Starch/Strke 2014, 66, 4157 DOI 10.1002/star.

201300106 41

REVIEW

Recent trend in the physical and chemical modication

of starches from different botanical sources: A review
Adeleke Omodunbi Ashogbon 1 and Emmanuel Temitope Akintayo 2

1
Faculty of Science, Department of Chemistry and Industrial Chemistry, Adekunle Ajasin University, Akungba-Akoko, Ondo State,
Nigeria
2
Faculty of Science, Department of Chemistry, Ekiti State University, Ado-Ekiti, Ekiti State, Nigeria

Starch is, after cellulose, the most abundant organic compound in nature. Modication of starch is Received: April 30, 2013
carried out to enhance the positive attributes and to eliminate the shortcomings of the native Revised: July 10, 2013
starches. Various methods have been developed to produce a range of modied starches with a Accepted: July 17, 2013
variety of characteristics and applications. Physically modied starches are simple and
inexpensive because they can be produced without chemicals or even biological agents. In
contrast, chemical modication is possible due to ubiquitous hydroxyl groups in starches that
have been exploited for over a century, principally in the preparation of starch esters and ethers,
but also in more subtle alterations, e.g., in order to tune the structure of starches for specic
applications. All these techniques tend to alter the highly exible starch polymer with changed
physicochemical properties and modied structural attributes of high technological value for the
food and non-food industries. Modication of starch is an ever evolving industry with numerous
possibilities to generate novel starches which includes new functional and value added properties
as demanded by the industry. This review aims to summarize the latest developments and recent
knowledge regarding physically and chemically modied starches. This paper covers physical
modication methods (pre-gelatinization, hydrothermal, and non-thermal processes), some
chemical modications and a combination of both.

Keywords:
Chemical / Physical / Properties / Starch Granules / Starch Modification

1 Introduction groundnut), some under-utilized legume (sword bean, jack

Starch is a naturally occurring, biodegradable, cheap,
renewable, and abundantly available polysaccharide molecule.
The different botanical sources of starches are cereal (wheat,
corn, rice, barley, oat, sorghum, millet, and rye), legume (lima
bean, garbanzo bean, lentil bean, red kidney bean, navy bean,
faba bean, mung bean, pinto bean, adzuki bean, eld pea,
cowpea, beach pea, green pea, grass pea, soybean, and
Correspondence: Adeleke Omodunbi Ashogbon, Faculty of Science,
Department of Chemistry and Industrial Chemistry, Adekunle Ajasin
University, Akungba-Akoko, Ondo State, Nigeria
E-mail: ashogbonwale@yahoo.com
Fax: 234-08059225829
Abbreviations: HHP, high hydrostatic pressure; PEF, pulsed electric
elds; PGS, pre-gelatinized starches; STMP, sodium
trimetaphosphate; STPP, sodium tripolyphosphate; UHP, ultra
high pressure
bean, and pigeon pea), root and tuber (cassava, potato, yam,
cocoyam, and sweet potato), and unripe fruit (banana,
plantain, mango, and pawpaw). Starch granules are mainly
found in seeds, roots and tubers, as well as in stems, leaves,
fruits and even pollens. The granules occur in all shapes and
sizes (spheres, ellipsoids, polygon, platelets, and irregular
tubules). The two main components of starch are amylose
(AM) and amylopectin (AP) and they differ signicantly in
their properties and functionality. AM has a high tendency to
retrograde and produce tough gels and strong lms. In
contrast, AP, when dispersed in water, is more stable and
produces soft gels and weak lms [1]. It is possible for
entanglements to occur between AM and AP, along with the
presence of minor components (proteins, PLs, and lipids), all
also have important impacts on the physicochemical proper-
ties of the starches from different botanical origin. The
industrial utilization of native starches is limited because of
inherent imperfect nature, such as water insolubility and their

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42 A. O. Ashogbon and E. T. Akintayo
tendency to easily retrograde and undergo syneresis and
therefore form unstable pastes and gels. Starch modication
does not only decrease retrogradation, gelling tendencies of
pastes and gel syneresis but also improves paste clarity and
sheen, paste, and gel texture, lm formation and adhesion.
Another aim of starch modication is to stabilize starch
granules during processing and make starch suitable for
many food and industrial applications. The functionality of
starch can be modied through physical, chemical, enzymatic,
biotechnological, or their combinations.
Physical modication of starch can improve water
solubility and reduce particle size. The methods involve
the treatment of native starch granules under different
temperature/moisture combinations, pressure, shear, and
irradiation. Physical modication also includes mechanical
attrition to change the physical size of starch granules.
Physical modication techniques are generally given prefer-
ence as they do not involve any chemical treatment that can be
harmful for human use. In contrast, chemical modication
involves the introduction of functional groups into the starch
molecules, resulting in markedly altered physicochemical
properties. The ubiquitous hydroxyl groups in starches are
the most obvious source of chemical modication that has
been exploited for over a century, principally in the
preparation of starch esters and ethers, but also in more
subtle alterations, e.g., in order to tune the structure of
starches for specic applications. Such chemical modication
strongly changes gelatinization, pasting, and retrogradation
behavior of starches from different botanical sources [2]. This
type of technique is intended to facilitate intra- and inter-
molecular bonds at random locations in the starch granules
for their stabilization [3]. Modication of starch is an ongoing
process as there are many possibilities. There is a huge
market for the many new functional and value added
properties resulting from these modications [4].
Generally, there are four broad classications of starch
modications: chemical, physical, enzymatic, and genetical.
This review is based on the rst two. A number of review
articles [59] on the subject of starch modication are
available. In the recent past years, there has been intense
research to develop new methods of starch modication with
more emphasis on physical and chemical modications.
Therefore this review aims to summarize the latest develop-
ments and recent knowledge regarding physically and
chemically modied starches from different botanical
sources.
2 Physical modification of starch
Although native starch has been used for food processing, the
physical properties of these starches and the colloidal sols
produced from them are limited in terms of the commercial
applications for which they are suited [10]. Most native
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Starch/Strke 2014, 66, 4157
starches are limited in their applications due to their
instability under various temperatures, shears, and pH
conditions. Additionally, most starch granules are inert,
insoluble at ambient temperature, highly resistant to
enzymatic hydrolysis and therefore lack specic functional
properties. Native starches are often modied to develop
specic properties such as solubility, texture, adhesion, and
heat tolerance, so as to be suitable for industrial applica-
tions [1116]. There are many different methods of modifying
starch biopolymers [1721].
Physical modication is simple, cheap, and safe because it
requires no chemicals or biological agents. Classication of
starches from different botanical sources based on physical
modications depends on whether the molecular integrity of
the starches are destroyed or preserved after the modication.
The former encompasses all the pre-gelatinization processes
(drum drying, spray drying, and extrusion cooking) where
starch granular order is loss together with partial de-
polymerization of starch components and the latter are the
hydrothermal processes, e.g., ANN and HMT where the
molecular integrity of the starches are preserved. Recently
new methods of physical modications of starches from
different botanical sources have been investigated and are as
follows: superheated starch [22]; iterated syneresis [23];
thermally inhibited treatment (dry heating) [24]; osmotic
pressure treatment [25]; multiple deep freezing and
thawing [26]; instantaneous controlled pressure drop (DIC)
process [27, 28]; mechanical activation with stirring ball
mill [29]; micronization in vacuum ball mill [30]; pulsed
electric elds (PEF) treatment [31]; corona electrical
discharges [32]. These new physical methods of starch
modication are listed in Table 1.
2.1 Pre-gelatinized starch (PGS)
Pre-gelatinized starches (PGS) refer to cooked starches that are
prepared by complete gelatinization and drying. Destruction of
the granular structure is the major physical event leading to
Table 1. Recent physical modication of starch
Physical modification Reference
Superheated starch Steeneken and Woortman [22]
Iterated syneresis Lewandowicz and
Soral-Smietana [23]
Thermally inhibited treatment Chiu et al. [24]
Osmotic-pressure treatment Pukkahuta et al. [25]
Multiple deep freezing and thawing Szymonska et al. [26]
Instantaneous controlled pressure Zarguili et al. [27]
Drop (DIC) process Maache-Rezzoug et al. [28]
Mechanical activation-with stirring ball mill Huang et al. [29]
Micronization in vacuum ball mill Che et al. [30]
Pulsed electric fields treatment Han et al. [31]
Corona electrical discharges Nemtanu and Minea [32]
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Starch/Strke 2014, 66, 4157
complete fragmentation and to the absence of optical
birefringence. The main properties of PGSs are increased
water absorption and water solubility upon dispersion in cold
water; this leads to instant starch slurries without heating.
Their functional properties are highly dependent upon the
cooking, botanical sources, and drying conditions.
Pre-gelatinization can be brought about by drum drying,
spray drying, and extrusion cooking. Of these, drum drying is
a common industrial practice for pre-gelatinization [3335].
PGSs have been mainly applied as thickener in many food
products such as baby food, instant soups, and instant
desserts [36].
Drum drying results in specic physicochemical mod-
ications of starch granules performed in two consecutive
stages; gelatinization and drying. It is capable of impacting a
variety of textures and porous structure to the product
dictated strongly by the intensity of the treatment, which are
expected to inuence its functional properties.
Drum drying is the most widely used technique at
industrial scale. The overall pre-gelatinization process occurs
in one or two steps. For the one step process, the starch slurry
is fed onto the drums that are used to gelatinization and to
dehydrate starch paste at the same time. For the two-step
process, the slurry is primarily cooked in a heat exchanger or
a high-temperature jet cooker and dehydrated by drum
drying [37]. Using double drum dryer and native rice starches
(NRSs) of different AM content, Nakorn et al. [36] found that
the water absorption index (WAI) and water solubility index
(WSI) of the PRS were higher than that of the native starch.
The higher WAI and WSI value of PRS were attributed to
higher macromolecular disorganization and degradation of
starch during thermal treatment. Additional reason was the
possession of weaker associative forces in the granules of PRS
when compared to the NRS. Utilizing XRD and SEM, the
PRS granular appeared to be disintegrated and holes were
observed on them and were structurally amorphous [36]. The
lower AM content PRS were more disintegrated than higher
AM content PRS and NRS due to increase release of soluble
component during thermal treatment [38].
Spray drying is a well known technology in the food
industry and is presently the most commonly utilized
microencapsulation method for ingredient [39, 40]. An ideal
spray-drying carrier requirement include good emulsifying
properties, good drying properties, non-hygroscopic charac-
ter, bland taste, inertness, or non-reactivity, high degree of
solubility, limited viscosity of solution at 3545%, and low
cost [41]. Spray-drying produces a uniformly cooked or
gelatinized starch with a minimum of shears. It is valuable in
the modication of material for use in tablet formulations
because spherical particles produced usually ow better than
the same product dried by conventional procedures and have
the least possible surface area, thus minimizing air
entrapment between the particles. The improvement in ow
and compression make the spray dried material suitable for
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43
use in the manufacture of tablets. This has been found to be a
useful property for pharmaceutical composites to support a
model based on excipient powders. Granules must have good
ow property for precise volumetric feeding of the material
into the die cavity and compressibility [10].
Spray dried glutinous rice starch (SGRS) prepared from
pre-gelatinized glutinous rice starch (GRS) was found to be
amorphous when determined by XRD and the irregular
shape of GRS granules changed to concave spherical shape as
revealed by SEM [10]. Spray-drying system is used to produce
spherical particles for improving the uidity of solid. Fruit
and vegetable powder have been produced using spray-
drying [42]. Spray dried sweet potato powders have a potential
to be added to various food system to provide a variety of
functional benets. Recently, Grabowski et al. [43] demon-
strated that sweet potatoes can be spray dried into appealing
powders.
The conventional methods of starch modication require
an excess of reagents and may cause environmental
contamination from un-reacted chemical [44]. Extrusion
technology is a high-temperature, short-time process with the
advantage of high versatility and absence of efuents, that
may overcome pollution by using reduced amounts of
reagents and moreover, a further hydrolysis of starch
desirable for microencapsulation purposes can be achieved.
During extrusion starch is heated, transported, and com-
pressed by the single screw or twin screw and pressed toward
a die at high temperature and pressure resulting in the
molecular changes. Extrusion-cooking conditions can convert
starch from a granular and semi-crystalline material into a
highly viscous, plastic material [45]. This conversion is
accompanied by disruption of the crystalline structure of
starch polymers and their reduction to smaller molecules [46].
The results of the impact of extrusion on RS content of
starches are conicting. Numerous studies reported a
decrease in the RS content (or increase digestibility) after
extrusion and ascribed this to the destruction of granular
structure (due to thermal treatment, high pressure and shear
forces) [47, 48]. Similarly Mahasukhonthachat et al. [49],
reported that the rate of starch digestion of sorghum was
increase by about 10 times after extrusion when compare with
non-extrudates. Extrusion cooking of high AM starches
(Gelose and Hylon VII) signicantly reduced their RS content
(from 45.7 to15.6% for Gelose and from 60.0 to 13.8% for
Hylon VII) [50]. In contrast, some other studies show an
increase in the values of RS after extrusion. Chanvrier
et al. [51] observed a slight increase in enzyme resistant (ERS)
content for wheat starch (from 0.8 to 2.8%) and normal maize
starch (from 1.5 to 2.1%) after extrusion.
2.2 Hydrothermal modifications
Two hydrothermal treatments that modify the physicochem-
ical properties of starch without destroying the granule
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44 A. O. Ashogbon and E. T. Akintayo Starch/Strke 2014, 66, 4157

structure are ANN and HMT. Both physical modications
occur at temperatures above the glass transition temperature
(Tq) but below the gelatinization temperature of the starch
granules. Essentially, hydrothermal modication can only
take place when the starch polymers in the amorphous phase
are in the mobile rubbery state of the semi-crystalline region.
A few minute is sufcient to bring about detectable changes
in the physicochemical properties of the starch. Both HMT
and ANN occur below the onset temperature of gelatinization
and have been shown to modify starch structure and
properties to different extents [7]. There is a need to
distinguish between the two terms (ANN and HMT). Both
HMT and ANN involve storage of starch at a specic
temperature and at a certain moisture level during a certain
time period. The term HMT is used when low moisture levels
(less 35% w/w) are applied. In contrast, ANN refers to
treatment of starch in excess water (less 65% w/w) or at
intermediate water (4055% w/w).
2.2.1 Annealing (ANN)
ANN of starch is the physical treatment of starch granules in
the presence of heat and water. The ANN of starch granules
can take place in excess water (76% w/w) or at intermediate
water content (40% w/w) and held at a temperature above the
Tq but below the onset (To) temperature of gelatinization
(Table 2) [5260] for a set period of time [61]. It has been
reported that treatment of corn starch for 15 min at elevated
pressure (600 MPa) ensued ANN even at 25C [62]. The latter
researchers indicated that elevated pressure can induce ANN
at a temperature lower than the characteristic Tq at
atmospheric pressure. The above pressure and temperature
were pointed out to cause structural changes in the crystalline
regions of AP.
The aim of ANN is to approach the Tq, which enhances
molecular mobility without setting gelatinization into
motion. Recently, Chung et al. [63, 64] have shown that
ANN of lentil, smooth pea and wrinkled pea starches decrease
granular swelling and AML and also increase gelatinization
temperatures, thermal stability and vulnerability towards
digestion by alpha-amylase. These authors attributed the
changes to increase in crystalline perfection and increased
interaction between AMAM and AMAP chains. It could be
rationalized that starch ANN is a crystal growth/perfection
and diffusion controlled non-equilibrium process. The
amorphous regions of semi-crystalline starch granules are
the area most susceptible to the initial water absorption and
plasticization. Before hydration the amorphous region is

Table 2. Annealing and gelatinization parameters for tuber and cereal starches

ANN parameters Gelatinization parameters

Starch source Temp (C) Steps Time (h) W:Sa) S:Wb) Toc) (C) Tpc) (C) Tcc) (C) DH (J/g) Reference

Potato (native) 59.1 61.9 66.8 18.3 Vermeylen et al. [52]

Potato (annealed) 51 single 24 2.01 64.9 66.8 71.1 18.3 Vermeylen et al. [52]
Potato (annealed) 50 single 72 10:01 61.1 63.1 70.7 18 Kohyama and sasaki [53]
Potato (annealed) 40 multi 24 3.01 Nakazara and Wang [54]
Cassava (native) 65.4 71.5 81.5 8.8 Atichokundomchai et al. [54]
Cassava (annealed) 51 single 72 3.01 70.7 74 81.3 9.4 Atichokundomchai et al. [54]
Waxy barley (native) 1:04:05 53 59 68.6 10.8 Qi et al. [56]
Waxy barley (annealed) 48 single 168 Excess 1:04:05 65.4 67.4 73.3 11 Qi et al. [56]
Normal maize (native) 1:05 56.9 67.7 76.5 17.6 Qi et al. [57]
Normal maize (annealed) 55 single 168 Excess 1:05 72.1 76.4 82.3 16.9 Qi et al. [57]
Waxy maize (annealed) 55 single 168 Excess 1:05 73.3 77.3 83.1 17.3 Qi et al. [57]
Wheat (native) 1:03 58.4 63.2 69 100 Shi [58]
Wheat (annealed) 52 single 4 3:01 1:03 67 69.4 73.2 8.8 Shi [58]
Waxy rice (native) 1:03 76.2 81.2 87.1 19.2 Shi [58]
Waxy rice (annealed) 70 single 48 3:01 1:03 86.9 90 93.7 19.6 Shi [58]
Normal rice (native) 1:03 67.7 73.5 78.7 13.2 Hormdokand Noomhorm [59]
Normal rice (annealed) 55 single 24 3:01 1:03 71.1 74.7 79.1 11 Hormdokand Noomhorm [59]
Normal barley (native) 1:03 61.3 65.3 72.8 10 Waduge et al. [60]
Normal barley (annealed) 50 single 72 3:01 1:03 66.7 69.8 77 10 Waduge et al. [60]
Waxy barley (native) 1:03 59.3 64.9 81.8 13 Waduge et al. [60]
Waxy barley (annealed) 50 single 72 3:01 1:03 66.2 70.2 82.9 13.4 Waduge et al. [60]

, data not reported.

a) Water: starch.
b) Starch: water.
c) Onset (TO), mid-point (TP) and conclusion (TC) temperatures of gelatinization.
DH Enthalpy of gelatinization.

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Starch/Strke 2014, 66, 4157
more glassy and static [65]; it is hydration of the starch
granules that increase the mobility of the amorphous regions.
This generates vibrational movement of tangential and radial
chains in both amorphous and crystalline domains [61]. With
the progress of ANN the initially weaker or imperfect
crystallites gradually disappear, while the rest of the
crystallites become more perfect due to fusion and re-
crystallization [7]. ANN can be carried out in different steps,
the most signicance is the single step ANN [52, 57, 6677].
The utilization of the double stage ANN [58, 77] and multistep
ANN [54, 78] have been conducted to a restricted extent.
The impact of ANN on the morphology, structure, and
properties of starches from different botanical sources has
been studied using DSC [57, 70, 74, 7981], SEM [60, 71, 76],
XRD [57, 60], 13C cross polarization/magic angle spinning-
NMR (13C CP/MAS-NMR) [61, 74], microscopy [60, 71],
vulnerability to acids [60, 78], granule swelling [59, 81, 82],
AML [60, 81], and rapid visco-analyzer (RVA) pasting
parameters [81].
Waduge et al. [60] found no changes in the granular
morphology of wheat, oat, lentil, barley (some cultivars), and
potato starches on ANN. In contrast, Kiseleva et al. [71]
indicated that the lens shaped granules of AM and waxy (wx)
wheat starches were slightly deformed on ANN. Hydrother-
mal treatment is known as a process which increases starch
crystallinity and its perfection [83], granule rigidity, polymer
chain realignment, partial crystallite melting, and starch
chain associations (AMAP or APAP) [75]. The hydrother-
mal treatments could suppress granule swelling, retard
gelatinization, and increase starch paste clarity. Starch gel
structure is altered and gel hardness increased [83, 84].
2.2.2 HMT
HMT of starches from different botanical origins refers to the
thermal agitation of starch granules at a temperature above
the Tq but below the gelatinization temperature for certain
duration and at limited moisture content (usually below
(35% w/w). Many studies have indicated the effects of HMT
on the morphology and physicochemical properties of
legume, root, tuber, and cereal starches, including important
changes in XRD pattern, crystallinity, starch chain inter-
actions, granules swelling, AML, viscosity, gelation param-
eters, pasting properties, retrogradation, enzyme, and acid
hydrolysis [8592].The physical properties of heat-moisture
treated starch depend on the starch origin and treatment
conditions used. HMT of legume starches at limited moisture
content (2227%) and high temperature (100120C) for 16 h
has been reported to change the structure and physicochemi-
cal properties of navy bean, lentil, smooth pea, wrinkled pea,
and pigeon pea [63, 64]. AML, granular swelling and peak
viscosity of pulse starches are shown to decrease when heat
moisture treated by the above researchers. In contrast, their
thermal stability, gelatinization temperatures, and vulnera-
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
45
bility toward a-amylase and acid hydrolysis increases. These
alterations were attributed to interplay of many factors: lipid
amylose complexes; arrangement of AM chains within the
amorphous domain; interactions between starch chains and
the AM to AP ratio. Yoenyongbuddhagal and Noomhorm [83]
reported that heat moisture-treated rice our could enhance
the cooking and textural qualities of rice noodles. Hormdok
and Noomhorm [59] applied HMT and ANN to rice starch for
noodle making, and revealed the possibility of utilizing these
starches in composites with poor quality rice our to produce
noodles of acceptable quality.
2.3 Non-thermal physical modification of starches
Most foods are thermally preserved by subjecting the
products to boiling (or even higher) temperatures for a few
seconds to several minutes. These high-energy treatments
usually diminish cooking avors, and cause loss of vitamins,
essential nutrients, and food avors in the product. To
overcome or minimize such disadvantages, the concept of
non-thermal treatment was born. Compared to traditional
thermal processes, non-thermal processes kills most patho-
genic or spoilage microorganisms and inactivates enzymes,
and minimize the loss of taste, color, texture, nutrients, and
heat labile functional components of foods. It has been
targeted as an effective complement or replacement to the
thermal processes, and had been successfully applied [9396].
Recent studies have indicated that different non-thermal
treatments affect the physicochemical properties of starch
differently. Some of the non-thermal processes are conducted
at high hydrostatic pressure (HHP) [9799], using ultrasound
effect [100103], PEF treatment [96, 104] and microwave
treatment of starches [105] from different botanical sources.
High pressure technology involves using a uniform
pressure throughout a product. In the food industry,
pressures ranging from 400 to 900 MPa can be used.
Generally, HHP treatment restricts the swelling power of
starch granules, so that their viscosity is lower compared to
heat processed starches [106]. Furthermore, starch gelatini-
zation is achievable at room temperature or below OC with
HHP treatment of starches from different botanical sources.
The literature is replete with works on HHP [98, 107115]
treatment of starch gel. It was reported that the properties of
starch pastes and gels obtained under high pressure
treatment differed from those of the heat-gelatinized
ones [116]. Blaszczak et al., [117] observed that the optical
birefringence of wx maize starch was instantly lost after its
treatment at 650 MPa for 3 min in excess water, it was
absolutely rendered amorphous. In contrast, the same
pressure of 650 MPa was not sufcient to evoke the
disappearance of the maltese cross in hylon VII
starch [117]. The molecular integrity and orderliness of
potato starch treated with 600 MPa for 3 min was slightly
distorted by HHP, however the crystallinity of the starch was
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46 A. O. Ashogbon and E. T. Akintayo
preserved [97]. The high pressure treatment (650 MPa/9 min)
of wx maize starch induced sufcient disruption of the
amorphous and semi-crystalline growth rings, irrespective of
their localization within the granules, which in turn led to
complete gelatinization [97]. Stute et al. [118] reported that
starches of different botanical origin gelatinized at different
pressure ranges. On the other hand, potato, barley, maize,
and wheat starches treated with high pressure retained their
granular shape and demonstrated limited swelling [116, 118].
A possible application of pressurized starch could be to use it
as a fat substitute, the starch granules might stimulate fat
droplet as they are considered as micro-particles of well-
dened size distribution [37, 118].
Ultrasound is the sound that is above the threshold of the
human ear (above 18 kHz). High power ultrasound (HPU)
represents a non-thermal processing method that has been
rapidly researched and used in the last 12 years. It offers the
opportunity to modify and improve some technologically
important compounds which are often used in food products.
Starch is one of them. Ultrasound is generated with either
piezoelectric or magnetostrictive transducers that create high-
energy vibrations. These vibrations are amplied and
transferred to a sonotrode or probe, which is in direct
contact with the uid [119, 120]. HPU is very important in the
following areas of food processing; extrusion, defoaming,
viscosity alteration, separation, ltration, crystallization,
homogenization, emulsication, and extraction. Other
applications of ultrasound include inactivation of enzymes
and bacteria by breaking the cell membranes due to the
violence of cavitation and the formation of free radicals. The
ultrasound methods have been applied to several kinds of
starch (sweet potato, tapioca, potato, and corn) and
polysaccharides [101]. The crystalline region of corn starch
granules was observed to be distorted when the native corn
starch was treated with a HPU of 24 kHz frequency [119]. The
latter researcher also reported decrease in enthalpy of
gelatinization (DH) when the modied starch was studied
with DSC. An effective way for the reduction of MW of
polysaccharides like starch and chitosan is to treat their
aqueous solution with 360 kHz ultrasound [100]. The
degradation of starch by applied ultrasound has been
attributed to OH radical formation and mechanochemical
effects.
When exposed to high electric eld pulses, cell mem-
branes develop pores which may be permanent or temporary,
depending on the intensity and treatment conditions. Low
intensity treatment has the potential to induce stress
reactions in plant cells resulting in the promotion of a
defense mechanism by increased production of secondary
metabolites [121]. An irreversible perforation of the cell
membrane reduces it barrier effect permanently and causes
cell death which can be applied for plant and animal raw
material disintegration [122] as well as for the non-thermal
inactivation of microorganisms. In comparison to other
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Starch/Strke 2014, 66, 4157
traditional thermal pasteurization, PEF technology is a non-
thermal food preservation method, which kills most
pathogenic or spoilage microorganisms and inactivates
enzymes, and minimize the lost of taste, color, texture,
nutrients, and heat liable functional components of
foods [123]. Apart from the works of Han et al. [104] on
corn starch, limited researches focused on the physiochem-
ical properties of starches due to the impact of PEF. Recent
studies by Han et al. [104] reported that different treatments
affect the physicochemical properties of starch differently.
When corn starchwater suspensions were processed in the
PEF with electric eld strength of 50 kV/cm [104] the
following results were obtained. The gelatinization tempera-
ture and enthalpy of the modied corn starch decreased with
the increase of electric eld strength. Furthermore, the starch
lost granule shape, and the crystallinity degree were
decreased signicantly. Meanwhile, the peak, breakdown
and nal viscosity of the modied corn starch were decreased
with increasing electric eld strength.
3 Chemical modification
Chemical modication involves the introduction of function-
al groups into the starch molecules, resulting in markedly
altered physicochemical properties. Such modication of
native granular starches profoundly changes the proximate
compositions, gelatinization, retrogradation, and pasting
characteristics. Chemical modication is intended to facili-
tate intra- and inter-molecular bonds at random locations in
the starch granule for their stabilization. The chemical and
functional properties achieved by modied starches depend,
inter alia, on starch source, reaction conditions (reactant
concentration, pH, reaction time, and the present of catalyst),
type of substituent, degree of substitution (DS), and the
distribution of the substituents in the starch molecule [124,
125]. Modication is generally achieved through derivatiza-
tion, such as acetylation, cationization, oxidation, acid
hydrolysis, and cross-linking. These techniques are however
limited due to issues concerning consumers safety and the
environment. There is an evolving new trend called dual
modication, which involves the combination of physical and
chemical agents, e.g., microwave-assisted acetylation or
HHP-assisted phosphorylation.
3.1 Cationic starch
Cationic starch is produced from the reaction of starch with
reagents containing amino, imino, ammonium, sulphonium,
or phosphonium groups. The free hydroxyls of the native
starch is commonly altered by using cationic monomer such
as 2,3-epoxypropyltrimethylammonium chloride (ETA) or
3-chloro-2-hydroxypropyltrimethyl ammonium chloride
(CTA) under wet or dry processes or a process in between
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Starch/Strke 2014, 66, 4157
the two processes. In the dry-cationization process (absence
of a liquid phase) reagent is sprayed to the dry starch during
extrusion; in the semi-dry method, reagent is sprayed onto
the starch and the mixtures are thermally treated. Both
methods above reduced environmental pollution. However,
by-products may be produced along with the desired
products [126], it might also be costly separating the net
product from the by-products. In the wet-cationization
method, reactions are processed homogeneously in dimethyl
sulphoxide (DMSO) or heterogeneously in an aqueous
alkaline suspension [127]. The latter researchers reported
that high-DS cationic derivative were prepared in aqueous
alkaline solutions, homogeneously with DMSO, and hetero-
geneously with ethanolwater. Usually, the high-DS cationic
starch is prepared by an aqueous procedure, as water favors
the diffusing of the cationic agent into the starch granule.
However, hydrolysis or other side reactions may compete for
the etherication of starch in the presence of water. Thus, it
is necessary to choose appropriate media in which water
is partially replaced in the reaction mixture by an active
solvent.
A further investigation by Wang et al. [128], making use of
corn starch, cationic reagent (ETA) and dioxaneTHFwater
(dioxaneTHFwater) medium, revealed that the granular
morphology and crystallinity of the modied corn starch
granules were destroyed. The damaged morphology of the
cationic corn starch granules were attributed to the
penetration of its interior by cationic reagent resulting in
subsequent enlargement and disintegration of the granules
(Fig. 1) [128]. The same work adduced the loss of crystallinity
to the effect of the aqueous alkaline environment during the
modication. In their own contribution, Kuo and Lai [129]
indicated that the changes in the pasting and thermal
properties of cationic corn starches correlated well with the
increase of DS, together with the characteristics of granular
morphology. They further reported the gradual reduction of
the structural and molecular integrity of cationic starches
with raising DS up to 0.04311, while evident physicochemical
and morphological changes took place when DS was further
increased to 0.1215. The cationic substitution by aqueous
methods is believed to occur mainly at the amorphous region,
as evidenced by the unchanged XRD patterns and persistent
birefringence under polarized light microscopy [126]. Sie-
mion et al. [130] also treated mixtures of starches and
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
47
semicarbazide hydrochloride with either conventional or
microwave heating and obtained a product that contained
cationic groups.
Generally, physicochemical properties as well as granular
morphology of starch were always altered after cationization,
especially those involving high DS. Furthermore, lower
pasting temperature, higher peak viscosity, and various
changes in setback were observed in the RVA of different
kinds of starches [131]. Additional facts are the smaller DH
and lower transition temperature of cationic starches when
compared to native starches as analyzed by DSC [126]. There
are many different applications of cationic starch; it is used
for water treatment as occulants [132] and as additive in
textile and cosmetic products [127]. Furthermore, some
researchers have found cationic starch to be useful in
dynamic coating additive for protein analysis in CE [133].
3.2 Cross-linked starch
Cross-linking has been used to modify native starch utilizing
various cross-linking agents such as sodium trimetaphos-
phate (STMP), sodium tripolyphosphate (STPP), epichloro-
hydrin (ECH), and phosphoryl chloride (POCl3) [2]. Other
cross-linking agents are adipicacetic mixed anhydride, and
mixture of STMP and STPP. ECH is no longer used for food
grade manufacturing in the U. S. because the chlorohydrins
are carcinogens. Chung et al. [134] reported cross-linking of
starch to be affected by many factors, such as starch source,
cross-linking reagent concentration and composition, the
extent of substitution, pH, reaction time and temperature.
The type of cross-linking agent determines the changes in
functional properties of a treated starch, because the
molecular structures of the cross-linked systems produced
by different cross-linking agents are different [135]. There-
fore, based on the reagent used for cross-linking, the nal
product is generally classied into three types: the rst type is
a mono-starch phosphate which is produced by esterication
of starch with ortho-phosphoric acid, sodium or potassium
ortho-phosphate, or STPP. The second classication is a di-
starch phosphate which is produced when a native starch is
reacted with STMP or POCl3. Final type of cross-linked starch
is a phosphated di-starch phosphate which resulted from
combined treatments of mono-starch phosphate and di-
starch phosphate [136, 137]. The botanical sources of starch
Figure 1. SEM pictures of starch gran-
ules: (a) native starch 1000
; (b) DS 0.54
cationic starch 200
; (c) DS 1.35 cationic
starch 200
. Reprinted from Carbohy-
drate Research, 2009, Volume 344, Issue
7, Page 851855, Page Wang, P.-X., Wu,
X.-L., Dong-Hua, X., Kun, X., Ying, T., Xi-
bing, D., Wen-bo, L., Preparation and
characterization of cationic corn starch
with a high degree of substitution in
dioxane-THF-water media [128], with
permission from Elsevier.
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48 A. O. Ashogbon and E. T. Akintayo
and conditions and methods used for its modication have
great inuence on the properties of the nal product.
Koo et al. [138] cross-linked corn starch with STMP/STPP
(99:1 w/w) and found that cross-linking decreased the SF
(SF), solubility and paste clarity of corn starch. Majzoobi
et al. [139] also reported lower water solubility and swelling
power (SP) when cross-linked wheat starch is compared to its
native counterpart. Identical results were realized by
Gunarantne and Corke [136] and Mirmoghtadaei
et al. [140] on reduction in solubility and SP of various
cross-linked starch systems. The decreased paste clarity is
consistent with results obtained by Kaur et al. [141] that cross-
linked starches showed lower paste clarity than their
counterpart native starches. These decreased paste clarity
of cross-linked starches were attributed to their being more
compact when compared to native starches. Furthermore, it
has been indicated that the reduced swelling of cross-linked
starches might be partly responsible for their decreased paste
clarity [141]. The decreased SF with increasing level of cross-
linking [138] concurs with the work of Mirmoghtadaie
et al. [140]. It is an established fact that cross-linking
strengthens the bonding between starch chains, thus
resulting in resistant to swelling. Koo et al. [138] found that
the solubility of cross-linked corn starch decreased with
increasing degree of cross-linking at all temperatures when
compared to native corn starch, identical patterns were
reported by Kaur et al. [141] for potato starches modied with
ECH and POCl3 at different concentrations. The above
phenomenon could possibly be due to increased density of
cross-links in the starch structure that prevent disintegration
of starch granules during the attainment of gelatinization
temperature by various starches [137].
In furtherance of their works on cross-linked corn starch,
Koo et al. [138] found no difference in the crystallinity of the
modied corn starch compared to the native starch. Identical
crystalline pattern was also observed in the treatment of wheat
starch with POCl3 [139]. This re-echoed the accepted fact that
cross-linking mainly take place in the amorphous regions of
the starch granules and did not alter the crystalline patterns of
starches. The SEM of native and cross-linked starch granules
differ signicantly. The native corn starch granules were
polygonally shaped with well-pronounced edges, whereas
cross-linked starch granules possessed slightly rough surface
and black zone on the granular surface (Fig. 2) [138]. Similar
results were reported by Carmona-Garcia et al. [3] on cross-
linked banana starch obtained by identical treatment of native
banana starch with STMP/STPP. Identical morphological
changes were also reported when native wheat starch was
cross-linked with POCl3 [139]. The black zones on the starch
granule surfaces indicate slight fragmentation and the
formation of deep grooves in the starch granules [142].
Hydroxypropylation and acetylation of starches also
increase granule surface area and granule porosity [143,
144]. Majzoobi et al. [139] reported that cross-linked wheat
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Strke 2014, 66, 4157
starch with large granules (A-types) possessed more spots
compared to smaller ones (B-types). Similarly, Hung
et al. [144] had previously indicated that A-granules are
affected more than B-granules by cross-linking agents. It has
been observed that the granule structures were severely
altered with increase in the concentration of the cross-linking
reagents [145]. The botanical source of the starch may also
affect the morphological properties as a result of chemical
modication [146]. In contrast, no changes were observed in
the size and shape of potato starch granules when cross-
linked by POCl3 [143].
Generally, cross-linking reduces the moisture, protein, and
fat contents of the native starches that were modied
irrespective of the botanical sources of the starches and the
cross-linking reagents involved, although the level of
reduction differ. These facts were corroborated by the ndings
of Carmona-Garcia et al. [3] when they treated banana starch
with different cross-linking agents. On a broader note,
Lawal [147] also reported reduction in proximate compositions
and AM content when cocoyam starches were separately
oxidized, acetylated, and acid-thinned.
3.3 Acetylated (Ac) starch
Acetylation is one of the common chemical method of starch
modication, it is achieved by esterication of native starch
with either acetic anhydride or vinyl acetate in the presence of
alkaline catalyst, e.g., NaOH, KOH, Ca(OH)2, Na2CO3 [125,
148]. The acetylation reactions are typically carried out in
water, though organic solvents also have been shown to be
effective [149, 150]. Ac starch is a starch ester that has been
extensively studied over the last two decades [125, 151155].
Introduction of acetyl groups reduces the bond strength
between starch molecules causing an increase in the swelling
power and solubility of the modied starch. Hydrogen
bonding is restricted in Ac starches as a result of inter- and
intra-molecular electrostatic repulsion in the starch
molecule [156]. Ac starches act as RS and have been observed
to increase large bowel SCFAs [157]. In Ac starch, parts of the
hydroxyl groups in anhydroglucose units have been converted
to acetyl groups. A low DS with 0.010.2 acetylated starch has
been applied in many areas, such as lm forming, binding,
adhesion, thickening, stabilizing, and texturing [158, 159]. Ac
starch with low DS is commonly obtained by esterication of
native starch with acetic anhydride in an aqueous medium in
the presence of an alkaline catalyst. However, high DS Ac
starches have received much attention in recent years for
their solubility in acetone and chloroform and for their
thermoplasticity. Furthermore, high DS Ac starches can have
very different properties such as hydrophobicity, melt
processibilty and a number of non-food applications, such
as tablet binders, hot melt adhesion, coating, cigarette lters,
biodegradable packaging materials and pharmaceutical
aspects have been suggested [150, 160]. Shogren [150]
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Starch/Strke 2014, 66, 4157
prepared a series of starch esters, such as Ac starches by high
temperature and pressure reaction. Chi et al. [161] also
prepared Ac starches with different DS by the reaction of the
native corn starch with acetic anhydride in the pressure of
acetic acid under varying reaction temperatures. They found
the modied corn starches possessed better hydrophobic
performance than the parent starches. Cloudiness and
syneresis of aqueous dispersions of waxy starches could
also be minimized through acetylation of AP outer
branches [162]. Acetylation reduces retrogradation tendency
of starches, however, level of DS of acetyl groups is a major
determinant in imparting desirable properties to the starch.
Although many studies on the esterication of starches
have been conducted [163165] recent focus is on the
application of green chemistry that is environmentally
friendly. Generally, high fatty acid esters of starches could
be prepared by reacting native starch with fatty acid vinyl
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
49
Figure 2. Scanning electron micrographs of native and
cross-linked corn starch prepared with different levels
of cross-linking with the mixture of STMP/STPP. (A)
Native, (B) cross-linked with 5% (w/w) STMP/STPP,
(C) cross-linked with 10% (w/w) STMP/STPP, (D)
cross-linked with 12% (w/w) STMP/STPP. Magnica-
tion: left 200
; right 500
. Reprinted from Food
Hydrocolloids, 2010, Volume 24, Issues 6-7, Page
619625 Koo, S. H., Lee, K. Y., Lee, H. G., Effect of
cross-linking on the physicochemical and physiologi-
cal properties of corn starch [138], with permission
from Elsevier.
esters, fatty acid chlorides, carboxylic acids, or FAME as
reactants in organic solvents such as toluene, pyridine or
DMSO [166172] and basic salts such as K2CO3, CH3COONa,
NaH2PO4, and CH3OK as catalyst. However, these organic
solvents are poisonous and exorbitant and therefore have
higher environmental impact than water. Hence, there is a
strong incentive to develop green, environmentally friendly
solvents for starch esterication. A possible solution is the use
of densied CO2. Super-critical or densied CO2 is non-
ammable, non-toxic, chemically inert and a green solvent.
It has been shown to be an excellent solvent and attractive
for polymer processing. Furthermore, CO2 can be easily
separated from the reaction mixture by depressurization
[173]. Recent works have described the production of fatty
acid starch esters using a fatty acid vinyl or methyl esters or a
fatty acid anhydride with supercritical CO2 as a solvent [171].
These methods have produced products with broad range of
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50 A. O. Ashogbon and E. T. Akintayo
DS values (0.010.31). Recently, other desirable green
solvent, ionic liquids (ILs) at ambient temperature were
considered for wide range of synthesis and catalysis because
of their possession of low melting points, wide liquid ranges,
and low or negligible vapor pressure. Of interest is the ILs
bearing the imidazolium structure, have been known to be
non-derivatizing medium capable of dissolving polysacchar-
ides, such as starch and cellulose [152, 174]. Using 1-butyl-3-
methylimidazolium chloride (BMIC), starch could dissolve in
it up to 15% w/w concentration at 80C [175]. Xie and
Wang [152] synthesized high fatty acid esters of corn starch by
reacting the starch with FAME using BMIC-IL as the reaction
medium. They found that the hydroxyl groups in the starch
molecules were converted into ester groups, additionally, the
morphology and crystallinity of the modied starch ester
granules were largely disrupted or altered.
3.4 Dual modifications
To further improve the properties and uses of starches,
chemical dual modication and other types of dual mod-
ications have been introduced in order to optimize the
functionality of modied starches. Generally, dual modica-
tions involve using a combination of chemical and physical or
chemical and enzymatic methods, but specically dual
chemical modications involve using two types of chemical
modication (e.g., acetylation/oxidation, cross-linking/acetyla-
tion, or cross-linking/hydroxypropylation) [3, 148, 176180].
The literature is also replete with plenty of works on the dual
modication involving combinations of different methods of
modications [19, 181184]. Chemical dual modications are
widely used in the food industry as emulsiers, binders and
thickeners; furthermore, they are also applied in the non-food
industry as heavy metal adsorbents.
Despite the benecial properties of Ac starch, it may not
meet all the diversity of physical and textural properties
required by many emerging food systems. Therefore,
enhancement of properties and functionalities of ultra high
pressure (UHP) treated acetylated corn starch is
possible [151]. A chemical dual modication using cross-
linking and phosphorylation on rice starch provided modied
rice starch with good freeze-thaw stability [182]. Restricted
starch solubility/swelling properties were observed when Ac
corn starch was treated at UHP [151]. The dual chemical
modication (Oxidation/acetylation) of non-conventional
sources of starch, e.g., plantain starch improve the physical
and chemical properties of the native plantain starch [179].
Wattanachant et al. [180] reported that sago starch was
suitable as a starch base for hydroxypropylation and cross-
linking and concluded that the swelling power of the starch
base is the most important factor which inuences dual-
modication. An efcient method of esterifying starch is by
microwave-assisted esterication to produce starch maleate
using the dry method and this give a reaction efciency of
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Starch/Strke 2014, 66, 4157
98% in a reaction time of 5 min [185]. Microwave-assisted
succinylated cassava starch can be produced with high
efciency [165], this method decrease the use of chemicals
and enhance production.
3.5 Other chemical modification methods
Acid modication is one of the oldest methods of starch
modication, and the derived degradation products have a
vast application potential. Acid-modied starch is widely used
in the food, paper, and textile, pharmaceutical, and other
industries [186, 187]. The method for the manufacture of
acid-thinned starch entails treating concentrated starch slurry
(3640% solid) with mineral acid (HCl or H2SO4) at
temperature below the gelatinization temperature for specic
period depending on the desired viscosity or degree of
conversion [188]. The mechanism of acid hydrolysis involved
the attack of the glycosidic oxygen atom of the native starch by
the hydroxonium ion and this result in cleavage and
depolymerization. Acid hydrolysis of starch proceeds ran-
domly, cleaving both a-1, 4 and a-1, 6 linkages and
shortening the chain length with time. Alpha-1, 4 linkage
and the amorphous regions containing a-1, 6 linkages are
more accessible to acid penetration and hydrolysis. Acid
modication involves a two-stage attack on the starch
granules. Acid attacks both AM and AP during the early
stages of acid treatment but preferentially attacks the
amorphous regions of the starch granule in the rst stage
and then attacks the more crystalline sections at slower
rate [189]. Many researchers [190, 191] hydrolyzed legumes
starches (smooth pea, wrinkled pea, adzuki bean, mung bean,
red kidney bean, green lentil, eld pea, beach pea, green pea,
grass pea, moth bean, rice bean, and horse gram) with 2.2 N
HCl and found that they all exhibited a two-stage solubiliza-
tion pattern. The same two-stage hydrolysis pattern has also
been reported for normal corn, wx corn, wheat, potato and
rice starches [192]. These authors reported a relatively fast rate
of hydrolysis during the rst 8 or 10 days, followed by a slower
rate between 10 and 20 days. They attributed the faster rst
stage to the hydrolysis or degradation of the more amorphous
parts of the starch granule and slow degradation during the
second stage to the erosion of the crystalline material. Singh
and Ali [193] reported the inuence of various mineral acids
(HCl, HNO3, H2SO4, and H3PO4) on acid hydrolysis of
wheat, maize, nger millet, chickpea, green gram, tapioca
and potato starches. They indicated that MW decrease after
modications, with H3PO4 causing the smallest effect while
HCl and HNO3 had the greatest MW reduction. Lawal [147]
extensively studied acid-thinning of new cocoyam starch and
concluded that the proximate compositions and Am content
of the acid-treated starches were reduced. Additionally, there
were no changes in the morphology and crystallinity of
the acid-modied cocoyam starch, there were increased
in the peak temperature and enthalpy of gelatinization. The
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Starch/Strke 2014, 66, 4157
acid-thinned starch of Lawal [147] recorded reduced swelling
capacity, improved solubility and increased in setback
viscosity parameter.
In recent times, oxidized (Ox) starches have attracted
much attention because they are widely utilized in the
food and non-food applications to provide surface sizing and
coating properties [194]. Oxidation involves the introduction
of carboxyl and carbonyl functional groups with subsequent
depolymerization of the starch. Such starches have been
established to be whiter in color and have reduced
retrogradation when compared to the parent starches [195].
Ox starch is commercially prepared by reacting starch with a
specied amount of oxidant under controlled temperature
and pH. Many oxidants such as hydrogen peroxide, peracetic
acid, potassium permanganate, sodium hypochlorite, chro-
mic acid, and nitrogen dioxide have been used to oxidize
starches [196198]. Sodium hypochlorite is the oldest and the
most popular commercial oxidant. The factors impacting
hypochlorite oxidation include, temperature, pH, hypochlo-
rite concentration, starch molecular structure, and starch
origin. Hydroxyl groups of starch molecules are rst oxidized
to carbonyl groups and then to carboxyl groups. Therefore,
the numbers of carbonyl and carboxyl groups in Ox starch
indicate the level of oxidation, which takes place primarily at
the hydroxyl groups of C-2, C-3, and C-6 position on a
D-glucopyranosyl unit [199201]. SEM has been widely used
to study starch granule morphology, both in native and Ox
starches from corn, rice and potato [195] and cocoyam
starches [147]. Adebowale and Lawal [202] studied the
functional properties and retrogradation behavior of mucuna
bean starch oxidized with sodium hypochlorite. They
reported decrease in the pasting temperature, peak viscosity,
breakdown viscosity, transition temperatures, gelatinization
and retrogradation enthalpies upon oxidation. Wang and
Wang [198] also studied the physiochemical properties of
common and wx corn starches oxidized by different levels of
sodium hypochlorite. It was reported that NaOCl oxidized
cocoyam starch possessed the following properties; reduction
in proximate compositions (ash content, fat content, crude
bre, protein) and AM content, no change in granule
morphology and crystallinity, reduction in swelling capacity
and markedly improved solubility when compared to the
parent (native) cocoyam starch [147]. Kantouch and
Dokki [203] studied the effect of NaOH concentration on
the gelatinization of hypochlorite-Ox corn starches. Kuakpe-
toon and Wang [204] also studied the structural and
physicochemical properties of Ox corn starches with varied
AM contents. They reported that the oxidizing agent
penetrate deeply into the amorphous regions and have
minimal effect on the crystalline regions. The formed bulky
carboxyl group on the starch molecules results in low
retrogradation and syneresis of the Ox starch paste, whereas
carbonyls play a minor role in the prevention of retrograda-
tion of starches.
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
51
4 Conclusions
The inherent shortcomings in native starches, such as
insolubility in cold water, loss of viscosity, and thickening
power after cooking, tendency to easily retrograde and loss
ordered structure after gelatinization and subsequent
syneresis in starchy food systems can be overcome. However,
these setbacks in unmodied starches can be easily mitigated
by physically and chemically modifying them. Physical
modication can be broadly divided into three: (a) PGSs;
(b) hydrothermally treated starches; and (c) non-thermally
treated starches.
Fully PGSs are obtained by heating the starch slurry above
the gelatinization temperature and drying it using drum
drying, extrusion, or spray drying. The most important
property of PGS is that it instantly hydrates and swells in
water at ambient temperature. PGSs are gelatinized, so their
molecular structures are destroyed, depolymerized and their
structural integrity and order are not retained or preserved.
That is why they are used as thickening agent in puddings,
pie llings, sauces, and baby foods. Hydrothermally treated
starches (ANN and HMT) modify the physicochemical
properties of starch, without destroying granular structure.
Hydrothermal treatment changes the physicochemical
properties of starches by improving crystalline perfection
and by facilitating interactions between starch chains. The
effects of ANN and HMT on starch are most readily
differentiated by using WAXS and DSC [205]. Non-thermally
treated starches are induced by UHP, HHP, PEF treatment,
microwave treatment and HPU treatment. Their effects on
the physicochemical and functional properties of starches
solely depend on the intensities of the forces or pressures
applied and the starch type. The appeal of physically modied
starch lies in its non-exorbitant and non-toxic nature because
of the non-utilization of chemicals or biological agents.
Chemical modication is generally achieved through
derivatization such as esterication, etherication, cross-
linking, cationization due to the presence of ubiquitous
hydroxyl groups on native starches. There is an evolving new
trend called dual modication, which involves the combina-
tion of physical and chemical methods, e.g., UHP-assisted
acetylation or HHP-assisted phosphorylation.
The authors have declared no conict of interest.
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