Art and Science behind Modified Starch Edible

Films and Coatings: A Review

Umar Shah, Farah Naqash, Adil Gani, and F. A. Masoodi

Abstract: Technological advances have led to increased constraints regarding food packaging, mainly due to envi-
ronmental issues, consumer health concerns, and economic restrictions associated therewith. Hence, food scientists and
technologists are now more focused on developing biopolymer packages. Starch satisfies all the principal aspects making
it a promising raw material for edible coatings/films. Modified starch has grabbed much attention, both at the academic
as well as at the industrial level, because these films exhibit dramatic improvement in filming properties without involving
any significant increase in cost of production. Various methods, additives used, and recent advances in the field of starch
film production are discussed in detail in this review, which also provides an overview of the available information along
with recent advances in modified starch film packaging.
Keywords: biopolymers, food packaging, modified starch

Introduction (amylose and amylopectin), and amylose readily forms coatings

Ongoing challenges like nonsustainable production, lack of re-
cyclability, health concerns, and insufficient mechanical and bar-
rier properties of packaging materials have prompted the food
packaging industries to employ edible films and coatings. Edible
films and coatings have attracted attention because they address
various key functions, such as extending maturity and senescence
periods, and reducing microbial growth, thereby assuring posthar-
vest quality of perishable foods (Jimenez and others 2013a). Various
bio-based packaging materials can be employed for short shelf-
life applications and for dry products that do not require a high
oxygen and/or water vapor barrier (Niazi and Broekhuis 2015).
The environment-friendly nature of biopolymers (starch, proteins,
polysaccharides, and lipids) with excellent keeping quality as well
as safety records adds value to edible films and coatings (Pierro
and others 2007, 2011; Tanese and others 2008; Mihindukula-
suriya and Lim 2014). To the best of our knowledge, among the
renewable sources with film-forming ability, starch satisfies all the
principal aspects, such as easy availability, high extraction yield,
nutritional value, low cost, biodegradability, biocompatibility, and
edibility with functional properties. This makes it a promising
material for edible coatings/films (Zahedi and others 2010; Ghan-
barzadeh and others 2011; Falguera and others 2011; Souza and
others 2012; Kowalczyk and Baraniak 2014; Dang and Yoksan
2015; Reis and others 2015). Starch films are odorless, tasteless,
colorless, nontoxic, and semipermeable to carbon dioxide, mois-
ture, oxygen, as well as lipid and flavor components. These prop-
erties bring effects similar to those promoted by storage under
controlled or modified atmosphere. Starch contains 2 polymers
MS 20151851 Submitted 5/11/2015, Accepted 13/1/2016. Authors are with
Dept. of Food Science and Technology, Univ. of Kashmir, Jammu and Kashmir, India.
Direct enquiries to author Gani (E-mail: adil.gani@gmail.com).
and films due to its predominantly linear nature (Kramer 2009).
However, the semicrystalline (20% to 45%) nature of native starch
results in some undesirable drawbacks, such as its hydrophilic char-
acter, poor solubility, poor mechanical properties, uncontrollable
paste consistency, and low freeze-thaw stability during film for-
mation (Liu and others 2009; Xie and others 2013; Dang and
Yoksan 2015; Sabetzadeh and others 2015). In order to overcome
these flaws, and to modify the starch film characteristics, various
modification techniques can be employed: physical, chemical, en-
zymatic, and genetic, and addition of additives or a combination
of treatments. These would improve starch properties by alter-
ing starch molecular structure. Color and transparency are also
important properties of packaging films in terms of general ap-
pearance, consumer acceptance, and utilization and are to be kept
under consideration while modifying the starch (Dang and Yok-
san 2015). Modified starch films have gained both academic and
industrial attention because they are biodegradable, have low cost,
and possess good solubility and improved mechanical properties.
Shah and others (2015) reviewed the recent advances in the ap-
plication of starch, as a component of active and nanocomposite
packaging films. The objective of this review is to summon all
the valid physical, chemical, and dual methods including recent
advances in starch filmmaking and to provide suggestions for fur-
ther research. The following sections discuss various techniques
applied to starches, the resulting starches thus produced, and the
effects they have on film properties.
Chemical Modifications
Starches such as cross-linked, substituted, oxidized, acid-
hydrolyzed, and so on are produced as a result of chemical modifi-
cations. Table 1 displays various chemical modifications and their
effects on the starches.


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568 Comprehensive Reviews in Food Science and Food Safety r Vol. 15, 2016 doi: 10.1111/1541-4337.12197
Art and science behind modified starch . . .

Table 1Recent chemical modifications of starch for film preparation.

Starch type Agent Effect References

Cross-linked Glutaraldehyde Improvement in tensile strength, tensile modulus, tear Follian and others 2005; Tang
starches and burst, strength, and solubility and Alavi 2011; Ming and
others 2015;
Boric acid Excellent transmittance, mechanical properties, water Khan and others 2006
resistance, and strengthens the interbonding of the
molecule
Sodium trimetaphosphate Increased gel strength, water absorbance, resistance to Tang and Alavi 2005;
shear and decreased gel cohesiveness, clarity, and Dufresne 2014; Liu and
water solubility others 2014
Sodium trimetaphosphate + osmotic Increase in the viscosity with decrease in breakdown Liu and others 2014
pressure
Hydroxypropylation-acetylation and Decrease in swelling factor, and increase in gel strength, Gunaratne and others 2007;
hydroxypropylation-crosslinking decrease in rupture strength, gel elasticity, and Hoover and others 2010
adhesiveness
Lipids + trisodium trimetaphosphate Increased tensile strength of cross-liked films Barrios and others 2013
Substituted Acetic anhydride Increase in water solubility and pasting clarity, decrease Moad 2011; Zavarez and
Starches in pasting viscosities and gelling ability, glass others 2012
transition and gelatinization temperature, and
improved freeze-thaw stability of starch
Cationizing reagents containing the Cationizing reagents containing the amino, imino, Fonseca and others 2015
amino, imino, ammonium, or ammonium, or sulfonium groups
sulfonium groups
Carboxymethylation Increase in hydrophobicity, gel clarity, freeze-thaw Moad 2011; Zavarez and
stability, water-holding capacity, susceptibility to others 2012
shear-thinning, and reduced gelatinization
temperatures
Hydroxypropylation Clearer and more flexible films Moad 2012
Oxidized starch Sodium hypochlorite, ceric Gelatinization and retrogradation tendencies of starch Atichokudomchai and others
ammonium nitrate, hydrogen were reduced, increase in gel hardness, increased 2004; Olivato and others
peroxide, persulfate hydrogen bonding 2012; Falade and
Oluwatoyin 2015
Acid-hydrolyzed Organic acids, HCl, H2 SO4 Loss in pasting viscosities, decreased swelling power, Willet and others 1995; Van
starches increased solubility, broader range for gelatinization Soest and Borger 1997; Liu
temperature, and decreased tendency of and Thompson 1998;
retrogradation, surface morphology of the granules to Wuttisela and others 2009;
be eroded, increase in crystallinity percentage, water Zavareze and others 2012
solubility, reduced granule size, decrease in intrinsic
viscosity of starch, and decreased pasting viscosity

Cross-linked starches
Cross-linking is commonly employed to achieve an improved
compatibility and properties of starch. Starches with increased
numbers of cross-linkages exhibit improved water absorption ca-
pacity and maintain constant viscosity and texture. This makes
them desirable for maximum viscosity and optimum water sta-
bilization (Kramer 2009). Such starches are generally prepared
by treating native starch in an alkaline medium with reagents
such as glutaraldehyde, epichlorohydrin, citric acid, hexam-
ethoxymethylmelamine, boric acid, borax, sodium trimetaphos-
phate, and trisodium trimetaphosphate (Liu and others 2014; Li
and others 2015). Sodium trimetaphosphate is nontoxic and acts as
a cross-linking agent, resulting in increased gel strength, water ab-
sorbance, resistance to shear, and decreased gel cohesiveness, clar-
ity, and water solubility (Zhu and Wang 2014). Starch, cross-linked
(10 wt% to 20 wt%) with glutaraldehyde significantly improved
tensile strength, tensile modulus, tear and burst strength, and sol-
ubility. The hydrophobic nature of the cross-linked starch is due
to more numbers of carbon chains than that of native starch (Kim
2014). It is important to note that the increase in degree of cross-
linking is inversely proportional to pasting properties and enzyme
susceptibility. Cross-linking of starch films by boric acid resulted in
excellent transmittance, mechanical properties, and increased resis-
tance to water. Increasing the concentration of boric acid improves
cross-linking and, consequently, strengthens the interbonding of
the molecules (Yu and Wang 2007). The multicarboxyl structure
of citric acid allows it to act as a cross-linking agent (Ghanbarzadeh
and others 2011). Yu and Wang (2007) reported that cross-linked
starch molecules reinforce intermolecular binding (covalent bonds
and hydrogen bonds), thus improving the mechanical and water
resistibility of the film. However, cross-linked starch limits its use
in film formation. This is because, to achieve full functionality, a
majority of the starch granules and amylose/amylopectin polymers
should be fully dispersed in the aqueous medium (Kramer 2009).
Hence, cross-linking is usually combined with other treatments
to overcome flaws associated with them. Kaur and others (2012)
reviewed various dual techniques in which starch was modified
employing a chemical method (sodium trimetaphosphate, used to
cross-link starch) in presence of physical treatment (osmotic pres-
sure). Sodium trimetaphosphate increases viscosity with a decrease
in breakdown, while osmotic pressure causes an increase in the ac-
tivity of the cross-linking agent. Cross-linking is also coupled with
phosphorylation that imparts good freeze-thaw stability (Deetae
and others 2008). Dual techniques involving hydroxypropylation-
acetylation and hydroxypropylation-cross-linking were adopted to
decrease the swelling factor and amylose leaching of starch, rupture
strength, gel elasticity, adhesiveness, and increase the gel strength
(Gunaratne and others 2007; Das and others 2010). Addition of
lipids to a hydrocolloid matrix by overcasting or emulsion tech-
nique leads to increased tensile strength of cross-linked bi-layer
films (Baldwin and others 1997). Starch nano-particles, esterified
using Candida antarctica lipase B (CAL-B), retained their nano-
dimension upon the removal of surfactant when dispersed in water.
Lower retrogradation was seen when starch was modified through
esterification with ferulic acid at low-temperature storage com-
pared to native starch. Photo-curing technique, in which light
is used as cross-linking agent, is seen to improve cross-linking
of polymers as their functional groups undergo light-induced


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Art and science behind modified starch . . .

Table 2Mechanical properties of films made from modified starches.

Film material Modification agent Effect on film properties References

Dual-modified rice starch
Modified rice starch
Cross-linked dark cush-cush
yam and cassava starch
Starch/CMC
Modified corn starch
Tapioca starch
Oxidized starch
Cross-linked starch
Melt-blended starch
Starch/polyester blend
Starch/Polyvinyl alcohol
Starch-clay nanocomposite
Maize starch
Corn starch
Hydroxypropylation followed
by cross-linking
Hydroxypropylation
Sodium trimetaphosphite
Carboxymethyl cellulose
Citric acid and CMC
Sorbates
Chlorine
Citric acid
Polycaprolactone
Polyethylene glycol
Citric acid
Malic acid
Tartaric acid
Hydrophilic inorganic salts
Polysorbates
Starch nanoparticles
prepared by TEMPO (2,2,6,6-
tetramethylpiperidin 1-oxyl)
mediated oxidation
Chitin and chitosan
Increased tensile strength and elongation at break, Woggum and others 2014
increased strength, flexibility, solubility, decreased
crystallinity, and opacity
Increased film solubility, elongation at break, and Woggum and others 2015
transparency
Improved mechanical properties, maximum flexibility, Gutierrez and others 2015
and increased thickness
Increased ultimate tensile strength (UTS) Ghanbarzadeh and others
2010
Increased UTS Ghanbarzadeh and others
2011
Decreased storage modulus, and an increased loss Fama and others 2005
factor, delayed rupture
Reduced water solubility Fonseca and others 2015
Increased integrity, reduced crystallinity, and Seligea and others 2016
retrogradation
Reduced tensile behavior Ortega-Toro and others 2016
Increased extensibility, reduced elastic modulus, and
tensile stress at break
Increased tensile strength at higher citric acid and Olivato and others 2012
tartaric acid, and intermediate malic acid
concentration, increased homogeneity
Increased water absorption and plasticization, Jiang and others 2016
elongation at break, decreased crystallinity, and
tensile strength
Decreased tensile strength, increased elongation at Barzegar and others 2014
break
Increased tensile strength, elongation at break, and Fan and others 2016
Youngs modulus
Better elastic and viscous response indicated by positive Lopez and others 2014
effect on storage and loss modulus

Table 3Barrier properties of modified-starch films.

Film Modification Effect on

material agent
Dual-modified rice starch Hydroxypropylation followed
by cross-linking
Cross-linked chitosan/starch Glutaraldehyde
composite
Starch/CMC Carboxymethyl cellulose
Modified corn starch Citric acid and CMC
Cross-linked starch Citric acid
Starch/polyester blend Citric acid and Tartaric acid
Oxidized starch Chlorine
Etherified starch Polyvinyl alcohol
Starch/PVA Citric acid Glutaraldehyde
Cassava starch Stearic acid
Maize starch Starch nanoparticles prepared
by TEMPO (2,2,6,6-
tetramethylpiperidine-1-
oxyl) mediated
oxidation
Corn starch Chitin and chitosan
film properties References
Reduced water vapor permeability (WVP) Woggum and others 2014
Improved water barrier performance Li and others 2013
Reduced WVP, Ghanbarzadeh and others
2010
Improved water vapor barrier properties Ghanbarzadeh and others
2011
Reduced WVP Seligea and others 2016
Reduced WVP at higher acid concentrations Olivato and others 2012
Increased water barrier at higher oxidation Fonseca and others 2015
Reduced WVP with increased concentration, higher Isotton and others 2015
hydrophilicity and wettability
Improved protection against UV-visible light Pour and others 2015
Reduced WVP Schmidt and others 2013
Reduced WVP and water vapor transmission rate Fan and others 2016
Reduced WVP Lopez and others 2014

reactions (Tang and Alavi 2011). Follain and others (2005), and
Khan and others (2006) reported that photo-curing (ultraviolet) of
starch film resulted in lower brittleness and higher tensile strength,
and also a decrease of water absorption. Biodegradable films from
dual-modified rich starch were produced by hydroxypropylation
of rice starch, followed by cross-linking (propylene oxide). The
films showed an increased tensile strength and elongation at break.
This established that, modified starch films were stronger and more
flexible than native starch films. The film solubility also increased
because of increased hydrophilicity due to hydroxypropyl groups.
The water vapor permeability (WVP) of dual-modified rice starch
films was lower than the native starch films. However, the water
barrier properties were largely unaffected by the concentration of
cross-linking agent. The film crystallinity and transparency val-
ues decreased with increasing the concentration of cross-linking
agent. The films were less opaque, as lower transparency values
imply higher transparency in the film (Woggum and others 2014).
Table 2 summarizes the effect of modified starches on mechani-
cal properties of the films. Cross-linked chitosan/starch composite
films, prepared using solvent evaporation method show improved
water barrier performance. This is attributed to cross-linking;
however, the compatibility of the blends deteriorates after cross-
linking (Li and others 2013). Chemically modified starch is also
obtained from dark cush-cush yam (Dioscorea trifida) and cassava
(Manihot esculenta C.) by cross-linking with sodium trimetaphos-
phate. Films obtained from the modified starch show excellent

570 Comprehensive Reviews in Food Science and Food Safety r Vol. 15, 2016 
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Art and science behind modified starch . . .
mechanical properties and maximum flexibility, owing to stronger
plasticizerstarch interactions. However, the films tend to be per-
meable to water vapor due to hydrophilicity (Gutierrez and others
2015). Biodegradable and nonretrogradable films obtained from
starch and glycerol were analyzed for the effect that citric acid had
on them as a cross-linking agent. The WVP of the films decreased
with the addition of citric acid, and retrogradation of the starch
was prevented due to a network formed by citric acid. The films
maintained their integrity in dimethylsulfoxide (DMSO) during
the swelling test, compared to the native starch films that were
completely soluble. Cross-linking confers an increased resistance
of the films to disarm, allowing them to swell (Seligea and others
2016). The barrier properties of the films resulting from modified
starches are presented in Table 3.
Substituted starches
The carbohydrate polymer inside the starch granule can be co-
valently substituted with different functional groups using succinic
anhydride, acetic anhydride, and propylene oxide to improve the
properties of starch for film-making (Hoover and others 2010).
These newly formed derivatives are tailor-made to gain an edge
in a new product formulation, and they also extend the shelf-life.
Substitution results in increased water affinity, lower starch gela-
tinization temperature, better hydration, and less firm gel with
better clarity. The effect of different functional groups (hydroxyl
and carboxyl groups) on physical properties of starch film has
been studied and it has been concluded that functional groups
increase the flexibility and strength of the film. Addition of ad-
ditives improved tensile strength and elongation. These changes
are brought about because of steric hindrance caused by newly
attached functional groups that do not allow water to weep out,
prevent re-association, and, consequently, the gel becomes more
resistant. Substitution with acetic anhydride in an alkaline solution
(acetylation) results in an increase in water solubility and pasting
clarity, decreases in pasting viscosity and gelling ability, and im-
proved freeze-thaw stability of starch. Hydroxypropylated starches
produce films that are clearer and more flexible compared to those
produced from native starch (Kramer 2009; Hoover and others
2010). Polycaprolactone-and polystyrene-grafted starch nanocrys-
tals were obtained by grafting approaches without change in their
crystallinity (Dufresne and others 2014).
Oxidized starch
Starches from corn, potato, cassava, and beans can be oxidized
(Zavareze and others 2012). Very few studies have been carried out
using oxidized starches to produce biodegradable films. Oxidized
starches are applied to deep-fried food as coatings (beer-battered
coating, French fries, and various coatings applied to meats, fish,
and vegetables) to improve their eating quality by retaining crispi-
ness and by delivering seasoning to the surface. Moad (2011) re-
viewed various chemical oxidants such as hypochlorite, perman-
ganate, ceric ammonium nitrate, hydrogen peroxide, persulfate,
periodate, and dichromate for obtaining improved and desired
product properties. Their mechanism of action varies according to
reagents and process conditions (Hoover and others 2010; Fonseca
and others 2015). Oxidation of starch leads to increased interaction
among polymer chains, affecting the crystallinity and flexibility of
the film and, thereby, causing an increase in the tensile strength of
the resulting films (Zhang and others 2009). Adebowale and Lawal
(2003) showed that the gelatinization and retrogradation tendency
of starch is reduced on oxidation with sodium hypochlorite. The
gel hardness of cassava starch oxidized with sodium hypochlorite

C 2016 Institute of Food Technologists Vol. 15, 2016 r Comprehensive Reviews in Food Science and Food Safety 571
increased due to hydrogen bonding as compared to native starch
because of formation of carboxyl and carbonyl groups and reduc-
tion in the size of amylose molecules. For some coatings, moisture
permeability is desirable because water vapor should escape from
food during cooking without blowing off pieces of the coating
into the fryer. Oxidized starch films with active chlorine possess
lower water solubility compared to that from native starch. This
happens due to the increased interactions between the amylose
molecules, and the bonds that are formed by the oxidation of
starch, reducing the capacity to absorb water (Zavareze and others
2012). However, the starch oxidation does not seem to affect the
lightness of the films. Increasing the extent of oxidation improves
the water barrier properties (Fonseca and others 2015).
Acid-hydrolyzed starches
Acid hydrolysis is a chemical treatment largely used in the food
industry to prepare glucose syrups from starch (Dufresne and oth-
ers 2014). Acid-hydrolyzed starch is a type of chemically modified
starch, which is produced by treating starch granules with mineral
acid such that starch molecules are partially depolymerized to a
desired extent. Acid-modified starches are usually applied to imita-
tion cheese, jelly candies, processed meats, and to extruded cereals
and snacks (Kramer 2009). Acid hydrolysis leads to loss in pasting
viscosities, decreased swelling power, increased solubility, broader
range for gelatinization temperature, and decreased tendency to
retrogradation as compared to native starches (Atichokudomchai
and others 2003, 2004). The modification of starch through acid
hydrolysis depends on the type of solvent used, reaction temper-
ature, and reaction time. Acid modification or thinning partially
disbranches amylopectin, which is located within amorphous re-
gions of the granule. This causes an increase in the linear compo-
nent of the treated starch, and thus confers predominance to the
amylose-like behavior (Kramer 2009). Acid hydrolysis of starch
causes surface morphology of the granules to erode without for-
mation of the pores on the surface (Atichokudomchai and others
2003, 2004). Organic acids, by degrading starch chains to dex-
trin and fragments of low molecular weight, promote hydrolysis
of starch (Olivato and others 2012). The short-chain polymers
(dextrin and maltodextrin) have high efficiency of film formation
in comparison to native starch. Falade and Oluwatoyin (2015) re-
ported a considerable change in color value of starch with acid
hydrolysis and concluded it to be a result of change in purification
and separation of some heterogeneous materials. Botanical origin
of the starch determines the critical time corresponding to fast
or slow hydrolysis; and the hydrolysis is faster using hydrochlo-
ric acid (HCl) rather than sulfuric acid (H2 SO4 ) (Dufresne and
others 2014). The enzymatic pretreatment of starch is carried out
in order to reduce the time of hydrolysis. Scanning electron mi-
croscopy (SEM) and chemical force microscopy showed that acid
treatment to starch causes erosion at the surface without forma-
tion of pores (Atichokudomchai and others 2004; Wuttisela and
others 2009). Acid-treatment causes an increase in the percentage
of crystallinity, polymorphic changes (C-type to A-type) in starch,
an increase in water solubility, reduced granule size, and decreased
intrinsic and pasting viscosity of starch (Zhu and others 2014).
Yang and others (2014) reported that citric acid, used as process
additive to modify or improve the processability and mechanical
properties of starch, resulted in an increased melting flow index
of starch. Acid-hydrolyzed pinhao starch was employed to prepare
biofilms. Modified starch films were more soluble in water com-
pared to those prepared from native starch, and possessed reduced
WVP. For use of biofilms as packaging materials, they should
Art and science behind modified starch . . .

Table 4Thermal properties of modified-starch films.

Film Modification Effect on

material agent
Plasticized sago starch Sorbitol
Starch/HPMC Citric acid
Acid-hydrolyzed starch Hydrochloric acid
Corn starch Stearic acid Palmitic acid
Etherified starch Glycerol sorbitol
Starch/polyvinyl alcohol Hydrophilic inorganic salts
Maize starch Starch nanoparticles
prepared by TEMPO
(2,2,6,6-
tetramethylpiperidine
1-oxyl) mediated
oxidation
Corn starch/chemically Birch cellulose
modified starch
nanoparticles
film properties References
Improved heat sealability and reduced onset Abdorreza and others 2011
temperatures
Reduced glass transition temperature Otega-Toro and others 2014
Increased heat resistance Luchese and others 2015
Decreased glass transition temperature at low aw Jimenez and others 2013b
Single endothermic peak indicating homogeneity Isotton and others 2015
Reduced glass transition temperature Jiang and others 2016
Increased melting temperature, heat enthalpy Fan and others 2016
High thermal stability evidenced by increased maximum Teaca and others 2013
decomposition temperatures

possess good mobility at room temperature. At the glass transition the disadvantage of being crystalline, and thus gelatinize at higher
temperature (Tg ), the glassy structure of the biofilm changes to temperatures. High-amylose starches have been used to extend the
elastomeric. Acid hydrolysis did not affect the Tg of the films. The shelf-life of deep-fried foods (textural quality) after they have left
biofilms had good resistance at high temperatures, as revealed by the fryer (US patent 5976607). These high-amylose starches are
the mean melting temperature of 135 5 C (Luchese and others used to make films and coatings, and they were also used in coatings
2015). Thermal properties exhibited by the modified starch films prepared for Apollo space flights. Lourdin and others (1995) stud-
are shown in Table 4. ied and found that increasing the percentages of amylose increased
the tensile strength and elongation. Pagella and others (2002) also
Dextrins and maltodextrins found high-amylose starches to produce freestanding films with
During manufacture of dextrins, partial depolymerization fol- high commercial acceptability. High-amylose rice and pea starch
lowed by repolymerization of glucose polymers, in linkages dif- films had excellent oxygen barrier properties, better than those of
ferent from (14) and (16) glycosidic bonds takes place protein-based alternatives (Mehyar and Han 2004; Kramer 2009).
(Kennedy and Fischer 1984). Acids are also employed and the
variables include starch type, amount/type of acid, and moisture Use of Additives for Starch Modifications
content during heating, and time/temperature of heating. Dextrin Due to the brittle nature and lack of mechanical integrity in
products can be soluble in cold water, and have fair film forma- starch-based films, additives are incorporated for conventional
tion properties and good adhesive properties. Dextrins are often packaging that potentially improve mechanical properties as well
coated to confectionery products, edible glues, and sealants. In as processability of starch films (Mehran Ghasemlou and others
confectionery products, they serve as alternatives to gum acacia. 2013). Food additives such as antioxidants, antimicrobial agents,
Maltodextrins have a number of advantages as additives to ed- and nutrients are added to film and coating formulations for im-
ible films. At concentrations up to 70% (w/v), maltodextrins are proving their functional characteristics, such as enhancing film-
water-soluble and have good film-forming properties. Owing to forming ability of solutions, suspensions, and emulsions, promot-
their relatively lower molecular weight and slightly hygroscopic ing adherence of a coating to the support, or controlling flow and
properties, they can reduce the brittleness of starch films through spread properties of coating solutions, suspensions, and emulsions.
plasticization and humectant effect (Zhang and Han 2006). Be- Table 5 highlights the effects brought about by the incorporation
ing of intermediate molecular weight, they form weak coatings of additives into starch films. It is well known for polymer blends
on their own with good oxygen barrier properties. Drying often that the morphology control of the respective phases is a key factor
gets prolonged for coating solutions with excessively high solids in achieving the desired material properties (Xie and others 2013).
content compared to those in the range of 20% to 40%. This ob- Ascorbic acid as an antioxidant and transglutaminase as enzyme can
servation is probably due to an increase in the hygroscopicity of promote intra- or intermolecular bonds, also increase solubiliza-
smaller-molecular-weight components and water-binding capa- tion of biopolymers, and, consequently, help in the modification
bility of larger starch-like fractions (Zhang and Han 2006). Before of starch. It is important to note that for almost any application the
excessive viscosity, sweetness, or undesirable flavors are observed, ordered granular structure of starch is disrupted by heating with a
10% to 20% (w/v) solids of maltodextrins can be added to the plasticizer or gelatinization agent (Liu and others 2009; Chen and
solution (Kramer 2009). others 2011).
Various techniques have been used to process starch such as
High-amylose starch solution-casting, internal mixing, extrusion, injection-molding,
Starch is a hydroxy-functional polymer and most processes for and compression-molding and in almost all techniques water is
chemical modification of starch depend on the intrinsic reactivity needed as a plasticizer. Starch is not a real thermoplastic polymer,
of the hydroxyl groups. Genetic mutants of corn (maize), hav- but by addition of water it can be processed after gelatinization
ing higher amylose-to-amylopectin ratios than typical, are used to (Angellier and others 2006; Gonzalez and others 2015). Water
produce high-amylose starches. Films are produced from starches improves the conductivity by improving the movement of starch
with amylose contents of 50%, 70%, or even 90%. High-amylose chains. The 3-dimensional architecture and semicrystalline nature
starches are widely used in applications requiring firm gels and of starch are disrupted by heating in water, consequently caus-
some loss of water, such as jellied candies. However, they have ing phase transition from an ordered granular structure into a

572 Comprehensive Reviews in Food Science and Food Safety r Vol. 15, 2016 
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Art and science behind modified starch . . .

Table 5Recently used additives for starch film preparation.

Additives Agent Effect References

Polyols and sugars Glycerin Less brittle and less retrogradation, improved Lawton and Fanta 1994; Zaritzky
mechanical properties, flexibility, and transparency 2004; Abdorezza and others 2011;
Battegazzorea and others 2015
Sorbates Minimized surface microbial contamination Garcia and others 2000a; Flores and
others 2007
Sorbate Crystal growth and recrystallization of starch Lucia and others 2005
Isosorbide Reduced retrogradation Battegazzorea and others 2015
Lipids and waxes High-melting waxes Enhanced moisture barrier properties Slavutsky and Bertuzzi 2015
Lipids Improved transparency and vapor permeability Jong and Shellhammar 2005
Emulsifiers Lecithin Lowers surface tension and allows surface to coat the Kester and Fennema 1986
food
Antioxidants Carboxylic acid Delays water uptake, improves mechanical properties, Olivato and others 2012
higher tensile strength than glycerol
Citric acid Promotes grafting and cross-linking resulting in denser Fan and Sunan 2014
structure.
Natural extract from Lowers surface tension, improves mechanical properties Barbosa and others 2014
brewery waste
Malic acid Recrystallization or onset of retrogradation Prospero and others 2007
Malic acid and citric acid Improvement in strength, decreases swelling and Fan and Sunan 2014
+ glycerol solubility of film, improved tensile strength, thermal
stability, and decreased dissolution of starch films in
water

disordered state (Xie and others 2013). Higher water addition
causes crystallite formation in starch, and on swelling it might be
pulled apart (Xie and others 2013).
Since the decomposition temperature of native starch is lower
than its melting temperature before gelatinization, addition of plas-
ticizer is important during thermal processing. Addition of water
as a plasticizer leads to poor mechanical properties that vary with
humidity (brittleness at lower humidity and softness at high hu-
midity), but it reduces viscosity during thermal processing. The
effect of water as plasticizer depends on various factors such as
processing history and the presence of other additives. Various
plasticizers have been used in combination with water, to obtain
the conditions suitable for gelatinization (Wiedmann and Strobel
1991; Liu 2009) which is discussed as follows:
Polyols and sugars
While formulating films, various polyhydric alcohols (propy-
lene glycol, sorbitol, glycerol, and sucrose) are added to modify
the properties of films, which consequently cause changes in their
flexibility and extensibility (Fama and others 2005). The starch
films without plasticizers are very brittle as compared to the films
with plasticizers (Abdorreza and others 2011). Coatings with plas-
ticizers have lower values of WVP, and those without plasticiz-
ers have higher corresponding values (Parris and others 1997).
Adding plasticizers to the starch-based coatings, makes them ho-
mogeneous, and effective enough to cover whole of the fruit
surface, otherwise the coatings are brittle and possess undesirable
cracks. The effectiveness of a plasticizer depends upon 3 factors:
size, shape, and compatibility with the protein matrix. Due to
its nonsweet, nontoxic, and inexpensive nature, glycerin has been
granted GRAS (generally recognized as safe) status by the U.S.
FDA (Kramer 2009), for use in starch film preparation. Glyc-
erin forms a plasticizer or humectant that maintains an adequate
moisture level for a continuous film casting. Keeping the film
hydrated assures adequate flexibility and resiliency. Broadly speak-
ing, starch-based films are very strong, their moisture content, and
relative humidity of the storage environment directly determines
their strength. When subjected to relative humidity below 20% Lipids and waxes
to 25%, cracks are developed in starch-based edible films. Use of
glycerin and other polyols can lower tolerances to 10% to 15% palmitic acid, soybean oil, and sunflower oil, and others, as they
relative humidity (Kramer 2009). Glycerol causes improvement in have lower vapor permeability than natural waxes (Rojas-Argudo
the mechanical and optical properties, improves flexibility, and re-
duces the polymer chains or causes change in network structure of
the resulting starch edible films (Lawton and Fanta 1994; Yang and
Paulson 2000; Myllarinen and others 2002; Mali and others 2004;
Chiumarelli and others 2014). The use of dual plasticizers (glyc-
erol and urea) leads to the formation of more stable and stronger
hydrogen bonds with starch and water than any single plasticizer
(Rahman and others 2010; Sin and others 2010). Battegazzore and
others (2015) reported that, Isosorbide as a green plasticizer has
also gained importance similar to that of glycerin. Sorbates also
have been granted GRAS status and they minimize the surface mi-
crobial contamination of films (Flores and others 2007; Barzegar
and others 2014). Sorbitol and glycerol demonstrated a lower plas-
ticizing efficacy than sucrose (Arvanitoyannis and Billaderis 1998).
Liu and others (2009) used plasticizers, which dramatically reduced
the film flexibility because of internal hydrogen-bonding between
polymer chains. The amount of plasticizers used, should there-
fore be optimized, as they have adverse effects on the mechanical
and barrier properties of the films (Garcia and others 2000a). For
sugars such as glycerol and sorbitol, various scientists give typical
concentrations to be used in the starch-based formulations, which
range between 0 to 50 g/L. In case of modified starches, plasticizers
decrease intermolecular attraction, increase mobility of polymers,
and decrease tensile strength of the film (Maria Rodriguez and
others 2006). Oxidized starch with glycerol produces less viscous
and better filming properties (Kuakpetoon and others 2006). Ed-
ible films, which are slowly dried, have more crystalline fractions
and vice versa (Flores and others 2007), and the presence of plas-
ticizers (sorbate) can limit crystal growth and recrystallization of
starch. Films prepared from tapioca-starch containing sorbates were
subjected to dynamic mechanical thermal analysis during 8 wk of
storage. Sorbate incorporation resulted in a decrease in the storage
modulus (E) and an increase in the tangent of phase angle (tan )
after 2 wk of storage. Films with sorbate showed increasing ten-
dency to rupture with storage time, but the films without sorbate
presented rupture for all storage periods (Fama and others 2005).
Lipids commonly used for films and coatings are stearic acid,


C 2016 Institute of Food Technologists Vol. 15, 2016 r Comprehensive Reviews in Food Science and Food Safety 573
Art and science behind modified starch . . .
and others 2009). Chiumarelli (2014) and Jimenez and others
(2013a) reported that on addition of lipids as additive to starch
films, the inner structure, as well as the film surface, gets affected
and consequently causes improvement in barrier, mechanical, and
optical properties of the resulting film. The addition of lipid
nanolayer is reported to confer better gas and water barrier proper-
ties in the resulting film, as the hydrophobic nature of oils restrict
migration of gas and vapor. Starch coating on a lipid nanolayer
(sunflower oil) resulted in an increase in the tensile strength, low-
ered water diffusion coefficients, and decreased diffusivity with wa-
ter activity in relation to starch-based films (Slavutsky and Bertuzzi
2015). Since the starch films are moisture sensitive, by the addition
of oils this can be reduced (Garcia and others 2000a). Drawbacks
of lipids and oil addition are that, they reduce the transparency
and melting temperature of the films, cause solvent volatilization,
and leave an after-taste (Rhim and Shellhammer 2005).
Emulsifiers and wetting agents
Wetting agents or surfactants are added to coating solutions
to improve coating efficiency. The addition of a little lecithin or
other emulsifiers to the coating solution lowers surface tension and
allows the solution to coat the food (Kramer 2009). Besides, some
lipophilic compounds, such as vegetable oils, and fatty acids can
also act as emulsifiers and plasticizers (Kester and Fennema 1986;
Donhowe and Fennema 1994). Emulsion-based films, however,
are less efficient in controlling water transfer than bilayer films as
homogeneous distribution of lipids is not achieved (Falguera and
others 2011).
Antioxidants
Natural antioxidants (organic acids, phenolic acids, terpenes,
tocopherols, carotenoids, and vitamins) have been studied, tested,
and used in starch film-based packaging to improve oxidative sta-
bility of products for prolonged storage (Siripatrawan and Harte
2010; Olivato and others 2012). Polycarboxylic acids are non-
toxic, delay water uptake, improve mechanical properties, have
higher tensile strength, and lower cost than glycerol. Citric acid
and malic acid are used as additives in starch films, as they are
inexpensive, nontoxic, show improved thermal and water stability,
and inhibit retrogradation (Niazi and Broekhuis 2015). Citric acid
has been used as an additive to promote cross-linking in cornstarch
films too. It is expected that polycarboxylic acids (citric, malic, and
tartaric acids) will act to promote grafting and cross-linking be-
tween polymers and, consequently, improve compatibility. Reddy
and Yang (2010) reported that starch films with added citric acid
underwent cross-linking reactions, producing a denser structure
that experienced reduced weight loss and WVP. Addition of or-
ganic acids to starch film increased water solubility. Tang and Alavi
(2011) reported that starch film containing citric acid was bet-
ter than glycerol- or sorbitol-based film. Multifunctional organic
acids (malic acid) promote esterification and trans-esterification
as they interact with hydroxyl groups (carboxyl and ester group)
of starch (Olivato and others 2012). Benzoic and sorbic acids as
nano-sized solubilisates can be used in film preparation as additives
(Cruz-Romero and others 2013). Active packaging systems utiliz-
ing natural extracts such as rosemary, oregano, and green tea with
both antioxidants and antimicrobial properties have increased the
stability of different meat products and thus extended their shelf-
life (Camo and others 2011). Barbosa-Pereira and others (2014)
developed an active packaging film by incorporating a natural ex-
tract obtained from a brewery waste stream into a polymer film.
These natural extracts contain various antioxidant phenolic com-
574 Comprehensive Reviews in Food Science and Food Safety r Vol. 15, 2016
pounds such as flavonols (catechin, gallocatechin, and epigallo-
catechin) and hydroxycinnamic and hydroxybenzoic acids (gallic
acid, caffeic acid, p-coumaric acid, and ferulic acid). The free
radical-accepting and chain-breaking nature of these compounds
allows them to act as free radical scavengers (Barbosa-pereira and
others 2014). Active packaging films based on rice starch-glycerol,
were developed by the addition of ascorbic acid and butylated hy-
droxytoluene (BHT). The addition of antioxidants improved their
water resistance and water vapor barrier properties, increased the
elastic modulus, glass transition temperature, and enthalpy of tran-
sition (Ashwar and others 2015). Recent studies have focused on
the use of nano-composites for the development of new types of
active packaging (Bradley and others 2011; Silvestre and others
2011; Busolo and Lagaron 2012). Niazi and Broekhuis (2015) re-
duced recrystallization or onset of retrogradation of starch by using
a natural plasticizer (malic acid) and reported that the reduction
in retrogradation correlated with high moisture absorption. It is
pertinent to mention that the rate of retrogradation depends on
the concentration of the hygroscopic plasticizer used. They also
reported an increase in tensile strength of film by incorporation
of sodium benzoate as photosensitizer to produce reactive radicals
that initiate subsequent cross-linking reactions under UV irradia-
tion. UV irradiation to starch film containing malic and citric acid
as plasticizer and glycerol as co-plasticizer improves the strength of
the film and decreases swelling and solubility of film. The cross-
linking effect of citric acid improved tensile strength and thermal
stability, and decreased dissolution of starch films in water and
formic acid (Reddy and others 2010).
Montmorillonite and cellulose nanocrystals
Nanofillers (montmorillonite and cellulose) have been incor-
porated in starch films as they were seen to improve functional
properties of starch. The extent of nanoparticle dispersion into
the starch matrix defines the improvements in functional prop-
erties of starch nanocomposite films. The strength of interaction
between starch chains and nanofiller particles reduces film affinity
with water (Slavutsky and others 2012, 2014).
Physical Modifications
Many emerging food preservation techniques such as use of
high pressure, pulsed electric field, electrolyzed water, irradiation,
ozone, and ultrasound treatment, have been widely studied and
have offered promising results with food modifications (Samperdo
and others 2010; Arzeni and others 2012). These methods are of
importance as they decrease use of chemicals to enhance produc-
tion. Some physical modifications of starch and their effects are
highlighted in Table 6.
Modification by ultrasound waves
Ultrasound is one of the most important green technologies
used in food science (Chemat and others 2011; Awad and others
2012). Ultrasound is a sound wave with frequency ranging from
2 104 to 109 kHz. It is generated with either piezoelectric or
magneto-strictive transducers that create high-energy vibrations.
These vibrations are amplified and transferred to a sonotrode or
probe, which directly contacts the fluid. Ultrasonic cavitation is
a series of dynamic processes of bubbles in the liquid when it is
exposed to an ultrasonic field. Cavities filled with gas or vapor
form as the pressure decreases, and they collapse as the pressure
increases again. The collapsing of cavities gives rise to hot spots,
creating a high temperature and pressure (pressure up to several
hundred MPa, temperature above 5000 C), with a strong shock

C 2016 Institute of Food Technologists
Art and science behind modified starch . . .

Table 6Recent physical modifications of starch for film preparation.

Physical
modification Effect References
Ultrasonic waves Reduced reaction time, enhanced degree of substitution, disrupted Huidan and others 2005; Jambrak
crystalline structure, reduced dead angle, solubilization of and others 2010; Tang and Alavi
residual starch 2011; Hu and others 2015
Microwave radiation Increased water solubility, reduced crystallinity, reduced viscosities Bertolini and others 2001; Wang and
of pasting, decreased enzyme susceptibility, gel clarity, and gel others 2012;
transparency
Osmotic pressure treatment Reduced pasting properties, increased viscosity with decrease in Klein and others 2014
breakdown, enhanced moisture barrier properties, and tensile
strength
Pulsed electric fields Starch disruption and crystallinity, decreased viscosity during Zhong and others 2009, 2012
pasting, increased aggregation, rearrangement or destruction of
starch molecules, increased gel consistency, and gel clarity
Moist heat treatments Low swelling, high thermal stability and pasting viscosity, increased Klein and others 2013
gel hardness
Annealing Enhanced enzyme susceptibility, color change Chung and others 2009; Otegbayo
and others 2006
Gamma-irradiation Increased gel strength, decreased melting point, melting enthalpy, Wu and others 2002; Gani and others
improved mechanical, and swelling properties 2012; Ashwar and others 2014
Dry heating Enhanced water-binding capacity Lim and others 2015

wave and a jet at the speed of 400 km/s (Swamy and others 2005;
Hemwimol and others 2006). This extreme and unique environ-
ment, enables the use of ultrasonic cavitations not only in the field
of cleaning, but also in medicine, biology, marine science, avi-
ation, food industry, chemical engineering, and light industries.
Use of ultrasound as a nonthermal technology has also gained
considerable importance because it is eco-friendly and nontoxic,
enhances microbial safety and, consequently, shelf-life (Kentish
and Ashokkumar 2011; Gani and others 2016). Ultrasound com-
monly leads to the formation of cracks, pores, and damage to the
starch granules (Sujka and Jamroz 2013). Dual frequency ultra-
sound is known to cause significant increase of the cavitational
event, reduction in the dead angle caused by standing waves, and
improvement in the sonochemical productivity, compared to sin-
gle frequency ultrasound (Jambrak and others 2010). Sivakumar
and others (2002) used the dual-frequency ultrasound system to
study the kinetics of degradation of p-nitrophenol. They com-
bined 28 kHz and 0.87 MHz ultrasound into a new device for
the first time and studied the cavitational yield using electrochem-
ical and the iodine release method. The cavitational yield using
dual-frequency ultrasound was found to be higher than that from
2 single ultrasounds taken together. Zeng and others (2005) used
dual-frequency ultrasound to study cavitational yield by iodine re-
lease. Single-frequency ultrasounds decrease the viscous resistance
of starch paste, by rupturing the macromolecular chains of starch
and destroying its crystalline structure (Baxter and others 2005;
Hu and others 2015). Thus, dual frequency ultrasound has more
significant effect on starch modification than single-frequency
ultrasound. Under administration of lower frequency, the forma-
tion of cavitations is less in comparison to higher frequency and,
consequently, film formation is good. Starch treated with single
and dual ultrasound frequency showed decrease in peak viscosity
and gelling property, whereas thermal stability and retrogradation
were enhanced, while no change in cold stability was seen. As the
treatment frequency increases peak viscosity decreases. An increase
in frequency led to the formation of many dents and holes on the
surface of starch granules (Hu and others 2015). Compared to
starch treated by single-frequency ultrasound, the dual-frequency
sonicated starch has damages that are more obvious. Maize starch
was treated with ultrasound frequency at 20 kHz for the produc-
tion of edible film formation. Gelatinized maize starch dispersions
treated with ultrasound produced films with good transparency,
improved moisture resistance, and conferred stronger structure.
The effect of ultrasound on starch depends on many parameters
such as properties of the starch dispersion, namely, starch type and
concentration (Sujka and others 2013; Chan and others 2015),
the gas type of the atmosphere (Degrois and others 1974), the
temperature of the system (Zuo and others 2009), the parameters
of ultrasonication such as the frequency, power, time, and tem-
perature of the treatment, the amount of energy input (Jambrak
and others 2010), duration of the treatment (Huang and oth-
ers 2007; Zuo and others 2009), and formation of gas bubbles
in the suspension medium (Tomasik and others 1995). Zhu and
others (2014) reviewed that the ultrasonication of starch reduces
the reaction time and enhances the degree of substitution (for
example, acetylation, hydroxypropylation, octenyl-succinylation,
and carboxymethylation) from various products including potato,
maize, and yam. Rapidly collapsing bubbles could also give rise
to shear force that may break the polymer chains. At lower tem-
peratures during ultrasound, water molecules do not diffuse inside
the amylopectin chain and no plasticization of the amylopectin
phase takes place. Ultrasound was the first method through which
nano-sized starch particles were produced. Based on wide-angle
X-ray diffraction analysis, ultrasonication disrupted the crystalline
structure in the starch and appeared to lead to nanoparticle forma-
tion that had a low crystallinity or an amorphous structure (Kim
and others 2014). Hu and others (2015) treated aluminum foil
with both single and dual-ultrasound treatment and concluded
that dual-frequency ultrasound damages the foil more than single-
frequency ultrasound. This is because dual-frequency ultrasound
has stronger cavitation effect than that of single-frequency ultra-
sound. The most noticeable effect of sonication is that it helps
in the solubilization of residual starch aggregates which otherwise
remain in the film.
Microwave-radiation
Microwave-radiation increases water solubility and reduces crys-
tallinity and viscosity of pasting and gel transparency (Bertolini
and others 2001; Lan and others 2012). A dual treatment (mi-
crowave and ultrasound irradiation) was used for the esterification
of carboxy-methyl cold water-soluble starch with ocetenyl succinic
anhydride. The film so produced had excellent emulsifying and
surfactant properties (Cizova and others 2008). Microwave-assisted


C 2016 Institute of Food Technologists Vol. 15, 2016 r Comprehensive Reviews in Food Science and Food Safety 575
Art and science behind modified starch . . .

starches have high potential for surface-coating and biochemical tally friendly, and one of the better understood physical mod-
material applications (Rajan and others 2008). Microwave-assisted ifications of starch. Moist-heat-treated starch had higher tensile
esterification for the production of starch maleate had a very high strength in comparison with native starch (Hoover and others
reaction efficiency, up to 98%. Kaur and others (2012) reported 2010; Zavareze and others 2012). Klein and others (2013) re-
that microwave-irradiation offers a facile synthesis of starch es- ported lower swelling, high thermal stability, and pasting viscosity
ters, including inorganic starch esters such as phosphates. Fur- of heat-treated starch in comparison to native starch and other
thermore, the effect of microwave-assisted preparation of sulfated starches. They suggested this treatment to be effective for gel
(Staroszczyk and others 2007), borate (Staroszczyk and others formation with improved film-forming capacity. The moist heat
2009), silicate (Staroszczyk and others 2009; Staroszczyk and Janas treatment causes a significant decrease in the pasting temperature,
2010), and zincate starch has been extensively studied. The in- peak viscosity, holding viscosity, final viscosity, and setback as it
crease in swelling, pasting viscosity, and gel clarity and the decrease promotes interaction between amylose-amylose and/or amylose-
in enzyme susceptibility was seen in starch treated with octenyl amylopectin chains (Zavareze and others 2012). Highly associated
succinate through microwave-radiation ( Jyothi and others 2005; starch granules display a greater resistance towards swelling, owing
Cova and others 2010). Microwave- and infrared-treated starches to an extensive and strongly bonding micelle structure. Therefore,
show improved physico-chemical and functional properties. Such they affect the film forming capability of starch. The structure and
starches had a higher water absorption capacity and light trans- physicochemical properties of some pulse starches are altered by
mittance and reduced syneresis (Shah and others 2016). These moist heat treatment (Chung and others 2009). The degree of
treatments greatly influence the properties of starch and quality of change depends on amylose content, interactions between starch
the final product. chains, arrangement of amylose chain within the amorphous do-
mains, and lipid-amylose complexes in starch. Starches were more
Osmotic pressure treatment stable during hydrothermal treatment (moist heat treatment) and
Osmotic pressure treatment was carried out in the presence had reduced breakdown (reduction in viscosity, reduced leaching
of salt for starch modification and no chemical was involved; of amylose) since hydrothermally treated starches promote interac-
thus there is no concern for effect on environment and safety tion between amylose-amylose and amylose-amylopectin (Chung
(Pukkahuta and others 2007). The use of osmotic pressure, with and others 2009). Sweet potato starch treated with moist heat be-
the addition of sodium sulfate and sodium chloride, increased came short and stable for shearing. The gel hardness and adhesive-
the cross-linking efficiency. X-ray diffraction patterns remained ness significantly increased compared to that of the native starch.
unaffected, but swelling and partial gelatinization of the granules The increased gel hardness is due to the interactions between starch
took place by the application of high pressure. With an increase chains (Collado and Corke 1999). Dual autoclaving-retrogradation
in pressure, the percentage of crystallinity and gelatinization also treatment also improved the physicochemical properties of rice
increases. Klein and others (2014) reported that ozone oxidation starch, decreasing its breakdown viscosity and transition tempera-
of starch reduces pasting by affecting the morphology, and these ture range (Ashwar and others 2016).
changes are brought about by different reaction conditions.
Annealing
Pulsed electric field Annealing involves treating starch in excess water (< 65% w/w)
Use of pulsed electric field as a nonthermal physical treatment or at intermediate water content (40% to 50% w/w). It is done at
for starch modification is among the emerging green technologies. the temperature below the onset of gelatinization with a limited
Electric field causes starch disruption resulting in decreased viscos- amount of moisture content (Hoover and others 2010). Annealing
ity during pasting, consequently affecting film formation. Native aims to enhance the molecular mobility without triggering gela-
starch granules have smooth, oval, and irregularly shaped surface tinization, by approaching the glass transition temperature (Chung
morphology. After subjecting them to pulsed electric field rough- and others 2009). Heating at 60 C enhanced the enzyme suscep-
ness or surface damage emerged and on further increase in the tibility to a mixture of fungal amylase and glucoamylase (Shariffa
treatment some pits emerged and small starch particles aggregated and others 2009). Falade and Oluwatoyin (2015) reported that,
together forming bigger ones (Han and others 2012). The possi- while modifying starches by annealing, there was a significant re-
ble explanation for this might be a loss in granule envelopes (Han duction in L* and b* color values and an increase in a* value.
and others 2009). Pulsed electric field treatment was seen to offer The possible explanation of color change might be purification
higher energy for the reaction between tapioca starch granules and and separation of some heterogeneous materials. Annealing had
water molecules, consequently destroying the crystalline region of variable effect on the water absorption capacity of the starches
starches. This resulted in a distinct trend for tapioca starch gran- and, consequently, affected the filmmaking process (Otegbayo and
ules to transform from a crystalline to a noncrystalline nature. The others 2006).
fragmented starch produced by pulsed electric field can absorb
Gamma-irradiation
water more effectively and swell more easily, which results in an
increase of aggregation among particles (Han and others 2009). Various chemical changes, such as degradation of macro-
Pulsed electric field as a physical technique for starch modification
molecules leading to formation of carbonyl and carboxyl deriva-
is prone to cause rearrangement, destruction of starch molecules,
tives, are induced by gamma-irradiation in starch (Ciesla and others
and reductions in gelatinization, viscosity, crystallinity, solubility,
2014). Starch granules can be destroyed by gamma-irradiation and
gel consistency, and gel clarity (Kaur and others 2012). increasing the dose increases breakdown resulting in the softer
gel consistency (Yu and Wang 2007). Gel consistency generally
Moist-heat treatments has a positive effect on the eating quality of starch (Wu and oth-
Moist heat treatment involves a low moisture level (10% to ers 2002), which implies that gamma-irradiation positively effects
30%) and high-temperature heating (90 C to 120 C) for eating quality (Yu and Wang 2007). Gamma and electron beam
15 min to 16. This is one of the easiest, cheapest, environmen- irradiation cause an increase in gel strength and decrease melting

576 Comprehensive Reviews in Food Science and Food Safety r Vol. 15, 2016 
C 2016 Institute of Food Technologists
Art and science behind modified starch . . .
point and melting enthalpy. Lower doses of gamma-irradiation im-
prove the mechanical and swelling properties of films. Ashwar and
others (2014) reported that gamma-irradiation causes increases in
carboxyl content and transmittance and water absorption capac-
ity while it decreases swelling index, apparent amylose content,
syneresis, and pasting properties. With an increase in the dose of
gamma-irradiation in rice starch, a decrease in syneresis was seen
(Gani and others 2013). Furthermore, starch granular structure or
microstructure is deformed under the irradiations dose (Gani and
others 2012).
Dry heating
Dry heat is a simple and safe method that changes the physico-
chemical properties of starch without destroying granule structure.
Waxy starch treated with dry heat displayed a decrease in pasting
temperature. Dry heating (high temperature and low pH) of aque-
ous mixtures of starch is simple and economical. Gul and others
(2014) reported that starches with CMC and without heat treat-
ment exhibit lower peak viscosity. Ionic gums (alginates, CMC,
and so on) adhere to starch granules and the surface acquires a net
negative charge. This renders water molecules unable to reach the
starch granules, thus delaying starch granule swelling, and after the
heating the final viscosity of the starch increases (Lim and others
2015). While comparing dry-heat-treated starch with the control,
it was seen that water-binding capacity of starch increases with an
increase in the heat treatment and, consequently, the film prop-
erties are altered (Gul and others 2014). Sun and others (2014)
reported that a heat treatment of starch changes thermal proper-
ties (decrease in gelatinization and enthalpy values). Starch solution
superheated to a temperature between 180 C and 220 C, pro-
duced spreadable particle gels with spherulite morphology and a
cream-like texture upon cooling. Dry superheated starches mixed
with cold water are able to acquire immediate gel-like texture
(Steeneken and Woortman 2009).
Conclusion
Recent achievements in polymer science have added to our
knowledge. Starch as a packaging material is economically viable,
and hence, modified starch films are proposed to be important tools
to overcome existing challenges that are associated with packaging
materials. They result in enhanced shelf-life and improved quality,
safety, and security of foods. Various modification methods have
been developed to produce films/coatings with improved forming
capacities giving them increased applicability in both industrial and
academic research. The modified starch films have shown excellent
forming properties, such as air and moisture barrier, heat-sealing
capacity and more. The addition of additives in starch films is
required to obtain a more ductile and flexible material which
would improve film-handling. Starch consisting of crystalline and
amorphous domains is a possible candidate for organic nano-fillers
because the amorphous domains can be removed under certain
conditions. Multiple modifications to obtain tailored starch films
with desired functional properties could be looked into in the
future.
Acknowledgments
The authors are thankful to the Ministry of Food Processing,
Govt. of India, for their financial assistance.

C 2016 Institute of Food Technologists Vol. 15, 2016 r Comprehensive Reviews in Food Science and Food Safety 577
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