Kavlani Neelam et al.

IRJP 2012, 3 (5)

INTERNATIONAL RESEARCH JOURNAL OF PHARMACY
www.irjponline.com ISSN 2230 8407
Review Article

VARIOUS TECHNIQUES FOR THE MODIFICATION OF STARCH AND THE

APPLICATIONS OF ITS DERIVATIVES
Kavlani Neelam*, Sharma Vijay, Singh Lalit
Department of Pharmacy Shri Ram Murti Smarak college of Engineering and Technology, (Pharmacy), Bareilly, India
Article Received on: 10/03/12 Revised on: 24/04/12 Approved for publication: 09/05/12

*Email: neelam.kavlani@gmail.com
ABSTRACT
Starch is a major carbohydrate easily extractable from various native sources, like potato, maize, corn, wheat, etc, which finds wide application in various food
and non food industries. Since time immemorable various attempts are being made in order to modify this highly flexible polymer with an aim to enhance the
positive attributes and eliminate the short comings of the native starches. Modifications are generally made by physical methods like osmotic-pressure
treatment, deep-freezing and thrashing; chemical methods that primarily include derivatizations such as etherification, esterification and crosslinking,
oxidation, cationization and grafting of starch; enzymatic degradation techniques and genetical modifications which involves the transgenic techniques
targeting the various enzymes involved in starch biogenesis. All these techniques tends to produce a variety of derivatives with altered physicochemical
properties and modified structural attributes of high technological value for instance carboxymethylated starch used as a binding and disintegrating agent. This
review summarizes the various methods of starch modification that can be employed to produce a novel molecule with substantial applications in various
industries including a large number of advances in pharmaceutical industry along with the future prospectives.
KEYWORDS: Osmotic-pressure treatment, Enzymatic degradation, Transgenic techniques

INTRODUCTION along with useful structural attributes. There is a huge market

Starch is a naturally occurring, biodegradable, inexpensive for the many new functional and added value properties
and abundantly available polysaccharide molecule. It is resulting from these modifications. A number of review
widely distributed in the form of tiny granules as the major articles8-10 on the subject of starch modification are available.
reserve carbohydrate in stems, roots, grains, and fruits of all However in the last few years there has been intense research
forms of green leafed plants. Cereal grains, such as corn, by various pharmaceutical professional to quest for an
wheat, sorghum, and tubers, and roots, such as potato, appropriate modification method that can yield a suitable
tapioca, arrowroot, etc., are some of the commercial sources candidate to be used as pharmaceutical excipient in
of starch for industrial exploitation. It consists of glucose improvised drug delivery systems. This review covers the
units (C6H10O5)n with n ranging from 300 to 1000. Starch is various techniques that yield modified starches for
composed of a mixture of two polymers called amylose and pharmaceutical as well as other industrial applications.
amylopectin. Amylose is a linear polymer with molecular Physical methods
weight of less than 0.5 million Dalton (degree of Physical modification of starch is mainly applied to change
polymerization of 15 1026 103) depending on its the granular structure and convert native starch into cold
botanical source. Amylose macromolecules consist of a-D- water-soluble starch or small-crystallite starch. These set of
glucopyranose units joined by - 1,4 acetal linkages. techniques are generally given more preference as these do
Amylopectin molecules are much larger and highly branched not involve any chemical treatment that can be harmful for
with molecular weight of 50100 million Dalton and degree human use. A large no of physical methods are available
of polymerization of about 3 1053 106. The molecules today that include:
contain -1,4 linear bounds, and is branched through -1,6 1. Heatmoisture treatment
linkages1-2. Heatmoisture treatment (HMT) of pulse starches at
In addition to being a major food item, it is currently used restricted moisture levels (2227%) and high temperature
industrially as coatings and sizing in paper, textiles and (100120 C) for 16 h has been shown to alter the structure
carpets, as binders and adhesives, as absorbants3, and as and physicochemical properties of smooth pea, wrinkled pea,
encapsulants4 bone replacement implants5, bone cements6, navy bean, lentil and pigeon pea starches11-15. HMT of pulse
drug delivery systems, and tissue engineering scaffolds7. starches has been shown by the above authors to decrease
However, in native state it exhibits limited applications due amylose leaching, granular swelling and peak viscosity, and
to low shear stress resistance and thermal decomposition, to increase thermal stability, gelatinization temperatures and
high retrogradation and syneresis, in addition to poor susceptibility towards -amylase and acid hydrolysis. These
processability and solubility in common organic solvents. changes were attributed to an interplay of factors such as: (1)
Therefore, to meet the demanding technological needs of amylose content, (2) interactions between starch chains, (3)
today, the properties of starch are modified by a variety of arrangement of amylose chains within the amorphous
modification methods. Starch modification is aimed at domains and (4) lipidamylose complexes.
correcting one or some of the abovementioned shortcomings, 2. Annealing
which will enhance its versatility and satisfy consumer Annealing refers to treatment of starch in excess water
demand. (<65% w/w) or at intermediate water contents (4050% w/w)
The techniques for starch modification have been broadly at temperatures below the onset temperature of gelatinization.
classified into four categories; physical, chemical, enzymatic The physical aim of annealing is to approach the glass
and genetical modifications, that aim to produce various transition temperature, which enhances molecular mobility
novel derivatives with improvised physiochemical properties without triggering gelatinization. Annealing of lentil, smooth
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pea and wrinkled pea starch11-12,16-17 has also been shown to Further, UHP-treated starch that is little or partially
decrease granular swelling and amylose leaching and to gelatinized maintains its granular structure51-53, and restricts
increase gelatinization temperatures, thermal stability, and amylose leaching from granules and granule swelling
susceptibility towards a-amylase. These changes were capacity52-54. Moreover, UHP treatment has been shown to
attributed by the above authors to an increase in crystalline transit A-type crystallite pattern to B-type crystallite
perfection and increased interaction between amylose pattern54-55. These noted physical and structural
amylose and amylose amylopectin chains. characteristics of UHP-treated starch granules are anticipated
3. Retrogradation to impact its reactivity in starch chemical modification and
The retrogradation process is defined as the linking of starch modified starch property.
chains into ordered crystalline structures18. The linear 6. Glow Discharge Plasma Treatment
fraction of starch is particularly susceptible to retrogradation. A glow discharge plasma is used which can produce high
Amylose crystals are characterized by high thermostability energy electrons and other highly active species at room
(dissolution in water at 120-150 C) and resistance to the temperature. This approach has been extensively used in
activity of amylase. Amylopectin, being the branched fraction material modification56. When applied to starch, the highly
of starch is, however, slowly retrogradable; whilst crystalline active species can excite chemical groups in starch, inducing
forms appearing only on the outside of the globule are modification process without the assistance of other
characterized by a significantly lower temperature (40-70 C) chemicals. Thermal degradation is minimized. Starch is
of re-pasting and an increased susceptibility to amylases highly cross linked by glow discharge plasma, without the
activity than the retrograded amylose19. The productivity and assistance of conventional chemical agents, thus avoiding any
properties of the retrograded starch obtained have been environmental concerns57.
reported to be largely affected by: origin of starch20-21, 7. Osmotic-Pressure Treatment
amylose content22-23, length of the amylopectin end chains24- Osmotic-pressure treatment (OPT) was carried out in the
25
, density of the paste26-27, physical28-29 or chemical30-31 presence of high salt solutions58. Starch solution was
modifications, the presence of other compounds29,32-34 as well suspended in sodium sulphate to obtain a uniform starch
as by paste storage conditions35. Recrystallization of starch suspension and heat distribution. The potato-starch treated
occurs most easily at a temperature approximating 0 C, but changed from a B to an A type after treatment with the
also at temperatures over 100 C, yet then it applies to gelatinization temperatures increasing significantly. A
amylase only. The retrogradation is intensified by the uniform heat distribution is provided for using this method as
application of repeated freezing and defrosting of the starch compared to heat-moisture treatment and modified starch is
paste27. The resulting starch thus produced is known as able to be produced in a large scale.
resistant starch that demonstrates resistance to digestibility by 8. Thermal Inhibition
amylase enzymes and thus can be as an alternative nutrient Thermal inhibition of starch is done by dehydrating starch
aid for diabetic patients and as a rate controlling polymer coat until it is anhydrous (<1% moisture) and treating it to a
in controlled drug delivery systems. temperature of 100 C or greater for a period of time enough
4. Freezing to inhibit starch. An alkaline condition enhanced the effect of
Freezing is a physical treatment widely applied for heating. Pastes formed from theses starches had increased
preservation, drying and lyophilisation of starchy food36-37. It resistance to viscosity breakdown and a non-cohesive
is also used for sample preparation in granule structural texture59. Thermal inhibition with ionic gums had sodium
investigations by means of many physical methods, for alginate, CMC and xanthan behaving as crosslinking agents
instance in scanning electron microscopy (SEM) or and were able to form graft copolymers through ester
transmission electron microscopy (TEM)38-41. It was reported formation60.
that freezing influenced textural and gelatinization 9. Gelatinization
characteristics of starch42-43. It was also considered to cause The process of gelatinization causes substantial changes in
some changes in the nutritional properties of starch44. both the chemical and the physical nature of granular starch
Freezing of starch sols resulted in their coacervation and due to the rearrangement of intra- and intermolecular
increasing retrogradation, while pregelatinised starch became hydrogen bonding between the water and starch molecules
less sensitive to retrogradation and stayed smooth after the resulting in the collapse or disruption of molecular orders
process43,45 as well as Perry and Donald (2001)46 reported that within the starch granule61. This results in irreversible
some reversible structural disorder of starch granules changes in the starch properties62. Evidence of the loss of an
occurred at sub-zero temperatures. Freezing water inside or organized structure includes irreversible granule swelling,
outside of the starch granule seems to be a particularly loss of bifringence and crystallinity63,64.
effective way for modification for potato starch. This is Chemical Modifications
because the starch B granules contain a significant amount of Chemical modification involves the introduction of
structural water, which determines the granular inner functional groups into the starch molecule, resulting in
structure. markedly altered physico-chemical properties. Such
5. Ultra High Pressure Treatment modification of native granular starches profoundly alters
UHP treatment of the starchwater suspension reversibly their gelatinization, pasting and retrogradation behavior. The
hydrates amorphous regions within granules, leading to the chemical and functional properties achieved when modifying
granule swelling and crystalline region distortion, and thus, starch by chemical substitution depend, inter alia, on starch
the crystalline regions become more accessible to water47-50. source, reaction conditions (reactant concentration, reaction
Finally, starch granules are non-thermally gelatinized over a time, pH and the presence of catalyst), type of substituent,
critical pressure level which varied depending on botanical extent of substitution (degree of substitution, DS1; or molar
sources and crystal packing arrangements of starch47,50-52. substitution, MS2), and the distribution of the substituents in

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the starch molecule65-69. Modification is generally achieved Starch phosphorylation is the earliest method of starch
through derivatization such as etherification, esterification, modification72. The reaction gives rise to either monostarch
cross-linking and grafting of starch; decomposition (acid or phosphate or distarch phosphate (cross-linked derivative),
enzymatic hydrolysis and oxidization of starch). These depending upon the reactants and subsequent reaction
techniques are however limited due to issues concerning conditions. Monoesters, rather than diesters, are produced
costumers and the environment. These techniques include: with a higher level of phosphate substitution on starch. The
1. Etherification & Esterification introduction of phosphate substitution on amylose or outer
This method primarily includes substitution of hydrophilic branches of amylopectin prevents linearity of molecular
hydroxyl groups of starch by various hydrophobic functional chains due to steric hindrance. Thus, a situation is achieved
groups resulting into hyproxypropylation, where individual chain segments can no longer approach
carboxymethylation, acetylation, succinylation, etc. each other closely enough to establish intermolecular or
The carboxymethyl substitution of starch hydroxyl groups intramolecular association; they, therefore, lead to a better
gives rise to derivatives that are cold water-soluble. To paste clarity. The phosphate diester starches have the
prevent starch gelatinization, the reaction has to be carried phosphate esterified with two hydroxyl groups, very often
out in an organic medium. Carboxymethyl starch, under the from two neighboring starch molecules73. This leads to the
name sodium starch glycolate, is used in the pharmaceutical formation of a covalent bridge or cross-linking. Phosphate
industry as a disintegrant and as a sizing and printing agent in cross-linked starches show resistance to high temperature,
the textile industry. Highly substituted derivatives are low pH, high shear, and leads to increased stability of the
possible. swollen starch granule. They improve viscosity and textural
In acetylation, hydrophilic hydroxyl groups are substituted properties of the starch. As a thickener and stabilizer, starch
with hydrophobic acetyl groups. Acetylation makes starch phosphate diesters are superior to unmodified starches. They
more hydrophobic and prevents the formation of hydrogen also provide resistance to gelling and retrogradation, and do
bonding between hydroxyl groups and water molecules. not synerese on storage.
Since the tendency of an aqueous starch dispersion to Derivatization of starch with an ionic substituent group such
increase in viscosity on cooling and finally to gel is related to as succinate at low degree of substitution (DS) converts it
the association of amylose molecules, a treatment such as into a polyelectrolyte, which makes it acquire typical
acetylation which retards or eliminates this crystallization or properties of a polyelectrolyte like increased hydrophilic
retrogradation will effect stabilization of the starch sol. character and increased solution viscosity74. This
Acetylation also prevents or minimizes association of modification is also known to weaken the internal bonding
amylopectin outer branches. This is of practical value in that holds the granules together. In addition starch succinate
many industrial and food applications because such offers very desirable properties such as low-temperature
associations can cause cloudiness and syneresis in aqueous stability, high-thickening power, and low-gelatinization
dispersions of starches70. temperature, clarity of cooked food, good film-forming
Hydroxypropylated starches are generally prepared by properties and reduced tendency to retrograde.
etherification of native starch with propylene oxide in the High cationic properties have been observed for starch
presence of an alkaline catalyst. The hydroxypropyl groups citrates. The reaction is facilitated thermochemically by the
introduced into the starch chains are capable of disrupting the dry heating (120 C for 24 h) of citric acid to an anhydride,
inter- and intra-molecular hydrogen bonds, thereby which reacts with starch to form an adduct, followed by
weakening the granular structure of starch, leading to an further reaction to yield cross-linked starch citrate. The
increase in motional freedom of starch chains in amorphous reaction can be controlled to maximize reaction efficiency,
regions. Hydroxyethyl starch, prepared by reaction with minimize cross-linking, and maximize carboxyl content.
ethylene oxide, was of considerable biomedical interest as a They are used to remove toxic, heavy metal ions in water
blood plasma expander and also as a cryoprotective agent for purification (industrial waste water) as biodegradable ion-
erythrocytes71. exchange materials against the petrochemically derived ion-
exchange resins .

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2. Cross-Linking increased as hydrolysis proceeded. The method for the

Cross-linking reinforces the hydrogen bonds in the granule manufacture of acid thinned starch entails treating
with chemical bonds that act as a bridge between the starch concentrated starch slurry with mineral acid at temperatures
molecules. Important factors in the cross-linking reaction below gelatinization temperature for specific period
include chemical composition of reagent, reagent depending on the desired viscosity or degree of conversion.
concentration, pH, reaction time and temperature. Because Effect of different acids (HCl, HNO3, H2SO4 and H3PO4)
the degree of cross-linking for food starch is very low, the under similar conditions of treatment on molecular weight,
extent of reaction and yield of cross-linked starch are difficult alkali fluidity number, iodine binding capacity and intrinsic
to measure chemically; hence there is a need for physical viscosity of various starches has also been studied77.
property measurement. When phosphorus oxy chloride 4. Oxidation
(phosphoryl chloride, POCl3, MW153.3) is added to starch Oxidized starch is produced by reacting starch with a
slurry under alkaline conditions (pH 812), the hydrophilic specified amount of oxidizing reagent under controlled
phosphorus group immediately reacts with the starch temperature and pH78. Oxidation causes depolymerisation,
hydroxyls, forming a distarch phosphate65. which results in a lower dispersion viscosity and introduces
Cross-linking alters, not only the physical properties, but also carbonyl and carboxyl groups, which retard
the thermal transition characteristics of starch, although the Recrystallization79.
effect of cross-linking depends on the botanical source of the 5. Dual Modification
starch and the cross-linking agent. Decrease in retrogradation These include methods that involve the chemical reaction in
rate and increase in gelatinization temperature has been the presence of a specific physical environment or an
observed with cross-linked starch, and these phenomena are enzymatic treatment that make serve to enhance the rate of
related to the reduced mobility of amorphous chains in the derivatization or can enhance the degree of substitution in
starch granule as a result of intermolecular bridges75. some instances. Microwave-assisted esterification to produce
However, Jyothi et al.76 showed that cross-linked starch has starch maleate using the dry method had a reaction efficiency
more pronounced syneresis than has native starch because of of up to 98% and a reaction time of less than 5 min. This is
ordered structure in the starch paste, thus resulting in a higher thought to be an efficient method in esterifying starch80. The
degree of retrogradation. high efficiency in producing succinylated cassava starch with
3. Acid Treatment microwave assistance was also observed by Jyothi et al,
In acid modification, the hydroxonium ion attacks the (2005)81. This is a good method to decrease the use of
glycosidic oxygen atom and hydrolyses the glycosidic chemicals to enhance production.
linkage. An acid acts on the surface of the starch granule first Microwave and ultrasound irradiation was used for the
before it gradually enters the inner region. Acid modification Esterification of carboxymethyl cold-water-soluble potato
changes the physicochemical properties of starch without starch with octenyl succinic anhydride. They were positively
destroying its granule structure and the properties of acid- able to shorten the esterification time from a few hours to a
thinned starches differ according to their origin70. The few minutes. The derivatives displayed excellent emulsifying
gelatinization temperature and the breadth of the and surfactant performance properties82. A combined method
gelatinization endotherm have also been shown to increase on of modification using crosslinking and phosphorylation on
acid hydrolysis. The retrogradation rate of acid thinned starch

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rice starch provided modified rice starch with good freeze- starch granules. Cyclomaltodextrins are also formed in situ,
thaw stability. with the retention of CDs in the granule and this leads to the
Modified corn and mung bean starch was prepared by production of a new material that has properties of starch
treating native starch with a mixture of fungal -amylase and granules and Cyclomaltodextrins. Formation of complexes of
glucoamylase followed by hydroxypropylation with organic molecules with Cyclomaltodextrins provides
propylene oxide. This partial enzymatic hydrolysis produces stabilization of light, heat and oxygen-sensitive materials in
modified starch that possesses significantly different the starch granules and also a mechanism for their slow
functional properties to that of hydroxypropyl starch prepared release besides providing special tastes, odors and flavors to
under normal conditions83. the starch granules.
Rajan et al., 2007 have also demonstrated that the use of Genetic Modification
fungal lipase to enhance the Esterification of cassava starch These set of techniques involve transgenic technology that
using recovered coconut oil gives thermoplastic starch which targets the enzymes involved in starch biosynthesis thus
has got wide use in plastic industry, pharmaceutical avails the advantage over environmentally hazardous post
industries, and in biomedical applications such as materials harvest chemical or enzymatic modifications. Genetic
for bone fixation and replacements, carriers for controlled modification can be carried out by the traditional plant-
release of drugs and other bioactive agents. Unlike chemical breeding techniques or through biotechnology88.
esterification, enzymatic esterification is ecofriendly and 1. Amylose-Free Starch
avoids the use of nasty solvents. Amylose-free waxy starch was produced by the simultaneous
Enzymatic Modifications antisense downregulation of three starch synthase genes
This involves the exposure of starch suspensions to a no of (Granular Bound Starch Synthetase, Starch Synthetase II and
enzymes primarily including hydrolyzing enzymes that tend Starch Synthetase III), that resulted in waxy starch with small
to produce highly functional derivatives. Origin of this amylopectin chains. Generally mutant maize is grown on
technique can be dated back to the times when glucose syrup commercial scale, through modified corn, wheat, sorghum,
or high fructose corn syrup was produced. amaranth are also available. Waxy starch thus produced is
The enzymes amylomaltases(-1,4-1,4 glucosyl generally used in food industry as it gelatinizes easily,
transferases) found in eukarya, bacteria and archea yielding clear pastes that will not gel.
representatives, breaks an -1,4 bond between two glucose 2. High-Amylose Starch
units to subsequently make a novel -1,4 bond producing a High-amylose starch in cereals is produced by a mutation in
modified starch that can be used in foodstuffs, cosmetics, the gene that encodes starch-branching enzyme (SBE) IIb,
pharmaceutics, detergents, adhesives and drilling fluids. It is which is also known as amylose extender (ae). In potato,
also a good source of plant-derived substitute for gelatin discovery of the corresponding gene and the downregulation
except that it forms a turbid gel whereas gelatin gels are of its expression in tubers using antisense techniques enabled
transparent84. In the study by Hansen, Blennow, Pedersen, the production of starches that have slightly increased
Nrgaard, and Engelsen (2008)85 on gel texture formed in the amylose levels89. However, both SBEI and SBEII had to be
modification of potato, high-amylose potato, maize and pea inhibited to create starches with amylose levels of more than
starch with amylomaltase (AM) isolated from the 60%90. Recently, a more efficient method of inhibiting gene
hyperthermophilic bacterium Thermus thermophilus, there function using single domain antibodies against SBEII was
was an improvement in gel texture compared to the parent used to produce starches that had even higher amylose
starch. All the modified starches showed broadened levels91.
amylopectin chain length profiles. The derivative thus produced serves as an important
Cyclomaltodextrinase (CDase; EC 3.2.1.54), isolated from precursor for the development of coating polymers that are
alkalophilic Bacillus sp. I-5 (CDase I-5) was used to modify resistant to enzymatic degradation and can be used in colon-
rice starch to produce low-amylose starch products. The targeted drug delivery systems. High-amylose starches can
amylose content was found to have decreased significantly also be processed into resistant starch, which has nutritional
from 28.5 to 9% while there was no significant change in the benefits92.
side chain length distribution of the amylopectin. Storage of 3. Altered amylopectin structure
the modified rice starch at 4 C for 7 days, showed that the Amylopectin synthesis is governed by a no of enzymes
retrogradation rate had significantly retarded compared to the including starch Synthetase, branching enzymes and
control sample86. debranching enzymes each of which also has an isoforms.
Treatment of maize starch with -amylase, -amylase and Therefore the downregulation of any one enzyme fails to
transglucosidase, maltogenic produce an entirely new amylopectin features. However the
-amylase, and maltogenic -amylase and transglucosidase, inhibition of SS II and SS III isoforms in a few rice species
resulted into significant reduction in digestion rate by 14.5%, demonstrates functional derivatives with low gelatinization
29.0%, 19.8%, and 31.0%, respectively producing resistant temperature (below 50 C).
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