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Food Hydrocolloids 26 (2012) 398e404

Contents lists available at ScienceDirect

Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Progress in starch modification in the last decade


Bhupinder Kaur, Fazilah Ariffin, Rajeev Bhat, Alias A. Karim*
Food Biopolymer Research Group, Food Technology Division, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Modification of starch is carried out to enhance the positive attributes and eliminate the shortcomings of
Received 3 September 2010 the native starches. Modification of starch is an ever evolving industry with numerous possibilities to
Accepted 17 February 2011 generate novel starches which includes new functional and value added properties as a result of
modification and as demanded by the industry. In this paper, we will highlight the many current
Keywords: methods that have been discovered in starch modification which includes four broad areas that are
Modification of starch
chemical, physical, enzymatical and genetical modification.
Chemical
Ó 2011 Published by Elsevier Ltd.
Physical
Enzymatic
Genetic/biotechnology

1. Introduction production costs, increase product all through, eliminate batch


rejects, ensure product consistency and extend shelf-life whilst
Starch is made up of two fractions: amylose which is made up of clearly making starch relevant in all stages of a food product’s life-
essentially a-(1 / 4) D-glucopyranosyl units and amylopectin cycle (Murphy, 2000; Wurzburg, 1986). Modification of starch is an
which is made up of a large number of short chains linked together ongoing process as there are numerous possibilities. There is a huge
at their reducing end side by a a-(1 / 6) linkage (Biliaderis, 1998). market for the many new functional and added value properties
Starch affects texture, viscosity, gel formation, adhesion, binding, resulting from these modifications.
moisture retention, film formation and product homogeneity. It is Over the last few decades, starch has been modified by various
used mainly in soups, sauces and gravies, bakery products, dairy methods to achieve functionalities suitable for various industrial
confectionery, snacks, batters and coatings and meat products applications. Basically there are four broad based kinds of modifi-
(Davies, 1995). Non-food applications of starch include in the field cations; chemical, physical, enzymatical and genetical. A number of
of pharmaceuticals, textiles, alcohol-based fuels and adhesives. review articles (BeMiller, 1997; Jobling, 2004; Tharanathan, 2005)
New uses of starch include low-calorie substitutes, biodegradable on the subject of starch modification are available. However, within
packaging materials, thin films and thermoplastic materials with the last decade there has been intense interest among researchers
improved thermal and mechanical properties (Biliaderis, 1998). to develop novel methods of starch modification with more
Modification of starch was carried out to overcome shortcomings emphasis on enzymatic, physical and genetic modifications.
of native starches and increase the usefulness of starch for industrial Therefore this paper was written to bring forward all the new
applications. Native starches when cooked can easily retrograde and modifications that have taken place in the last decade.
there is a gelling tendency of pastes besides easily undergoing
syneresis. Therefore starch modification not only decreases retro-
gradation, gelling tendencies of pastes and gel syneresis but also 2. Chemical modification
improves paste clarity and sheen, paste and gel texture, film
formation and adhesion (BeMiller, 1997). Modification of starches Chemical modification of starch involves the polymer molecules
has brought about an evolution of new processing technologies and of the starch granule in its native form. Modification is generally
market trends. These highly functional derivatives have been achieved through derivatization such as etherification, esterifica-
tailored to create competitive advantage in a new product, improve tion and crosslinking, oxidation, cationization and grafting of
product aesthetics, simplify product proclamation, lower recipe/ starch. However, there has been dearth of new methods in chemical
modifications as this kind of modification gives rise to issues con-
cerning consumers and the environment. There has been a trend to
* Corresponding author. Tel.: þ60 4 653 2221; fax: þ60 4 657 3678. combine different kinds of chemical treatments to create new kinds
E-mail address: akarim@usm.my (A.A. Karim). of modifications. Similarly, chemical methods have been combined

0268-005X/$ e see front matter Ó 2011 Published by Elsevier Ltd.


doi:10.1016/j.foodhyd.2011.02.016
B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404 399

with physical modifications such as microwave, radiation and 2.2. Dual modifications
extrusion to produce modified starch with specific functional
properties. Overall advantages of these modifications were to Starch modification using a combination of chemical and
shorten the time of modification and increase production. physical or chemical and enzymatical methods have grown rapidly.
Some of the recent chemical modifications that have been A combined method of modification using crosslinking and phos-
studied are summarised in Table 1. phorylation on rice starch, provided modified rice starch with good
freeze-thaw stability (Deetae et al., 2008).
Crosslinking of tapioca starch with sodium trimetaphosphate in
2.1. Starch esters the presence of osmotic-pressure enhancing salts caused an
increase in the peak and final viscosity with a decrease in break-
Development of new methods to produce hydrophobic starch down. Enhancement of osmotic pressure increases the activity
has been carried out in the last decade to produce hydrophobic of the crosslinking agent (Varavinit, Paisanjit, Tukomane, &
starch as an alternative to the process patented by National Starch Pukkahuta, 2007). Starch-based hydrogels were prepared by UV-
and Chemical Corporation. induced polymerization of acryloylated starch with zwitterionic
Modification of maize and cassava starch with microwave monomer 3-dimethyl(methacryloyloxyethyl) ammonium propane
radiation was used to esterify free fatty acids with lipase as catalyst. sulfonate (DMAPS). A unique salt-tolerant swelling behaviour was
The free fatty acids were obtained from recovered coconut oil observed for this modified starch (Li & Zhang, 2007). Starch
which was hydrolysed with lipase. A DS (degree of substitution) of modified through esterification with ferulic acid giving rise to
1.1 was obtainable using microwave radiation for esterification with starch ferulate showed lower viscosity, higher water holding
hydrolysed coconut oil and DS 0.33 when palmitic acid was the acyl capacity and much less retrogradation during low temperature
donor. These modified starches have potential uses in the surface storage compared to native starch (Ou, Li, & Yang, 2001).
coating materials and biomedical materials applications (Rajan, Microwave-assisted esterification to produce starch maleate
Prasad, & Abraham, 2006; Rajan, Sudha, & Abraham, 2008). using the dry method had a reaction efficiency of up to 98% and
Hydrophobically modified starch was prepared by enzyme-cata- a reaction time of under 5 min. This is thought to be an efficient
lyzed reaction of starch and alkenyl ketene dimer (AKD), which is method in esterifying starch (Xing, Zhang, Ju, & Yang, 2006). The
a fatty acid residue. Enzymes used were lipases from Pseudomonas high efficiency in producing succinylated cassava starch with
sp. and Pseudomonas fluorescens. This modified starch can be used microwave assistance was also observed by Jyothi, Rajasekharan,
as an ingredient in applications where high solution viscosity and Moorthy, and Sreekumar (2005). This is a good method to
hydrophobic interactions are required for example as paint thick- decrease the use of chemicals to enhance production.
ener, construction material, emulsion stabiliser and emulsifier in Microwave and ultrasound irradiation was used for the esteri-
cosmetics (Qiao, Gu, & Cheng, 2006). fication of carboxymethyl cold-water-soluble potato starch with
Selective esterification of starch nanoparticles was done using octenylsuccinic anhydride. They were positively able to shorten the
Candida antarctica Lipase B (CAL-B) in its immobilized and free esterification time from a few hours to a few minutes. The deriva-
forms as catalyst. Acylation reactions were made accessible for the tives displayed excellent emulsifying and surfactant performance
starch nanoparticles by formation of Aerosol-OT (AOT, bis(2-eth- 
properties (Cí zová, Sroková, Sasinková, Malovíková, & Ebringerová,
ylhexyl) sodium sulfosuccinate) to stabilise the microemulsions. 2008).
Acylations of 3-caprolactone (CL), vinyl stearate, and maleic anhy- Karim, Sufha, and Zaidul (2008) prepared modified corn and
dride were obtained when AOT-coated dispersions of starch mung bean starch using a dual modification process, whereby the
nanoparticles in toluene were exposed to physically immobilized native starch was treated to partial enzymatic hydrolysis using
CAL-B (Novozym 435). The modified starch nanoparticles were a mixture of fungal a-amylase and glucoamylase followed by
found to retain their nanodimensions upon the removal of the hydroxypropylation with propylene oxide. The resultant modified
surfactant when dispersed in DMSO or water (Chakraborty, Sahoo, starch proved to have significantly different functional properties
Teraoka, Miller, & Gross, 2005). compared to hydroxypropyl starch prepared with untreated native
starch.

2.3. Other methods


Table 1
Recent chemical modification of starch.
The process of ozonation, oxidises starch and is a powerful
Chemical modification References
oxidant as it has an extra oxygen atom. During the ozonation
Microwave radiation with lipase as catalyst Rajan et al. (2006, 2008) process the carboxyl and carbonyl contents were found to increase
Hydrophobic reaction of starch and Qiao et al. (2006)
with the time of exposure to ozone. There was a difference in the
alkenyl ketene dimer
Esterification of starch nanoparticles Chakraborty et al. (2005) extent of starch oxidation among starches from different sources
with lipase as a catalyst (Chan, Bhat, & Karim, 2009). Ozonated starches were found useful
Dual modified crosslink-phosphorylated Deetae et al. (2008) as thickening agents whereas those treated in the presence of
Crosslinking coupled with osmotic Varavinit et al. (2007) amino acids were suitable alternatives to highly chemically oxi-
pressure
Starch-based hydrogels prepared by UV Li and Zhang (2007)
dised starch (An & King, 2009). Ozone is a clean and powerful
photopolymerization oxidant and leaves no residues behind unlike hypochlorite oxida-
Starch esterified with ferulic acid Ou et al. (2001) tion process where large amount of salts are produced (Kesselmans
Microwave-assisted synthesis of starch Xing et al. (2006); & Bleeker, 1997).
maleate and starch succinates Jyothi et al. (2005)
Microwave and ultrasound irradiation 
Cí zová et al. (2008)
Hydroxypropylation and enzymatic Karim et al. (2008) 3. Physical modification
hydrolysis
Ozone-oxidised starch Kesselmans and Bleeker (1997); Physical modification can be safely used as a modification
An and King (2009); process in food products as it does not involve any chemical pres-
Chan et al. (2009)
ence. There has been a wave of new methods in the physical
400 B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404

modification of starches. Some of the new physical modifications 100 C or greater for a period of time enough to inhibit starch. An
that have been investigated in the last decade are given in Table 2. alkaline condition enhanced the effect of heating. Pastes formed
“Osmotic-pressure treatment” (OPT) was carried out in the from theses starches had increased resistance to viscosity break-
presence of high salt solutions (Pukkahuta, Shobsngob, and down and a non-cohesive texture (Chiu, Schiermeyer, Thomas, &
Varavinit, 2007). Starch solution was suspended in sodium Shah, 1998). Thermal inhibition with ionic gums had sodium algi-
sulphate to obtain a uniform starch suspension and heat distribu- nate, CMC and xanthan behaving as crosslinking agents and were
tion. The potato-starch treated changed from a B to a A type after able to form graft copolymers through ester formation (Lim, Han,
treatment with the gelatinization temperatures increasing signifi- Lim, & BeMiller, 2002).
cantly. A uniform heat distribution is provided for using this Superheated starches were prepared by heating a starch solu-
method as compared to heat-moisture treatment and modified tion to a temperature between 180 and 220  C to produce
starch is able to be produced in a large scale. spreadable particle gels with spherulite morphology and cream-
Deep freezing and thawing of moistened starch increased the like texture upon cooling. Dry superheated starches mixed with
crystallinity of the granules (Szymon  ska, Krok, & Tomasik, 2000) cold water are able to give immediate gel-like texture (Steeneken &
but multiple deep freezing and thawing (Szymon  ska, Krok, Woortman, 2009).
Komorowska-Czepirska, & Re˛ bilas, 2003) caused an irreversible Extrusion heating (EH) and fluidized bed heating (FBH) was
disruption of the crystalline order. Iterated syneresis was similar to used on amaranth starch-rich fraction. EH caused a high degree of
multiple deep freezing and thawing. The freezing and thawing was granule disruption and almost complete loss of crystallinity
repeated until the moisture content in the solid phase was less than whereas FBH saw some loss of crystallinity but granule integrity
20%. All modified starches showed a change towards B-type X-ray was preserved (González, Carrara, Tosi, Añón, & Pilosof, 2007).
diffraction pattern indicating a disruption of the crystalline prop-

erty (Lewandowicz & Soral-Smietana, 2004). Again as there are no 4. Enzymatic modification
chemicals involved then there is no concern for the effect on the
environment and safety issues to be addressed. Enzymatic modification has mainly used hydrolyzing enzymes
The instantaneous controlled pressure drop, DIC, process in its modification and one of its products is syrup be it glucose
involves a short pressurisation obtained as a result of injection of syrup or high fructose corn syrup. With research, there are more
saturated steam at a fixed pressure and predetermined time before enzymes being identified for use in modification of starch.
it drops towards vacuum (Maache-Rezzoug et al., 2009; Zarguili, The use of amylomaltases (EC 2.4.1.25) to modify starches is
Maache-Rezzoug, Loisel, & Doublier, 2006). Gelatinization transi- expected to find applications in the food industry as a plant and
tion temperatures and enzymatic hydrolysis increased whereas chemical free alternative to gelatine (Euverink & Binnema, 1998).
gelatinization enthalpy decreased after treatment. Starch treated with a-1,4ea-1,4 glucosyl transferases also known as
The use of friction, collision, impingement, shear and other amylomaltases is used in forming a thermoreversible gel. This is
mechanical actions to alter the crystalline structures and properties done by breaking an a-1,4 bond between two glucose units to
of the starch granule refers to mechanical activation or micron- subsequently make a novel a-1,4 bond. These enzymes are found in
ization. This process causes large particles to crush to form smaller the Eukarya, bacteria and archaea representatives. The enzyme
particles whereas the tiny particles agglomerate and form large used has to be free of enzymatic components that can cause
particles. The gelatinization temperature and viscosity is decreased undesirable damage to the starch molecule. The starches that can
for the treated sample (Che, Li, Wang, Chen, & Mao, 2007; Huang, be used for modification should contain amylose such as potato,
Lu, Li, & Tong, 2007). maize, wheat, rice and tapioca starch. The average molecular
A non-thermal food preservation method, pulsed electric field weight, reducing power and branching percentage remain
(PEF) technology has been used to study the effect of the treatment unchanged from the starting material. It is believed a mutual re-
on starch. Re-arrangement and destruction of starch molecules arrangement between the starch molecules has occurred without
were observed as well as a decrease in gelatinization properties, an increase in oxidation-sensitive places or parts having reducing
viscosity and crystallinity (Han, Zeng, Zhang, & Yu, 2009). The activity. Little or no retrogradation occurs. This modified starch can
solubility, gel consistency and clarity of starches decreased with be used in foodstuffs, cosmetics, pharmaceutics, detergents, adhe-
increase of exposure time to corona electrical discharges (Nemtanu sives and drilling fluids. It is also a good source of plant-derived
& Minea, 2006). substitute for gelatine except that it forms a turbid gel whereas
Thermal inhibition of starch is done by dehydrating starch until gelatine gels are transparent (Euverink & Binnema, 1998; Kaper, van
it is anhydrous (<1% moisture) and treating it to a temperature of der Maarel, Euverink, & Dijkhuizen, 2003; van der Maarel et al.,
2005). Similar work was also done by Oh, Choi, Lee, Kim, and
Moon (2008) on granular corn starch. The thermodynamics of
Table 2
this gelatine-like starch-based system was studied by Hansen,
Recent methods of physical modification of starches.
Blennow, Pedersen, and Engelsen (2009). An amylomaltase-modi-
Physical modification References fied potato starch has been used as a fat replacer and enhancer of
Osmotic-pressure treatment Pukkahuta et al. (2007) creaminess in yoghurt (Alting et al., 2009). In the study by Hansen,
Deep freezing Szymon  ska et al. (2000)
Blennow, Pedersen, Nørgaard, and Engelsen (2008) on gel texture
Multiple deep freezing and thawing Szymon  ska et al. (2003)
Instantaneous controlled pressure Zarguili et al. (2006);
formed in the modification of potato, high-amylose potato, maize
drop (DIC) process Maache-Rezzoug et al. (2009) and pea starch with amylomaltase (AM) isolated from the hyper-
Mechanical activation-with stirring Huang et al. (2007) thermophilic bacterium Thermus thermophilus, there was an
ball mill improvement in gel texture compared to the parent starch. All the
Micronization in vacuum ball mill Che et al. (2007)
modified starches showed broadened amylopectin chain length
Pulsed electric fields treatment Han et al. (2009)
Corona electrical discharges Nemtanu and Minea (2006) profiles. Fig. 1 shows a schematic representation of the reaction
Thermally inhibited treatment Chiu et al. (1998); Lim et al. (2002) taking place.
(dry heating) A putative glycogen branching enzyme (GBE) was cloned and
Iterated syneresis 
Lewandowicz and Soral-Smietana (2004) expressed from Streptococcus mutans, thereafter known as SmGBE.
Superheated starch Steeneken and Woortman (2009)
This enzyme differs from the first bacterial GBE group in that it is
B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404 401

Fig. 1. Schematic representation of the enzymatic conversion of potato-starch-derived amylose and amylopectin into ATS by amylomaltase. Reprinted from Alting et al. (2009),
Copyright (2009) with permission from Elsevier.

encoded with four highly conserved regions of the a-1,4-GBE family a maximum yield of 3.4 and 100% retention inside waxy maize
and does not have the extra N-terminal stretch. SmGBE is able to starch granules. Cyclomaltodextrins are also formed in situ, with
modify starches and produce shorter branches with more branched the retention of CDs in the granule and this leads to the production
structure compared to native starch. Starch retrogradation is also of a new material that has properties of starch granules and
retarded with enzyme reaction due to low temperature storage cyclomaltodextrins. Formation of complexes of organic molecules
(Kim, Ryu, Bae, Huong, & Lee, 2008). Cyclomaltodextrinase (CDase; with cyclomaltodextrins provides stabilisation of light, heat and
EC 3.2.1.54), isolated from alkalophilic Bacillus sp. I-5 (CDase I-5) oxygen-sensitive materials in the starch granules and also a mech-
was used to modify rice starch to produce low-amylose starch anism for their slow release besides providing special tastes, odors
products. The amylose content was found to have decreased and flavours to the starch granules.
significantly from 28.5 to 9% while there was no significant change
in the side chain length distribution of the amylopectin. Storage of 5. Genetic/biotechnology modification
the modified rice starch at 4  C for 7 days, showed that the retro-
gradation rate had significantly retarded compared to the control The advancement of genetic engineering technologies has
sample (Auh et al., 2006). made the genetic modification of starch in planta possible by tar-
As GI (glycemic index) in foods is related to diabetes, predia- geting the enzymes of the starch biosynthetic pathway. This
betes, cardiovascular disease and obesity (Ludwig, 2002) it is transgene technology has a potential to produce novel starches
becoming important to have more low GI foods to control these which can reduce or eliminate the use of environmentally
diseases. One of the methods is to produce foods containing starch hazardous post-harvest chemical and enzymatic modification
that is digested slowly. There was a significant reduction of rapidly (Davis, Supatcharee, Khandelwal, & Chibbar, 2003). The activity of
digested starch by 14.5%, 29.0%, 19.8%, and 31.0% for maize starch these enzymes affects the reactivity, functionality, applicability in
modified with b-amylase, b-amylase and transglucosidase, malto- food processing and food applications of these modified starches
genic a-amylase, and maltogenic a-amylase and transglucosidase, therein enabling a market for “niche” products. Genetic modifica-
respectively. An increase in the starch branch density and crystal- tion can be carried out by the traditional plant-breeding techniques
line structure in the modified starches was thought to contribute to or through biotechnology (Johnson, Baumel, Hardy, & White, 1999).
the slow digestion (Ao et al., 2007). The genetic modification that is carried out uses the methods as
In the reaction of glucoamylase (1,4-a-D-glucan glucohydrolase, shown in Fig. 2.Some of the modification of starches that has been
EC 3.2.1.3) with starch, 8e32% of the D-glucose remains inside the done genetically are shown in Table 3. The data in the table has
granule during the early stages of the reaction, but over 80% of the been adapted from Jobling (2004).
D-glucose is found in the reaction supernatant outside the granule Repression of GWD (starch phosphorylating enzyme R1) was
during the later stages of the reaction. Kim and Robyt (1999) used in the alteration of specific structural motifs of potato starch
reacted glucoamylase with waxy maize, maize and amylomaize-7 (Viksø-Nielsen, Blennow, Jørgensen, Jensen, & Møller, 2001). An
starches to retain 100% of the D-glucose produced inside the Escherichia coli glg B encoding a glycogen branching enzyme from
granule by controlling the length of time of the reaction and the a patatin promoter onto potato lines was done by Wischmann et al.
type of starch. The amount of water used in the reaction was also (2005). Starch containing amylopectin molecules with a relatively
decreased to an amount equal to the weight of starch which gave higher number of amylopectin branches and higher amount of
a solid-granule reaction system. The amount of water used was short amylopectin chains with lower content of phosphate was
enough for hydrolysis to take place, but the solid granules did not obtained. This starch also gave rise to hard and adhesive gels.
allow diffusion of the D-glucose. The starch granules containing AGPase (ADP-glucose pyrophosphorylase) was used as a catalyst to
D-glucose, rapidly diffuse out the D-glucose when suspended in increase the total cassava root biomass by 2.6 fold (Ihemere, Arias-
water. Besides this the same authors (Kim & Robyt, 2000) worked Garzon, Lawrence, & Sayre, 2006). When a full length cDNAs
with cyclomaltodextrin glucanosyltransferase (CGTase, EC 2.4.1.19) encoding a second starch branching enzyme (SBE A) isoform was
in the presence of isoamylase to produce cyclodextrins (CDs) with isolated and an antisense SBE A RNA was generated on transgenic
402 B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404

Fig. 2. Modification of starch and their end-uses. The makeup, modification and levels of starch can be manipulated via genetic and biochemical means. The resulting changes can
alter the properties and applications of starch. Note: the text shades used in the modification portion correspond to those found under end-uses. An arrow pointing upwards
indicates an increase in the level of an enzyme; an arrow pointing downwards indicates a decrease in the level of an enzyme; a plus symbol indicates the addition of reactive groups.
Abbreviations: DBE, debranching enzyme; GBSSI, granular-bound starch synthase I; SBE, starch branching enzyme; SBE A, class A SBE; SS, starch synthase. Reprinted from Slattery,
Kavakli, and Okita (2000), Copyright (2000) with permission from Elsevier.

potato plants, a complete reduction in SBE A was observed. The levels of phosphorous was observed too (Jobling et al., 1999).
composition and structure of the potato starch was completely Similar observation had been detected by Safford et al. (1998).
altered in that the average chain length of amylopectin was greater. Potato starches of low SBE values showed an increase of up to 5  C
This caused an increase in the apparent amylose content and higher in DSC peak temperature and viscosity onset temperature. This was

Table 3
Genetic modification of starch.

Modified Starch Enzyme Properties Reference


Amylose-free Maize-commercial, barley, Crossing partial waxy - Gelatinises easily, Sharma, Sissons, Rathjen, and
waxy sorghum, amaranth, wheat, mutants, - Clear paste, Jenner (2002); Ishada, Miura, Noda,
sweet potato, potato Inhibition of GBSS - Stabiliser, thickener, and Yamauchi (2003);
- Emulsifier, Kimura et al. (2001); Noda et al. (2002);
- Improved freeze-thaw Zheng and Sosulski (1998);
stability Jobling, Westcott, Tayal, Jeffcoat,
Potato Inhibition of GBSS, and Schwall (2002); Fulton et al. (2002);
SS II, SS III Jobling (2004)

High-amylose Maize-commercial Mutation of SBE IIb, - High gelling strength Bird, Brown, and Topping (2000);
starch (50, 70, 90% amylose), Inhibition of SBE I - Film forming ability Jobling et al. (1999, 2003);
cereals, potato, & SBE II for - Resistant starch Schwall et al. (2000); Morell et al. (2003)
amylose 60% and - Adhesive
greater,
Inhibition of SBE II for still - Starch does not swell when
higher amylose content, heated to 100 C
SS IIa is missing - Increased short chains
in amylopectin
Barley sex6 mutant - Lower gelatinization
temperature

Altered amylopectin Potato SS II and SS III isoforms - Low gelatinization Edward et al. (1999); Umemoto, Yano,
structure Rice inhibited temperatures (<50  C) Satoh, Shomura, and Nakamura (2002)

Phosphate content Potato Inhibition of GWD - Performance of potato starch Lorbeth, Ritte, Willmitzer,
does not correlate directly with and Kossmann (1998);
phosphate level Ritte et al. (2002);
Blennow, Hansen, et al. (2003);
Blennow, Bay-Smidt,
Leonhardt, Bandsholm, and Madsen (2003)

Granule size Cereal Isoamylase - Effects granule number Burton et al. (2002); Dinges, Colleoni,
and number and form James, and Myers (2003)

Abbreviations: GBSS-granular-bound starch synthase; SS-starch synthase; SBE-starch branching enzyme; GWD- a-glucan water dikinase.
B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404 403

speculated to be due to an alteration in amylopectin branch Bird, A. R., Brown, I. L., & Topping, D. L. (2000). Starches, resistant starches, the
gut microflora and human health. Current Issues in Intestinal Microbiology, 1,
patterns.
25e37.
Three mutagenised grains of the diploid oat, Avena strigosa Blennow, A., Bay-Smidt, A., Leonhardt, P., Bandsholm, O., & Madsen, M. H. (2003).
Schreb, was identified: mutants lam-1, lam-2 and sga-1. lam-1 and Starch paste stickiness is a relevant native starch selection criterion for wet-end
lam-2 lacked in GBSS activity and amylose component therefore paper manufacturing. Starch/Stärke, 55, 381e389.
Blennow, A., Hansen, M., Schulz, A., Jørgensen, J., Donald, A. M., & Sanderson, J.
representing mutations of the waxy type. The nature of mutation in (2003). The molecular deposition of transgenically modified starch in the starch
sga-1 is yet to be discovered (Verhoeven, Fahy, Leggett, Moates, & granule as imaged by functional microscopy. Journal of Structural Biology, 143,
Denyer, 2004). 229e241.
Burton, R. A., Jenner, H., Carrangis, L., Fahy, B., Fincher, G. B., Hylton, C., et al. (2002).
Starch granule initiation and growth are altered in barley mutants that lack
6. Conclusions and future outlook isoamylase activity. Plant Journal, 31, 97e112.
Chakraborty, S., Sahoo, B., Teraoka, I., Miller, L. M., & Gross, R. A. (2005). Enzyme-
catalyzed regioselective modification of starch nanoparticles. Macromolecules,
The challenges involved in starch modification involve modifi- 38, 61e68.
cation of starch that is safe to the consumer and kind to the envi- Chan, H. T., Bhat, R., & Karim, A. A. (2009). Physicochemical and functional prop-
ronment. The physical, enzymatic and genetic modification of erties of ozone-oxidized starch. Journal of Agricultural and Food Chemistry, 57,
5965e5970.
starch has been most promising with a large number of newer Che, L.-M., Li, D., Wang, L.-J., Chen, X. D., & Mao, Z.-H. (2007). Microniation and
methods in starch modification. Osmotic-pressure treatment, hydrophobic modification of cassava starch. International Journal of Food Prop-
multiple deep freezing and thawing as well as ozone-oxidised erties, 10, 527e536.
Chiu, C.-W., Schiermeyer, E., Thomas, D. J., & Shah, M. B. (1998). Thermally inhibited
starch modification are capable of producing a variety of starches starches and flours and process for their production. U.S. Patent 5,725,676.
with numerous properties that will be applicable in the food 
Cízová, A., Sroková, I., Sasinková, V., Malovíková, A., & Ebringerová, A. (2008).
industry. Carboxymethyl starch octenylsuccinate: microwave- and ultrasound-assisted
synthesis and properties. Starch/Stärke, 60, 389e397.
The use of amylomaltases in producing thermoreversible gel is Davies, L. (1995). Starch-composition, modifications, applications and nutritional
a breakthrough in having an alternative product for gelatine and value in foodstuffs. Food Technology Europe, 6/7, 44e52.
products using gelatine. However, certain issues need to be Davis, J. P., Supatcharee, N., Khandelwal, R. L., & Chibbar, R. N. (2003). Synthesis of
novel starches in planta: opportunities and challenges. Starch/Stärke, 55,
considered before amylomaltase-modified starch can find appli-
107e120.
cation as a gelatin alternative. As pointed out by Hansen et al. Deetae, P., Shobsngob, S., Varanyanond, W., Chinachoti, P., Naivikul, O., &
(2008), the textural profile of starch gels was very different from Varavinit, S. (2008). Preparation, pasting properties and freeze-thaw stability of
dual modified crosslink-phosphorylated rice starch. Carbohydrate Polymers, 73,
gelatin. The elasticity of gelatin gels was much higher, making them
351e358.
firmer than starch gels. In addition, amylomaltase-modified Dinges, J. R., Colleoni, C., James, M. G., & Myers, A. M. (2003). Mutational analysis of
starches formed opaque gels, while gelatin gels were fully trans- the pullulanase-type debranching enzyme of maize indicates multiple func-
parent. Therefore, Kaper et al. (2005) suggested that amylomaltase- tions in starch metabolism. The Plant Cell, 15, 666e680.
Edward, A., Fulton, D. C., Hylton, C. M., Jobling, S. A., Gidley, M., Rossner, U., et al.
modified starch should not be regarded as a replacement for gelatin (1999). A combined reduction in activity of starch synthases II and III of potato
but rather as an extension of the variety of available gelling prod- has novel effects on the starch of tubers. Plant Journal, 17, 251e261.
ucts with their own specific applications. Products using dual or Euverink, G. J. W., & Binnema, D. J. (1998). Use of modified starch as an agent for
forming a thermoreversible gel. European Patent WO 98/15347.
more modification processes are also being looked at for forming Fulton, D. C., Edwards, A., Pilling, E., Robinson, H. L., Fahy, B., Seale, R., et al. (2002).
new novel products with conventional and non-conventional Role of granule-bound starch synthase in determination of amylopectin struc-
properties. Genetic modification has come a long way and now ture and starch granule morphology in potato. Journal of Biological Chemistry,
277, 10834e10841.
there is a greater understanding of biosynthesis pathway of starch González, R., Carrara, C., Tosi, E., Añón, M. C., & Pilosof, A. (2007). Amaranth starch-
making it easier to be manipulated. rich fraction properties modified by extrusion and fluidized bed heating. Leb-
Starch modification has come a long way since it was first ensmittel-Wissenschaft und-Technologie, 40, 136e143.
Han, Z., Zeng, X., Zhang, B., & Yu, S. (2009). Effect of pulsed electric fields (PEF)
carried out in the 1800s. As with any modification, the possibilities
treatment on the properties of corn starch. Journal of Food Engineering, 93,
are numerous with starch modification but there should be an eye 318e323.
on the safety and health measurements taken for consumers and Hansen, M. R., Blennow, A., Pedersen, S., & Engelsen, S. B. (2009). Enzyme modifi-
cation of starch with amylomaltase result in increasing gel melting point.
the environment.
Carbohydrate Polymers, 78, 72e79.
Hansen, M. R., Blennow, A., Pedersen, S., Nørgaard, L., & Engelsen, S. B. (2008). Gel
Acknowledgments texture and chain structure of amylomaltase-modified starches compared to
gelatine. Food Hydrocolloids, 22, 1551e1566.
Huang, Z.-Q., Lu, J.-P., Li, X.-H., & Tong, Z. F. (2007). Effect of mechanical activation
Dr. Bhupinder Kaur is the recipient of USM Post-Doctoral on physico-chemical properties and structure of cassava starch. Carbohydrate
Fellowship in Research. Polymers, 68, 128e135.
Ihemere, U., Arias-Garzon, D., Lawrence, S., & Sayre, R. (2006). Genetic modification
of cassava for enhanced starch modification. Plant Biotechnology Journal, 4,
References 453e465.
Ishada, N., Miura, H., Noda, T., & Yamauchi, H. (2003). Physical properties of white
Alting, A. C., van de Velde, F., Kanning, M. W., Burgering, M., Mulleners, L., Sein, A., salted noodles from near-isogenic wheat lines with different wax protein-
et al. (2009). Improved creaminess of low-fat yoghurt: the impact of amylo- deficiency. Starch/Stärke, 55, 390e396.
maltase-treated starch domains. Food Hydrocolloids, 23, 980e987. Jobling, S. (2004). Improving starch for food and industrial applications. Current
An, H. J., & King, J. M. (2009). Using ozonation and amino acids to change pasting Opinion in Plant Biology, 7, 210e218.
properties of rice starch. Journal of Food Science, 74, 278e283. Jobling, S. A., Jarman, C., Teh, M. M., Holmberg, N., Blake, C., & Verhoeyen, M. E.
Ao, Z., Simsek, S., Zhang, G., Venkatachalam, M., Reuhs, B. L., & Hamaker, B. R. (2003). Immunomodulation of enzyme function in plants by single-domain
(2007). Starch with a slow digestion property produced by altering its chain antibody fragments. Nature Biotechnology, 21, 77e80.
length, branch density, and crystalline structure. Journal of Agricultural and Food Jobling, S. A., Schwall, G. P., Westcott, R. J., Sidebottom, C. M., Debet, M., Gidley, M. J.,
Chemistry, 55, 4540e4547. et al. (1999). A minor form of starch branching enzyme in potato (Solanum
Auh, J.-H., Chae, H. Y., Kim, Y.-R., Shim, K.-H., Yoo, S.-H., & Park, K.-H. (2006). tuberosum L.) tubers has a major effect on starch structure: cloning and char-
Modification of rice starch by selective degradation of amylose using alka- acterisation of multiple forms of SBE A. The Plant Journal, 18, 163e171.
lophilic Bacillus cyclomaltodextrinase. Journal of Agricultural and Food Chemistry, Jobling, S. A., Westcott, R. J., Tayal, A., Jeffcoat, R., & Schwall, G. P. (2002). Production
54, 2314e2319. of freeze-thaw stable potato starch by antisense inhibition of three starch
BeMiller, J. N. (1997). Starch modification: challenges and prospects. Starch/Stärke, synthase genes. Nature Biotechnology, 20, 295e299.
49, 127e131. Johnson, L. A., Baumel, C. P., Hardy, C. L., & White, P. J. (1999). Identifying valuable
Biliaderis, C. G. (1998). Structures and phase transitions of starch polymers. In corn quality traits for starch production. A project of the Iowa Grain Quality
R. H. Walter (Ed.), Polysaccharide association structures in food (pp. 57e168). Initiative Traits Task Team. Ames, IA: Center for Crops Utilization Research, Iowa
New York: Marcel-Dekker, Inc. Agriculture & Home Economics Experiment Station, Iowa State University.
404 B. Kaur et al. / Food Hydrocolloids 26 (2012) 398e404

Jyothi, A. N., Rajasekharan, K. N., Moorthy, S. N., & Sreekumar, J. (2005). Microwave- Ou, S., Li, A., & Yang, A. (2001). A study on synthesis of starch ferulate and its
assisted synthesis and characterization of succinate derivatives of cassava biological properties. Food Chemistry, 74, 91e95.
(Manihot esculenta Crantz) starch. Starch/Stärke, 57, 556e563. Pukkahuta, C., Shobsngob, S., & Varavinit, S. (2007). Effect of osmotic pressure on
Kaper, T., van der Maarel, M. J. E. C., Euverink, G. J. W., & Dijkhuizen, L. (2003). starch: new method of physical modification of starch. Starch/Stärke, 58, 78e90.
Exploring and exploiting starch-modifying amylomaltases from thermophiles. Qiao, L., Gu, Q.-M., & Cheng, H. N. (2006). Enzyme-catalyzed synthesis of hydro-
Biochemical Society Transactions, 32, 279e282. phobically modified starch. Carbohydrate Polymers, 66, 135e140.
Kaper, T., Talik, B., Ettema, T. J., Bos, H., van der Maarel, M. J. E. C., & Dijkhuizen, L. Rajan, A., Prasad, V. S., & Abraham, T. E. (2006). Enzymatic esterification of starch
(2005). Amylomaltase of Pyrobaculum aerophilum IM2 produces thermorever- using recovered coconut oil. International Journal of Biological Macromolecules,
sible starch gels. Applied and Environmental Microbiology, 71, 5098e5106. 39, 265e272.
Karim, A. A., Sufha, E. H., & Zaidul, I. S. M. (2008). Dual modification of starch via Rajan, A., Sudha, J. D., & Abraham, T. E. (2008). Enzymatic modification of cassava
partial enzymatic hydrolysis in the granular state and subsequent hydrox- starch by fungal lipase. Industrial Corps and Products, 27, 50e59.
ypropylation. Journal of Agricultural and Food Chemistry, 56, 10901e10907. Ritte, G., Lloyd, J. R., Eckermann, N., Rottmann, A., Kossmann, J., & Steup, M. (2002).
Kesselmans, R. P. W., & Bleeker, I. P. (1997). Method for oxidizing dry starch using The starch related R1 protein is an alpha-glucan, water dikinase. Proceedings of
ozone. World Intellectual Property Organization. WO/1997/032902. the National Academy of Sciences of the United States of America, 99, 7166e7171.
Kim, E.-J., Ryu, S.-I., Bae, H.-A., Huong, N. T., & Lee, S.-B. (2008). Biochemical char- Safford, R., Jobling, S. A., Sidebottom, C. M., Westcott, R. J., Cooke, D., Tober, K. J., et al.
acterisation of a glycogen branching enzyme from Streptococcus mutans: (1998). Consequences of antisense RNA inhibition of starch branching enzyme
enzymatic modification of starch. Food Chemistry, 110, 979e984. activity on properties of potato starch. Carbohydrate Polymers, 35, 155e168.
Kim, Y.-K., & Robyt, J. F. (1999). Enzyme modification of starch granules: in situ Schwall, G. P., Safford, R., Westcott, R. J., Jeffcoat, R., Tayal, A., Shi, Y. C., et al. (2000).
reaction of glucoamylase to give complete retention of D-glucose inside the Production of very-high-amylose potato starch by inhibition of SBE A and B.
granule. Carbohydrate Research, 318, 129e134. Nature Biotechnology, 18, 551e554.
Kim, Y.-K., & Robyt, J. F. (2000). Enzyme modification of starch granules: formation Sharma, R., Sissons, M. J., Rathjen, A. J., & Jenner, C. F. (2002). The null-4A allele at
and retention of cyclomaltodextrins inside starch granules by reaction of the waxy locus in durum wheat affects pasta cooking quality. Journal of Cereal
cyclomaltodextrin glucanosyltransferase with solid granules. Carbohydrate Science, 35, 287e297.
Research, 328, 509e515. Slattery, C. J., Kavakli, I. H., & Okita, T. W. (2000). Engineering starch for increased
Kimura, T., Otani, M., Noda, T., Ideta, O., Shimada, T., & Saito, A. (2001). Absence of quantity and quality. Trends in Plant Science, 5, 291e298.
amylose in sweet potato (Ipomea batatas (L.) Lam.) following the introduction of Steeneken, P. A. M., & Woortman, A. J. J. (2009). Superheated starch: a novel
granule-bound starch synthase I cDNA. Plant Cell Reports, 20, 663e666. approach towards spreadable particle gels. Food Hydrocolloids, 23, 394e405.

Lewandowicz, G., & Soral-Smietana, M. (2004). Starch modification by iterated Szymon  ska, J., Krok, F., Komorowska-Czepirska, E., & Re˛ bilas, K. (2003). Modification
syneresis. Carbohydrate Polymers, 56, 403e413. of granular potato starch by multiple deep-freezing and thawing. Carbohydrate
Li, J.-M., & Zhang, L.-M. (2007). Characteristics of novel starch-based hydrogels Polymers, 52, 1e10.
prepared by UV photopolymerization of acryloylated starch and a zwitterionic Szymon  ska, J., Krok, F., & Tomasik, P. (2000). Deep-freezing of potato starch. Inter-
monomer. Starch/Stärke, 59, 418e422. national Journal of Biological Macromolecules, 27, 307e314.
Lim, S.-T., Han, J.-A., Lim, H. S., & BeMiller, J. N. (2002). Modification of starch by dry Tharanathan, R. N. (2005). Starch-value addition by modification. Critical Reviews in
heating with ionic gums. Cereal Chemistry, 79, 601e606. Food Science and Nutrition, 45, 371e384.
Lorbeth, R., Ritte, G., Willmitzer, L., & Kossmann, J. (1998). Inhibition of starch- Umemoto, T., Yano, M., Satoh, H., Shomura, A., & Nakamura, Y. (2002). Mapping of
granule-bound protein leads to modified starch and repression of cold sweet- a gene responsible for the difference in amylopectin structure between
ening. Nature Biotechnology, 16, 473e477. japonica-type and indica-type rice varieties. Theoretical and Applied Genetics,
Ludwig, D. S. (2002). The glycemic index: physiological mechanisms relating to 104, 1e8.
obesity, diabetes, and cardiovascular disease. Journal of the American Medical Varavinit, S., Paisanjit, W., Tukomane, T., & Pukkahuta, C. (2007). Effects of osmotic
Association, 287, 2414e2423. pressure on the crosslinking reaction of tapioca starch. Starch/Stärke, 59,
Maache-Rezzoug, Z., Maugard, T., Zarguili, I., Bezzine, E., El Marzouki, M.-N., et al. 290e296.
(2009). Effect of instantaneous controlled pressure drop (DIC) on physico- Verhoeven, T., Fahy, B., Leggett, M., Moates, G., & Denyer, K. (2004). Isolation and
chemical properties of wheat, waxy and standard maize starches. Journal of characterisation of novel starch mutants of oats. Journal of Cereal Science, 40,
Cereal Science, 49, 346e353. 69e79.
van der Maarel, M. J. E. C., Capron, I., Euverink, G.-J. W., Bos, H. Th., Kaper, T., Viksø-Nielsen, A., Blennow, A., Jørgensen, K., Jensen, A., & Møller, B. L. (2001).
Binnema, D. J., et al. (2005). A novel thermoreversible gelling product made by Structural, physicochemical, and pasting properties of starches from potato
enzymatic modification of starch. Starch/Stärke, 57, 465e472. plants with repressed r1-gene. Biomacromolecules, 23, 836e843.
Morell, M. K., Kosar-Hashemi, B., Cmiel, M., Samuel, M. S., Chandler, P., Rahman, S., Wischmann, B., Blennow, A., Madsen, F., Jørgensen, K., Poulsen, P., & Bandsholm, O.
et al. (2003). Barley sex6 mutants lack starch synthase IIa activity and contain (2005). Functional characterisation of potato starch modified by specific in
a starch with novel properties. Plant Journal, 34, 173e185. planta alteration of the amylopectin branching and phosphate substitution.
Murphy, P. (2000). Starch. In G. O. Philips, & P. A. Williams (Eds.), Handbook of Food Hydrocolloids, 19, 1016e1024.
hydrocolloids (pp. 41e65). USA: CRC Press. Wurzburg, O. B. (1986). Nutritional aspects and safety of modified food starches.
Nemtanu, M. R., & Minea, R. (2006). Functional properties of corn starch treated Nutrition Reviews, 44, 74e79.
with corona electrical discharges. Macromolecular Symposia, 245e246, 525e528. Xing, G.-X., Zhang, S.-F., Ju, B.-Z., & Yang, J.-Z. (2006). Microwave-assisted synthesis
Noda, T., Kimura, T., Otani, M., Ideta, O., Shimada, T., Saito, A., et al. (2002). Physi- of starch maleate by dry method. Starch/Stärke, 58, 464e467.
cochemical properties of amylose-free starch from transgenic sweet potato. Zarguili, I., Maache-Rezzoug, Z., Loisel, C., & Doublier, J.-L. (2006). Influence of DIL
Carbohydrate Polymers, 49, 253e260. hydrothermal process conditions on the gelatinization properties of standard
Oh, E. J., Choi, S. J., Lee, S. J., Kim, C. H., & Moon, T. W. (2008). Modification of maize starch. Journal of Food Engineering, 77, 454e461.
granular corn starch with 4-a-glucanotransferase from Thermotoga maritime: Zheng, G. H., & Sosulski, F. H. (1998). Determination of water separation from
effects on structural and physical properties. Journal of Food Science, 73, cooked starch and flour pastes after refrigeration and freeze-thaw. Journal of
158e166. Food Science, 63, 134e139.

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