waxy barley: Paste properties and freeze–thaw
Structure, 12, 181–193. stability. Cereal Chemistry, 67, 202–208.
ARTICLE IN PRESS
22 J. Singh et al. / Food Hydrocolloids 21 (2007) 1–22

Wurzburg, O. B. (1986a). Nutritional aspects and safety of modified food Yoneya, T., Ishibashi, K., Hironaka, K., & Yamamoto, K. (2003).
starches. Nutrition Reviews, 44, 74–79. Influence of cross-linked potato starch treated with POCl3 on DSC,
Wurzburg, O. B. (1986b). Cross-linked starches. In O. B. Wurzburg (Ed.), rheological properties and granule size. Carbohydrate Polymers, 53,
Modified starches: Properties and uses (pp. 41–53). Boca Raton, FL: 447–457.
CRC Press. Yook, C., Pek, U. H., & Park, K. H. (1993). Gelatinization and
Xu, A., & Seib, P. A. (1997). Determination of the level and position of retrogradation characteristics of hydroxypropylated cross-linked rices.
substitution in hydroxypropylated starch by high- resolution 1H-NMR Journal of Food Science, 58, 405–407.
spectroscopy of alpha-limit dextrins. Journal of Cereal Science, 25, Zheng, G. H., Han, H. L., & Bhatty, R. S. (1999). Functional properties of
17–26. cross-linked and hydroxypropylation waxy hull-less barley starches.
Yeh, A. I., & Yeh, S. L. (1993). Property differences between Cereal Chemistry, 76, 182–188.
cross-linked and hydroxypropylated rice starches. Cereal Chemistry, Zobel, H. F., Young, S. N., & Rocca, L. A. (1988). Starch gelatinization.
70, 596. An X-ray diffraction study. Cereal Chemistry, 66, 443–446.

Вам также может понравиться