Food Hydrocolloids 50 (2015) 174e192

Contents lists available at ScienceDirect

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

Review

Environment friendly green composites based on soy protein

isolate e A review
Rekha Rose Koshy a, Siji K. Mary a, Sabu Thomas b, c, Laly A. Pothan a, *
a
Department of Chemistry, Bishop Moore College, Mavelikara 690101, Kerala, India
b
School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala, India
c
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam 686560, Kerala, India

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

Article history: As a result of the growing environmental awareness (e.g., increased pollution, increasing demand for
Received 11 December 2014 biodegradable materials, material need for CO2 neutrality and low greenhouse gas emissions, new
Received in revised form environmental laws and regulations), manufacturers and scientists are keen to study novel environ-
23 March 2015
mental friendly materials. Soy protein isolate (SPI), a protein with reproducible resource, good
Accepted 22 April 2015
Available online 30 April 2015
biocompatibility, biodegradability and processability has a significant potential in the food industry,
agriculture, bioscience and biotechnology. The aim of this review is to offer a comprehensive view of the
recent state of art of eco-materials based on Soy Protein Isolate (SPI) with special reference to organic
Keywords:
Soy protein isolate
and inorganic fillers in the macro, micro and nano scale. Moreover, some applications of SPI-based
Biopolymer materials, especially in the field of food preservation and packaging technology, are also discussed.
Biocomposites © 2015 Elsevier Ltd. All rights reserved.
Bionanocomposites
Food preservation
Packaging

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2. Biodegradable composite films based on proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
3. Biodegradable composite films based on soy proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.1. Biodegradable composite films based on soy protein isolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.1.1. Processing techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.1.2. Effect of plasticizer on soy protein isolate composite films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.1.3. Effect of chemical and enzymatic modification on soy protein isolate matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.2. SPI-organic filler biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
3.2.1. Soy protein isolate-cellulose composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
3.2.2. Soy protein isolate-Lignocellulosic natural fiber composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.2.3. SPI e chitin and SPI e chitosan composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.2.4. SPI e starch composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.2.5. SPI e other polymer biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.3. SPI-organic filler reinforced bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.4. SPI e inorganic fillers reinforced bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3.4.1. SPI e clay bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3.4.2. SPI e metal and metal oxide bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
3.4.3. SPI e other bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5. Future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

* Corresponding author. Tel.: þ91 479 2301730.

E-mail address: lapothan@gmail.com (L.A. Pothan).

http://dx.doi.org/10.1016/j.foodhyd.2015.04.023
0268-005X/© 2015 Elsevier Ltd. All rights reserved.
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192 175

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

1. Introduction vegetables (Ghavidel et al., 2013; Ghidelli, Mateos, Rojas-Argudo, &

rez-Gago, 2014).
Pe
In recent years there has been a great interest to utilize
renewable biomass (Echeverría, Eisenberg, & Mauri, 2014; Espitia,
Du, Avena-Bustillos, Soares, & McHugh, 2014; Fagundes, Palou,
2. Biodegradable composite films based on proteins
Monteiro, & Pe
rez-Gago, 2014; Farahnaky, Dadfar, & Shahbazi,
2014; Galus & Lenart, 2013; Ghanbarzadeh, Oleyaei, & Almasi,
Films, casings and coatings made from polysaccharides and
2014; Gonz
alez & Alvarez Igarzabal, 2013; Guerrero, Garrido,
proteins are effective barriers against oxygen (O2), carbon dioxide
Leceta, & de la Caba, 2013; LaMantia & Morreale, 2011; Mitra, 2014;
(CO2) and low polarity compounds. In comparison with poly-
Nur Hanani, Roos, & Kerry, 2014; Song & Zheng, 2014) in the
saccharide films, protein films show considerably lower O2 and CO2
manufacture of high-quality, cost-competitive and biodegradable
permeabilities and CO2/O2 permeability ratio (Kaewprachu &
consumer goods as a means to reduce the consumption and the
Rawdkuen, 2014; Taylor, Song, & Zheng, 2014). An additional
dependence on petro-chemical feedstock and to diminish envi-
advantage is that proteins can be processed by diverse methods
ronmental pollution. The substitution of petroleum-based plastics
such as dissolution-solvent evaporation or thermo-mechanical
with bio-based plastics in the manufacture of packaging and
methods to produce films with excellent oxygen barrier proper-
biomedical materials will reduce the dependency of plastics on
ties and suitable mechanical properties (Ciannamea, Stefani, &
fossil fuels and the pressure on landfills from plastic solid wastes

Ruseckaite, 2014). The unique structure of proteins (based on 20
(Alvarez-Ch
vez, Edwards, Moure-Eraso, & Geiser, 2012). Thus,
a
different monomers) provide a wider range of functional proper-
around the world many scientists have focused their research on
ties, especially a high intermolecular binding potential which can
using materials from nature. The ideal biodegradable packaging
form bonds at different positions (Gonz
alez, Strumia, & Alvarez
materials are obtained from renewable biological resources, usually
Igarzabal, 2011). The secondary, tertiary and quaternary struc-
called biopolymers, with excellent mechanical and barrier prop-
tures of proteins result in various interactions and bindings,
erties and biodegradability. Biopolymer or biodegradable plastics
differing in position, type and energy (Silva et al., 2014), and the
are polymeric materials in which at least one step in the degrada-
mechanical properties of protein-based edible films are also better
tion process is through metabolism of naturally occurring organ-
than those of polysaccharide and fat-based films. One of the main
isms (Rhim, Park, & Ha, 2013). In particular, packaging films and
research areas in food packaging has focused on developing new
containers made of natural biodegradable polymers are of partic-
packaging techniques capable of improving food preservation
ular interest due to their compostability, since most of these
properties based on their interaction with packaging. Such tech-
products have a relative short service life ending up in landfills. In
niques are known as “active packaging systems”. An active pack-
this sense, protein-based materials have been proved to be
aging can be defined as a type of material that changes its
completely degrading in 50 days when buried in farmland soils
packaging conditions to extend shelf life, interacting directly with

lix, Martín-Alfonso, Romero, & Guerrero, 2014). Therefore, the
(Fe
the food, enhancing security and maintaining quality. In particular,
development of biodegradable biopolymer-based materials cannot
the antimicrobial packaging is one of the most innovative and
only solve the “white pollution” problem but also ease the over-
promising active packaging types developed over the last decade,
dependence on petroleum resources (Song, Tang, Wang, & Wang,
which includes systems capable of inhibiting microorganism action
2011).
lez & Alvarez Igarzabal,
and avoiding loss of food quality (Gonza
Biopolymers from food resources meet the growing worldwide
2013). Previous literature have shown that protein coatings on
need for eco-friendly, sustainable materials (Saenghirunwattana,
films would require relatively lower amounts of added antimicro-
Noomhorm, & Rungsardthong, 2014; Sirvio €, Kolehmainen,
bial agents to reach the desired effect as compared to the synthetic
Liimatainen, Niinima €ki, & Hormi, 2014) (Chen, Remondetto, &
polymer or to other biopolymer films (Zhao, Yao, Fei, Shao, & Chen,
Subirade, 2006; Chiellini, Barghini, Cinelli, & Ilieva, 2008;
2013). Therefore, numerous proteins such as corn zein, wheat
Ghavidel, Davoodi, & Adib, 2013; Huang & Netravali, 2009), offer-
gluten, soy, peanut, cottonseed, sunflower, rice bran, serum albu-
ing alternative packaging option with excellent biodegradability
min, egg white, collagen, gelatin, myofibrils, casein, and whey
and a relatively low cost. There are two types of biodegradable
proteins have been studied as potential film-forming agents
polymers; edible and non-edible. Synthetic films made from
(Kumar & Gupta, 2012). Also, these protein films can be blended
polyethylene, polyvinylchloride, polyamides etc are examples of
with other proteins (Bai, Xu, Liao, & Liu, 2013), polysaccharides (Li,
non edible food packaging. Biodegradable materials derived from
Wei, Fang, Zhang, & Zhang, 2013) and lipids (Guerrero, Nur Hanani,
food ingredients such as polysaccharides, proteins and lipids are
Kerry, & de la Caba, 2011) to form composite films. In addition, a
edible and have attracted considerable interest in recent years due
new class of materials represented by bio-nanocomposites with
to their potential abilities to replace traditional plastics and to act as
enhanced barrier, mechanical and thermal properties has also been
food contact edible films and/or coatings (Nur Hanani et al., 2014).
considered as a promising option in improving the properties of
A major objective in preparing films for many foods (e.g., fresh fruit
these biopolymer-based packaging materials. The main objective of
and vegetables) is to ensure that the generated films afford physical
producing biocomposite and bionanocomposite films is to improve
and chemical properties necessary to maintain transmission of
the permeability or mechanical properties as dictated by the need
various gases and liquids at the same rates as they occur within
of a specific application and to replace synthetic plastic products
their native systems (Nandane & Jain, 2014). In addition, edible
and to make the environment free of plastic wastes (Behera,
coatings have been studied for extending shelf life of some fresh
Avancha, Basak, Sen, & Adhikari, 2012). Among these biodegrad-
fruits so as to prevent enzymatic browning of fresh-cut fruits and
able protein films, soy protein-based films possess high potential
176 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
for commercial application as food packaging films through their
associated and unique characteristics.
3. Biodegradable composite films based on soy proteins
Owing to its sustainability, abundance, low cost and function-
ality, soy protein has attracted great research interest for the
development of environment friendly protein materials with
potentially good properties, such as regeneration, biocompatibility,
biodegradability, etc. (Echeverría et al., 2014; Fe
lix et al., 2014;
Garrido, Etxabide, Pen ~ alba, de la Caba, & Guerrero, 2013; Gupta &
Nayak, 2014; Silva et al., 2014). Soy protein has been widely used
in hydrogels, adhesives, plastics, films, coatings and emulsifiers,
and it has also been reported as a promising material for biotech-
nological and biomedical utilization (Zhao et al., 2013). While many
of the biodegradable resins such as poly (lactic acid), poly (hydroxy
alkanoates), etc. are hydrophobic in nature, and do not bond well to
plant-based fibers, others such as protein and soy-based resins
which contain polar groups show good adhesion to them and form
composites with good mechanical properties (Mitra, 2014). Soy
protein is extracted from soybean seeds that are used to obtain soy
oil and can be used for food packaging or edible films since it meets
food grade standards (Garrido et al., 2013). Soy proteins are
composed of a mixture of albumins and globulins, 90% of which are
storage proteins with globular structure, consisting mainly in 7S (b
conglycinin) and 11S (glycinin) globulins (Ciannamea et al., 2014;
Hsieh, Yu, Chang, Chen, & Tsai, 2014; Nishinari, Fang, Guo, &
Phillips, 2014; Yuan et al., 2014). Globulins are protein fractions in
which the subunits are associated via hydrophobic, hydrogen-
bonding and disulphide bonds (Shan et al., 2014). Soy proteins
consist of 20 different amino acids, including lysine, leucine,
phenylalanine, tyrosine, aspartic, glutamic acid, etc. (Fe
lix et al.,
2014).
Soy protein is commercially available in three different forms
from soybean processing plants, namely, soy flour (SF, 54% protein),
soy protein concentrate (SPC, 6572% protein) and Soy protein
isolate (SPI, 90% protein) (Saenghirunwattana et al., 2014). Soy
flour is made by grinding soybeans into a fine powder, which
contains about 56% protein and about 34% carbohydrates. Soy
protein concentrate, prepared by eluting soluble components from
defatted soy flour, contains more than 65% protein and 18% car-
bohydrates. Soy protein isolate is a highly refined or purified form
of soy protein with a minimum protein content of 90% on a
moisture-free basis. It is made from defatted soy flour which has
had most of the non protein components, fats and carbohydrates
removed (Kalman, 2014). In a recent study by Vasconcellos,
Woiciechowski, Soccol, Mantovani, and Soccol (2014), antimicro-
bial and antioxidant properties of b-conglyicinin and glycinin from
soy protein isolate (SPI) was analyzed and it was found that glycinin
peptides have better activity against almost all microbial strain;
however b-conglycinin peptides and glycinin peptides have
equivalent microbial activity against Escherichia coli. Assays showed
that antioxidant activity was dependent on the concentration of
glycinin and b-conglycinin peptides.
3.1. Biodegradable composite films based on soy protein isolate
As a natural material, the protein content of soy protein isolate
(SPI) is more than those of other soy protein products, which makes
it exhibit a higher film-forming ability. Moreover, SPI also produces
softer, more transparent and flexible films compared to those
derived from other sources (Gonza
lez et al., 2013), and they have
impressive gas barrier properties compared to films prepared from
lipids and polysaccharides. When SPI films are not moist, their O2
permeability is 500, 260, 540 and 670 times lower than that of films
based on low-density polyethylene, methylcellulose, starch and
pectin respectively (Song et al., 2011). However, SPI films do not
show satisfactory mechanical properties or water vapor barrier
properties in practical applications due to their inherent hydro-
philicity (SPI contains 58% polar amino acids that cause hydrophi-
licity (Choi, Kim, Hanna, Weller, & Kerr, 2003)) as well as the strong
molecular interaction of natural protein; and these properties
become poorer under highly humid conditions. Various methods to
enhance the physical properties of protein films have been sug-
gested. One of the most common solutions is using the appropriate
film formulation and preparation conditions.
3.1.1. Processing techniques
To form SPI films, the protein structures of the native state
would need to be denatured to reform new configurations via new
linkages within the protein molecule. Denaturation of the protein
can be induced by changes in pH, electrical force, mechanical force
or heat. Changing the pH away from the isoelectric point (4.2 e 4.6
for SPI) can cause the protein to unfold and to increase its solubility.
Casting leverages this phenomenon by evaporating solubilized SPI
solution on a flat surface forming film. Mechanical forces like
pressure and shear are known to break bonds and induce flow in an
extruder which is important for increasing intermolecular entan-
glement (Verbeek & van den Berg, 2010). Heat denaturation of
protein typically occurs above a certain threshold temperature. For
SPI, this is generally between 65 and 70  C. As the proteins unfold,
sulfhydryl and hydrophobic groups are exposed and disulfide
bonds are reformed, thereby forming new structural arrangements
(Cho, Park, Batt, & Thomas, 2007). Drying conditions (air temper-
ature and relative humidity) also influence the mechanical prop-
erties, solubility in water, and color of soy protein isolate films,
optimal conditions being 70  C and 30% RH for commercial SPI films
and 60  C and 60% RH for films from isolate obtained under labo-
ratory conditions (Denavi et al., 2009). There are two common
technologies to prepare protein films: wet (or solvent) process and
dry process (Garrido et al., 2013; Guerrero, Retegi, Gabilondo, & de
la Caba, 2010).
3.1.1.1. Wet process. Wet process, also called solution casting, is
based on the dispersion or solubilization of proteins in a solvent
medium using elevated pH to unfold the native proteins before
pouring the solution onto a flat surface, and drying. After drying,
the film can be peeled off the flat surface (Guerrero et al., 2013). For
a continuous process for solvent casting of films, parameters that
need to be determined for continuous film production are air
temperature, surface properties of the substrate upon which the
films are formed, flow rate and drying time. Films can be dried
under ambient conditions, with hot air, infrared energy or micro-
wave energy (Wang et al., 2013).
3.1.1.2. Dry process. The combination of thermal and mechanical
inputs can be used to disrupt intra and intermolecular interactions
of biopolymers by extrusion or mechanical mixing, common plastic
processing techniques. Plasticized materials could be extruded
(Zhang & Mittal, 2010), injection or compression molded (Reddy &
Yang, 2011) into articles in which the protein component forms
networks through disulfide bonds or amide bonds between free-
carboxyl and amino side groups on the protein chains.
Many researchers explored the effects of heat treatment (Fe
lix
et al., 2014; Nishinari et al., 2014), plasticization (Garrido et al.,
2013; Guerrero & de la Caba, 2010; Kokoszka, Debeaufort,
Hambleton, Lenart, & Voilley, 2010; Routray, Rout, Mohanty, &
Nayak, 2013), pH alteration (Ciannamea et al., 2014; Garrido et al.,
2013; Kaewprachu & Rawdkuen, 2014) or lipid addition (Atare
s,
Jesús, Talens, & Chiralt, 2010; Narine & Kong, 2005; Petersen
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
et al., 1999) on the functional properties of protein films. It has also
been known that soy proteins could not form a film at or near its
isoelectric point (pH 4.2e4.6) due to the coagulation. However,
proteins can be denatured and unfolded at pH values away from
their isoelectric point, thus exposing their functional groups and
increasing the intermolecular interactions. Thus the mechanical
properties of soy proteins can be affected by its pH. Most protein-
based films show better physical properties when processed in
alkaline conditions (pH 10) compared to those processed in acidic
conditions (Kim & Netravali, 2011).
3.1.2. Effect of plasticizer on soy protein isolate composite films
The combination of intermolecular disulfide bonding, hydrogen
bonding, hydrophobic interactions and electrostatic forces between
protein chains typically leads to brittle films (Mekonnen, Mussone,
Khalil, & Bressler, 2013). Therefore, incorporation of a plasticizer is
generally used to reduce protein chain-to-chain interaction and
induce film flexibility (Gurgel, Vieira, Altenhofen, Oliveira, & Beppu,
2011). The plasticizing effect is due to the ability of plasticizer
molecules to position them within the three-dimensional protein
network, increasing the free volume and facilitating the mobility of
the polymer chains (Ortega-Toro, Jime
nez, Talens, & Chiralt, 2014).
Plasticizers with low polarity are not good competitors for
hydrogen bonding sites and less effective in disrupting intermo-
lecular interactions in a protein matrix as compared to polar plas-
ticizers (Wihodo & Moraru, 2013). Water is the most effective
plasticizer for biopolymeric materials (Reddy & Yang, 2011). Other
common plasticizers for protein films include glycerol (molecular
weight ¼ 92) (Gurgel et al., 2011; Saenghirunwattana et al., 2014),
sorbitol (molecular weight ¼ 182) (Khalsa, Kim, & Netravali, 2009)
and polyethylene glycol (PEG) (molecular weight ¼ 400) (Nur
Hanani et al., 2014). Coconut oil has also been used as a plasti-
cizer in soy protein isolate based blend system (with poly capro-
lactone) (Hong et al., 2009), and the result shows that about 20 ml
of coconut oil in the PCL: SPI blends containing 10, 20 and 30% SPI is
enough to plasticize SPI blend and it was ascertained through the
change of the melting point and crystallinity.
For SPI films, glycerol is the most widely used plasticizer
because of its small size and hydrophilic nature, which makes it
compatible with SPI molecules (Ortega-Toro et al., 2014). The effect
of glycerol content on SPI plastic was studied by Routray et al.
(2013) by analyzing infrared analysis (FTIR), Differential Scanning
Calorimetry (DSC), Thermogravimetric Analysis (TGA) and tensile
testing. The FTIR spectrum of pure SPI and SPI with 30% glycerol
(wet base) is shown in Fig. 1(a) and (b). The main absorption peaks
are related to C]O stretching at 1630 cm1(amide I), NeH bending
at 1530 cm1 (amide II) and CeN stretching (amide III) at
Fig. 1. FTIR spectrum of (a) pure SPI and (b) SPI with 30% glycerol.
Reproduced with permission from (Guerrero et al., 2010).
177
1230 cm1. The broad band observed in the 3500e3000 cm1 range
is attributable to free and bound OeH and NeH groups, which are
able to form hydrogen bonding with the carbonyl group of the
peptide linkage in the protein (Tian, Xu, Yang, & Guo, 2011; Wang,
Zhou, et al., 2014).
The films with glycerol content lower than 25% by weight were
brittle, and it was not possible to cut samples for mechanical
analysis. On the other hand, the films obtained with glycerol con-
tent above 50% by weight were very sticky. However, films obtained
with 25% and 35% by weight of glycerol are flexible and they pre-
sent good mechanical properties. The use of plasticizers to break
intermolecular linkage that stabilizes the protein in their primitive
structure makes the protein chains mobile (Zolfi, Khodaiyan,
Mousavi, & Hashemi, 2014). Increasing the amount of glycerol
causes a decrease in tensile strength and an increase in elongation
at break due to the fact that glycerol reduces the interactions be-
tween protein chains, thereby increasing the chain mobility
(Guerrero, Leceta, Pen ~ alba, & de la Caba, 2014).
Thermogravimetric analysis of plasticized SPI films containing
30 wt% glycerol processed at pH 10 shows that the absolute weight
loss is small until approximately 150  C, moderate between 150  C
and 180  C, and significant above 180  C. For pure SPI, the weight
loss is small until 180  C, moderate until 200  C, but significant
beyond 200  C. The higher weight loss of plasticized samples can be
explained by the high vapor pressure (of more than 10 mm Hg) of
glycerol starting at about 170  C. Thus, the TGA study provides
valuable information on the processability of the protein/glycerol
mixtures, establishing the upper limit of thermal processing win-
dow at approximately 150  C (Guerrero & de la Caba, 2010).
3.1.3. Effect of chemical and enzymatic modification on soy protein
isolate matrix
Protein-based bioplastics have inferior mechanical properties to
commonly used synthetic polymers, principally due to their com-
plex composition, hydrophilic nature, impurities and high envi-
ronmental sensitivity. Protein denaturation induced by chemical
modification could disrupt its secondary, tertiary or quaternary
structures, exposing the amino acid side chains, and thereby intro-
ducing new interactions by means of hydrogen or ionic bonding
(Yue, Cui, Shuttleworth, & Clark, 2012). Modifications of the soy
protein matrix using stearic acid (Lodha & Netravali, 2005b), (3-
isocy-anatopropyl) triethoxysilane (ITES) (Huang & Netravali,
2009), phytagel (Huang & Netravali, 2006), glutaraldehyde (Nur
Hanani et al., 2014), glutaric dialdehyde (Fang et al., 2012),
phenolic acid (Insaward, Duangmal, & Mahawanich, 2014), etc. were
found to improve the tensile strength and resistance to water ab-
sorption of the protein sheets due to their hydrophobic nature.
178 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Table 1 shows the mechanical properties, water vapor permeability
(WVP) and TGA of native and modified soy protein isolates.
In contrast, the addition of Sodium Dodecyl Sulphate (SDS) sub-
stantially reduced (P < 0.05) the tensile strength (TS) of SPI films by as
much as 43% for films with 40% SDS (Rhim, Gennadios, Weller, &
Hanna, 2002). The reduced TS of SDS-containing SPI films were
related to the formation of “weaker” structures due to lack of hy-
drophobic interactions among neighboring protein molecular chains.
External cross-linking agents such as genipin (Gen) (Gonza
lez
et al., 2011), ZnSO4, epichlorohydrins (Zhong, Sun, & Wang, 2007)
glutaraldehyde (Huang & Netravali, 2007) and glutaric dialdehyde
(Fang et al., 2012) are also used to improve the mechanical prop-
erties and water stability of soy protein films. Recently, edible films
from SPI with phenolic compounds, rutin and epicatechin as
crosslinking agents were prepared (Friesen, Chang, & Nickerson,
2014), and the result showed that the addition of rutin signifi-
cantly increased puncture strength (9.3 N) over SPI alone (6.4 N)
whereas epicatechin had no effect. Ultrasonic and microwave
treatment has the potential to modify the properties of SPI. Mean
Tensile Strength (TS) of the SPI films increases twice by g-irradia-
tion. Irradiated SPI films had a smoother and glossy surface than the
control films. UV radiation treatments of proteins are known to
form cross-links, which mainly involve aromatic amino acid resi-
dues (Song, Zhou, Fu, Chen, & Wu, 2013).
Controlled enzymatic hydrolysis is an efficient method in the
modification of food proteins. It was pointed out by Yuan, Ren,
Zhao, Luo, and Gu (2012) that limited hydrolysis with pepsin was
sufficient to improve the surface properties of soy protein isolate. In
another study done by Zhang and Zhao (2013), a microbial trans-
glutaminase was used to cross-link soybean protein isolates in the
presence of gelatin to prepare a cross-linked composite soybean
protein-gelatin. The microbial transglutaminase was found to in-
crease the emulsifying stability, water holding capacity and me-
chanical stability of soy protein scaffolds by forming inter-
molecular or intramolecular covalent bonds (Chien & Shah, 2012).
Recently, microwave-assisted phosphorylation (MAP) was used to
improve the hydrophobicity and emulsifying properties of soy
protein isolate (Wang & Chi, 2012) and it was found that the
average particle diameter of SPI modified by MAP decreased
significantly to 1.91 mm and its hydrophobicity improved by 1.57
times compared to the blank control group.
Although research efforts for creating protein films to be used as
packaging materials have been going on for many years, the
physical properties of most biopolymer films developed to date are
still inferior to those of synthetic films such as Low Density Poly-
ethylene (LDPE), High Density Polyethylene (HDPE) or cellophane
(Wihodo & Moraru, 2013). Therefore blending of SPI with different
polymers was found to be the most useful methodology to improve
properties of SPI-based materials. Up to now, SPI has been blended
with different polymers to achieve the desired properties.
3.2. SPI-organic filler biocomposites
Incorporation of filler materials in order to improve the barrier
properties of polymers is a well known technique in food packaging
applications (Ozcalik & Tihminlioglu, 2013). Owing to the
Table 1
Mechanical properties, water vapor permeability and Thermogravimetric Analysis (TGA) values of native and modified soy protein isolates.
Matrix Tensile strength (MPa)
SPI 2.26 ± 0.48
Phytagel (40%) modified SPI (Lodha & Netravali, 2005a) 60.0
Stearic Acid (20%) modified SPI (Lodha & Netravali, 2005b) 30
availability of a wide variety of fillers, a first distinction within the
huge field of fillers can be done according to their chemical
composition. Accordingly, it is useful to distinguish between
organic fillers, namely those containing carbon atoms and most
often directly derived from biomass; and inorganic fillers, which
may also be of natural origin, but as a general rule, do not consist of
any carbon atoms. As both classes (organic and inorganic) encom-
pass a wide assortment of examples, each including many different
applications, a review of biocomposites of soy protein isolate with
fillers of these kinds will help us to understand the matrixefiller
interactions in a better way.
3.2.1. Soy protein isolate-cellulose composites
Celluloses are the most abundant renewable biopolymer found
in nature. Their amorphous region can be dissolved away by
controlled acid hydrolysis, while its water-insoluble highly crys-
talline region can be converted into a stable suspension by me-
chanical shearing. Wheat-bran cellulose (WC), microcrystalline
wheat-bran cellulose (MWC) and ultrasonic/microwave modified
MWC (MMWC) as fillers in SPI matrix were prepared by Wang et al.,
2013 by solution casting. It was observed that ultrasonic/micro-
wave assisted treatment can alter mechanical properties by
changing the characteristics of filler particles (average particle size
and size distribution, diameter, shape, and packing style), which
affects the adhesion of the filler and the polymer matrix. Fig. 2
plotted from the Origin software (Version 7.5, Origin Lab Corpora-
tion, US) reflects the SEM of the blend films through the variation
state of plane salient.
Edible films based on carboxymethyl cellulose (CMC) and soy
protein isolate (SPI), compatibilized by glycerol and crosslinked by
Maillard reactions, were prepared by solution casting by Su,
Huang, Yuan, Wang, and Li (2010). The Maillard reaction can
occur when protein is mixed with carbohydrates at elevated
temperature. This reaction leads to entanglement and intermo-
lecular crosslinked structures, which greatly reduces crystallinity
of SPI and is responsible for the colors of the transparent SPI/CMC
(CS) films and the enhanced heat-sealing ability above melting
temperature.
Biodegradable and biocompatible blend fibers from cellulose
and SPI in NaOH/thiourea/urea aqueous solvent by coagulating
with 10 wt% H2SO4/12.5 wt% Na2SO4 aqueous solution was
prepared by Zhang, Li, and Yu (2011). The structure analysis of
the prepared blend fibers indicated that there were strong
interaction and good miscibility between cellulose and SPI. On
one hand, there exist hydrogen bonds among hydroxyl groups in
cellulose macromolecules and amine, amide, carboxyl, and hy-
droxyl groups in SPI macromolecules, the interaction in or
among SPI macromolecules is stronger than that of cellulose, so
the addition of SPI macromolecules would destroy the crosslink
among cellulose macromolecules, and the resistance among
flow fields decreases; Furthermore, the addition SPI aqueous
was found to dilute the cellulose solution. The blend films can
be successfully prepared by dissolving the biopolymers in ionic
liquid 1-allyl-3-methylimidazolium chloride co-solvent and by
coagulating with water (Wu, Wang, Wang, Bian, & Li, 2009). It
provides promising applications in biomedical fields of
Young's modulus (MPa) Fracture strain (%) Moisture content (%)
184 206 19.15
896.5 ± 49.6 19.5 12.4
124.7 ± 8.1 154.1 ± 8.1 12.8
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192 179

Fig. 2. SEM (a) the surface of the SPI film, (b) the surface of WC, (c) the surface of MWC, (d) the surface of MMWC, (e) the section of SPI film, (f) the section of MWC.
Reproduced with permission from (Wang et al., 2013).

cellulose/SPI blend fibers as the functional materials while
keeping its mechanical characteristics intact.
A new natural cross-linker, genipin (Gen), about 10,000 times
less cytotoxic than glutaraldehyde was used to modify SPI in the
formation of films (Gonza
lez et al., 2011). The macroscopic exam-
ination revealed that the degradation of the different films in soil
strongly depends on the cross-linking degree. It was observed that
the film with no modification almost completely degraded in 14
days, whereas the SPI-Gly-Gen 10% remained unaltered after 33
days (Fig. 3).
Biodegradation behaviors of SPI/CMC blend films in both at-
mospheric environment and the simulated soil environment were
studied by Wang and Su (2014) CMC was added to SPI to reduce the
damaging effects of photodegradation including the visual effect,
the loss of mechanical properties, the changes in molecular weight
and the molecular weight distribution.
3.2.2. Soy protein isolate-Lignocellulosic natural fiber composites
Natural cellulosic fibers such as flax, jute, ramie, hemp, sisal and
pineapple have attracted attention as reinforcements for
180 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Fig. 3. Macroscopic appearance of the buried SPI films with 0%; 0.1%; 1%; 2.5%; 5%; 7.5% and 10% (w/w of SPI) of Gen after 0, 2, 6, 9, 14, 19, 23 and 33 day.
Reproduced with permission from (Gonz
alez et al., 2011).
composites due to many advantages of annually renewable, sus-
tainable, low cost, high specific modulus, lightweight, biodegrad-
able and biocompatible features (Siqueira, Bras, & Dufresne, 2010).
Soy in the forms of SPC and SPI has been used as matrix for
development of natural fiber reinforced composites. Completely
biodegradable soy protein/jute biocomposites have been developed
and have shown better mechanical properties than polypropylene/
jute composites (Reddy & Yang, 2011). Tensile and flexural prop-
erties of the ramie fiber/soy protein resin green composites were
compared to that of three common wood varieties (bass, cherry and
walnut) and it was found that ramie fiber/soy protein resin green
composites exhibited much higher tensile strength of over 270 MPa
in the longitudinal direction than the wood samples, all of which
had tensile strengths of lower than 140 MPa (Nam & Netravali,
2006). Tensile strengths of flax yarn/20% Phytagel modified SPI
composites (220 MPa) are four to five times stronger than soft steel
and are comparable to hardened steel, and may be used in indoor
structural applications. Effect of different fiber reinforcements on
the mechanical and water uptake property of soy protein matrix is
shown in Table 2.
3.2.3. SPI e chitin and SPI e chitosan composites
Chitin and chitosan are known to be cellulose analogues with a
(1,4)-b-N-acetyl glycosaminoglycan repeating structure and a
deacetylated derivative respectively (Ifuku & Saimoto, 2012;
Mincea, Negrulescu, & Ostafe, 2012). After cellulose, chitin is the
second most abundant biopolymer, occurring mainly in the exo-
skeletons of shellfish and insects, and the cell walls of mushrooms.
Chitin and chitosan have been investigated as an antimicrobial
material against a wide range of target organisms like algae, bac-
teria, yeasts and fungi in experiments involving in vivo and in vitro
interactions with chitosan in different forms (solutions, films and
composites). Generally, in these studies the chitosan is considered
to be a bacteriocidal (kills the live bacteria or some fraction therein)
or bacteriostatic (hinders the growth of bacteria but does not imply
whether or not bacteria are killed), often with no distinction be-
tween activities. Similarly to bacteria, the chitosan is also found to
posses antifungal activity and the activity is assumed to be fungi-
static rather than fungicidal with a potential to communicate reg-
ulatory changes in both the host and fungus. Generally, chitosan
has been reported as being very effective in inhibiting spore
germination, germ tube elongation and radial growth of fungi (Goy,
Britto,& Assis, 2009).
Chitin (CH) reinforced SPI bioplastics were prepared by Zheng,
Tan, Zhan, and Huang (2003), and it was found that the added CH
as a filler cannot strongly interact with SPI molecules, which results
in phase separation in blends. However, the incorporation of chitin,
similar to cellulose, decreased the breaking elongation, but
increased the tensile strength and rigidity of the materials, result-
ing from the rigid nature of the CH molecules. When the CH content
was higher than 10 wt%, the water absorption of the blends were
obviously lower than that of the sheets without CH, resulting from
the formation of a CH framework in the blends.
Soy proteins and chitosan are not completely miscible, possibly
due to a weak inter-molecular interaction reflected from the shift in
the NH and C]O bands in FTIR spectra of the blends compared to
pure chitosan (Silva et al., 2007). Due to their opposite charges,
cationic chitosan interacted with anionic SPI to form a
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192 181

Table 2
Effect of different fiber reinforcements on the mechanical and water uptake property of soy protein matrix.

Soy protein composites with Method of preparation Young Tensile Water Reference
modulus strength uptake %

Arylated SPI þ Ramie (30%) Hot pressing of fibers wetted using 942 MPa 18 MPa 20 ± 2 Kumar & Zhang, 2009
SPI resin
SPI þ Aligned Ramie (30%) Hot pressing of fibers wetted using Kumar & Zhang, 2009
Vertically SPI resin 250 MPa 20 MPa 113 ± 10
Horizontally 250 MPa 16 MPa 96 ± 12
Soy flour þ Ramie fiber Hot pressing of fibers wetted using 2.94 GPa 88.0 MPa __ Kim & Netravali, 2010b
Soy flour resin
SPI þ Flax yarn Manual winding 900 MPa 197 ± 15 MPa ___ Lodha & Netravali, 2005a
Glutaraldehyde modified soy Hot pressing of fibers wetted using 3710 MPa 259.5 MPa __ Chabba, Matthews,
flour þ Flax yarn SPI resin at 178 KN & Netravali, 2005
SPC þ Bamboo micro/nano fibers (30%) Hot pressing of the composite sheet 3019 MPa Fracture stress 11.9 Huang & Netravali, 2009
at a pressure of 8 MPa (75.7 MPa)
Fracture strain (4.9%)
SPC þ Bamboo micro/nano Hot pressing of the composite 3221 MPa Fracture Stress 11.0 Huang & Netravali, 2009
fibers þ silane, (3-isocyanatopropyl) sheet at a pressure of 8 MPa (80.0 MPa)
triethoxysilane (ITES) Fracture Strain (7.3%)
SPI þ Banana fiber (3.0 volume fraction) Hot pressing of composite sheet at ___ Kumar, Choudhary,
Untreated banana fiber a pressure of 10 tons 256 ± 7.9 MPa 1.62 ± 0.15 MPa Mishra, & Varma, 2008
Alkali treated (10%) banana fiber 420 ± 5.4 MPa 3.24 ± 0.12 MPa
SPI þ Jute fiber (40%) Compression molding pressure 6.1 ± 0.8 GPa 69.7 ± 14.6 MPa __ Reddy & Yang, 2011
139 MPa
SPC þ Hemp yarn (25%)pH ¼ 10 Impregnation of hemp yarns wound 6.54 ± 9.51 GPa 15.45 MPa __ Kim & Netravali, 2011
onto a metal frame into the precured
soy resins
SPC þ Longitudinal Ramie fiber (45%) Hot Pressing of composite 4.9 ± 17.3 GPa 271 MPa __ Nam & Netravali, 2006
SPC þ Transverse Ramie fiber films at 5 MPa pressure 0.9 ± 30.3 GPa 7.4 MPa
SPI þ Treated corn husk fiber (5%) Extrusion followed by compression Saenghirunwattana
Alkali molding 343 ± 8.34 MPa 13.66 ± 0.03 MPa 13.49 ± 0.31 et al., 2014
1.5% (w/v) Silane 422 ± 15.64 MPa 15.05 ± 0.46 MPa 12.53 ± 0.15
SPI þ Kapok Husk fiber (KH 40%) Solvent casting __ Husseinsyah, Chan,
Unmodified SPI/KH 200 MPa 4 MPa Kassim, Zakaria, &
Modified SPI/KH with 1% Glutaraldehyde 225 MPa 5.5 Mpa Ismail, 2014
Soy flour þ Jute þ Cellulose whisker (5%) Solution-induced intercalation 1877.287 ± 12.84 22 Iman, Bania, &
Without nanoclay 2363.098 ± 11.04 30.780 ± 1.252 Maji, 2013
With nanoclay (MPa) 52.591 ± 0.746
(MPa)
Soy flour þ Indian grass fiber Extrusion followed by Injection __ Liu, Mohanty, Askeland,
Untreated Molding 2.5 GPa 12 MPa Drzal, & Misra, 2004
Alkali treated (10%) 2.8 GPa 15.8 MPa
Soy flour modified with Fiber immersion in resin solution Khalsa et al., 2009
i) Agar 2999.33 ± 317.04 119.68 ± 16.98 15.01
ii) Sorbitol 2751.04 ± 307.9 141.45 ± 16.72 13.65
iii) kraft fluff pulp (NB416) þ Sisal Fiber 3468.87 ± 244.02 107.81 ± 12.78 14.62
(MPa) (MPa)
Soy flour modified with polyester Extrusion followed by injection 2000 MPa 20 MPa 18 Liu, Misra, Askeland,
amide þ Pineapple leaf fiber (PALF) molding Drzal, & Mohanty, 2005
Soy flour modified with polyester Extrusion followed by injection 2000 MPa 20 MPa ___ Mohanty et al., 2005
amide þ Industrial hemp fiber molding
SPI modified with (20%) stearic Fiber immersion in resin solution Lodha & Netravali, 2005b
acid þ Ramie fiber
Axial Ramie 5.82 ± 0.51 GPa 267.5 ± 66.5 MPa 12.6
Transverse Ramie 1.26 ± 0.26 GPa 9.6 ± 2.2 MPa
SPC modified with gelatin þ Sisal fiber Extrusion followed by injection 1370 MPa Fracture ___ Kim & Netravali, 2010a
molding stress ¼ 45.6 MPa
Fracture
strain ¼ 8.9%
SPC modified with Hot pressing of composite films 2.25 GPa 125 MPa ____ Chabba & Netravali, 2004
glutaraldehyde þ Flax yarn at 8 MPa pressure
SPC modified with Manual winding of flax FIBER 4.3 GPa 298 MPa ____ Huang & Netravali, 2007
glutaraldehyde þ Flax yarn þ Nanoclay followed by impregnation in resin
SPI modified with 20% Manual winding of flax fiber 3.10 ± 0.38 GPa 220 MPa 16.7 Lodha & Netravali, 2005a
phytagel þ Axial flax yarn followed by impregnation in resin

polyelectrolyte complex. Heated SPIeChitosan (CS) complex
exhibited improved solubility than SPI (less than 10%) and un-
heated SPIeCS mixture (about 50%) at pH 4.0 because of the
increased electrostatic repulsion (z-potential) after heat treatment.
The effects of mixing ratios, molecular weights (MW) and charge
densities (CD) of chitosan on the stability of heated SPIeCS complex
was analyzed by Yuan et al., 2013 and it was found that the
influence was mainly dependent on mixing ratios and charge
densities of chitosan. The immiscibility of chitosan-SPI blend
membranes can to a certain extent be reduced by introducing a
small amount of siloxane bond into the chitosan/soy protein system
(Silva et al., 2013). Tetraethoxysilane bound chitosan/soy protein
hybrid membranes (CSH) had significantly higher superficial en-
ergy (g) values indicating the generation of more reactive surface,
182 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
which could in turn influence the cell membrane interactions. An
illustrative representation of the CSH membranes is shown in Fig. 4.
CSH membranes were found to have extremely low cytotoxicity on
cells, which supports the concept that these materials could be
used in contact with the body. In addition, the CSH membranes had
good degradability and mechanical properties favoring their use in
guided tissue regeneration, long-term wound healing, during
which the membranes will be resorbed by the body during the
healing process.
Chitosan was used to modify cellulose/SPI composites by
blending or surface coating, with the aim of enhancing the physical
properties, cytocompatibility and hemocompatibility of the resul-
tant composites (Wang et al., 2011). Chitosan could interact with
both cellulose and SPI and enhance their properties. Chitosan
coating could alter the surface morphology of the original
Cellulose-Soy Protein Isolate Membrane (CSM) by covering the
pores on the CSM by forming a very thin layer during the coating
process. These changes were found to affect the microstructure,
physical properties and biological properties of the resulting
membranes.
Water sorption isotherms of soy protein isolate/carboxymethyl
chitosan (SPI/CMCH) blended films was studied by Rachtanapun
and Suriyatem (2012). The Guggenheim-Oswin, Bru-
nauereEmmetteTeller (BET) and Andersonede Boer (GAB) sorp-
tion model predictions were tested against the experimental data.
The isotherms showed that the equilibrium moisture content
(EMC) of the films increased with increasing CMCH content and the
EMC value sharply increased above water activity (aw) ¼ 0.55. The
BET model was found to be the best-fit model for SPI/CMCH
blended films at 25 ± 1  C.
Hemocompatibility of CH/SPI composite membranes was
improved by heparinization by Wang, Shi, et al. (2012). It was
observed that compared with chitosan/soy protein (ChS) mem-
branes, heparinized chitosan/soy protein (HChS) membranes
showed lower platelet adhesion, longer plasma recalcification
time (PRT), higher blood anticoagulant index (BCI), significant
thromboresistivity and a lower hemolysis rate due to the
heparinization.
3.2.4. SPI e starch composites
In recent years, great interest has been given to the study of
proteinepolysaccharide mixtures both in the industrial and aca-
demic sectors. The manipulation of the protein e polysaccharide
interactions offers the opportunity to control the delicate stability
and texture of food systems with multicomponent structures (Li
et al., 2013).
Optically clear and transparent oxidized potato starch/SPI films
were made by Galus and Lenart (2013) by casting method. Oxidized
Fig. 4. Illustrative representation of chitosan/soy protein hybrid (CSH) membranes.
Reproduced with permission from (Ifuku & Saimoto, 2012).
starch content significantly affected (P < 0.05) the tensile strength,
from 0.95 to 1.51 MPa, temperature at maximum degradation rate
from 64.8 to 74.2  C and water vapor permeability from
1.08  1010 to 3.89  1010 g/(mPas) at relative humidity differ-
entials of 30e50 and 30e100 % respectively, which indicates the
strong interaction between the two kinds of molecules. Effect of
addition of two modified potato starches (acetylated di-starch
phosphate and starch acetate) and two potato maltodextrins
showed that addition of starch and maltodextrin had a significant
effect on water vapor adsorption of soy films and increase of
diffusion coefficient from 1.73 to 2.60 m2 s1. Water vapor
permeability increased as relative humidity differentials increased
while all films demonstrated low values of tensile strength
(~1.14e1.96 MPa) and elongation at break (~25.6e34.7%) (Galus,
Mathieu, Lenart, & Debeaufort, 2012). Protein rich extruded prod-
ucts were prepared from soy protein isolate and corn flour blends
using a twin screw extruder and the physical properties of the
extruded product were evaluated by Yu, Ramaswamy, and Boye
(2013). It was found that a high extrusion processing temperature
with a high screw speed provides a high level of thermal and me-
chanical energy simultaneously, which leads to excessive structural
damage and breakdown, and hence slight increase in density. g-
irradiation affects soy proteins by causing conformational changes,
oxidation of amino acids, rupture of covalent bonds and formation
of protein free radicals. Through the irradiation technology, the SPI
molecule combines with the starch molecule firmly in favor of
increasing the material's capability and possessing a better exterior
appearance (Xu et al., 2012). Irradiation was found to significantly
decrease viscosity of the SPI/starch material due to the conforma-
tional change of protein molecules by oxygen radicals generated by
radiolysis of water.
Differential scanning calorimetry (DSC) has been used to study
changes in proteins and starches as a function of temperature in
SPI-Corn starch mixtures (Li et al., 2013). It was observed that the
higher amounts of SPI enhanced the thermal stability of corn starch
and raised its endothermic temperature in the mixture. On the
other hand, the presence of corn starch protects the SPI from
denaturation.
3.2.5. SPI e other polymer biocomposites
Flexible and transparent films from SPI and agar (AG) obtained
from Gelidium sesquipedale (Rhodophyta) were prepared by
thermo-molding method as well as casting (Guerrero et al., 2013;
Tian et al., 2011). It was observed that the casting films possessed
more homogeneous interfaces compared to the molding films,
leading to their superior mechanical properties. Fig. 5 shows the
tensile strength (a) and elongation at break (b) of soy protein/agar
(AG) blend films prepared from solution casting and thermo-
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192 183

Fig. 5. Tensile strength (a) and elongation at break (b) of soy protein/agar (AG) blend films prepared from solution casting and thermo-molding methods after conditioning at 43%
relative humidity for 1 week.
Reproduced with permission from (Tian et al., 2011).

molding methods after conditioning at 43% relative humidity for 1
week.
The behavior of the foodstuffs covered by three different films as
foodstuffs covering: a commercial polypropylene bag, SPI-Poly
Lactic Acid (PLA) 60/40 film without active agent (control) and
SPI-PLA 60/40 film containing natamycin as antifungal agent (0.33%
w/w of SPI) was studied by Gonz
alez and Alvarez Igarzabal (2013)
(Fig. 6). The behavior of the coated foodstuffs stored under
similar conditions for all foods was studied for a maximum period
of 55 days. Tensile strength (TS), elongation at break (EB) and
Young's modulus (E) of the control sample (SPI-100) were
1.08 ± 0.34, 24.63 ± 0.13 and 22.80 ± 6.14 respectively. It was
observed that the film-containing natamycin could delay the
appearance of mold in the tomato for more than 13 days with
respect to the polypropylene commercial bag. The study in apple
after 55 days concluded that the highest growth of mold was found
in the commercial polypropylene packaging, and that the appear-
ance of mold could be delayed for at least 29 days with respect to
the polypropylene commercial bag using the natamycin containing
film.
Biodegradable SPI/PLA blends plasticized with triacetin are
found to be suitable for the production of slow release fertilizer
systems (Calabria et al., 2012). Adipic anhydride-plasticized soy
protein (SP.A) blended with PLA was found to be useful as a sus-
tainable replacement for petroleum plastic in horticulture crop
containers (Yang et al., 2014). Incorporation of SP.A accelerated the
biodegradation rate of this binary blend significantly compared to
pure PLA.
Mechanical properties and water sensitivity of SPI films can be
improved by blending with poly (vinyl alcohol) (PVA) (Su, Huang,
Yang, & Yuan, 2008; Su, Huang, Zhao, et al., 2010; Su, Yuan,
Huang, & Xia, 2010). As PVA is the largest synthetic water-soluble
polymer produced in the world, it can be blended with soy pro-
tein polymers to form biodegradable composites, which would be
partially crystalline. The enhanced mechanical properties (tensile
strength of 49.2 MPa and percentage elongation at break of
50.4 MPa) can be attributed to the long-chain PVA molecules,
which contain manyeOH groups forming strong intra- and inter-
molecular interactions with protein molecules. Evidence for the
specific chemical interaction occurring between SPI and PVA is
obtained from the FTIR analysis of the composite film where the
strong hydrogen bond association appearing both in SPI and PVA at
2918e3565 cm1 shifts to a new absorption band at
2900e3100 cm1 (Fig. 7). Analysis of heat sealing properties of SPI/

Fig. 6. Visual analysis of foodstuffs behavior coated with a commercial polypropylene, SPI-PLA 60/40 film without active agent and SPI-PLA 60/40 film containing natamycin.
Reproduced with permission from (Gonz
alez & Alvarez Igarzabal, 2013).
184 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Fig. 7. FTIR spectra of Poly Vinyl Alcohol-SPI Blends.
Reproduced with permission from (Su et al., 2008).
PVA blend films showed that they obtain the desired sealing
properties when the PVA content exceeded 15% (Tai, Chen, Yang, &
Yang, 2014).
Carboxymethyl konjac glucomannan (CMKGM), one of the most
important derivatives of konjac glucomannan (KGM) and a typical
anionic polysaccharide that shows amphiphilic characteristics can
be blended with SPI to form films with increased mechanical
properties, thermal stability and water vapor barrier properties
(Wang, Xiao, et al., 2014). CMKGM and SPI are highly compatible in
blended film formation due to Maillard reactions and hydrogen
bond interactions between CMKGM and SPI.
Blend membranes of a natural polymer, sodium alginate (SA),
with the natural polymer SPI were prepared by solution casting
method and crosslinked with a mixture of glutaraldehyde and
acetone (Maruthi et al., 2014). Pervaporation dehydration of the
membranes was tested for water þ isopropanol mixture at 300  C.
The blend membranes of SA/SPI containing 50 wt% SPI showed
higher permeation flux for water þ isopropanol, whereas higher
selectivity up to 891 was observed for the blend membrane con-
taining similar wt% ratio from the aqueous streams. Alkylation with
sodium alginate and propylene glycol alginate (Rhim, Wu, Weller, &
Schnepf, 1999) was found to increase the mechanical strength and
water resistance of the SPI films. Moreover, drug carrying efficiency
of Ca crosslinked SA/SPI beads was tested by Zheng, Zhou, Chen,
Huang, and Xiong (2007). It was found that the swelling and drug
release properties were affected by pH conditions and showed
obvious differences under given pH of stomach, intestine and colon.
Moreover, the intestine and colon was found to be the optimal site
for prompt release of drugs.
Increase in optical transmittance of SPI-Gelatin composite films
is evidence for good compatibility between SPI and gelatin (Bai, Xu,
Liao, & Liu, 2013; Guerrero, Stefani, Ruseckaite, & de la Caba, 2011;
Kaewprachu & Rawdkuen, 2014). The pure SPI film and gelatin film
surfaces are hydrophilic in the presence of hydroxyl, amino and
carboxyl groups. The gelatin content had an important effect on
interaction force between SPI and gelatin, which would result in the
exposing of hydrophobic groups initially buried in SPI.
An edible oxygen barrier film pouch was fabricated from a heat
sealable corn zein (CZ) layer laminated on SPI film and used to
package olive oil condiments for use with instant noodles (Cho, Lee,
& Rhee, 2010). The oxygen permeability of the CZ/SPI film
(0.81  1018 m3 m/m2 s Pa) was lower than that of nylon-
metalocene catalyzed linear low-density polyethylene (NY/
mLLDPE) film (3.51  1018 m3 m/m2 s Pa) which is the material
usually used for such condiments. Egg white protein (albumen) and
soy protein systems used alone or in combination yield bio-plastics
that can be thermomechanically processed by injection molding,
although showing lower rheological and mechanical properties
than LDPE standards, under the selected processing conditions

lix et al., 2014).
(Fe
Lipids can be also used in composite films to improve the films'
ability to control water transport. Epoxydized soybean oil (ESO),
virgin extra olive oil variety picual (OO) or lactic acid (LA) have been
added to SPI-based films in order to improve the hydrophobic
character of the films prepared by compression (Guerrero, Nur
Hanani, et al., 2011). Plastics containing castor oil exhibited
improved tensile strength and Young's modulus and storage
modulus under high humidity (75% RH), compared with neat
glycerol plasticized protein plastics (Tian et al., 2012). Similar re-
sults were found while incorporating cinnamon or ginger essential
oils into soy protein matrix (Atare
s et al., 2010). Ginger oil made the
films less resistant to elongation and less stretchable although
lipideprotein interactions led to more resistant and stretchable
films in the case of cinnamon oil. Effects of the ratio of oleic acid to
stearic acid and ultrasonic/microwave assisted treatment on the
water vapor permeability (WVP) and contact angle of soy protein
isolate films showed that the prepared films (oleic acid: stearic
acid ¼ 2:3) had the lowest WVP value (0.1  1012 g cm1 s1 Pa1)
and highest contact angle value (135 ) (Wang, Zhou, et al., 2014).
Addition of 3% w/w citronella essential oil into bilayer films based
Table 3
Overview of the different types of soy protein isolate composites.

SPI composites Method of preparation Solvent used Plasticizer used Properties studied

SPI-cellulose composites
SPI/wheat-bran cellulose (WC) (Wang et al., 2013) Solution casting and Water Glycerol Tensile strength (TS), Elongation (E), Thermal property (Tg and TC), Water vapor
evaporation permeability (WVP), Oxygen permeability (OP)
SPI/carboxymethyl cellulose (CMC) Solution casting and Water Glycerol Tensile strength (TS), percentage elongation at yield point (P.E.Y.), Percent elongation
(Su, Huang, Yuan, et al., 2010; Su, evaporation at break (P.E.B), Thermal stability, Water solubility
Huang, Zhao, et al., 2010; Su, Yuan, et al., 2010)
SPI-chitin/chitosan composites
SPI/chitin (Zheng et al., 2003) Compression-molding at Water Glycerol Tensile strength (TS), Breaking elongation (εb), Young's modulus (E), Thermal property
160  C and 20 MPa (Tg, DH, tand), Water absorption, Crystallinity
SPI/chitosan (Silva et al., 2007) Solvent casting Acetic acid to e Contact angle, Surface energy
dissolve chitosan
SPI/carboxymethyl chitosan (Rachtanapun & Solution casting Water Glycerol Moisture sorption properties of films via moisture sorption empirical models
Suriyatem, 2012)
SPI/silane treated chitosan (Silva et al., 2013) In situ solegel process Acetic acid to Glycerol Contact angle, Storage modulus (E0 ), Loss factor (tan d), Degradation behavior, Water
dissolve chitosan absorption, Cytotoxicity
SPI-starch composites
SPI/oxidized potato starch (Galus and Lenart (2013) Solution casting and Water Glycerol Opacity, Contact angle, Tensile strength, Elongation at break, Water vapor permeability

R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192

evaporation
SPI/modified starch and maltodextrin Solution casting and Water Glycerol Diffusion coefficient of water vapor, Water vapor permeability, Tensile strength,
(Galus et al., 2012) evaporation Elongation at break, Color and microstructure
SPI/corn flour (Yu et al., 2013) Twin screw extrusion e e Water solubility index (WSI), Expansion ratio (ER), Rehydration ratio (RR)
SPI/starch (Xu et al., 2012) Y irradiation followed by Epichlorohydrin Water þ caprolactam Tensile strength (TS), Youngs modulus (E), Water absorption capacity (WAC), hunter
compression molding (1:3) þ succinic color values, Viscosity
anhydride
SPI-agar composites (Guerrero et al., 2013; Thermo-molding method Water Glycerol Tensile strength (TS), Elongation at break (E), Crosslinking densities
Tian et al., 2011) as well as casting
SPI-Poly Lactic Acid (PLA) composites Bi layer casting Chloroform to Glycerol Opacity, Contact angle, Swelling index (S), Moisture content (MC), Total soluble matter
(Gonza
lez and Alvarez Igarzabal (2013) dissolve PLA (TSM), Water vapor permeability (WVP), Tensile strength (TS), Thermal property,
Biodegradation, Behavior on food.
SPI/poly (lactic acid) (Calabria et al., 2012) Injection molding e Triacetin Thermal analysis, Viscoelastic behavior, Biodegradation, Fertilizer release
SPI/poly (vinyl alcohol) (Su, Huang, Solution casting and Water Glycerol Contact angle measurements, Moisture sorption, Water vapor permeability (WVP)
Yuan, et al., 2010; Su, Huang, evaporation method
Zhao, et al., 2010; Su, Yuan, et al., 2010)
SPI/poly (vinyl alcohol) (Su, Huang, Yuan, et al., 2010; Solution casting and Water Glycerol Color and transparency, Contact angle, Aerobic biodegradation, Water sensitivity,
Su, Huang, Zhao, et al., 2010; Su, Yuan, et al., 2010) evaporation method Mechanical behavior, Photo-oxidative effect
SPI/poly (vinyl alcohol) (Su et al., 2008) Solution casting and Water Glycerol Compatibility, Crystallinity, Tensile strength (TS), Percentage elongation at break
evaporation method point (P.E.B.), Thermal stability, Glass transition temperature (Tg)
SPI/Carboxymethyl Konjac Glucomannan (CMKGM) Solution casting and Water e Tensile strength (TS), Percent elongation at break (%E), Oxygen permeability,
(Wang & Su, 2014; Wang, Xiao, et al., 2014, evaporation method Contact angle, Biodegradability, Biocompatibility
Wang, Zhang, et al., 2014, Wang, Zhou, et al., 2014)
SPI/Sodium Alginate (SA) Solution casting and Water Glycerol Swelling studies, Refractive index, Glass transition temperature (Tg), Thermal stability,
membranes crosslinked evaporation method Pervaporation studies
with glutaraldehyde (Maruthi et al., 2014)
SPI/Ca2þ crosslinked Sodium Alginate Solution blending and Water e Swelling tests, Drug-release studies, Interaction between SPI and Alginate components
(Zheng et al., 2007) then Ca2þ crosslinking
SPI/Genipin (Gen) (Gonz
alez et al., 2011) Solution casting and Water Glycerol Opacity, Cross-linking degree (CL%), Moisture content (MC), Total soluble matter (TSM),
evaporation method Swelling ratio (S), Tensile strength (TS) Elongation at break (E), Water vapor
permeability (WVP), Indoor soil degradation
SPI/Gelatin (Bai et al., 2013) Solvent casting Water e Tensile strength (TS), Elongation at break (EB), Contact angle, Water vapor
transmission rate (WVTR)
SPI/Commercial Gelatin (bovine hide) (CG), Solution casting and Water Glycerol Water vapor permeability, tensile strength (TS), Elongation at break (EB), Film solubility
giant catfish skin gelatin (GG) evaporation method
(Kaewprachu & Rawdkuen, 2014)
SPI/Gelatin (Guerrero, Nur Hanani, et al., 2011; Compression molding Water Glycerol Moisture content, total soluble matter, Light absorption, Contact angle, Tensile
Guerrero, Stefani, et al., 2011) at a pressure of 12 MPa strength (s), Elongation at break (ε)
(continued on next page)

185
 186 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192

on SPI, lignin and formaldehyde was found to posses good anti-

Tensile strength (s), Elongation at break (ε), Young's modulus (E), Diffusion coefficient (D),
fungal activity against Fusarium oxysporum pathogen microor-

Enthalpy of denaturation, Degradation temperature, Diffraction pattern, Light absorption,

Tensile strength (TS), Elongation at break (EAB), Lap shear strength, Water contact angle,
ganism in bananas (Arancibia, Lo
pez-Caballero, Go

mez-Guille
n, &

Contact angle (CA), Kinetics of water uptake (WU), Optical transmittance (Tr), Storage
Surface hydrophobicity of proteins, Glass transition Tg, Protein extractability,Vicosity,
Elastic modulus (E0 ), Loss modulus (E00 ), Loss tangent (tan d), Uniaxial tensile strength

Optical properties, Contact angle, Moisture content (MC), Total soluble matter (TSM),

modulus (EM), Elongation (% E), Water vapor permeability (WVP), Optical properties
Lipid particle size, viscosity, Density, contact angle, Tensile strength (TS), film Elastic
sealability, olive oil packaging, Tensile strength (TS), Percent elongation at break (E)

Storage tensile modulus E0 , Loss modulus E00 , tan d, Tensile strength (s), Elongation
Montero, 2014). SPIelipids were combined with caseinates (so-
Water vapor permeability, oxygen permeability, Film solubility in hot water, Heat

shear modulus (G0 ), Loss modulus (G00 ), Total surface energy, Biodegradability and
dium or calcium) in different SPI:caseinate ratios with the aim of

Moisture content, Water absorption, Thermal degradation pattern, Tg and Tm,

improving water vapor barrier, mechanical and optical properties

Water vapor permeability (WVP), Puncture strength, Puncture deformation

of SPI films containing lipids (Monedero, Fabra, Talens, & Chiralt,
2010). Caseinate incorporation to SPI based films provoked an in-
crease of elastic modulus and tensile strength at break, mainly for
calcium caseinate. Both caseinates contributed to increase the
water vapor barrier properties of soy protein based films.
Hydrophobic materials were successfully prepared from SPI and
natural rubber (unvulcanized and pre-vulcanized) by blending via
at break (ε), Young's modulus (E), Thermal stability

freezing/lyophilizing by Tian, Zhang, Wu, Wang, and Chen (2010).

Softening point measurement, Biodegradability

The blend sheets exhibited good interface adhesion and good op-
tical transparency. The contact angle values of the blend sheets
measurements, Water uptake capacity

were dramatically enhanced with the increase in rubber, indicating

Biodegradability, Diffraction pattern
an improved hydrophobic surface compared to pure SPI sheets. The
unvulcanized rubber-soy protein sheets possessed superior me-
chanical properties, compared to the vulcanized rubber-soy protein
sheets. The blend sheets also exhibited good biodegradability.
A novel computerized method, LOTUS package, has been used
Properties studied

for evaluating the kinetic parameters of urea modified soy protein

biocompatibility

for various commercial applications (Das et al., 2011). Urea was

used to modify soy protein and did not act as a crosslinker as there
was no change in the absorption band of the neat SPI and SPI
modified with urea. The crystallinity has been calculated by using
the new computerized package method and it showed that the film
possessed amorphous region. The biodegradability of the modified
glycol for corn zein

SPI indicates that they degrade within reasonable time period.

Plasticizer used

sorbitol for SPI

Blend films of SPI with poly (butylene adipate) (PBA) based

Polyethylene
Glycerol and

Coconut oil

waterborne polyurethane (WPU) showed strong interfacial adhe-

Glycerol

Glycerol

Glycerol

Glycerol

Glycerol

sion as well as good miscibility between SPI and WPU (Zhang, Song,
Wang, & Wang, 2012). The contact angle value was increased with
e

an increase in WPU content, which implied that the surface hy-

Water (pH ¼ 4.5)

drophilicity/hydrophobicity of SPI can be modulated by the amount

Water for SPI
Solvent used

of WPU. Table 3 shows an overview of the different types of SPI

Ethanol for
corn Zein

composites.
Water

Water

Water

3.3. SPI-organic filler reinforced bionanocomposites

e

e
by compression molding
Method of preparation

The inclusion of nanoparticles in polymer systems to produce

Compression molding

Compression molding
Intensive mixing and

freezing/lyophilizing
at 12 MPa pressure

at 20 MPa pressure

the so-called nanocomposite materials has been shown to give

Hot melt blending
Injection molding

remarkable increases in tensile properties at low nanoparticle

Bi layer casting

Blending via
hot pressing

addition levels. Nanobiocomposites consist of a biopolymer matrix

followed

reinforced with particles (nanoparticles) having at least one

Casting

dimension in the nanometer range (1e100 nm) (Fernandes, Pires, &

Reis, 2013; Kumar, Depan, Singh Tomer, & Singh, 2009; Kumar,
Sandeep, Alavi, & Truong, 2011; Kumar, Sandeep, Alavi, Truong, &
Gorga, 2010b). The advantages of natural polysaccharide whiskers
or nanocrystals or nanofibers are their low cost, low density, high
specific strength and modulus, large surface to volume ratio, high
SPI/poly-ε-caprolactone (Hong et al., 2009)

flexibility, good dynamic mechanical, electrical and thermal prop-

erties, renewable character and biodegradability (Deepa et al.,
(Guerrero, Nur Hanani, et al., 2011;
SPI/Epoxydized Soybean Oil (ESO)

SPI/Natural rubber (Tian et al., 2010)

2011). Thus chitin whiskers, starch crystals and cellulose whiskers

SPI/Cinnamon oil SPI/Ginger oil
Guerrero, Stefani, et al., 2011)
SPI/Castor oil (Tian et al., 2012)

lix et al., 2014)
SPI/Corn Zein (Cho et al., 2010)

from various sources such as wood, tunicin, ramie, cotton, wheat

SPI/picual oil SPI/L-lactic acid

straw, bacterial cellulose and sugar beet are widely used to

SPI/Urea (Das et al., 2011)

strengthen soy protein materials.

s et al., 2010)

Environmental friendly thermoplastic nanocomposites were

Table 3 (continued )

successfully developed using a colloidal suspension of chitin

SPI/Albumen (Fe
SPI composites

whiskers (wet basis) as a filler to reinforce SPI plastics by Lu, Weng,

and Zhang (2004). Analysis showed that nanocomposites with
(Atare

lower whisker content exhibit a relatively uniform dispersion in the

SPI matrix than those with higher chitin content. Compared to a
glycerol plasticized SPI sheet, the chitin filled SPI composites
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
exhibited increase in Young's modulus and tensile strength from 26
to 158 MPa and 3.3e8.4 MPa, with increasing chitin content from
0 to 20 wt%.
Pea starch nanocrystals (StNs) were incorporated into an SPI
matrix to produce a class of full-biodegradable nanocomposites
(Zheng, Ai, Chang, Huang, & Dufresne, 2009). The StN with low
loading level (<2 wt%) (dry basis) showed a predominant rein-
forcing function, resulting in an enhancement in strength and
Young's modulus. Transparent and homogeneous SPI films rein-
forced with corn starch nanocrystals (SNC) were developed by
simple casting method by Gonza
lez and Alvarez Igarzabal (2014). It
was found that as the amount of SNC increased, the films became
more resistant, less elongable and more crystalline, and exhibited
lower affinity for water. In addition, performed assays demon-
strated that b-cyclodextrins (b-CD) containing SPI-SNC films were
able to sequester cholesterol when brought into contact with
cholesterol rich foods such as milk.
Environmental friendly SPI/cellulose whisker composites were
successfully prepared by Wang, Cao, and Zhang (2006) using a
colloidal suspension of cellulose whiskers from cotton linter pulp,
to reinforce SPI plastics. With the addition of 0e30 wt % (wet basis)
of cellulose whiskers, strong interactions occurred both between
the whiskers and between the filler and the SPI matrix, reinforcing
the composites and preserving their biodegradability.
Electrospun cellulose nanofiber reinforced SPI composite films
showed strong interfacial interactions at the cellulose nanofiber/SPI
interfaces (Chen & Liu, 2008). The incorporation of 20 wt% cellulose
nanofibers (dry basis) in the SPI matrix resulted in great improve-
ment of mechanical strength and Young's modulus by respectively
13 and 6 times more than neat SPI film. More interestingly, this
composite was translucent with light transmittance of over 75% at
700 nm.
3.4. SPI e inorganic fillers reinforced bionanocomposites
The inclusion of inorganic nano fillers into the soy protein ma-
trix results in a drastic change in matrix properties which depends
on many factors such as nanoparticle size, aspect ratio, surface area
and polymer/filler compatibility. Because of their very high surface
area to volume ratio, strong interfacial adhesion would exist be-
tween nanoparticle and matrix, which in turn leads to composites
with unique outstanding properties (such as higher mechanical,
thermal and barrier properties) in comparison to their conven-
tional microcomposite counterparts.
3.4.1. SPI e clay bionanocomposites
Clay minerals used in the manufacturing of nanocomposite
materials are natural or synthetic layered hydrated aluminum
phyllosilicates, often hydrated, with neutral or negative charged
layers (Unalan, Cerri, Marcuzzo, Cozzolino, & Farris, 2014). Clays
have high affinity for protein and so it is not surprising that good
results have been obtained with nanoclay fillers in regenerated
protein. These bionanocomposites can be obtained by several
methods which include in-situ polymerization, solution exfoliation
and melt intercalation. In the in-situ polymerization method,
monomers are intercalated into layered clays and subsequently
polymerized via heat, radiation or catalyst. In solution exfoliation,
layered clays are exfoliated into single platelets using a solvent and
the polymer is adsorbed onto the platelets by mixing in the clay
suspension. In melt intercalation, layered clays are mixed with the
polymer matrix in molten state (Ojijo & Sinha Ray, 2013).
Montmorillonite (MMT) (Mþ y .nH2O) (Al2-yMgy)Si4O10(OH)2
(where Mþ y refers to a generic monovalent interlayer cation) is the
most widely exploited clay for the fabrication of polymer/clay
nanocomposites (Mishra, Ramasamy, Lim, Ismail, & Majeed, 2014;
187
Shameli et al., 2011). SPI-MMT polymer clay nanocomposites
have been prepared using several methods like melt extrusion
(Kumar, Sandeep, Alavi, Truong, & Gorga, 2010a), casting
(Echeverría et al., 2014; Lee & Kim, 2010) and solution intercalation
(Chen & Zhang, 2006). The nanoclay was shown to become highly
exfoliated with surface positive charges on the globulins anchoring
into the negatively charged montmorillonite galleries, and good
nanoclay dispersion occurred due to electrostatic interactions and
hydrogen bonding. The sodiumeMMT curve reflected its charac-
teristic crystallographic structure with a peak of diffraction at
around 2q ¼ 72 corresponding to an interlaminar space of
d001 ¼ 1.2 nm. The diffraction spectra of the nanocomposite films
produced by casting method (Echeverría et al., 2014) were without
the characteristic MMT peak and also lacked the other peak at
lower angles. For bionanocomposite films of SPI-MMT produced by
melt extrusion, MMT layers was found to have a d-spacing of at
least 3.53 nm (corresponding to a 2q value of 2.5 ) which was
higher than the d-spacing value of 3 nm for SPIeMMT bio-
nanocomposite powder prepared by a solution intercalation
method at an MMT content of 16% (dry basis) (Chen & Zhang, 2006).
Higher d-spacing value in the case of melt extruded films was
attributed to the high shear mixing inside the twin-screw extruder.
Fig. 8 shows the XRD patterns of MMT and SPIeMMT bio-
nanocomposite powders with 0%, 5%, 10% and 15% MMT (dry basis)
contents produced by melt extrusion.
There was a significant improvement in mechanical (tensile
strength and percent elongation at break) and dynamic mechanical
properties (glass transition temperature and storage modulus),
thermal stability and water vapor permeability of the films with the
addition of MMT. The value of tensile strength increased from
2.26 ± 0.48 MPa to 15.60 ± 1.69 MPa as the MMT content increased
from 0 to 15% (dry basis). This is attributed to the high rigidity and
aspect ratio of MMT and interaction of SPI with MMT. Table 4
represents the mechanical properties of SPI-MMT bio-nano-
composites produced by different techniques.
The control drug delivery application of the SPI-MMT nano-
composite has been investigated by blending it with ofloxacin and
the drug delivery kinetics has been monitored by using the kinetic
equations at two different pH media (Nayak, 2011). It was seen that
50% drugepolymer composites have shown longer drug release
rates than the other composites. This suggests that the drugs in the
blend can be used to be suitable for the basic environment of the
Fig. 8. XRD patterns of MMT and SPIeMMT bio-nanocomposites with different MMT
contents.
Reproduced with permission from (Kumar et al., 2010b).
188 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Table 4
Mechanical properties of SPI-MMT bionanocomposites produced by different techniques.
SPI þ 10% MMT Solution intercalation (Chen & Zhang, 2006)
Tensile strength 14.48 MPa
Youngs modulus 587.6 MPa
% Elongation 5 23.98 ± 5.02
large intestine, colon and rectal mucosa for which there are
different emptying times.
Exfoliation is the desirable arrangement for improving the
properties of nanocomposites. However, exfoliation is harder to
achieve during processing because layered clays such as MMT have
a strong tendency to agglomerate because of their hydrophilic
nature. The d-spacing of the layered silicates can be increased by
ion exchange reaction of sodium ions present in natural MMT with
various organic cations such as primary or quaternary amine. The
influence of the type of organic modifier (primary and secondary
amine) and the extent of surface coverage of clay on the structure
and mechanical properties of nanocomposites based on SPI and
MMT have been investigated by Kumar et al. (2010a) and Swain,
Priyadarshini, and Patra (2012). The oxygen flow rate of the SPI-
Cloisite 30B bionanocomposites was found to be decreased in
proportion to clay loading. At 8% clay concentration (dry basis), the
oxygen permeability was reduced by 6 times as compared to the
virgin protein. This is because the clay nanoparticles act as physical
obstacle retarding the movement of the gas. As MMT content
increased to 10% (dry basis), the %E of Cloisite 20A and Cloisite 30B
films increased and then decreased above 10%.TS values of films
containing 10% of both modified MMTs are comparable to those of
low-density polyethylene (LDPE) and polyvinylidene chloride
(PVDC), which are currently used in food packaging applications.
Table 5 represents the effect of type and content of pure MMT and
modified MMTs on tensile strength of SPI-MMT films.
The drug delivery system of the SPI-Cloisite 30B nano-
composites were investigated by blending the nanocomposites
with curcumin at different pH media (Pradhan, Das, Palve, & Nayak,
2012). As in the case of SPI-MMT based drug delivery system, the
drugs in the SPI-Cloisite 30B blend can be used to be suitable for the
basic environment of the large intestine, colon and rectal mucosa
for which there are different emptying times. Interestingly, more
than 90 wt% curcumin is released from composites at pH 7.4 within
26 h, whereas less than 80 wt% of the drug is released at pH 1.2
within the same duration. This suggests that the drugs in the
composites can be used to be suitable for the basic environment.
Table 6 shows the thermogravimetric analysis (TGA) values at
50% weight loss of pure SPI and SPI-MMT bio-nanocomposites.
Soy protein has been utilized to develop nano-scaled delivery
systems. Nanoparticles have been successfully prepared with SPI by
two methods, ethanol desolvation and Ca2þ-induced cold gelation
both of which resulted in a particles size of 150e200 nm with
desirable stability (Teng, Luo, & Wang, 2013). These nanoparticles
were applied in the encapsulation of a number of therapeutic drug
curcumin. However, SPI exhibited a high digestibility in the
gastrointestinal tract. As a result, SPI-based nanoparticles are only
Table 5
Effect of type and content of pure MMT and modified MMTs on tensile strength of
SPI-MMT films (Kumar et al., 2010a).
SPIþ Tensile strength (MPa)
Pure MMT Cloisite 20A Cloisite 30B
0% MMT 2.26 ± 0.48 2.26 ± 0.48 2.26 ± 0.48
5% MMT (dry basis) 5.5 12.40 ± 0.65 15.11 ± 0.86
10% MMT (dry basis) 8.5 14.15 ± 0.33 16.19 ± 0.75
15% MMT (dry basis) e 13.66 ± 0.28 18.64 ± 0.23
Melt extrusion (Kumar et al., 2010b) Casting (Echeverría et al., 2014)
12.62 ± 0.54 MPa 8.5 MPa
15 e
5.5
capable for the delivery of bioactive compounds through injection,
while their application in oral administration is limited.
3.4.2. SPI e metal and metal oxide bionanocomposites
Silver is by far the most widely used metal for the generation of
functional (bio)nano-composite materials, due to its long time
known antimicrobial properties (Shameli et al., 2011). Compared to
other antimicrobial agents (e.g., molecular antimicrobial), silver is
effective against a wide spectrum of bacteria as well as fungi, algae
and possibly some viruses (Fei et al., 2013). Besides medical and
pharmaceutical applications, silver nanoparticles (AgNPs) are
increasingly used in the food industry; for example, to produce
(bio) polymer nanocomposites for food packaging applications.
Compared to silver, AgNPs-based nanocomposites provide slower
silver ion release rates into stored foods, but also lower acute
antimicrobial responses (Lo
pez-Carballo, Higueras, Gavara, &
Herna
ndez-Mun ~ oz, 2013). SPI based materials are very easy to be
polluted by bacteria and fungi because soy protein is a nutrient
substance for microorganisms, so it is in great demand to endow
SPI based materials with antimicrobial capacity with that of silver
(Zhao et al., 2013). An efficient and convenient biochemical way has
been introduced to synthesize AgNPs, using natural SPI as both
reducing and stabilizing agent by Zhao et al. (2013). SPI/AgNPs films
prepared by blending in situ prepared AgNPs-SPI solution showed
considerable antimicrobial activity against both Gram-positive
bacteria (Staphylococcus aureus) and Gram-negative bacteria
(E. coli) even when the Ag content was only 0.1%. When the Ag
content in the film was larger than 0.5% (w/w), almost all of the
bacteria were killed within 2 h. Therefore, the addition of AgNPs
was found to have the effect to prevent bacteria growth on the SPI
based materials, and thus prolong their useful life.
Metal oxides also exhibit excellent antimicrobial properties
against a wide spectrum of microorganisms. When nano-TiO2 were
incorporated into a polymer matrix such as packaging material,
they will provide protection against food-borne microorganisms as
well as odor, staining deterioration and allergens on the presence of
radiation of relatively low wavelength near the ultraviolet region
(Li et al., 2011). SPI (5.0 g/100 ml) films embedded with nano-TiO2
(0, 0.5, 1.0, 1.5 and 2.0 g/100 ml) were prepared by solution casting
(Wang, Zhu, Li, Fu, & Shi, 2012) and modified by ultrasonic/mi-
crowave assisted treatment (UMAT) by Wang, Zhang, et al. (2014).
Nano-TiO2 could react with SPI and these interactions can result in
stronger interfacial adhesion between nano-TiO2 and SPI matrix,
which leads to a higher efficiency of the stress transfer from the
matrix to the nanoparticles and hence an increase in tensile
strength.
Table 6
TGA values at 50% weight loss of pure SPI and SPI-MMT bio-nanocomposites (Kumar
et al., 2010a).
Temperature at 50% weight loss ( C)
Pure SPI films 355.5 ± 2.2
SPI þ 5% MMT 377.3 ± 2.6
SPI þ Cloisite 20A 367.7 ± 1.7
SPI þ Cloisite 30B 378.6 ± 2.3
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
3.4.3. SPI e other bionanocomposites
SPI-Boron Nitride (BN) nanocomposites were prepared by low
cost green technique (solution technique) where water was used as
the solvent by Dash and Swain (2013). Boron nitride has many
unique properties like thermal conductivity, high melting and
decomposition temperature (2700e3000  C) at a very low density
(2.25 g/cm3), high thermal stability, oxidation resistance, chemical
inertness, limited surface activity, non-wetability and lubricating
effect. The addition of nano boron nitride into soy protein was
found to improve the thermal stability, oxygen barrier property and
biodegradation of the matrix. It was also found that the hybrid
materials were resistant to mineral acid and alkali.
Nanocomposite materials were prepared via glycerol plasticized
soy protein as the matrix and in situ fabricated silica as the rein-
forcing phase by Tian (2011). The silica nanoparticles were syn-
thesized in the protein environment by sodium silicate as a
precursor. The results revealed that silica particles were homoge-
neously dispersed in soy protein matrix at a nanometer scale with
low silica addition (lower than 8%) (Ai, Zheng, Wei, & Huang, 2007).
Silica particles exhibited a high adhesion with protein matrix
through hydrogen bonding and confined the motions of soy protein
segments. The incorporation of silica as a reinforcing agent signif-
icantly improved the mechanical properties and thermal stability of
soy protein plastics. Addition of 0.3% nano-SiOx could make the
oxygen permeability and tensile strength of SPI film reach the
highest, while water-solubility became the lowest (Min et al., 2011).
Green nanocomposites were developed from SPI and dispersed
eggshell nanopowder (ESNP) using glycerol, a natural plasticizer, by
a solution casting process (Rahman, Netravali, Tiimob, & Rangari,
2014). Dispersion of ESNP in water was achieved by using a poly-
anionic dispersant via an adsorption mechanism. Significant im-
provements in Young's modulus, tensile strength and thermal
stability of SPI nanocomposite sheets were achieved as a result of
incorporation of well-dispersed ESNP. The developed ESNP-
incorporated SPI nanocomposite would be inexpensive and useful
to fabricate sustainable “green” composite structures.
From the studies it is clear that the addition of these nano re-
inforcements into the soy protein matrix will help to improve the
mechanical (stiffness, impact and wear resistance), flame retard-
ance (anti-flammable materials) and barrier properties (against
gases, vapors, and radiation) of the matrix. In addition, the use of
these (bio) nanocomposite coatings will help in an upstream
reduction of plastics, hence a less amount of plastics dumped into
the environment, which would help in facing the waste disposal
issue.
4. Conclusion
The review shows that soy protein isolate polymer execute very
interesting features of polymers such as flexural, shear strength,
tensile modulus, as well as exceptional material properties
including toughness, strength and elasticity, and can therefore be
called a novel bio-polymer. Polymer reinforcement technology of
soy protein with fillers (both macro and nano) offers an opportunity
to change the physical and mechanical properties of protein poly-
mer as per the desired products. Such modification will be helpful
to use them for various applications from micro (as biomaterial for
drug delivery application) to macro scale (as material for packaging,
tissue engineering and as bio-composite). In spite of all the modi-
fications and reinforcements of soy protein polymer, there still exist
some drawbacks, for example, high moisture sensitivity for
blending SPI with hydrophilic plasticizers or natural polymers, low
interfacial adhesion between SPI and hydrophobic plasticizers or
polymers, agglomeration of nanoparticles, as well as their weak
dispersion property in SPI matrix, toxicity of chemical cross-linkers
189
containing aldehyde groups, high price of radiation treatment,
degradation of SPI induced by high-UV irradiation, etc.
5. Future perspective
Massive chances still exist to create a new kind of blends of soy
protein polymer with new characteristics, which could be used for
both food and non-food packaging. For example, nanocellulose
obtained by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)
mediated oxidation can be added as filler into the soy protein matrix
to obtain enhanced properties (high mechanical reinforcement
ability and barrier property respectively). Also, the usage of ionic
liquid for compatibilizing the biopolymers and fabricating nano-
fibrous films and nanogels can be explored. Therefore, with the
present research and future perspectives in hand, soy protein based
biocomposite and bionanocomposite material is sure to capture the
market as a potential substitute for petroleum based plastics.
Acknowledgment
The authors are grateful to the University Grants Commission
(MRP (S)-1161/11-12/KLKE002/UGC-SWRO), Government of India,
for the financial support.
References
Ai, F., Zheng, H., Wei, M., & Huang, J. (2007). Soy protein plastics reinforced and
toughened by SiO2 nanoparticles. Journal of Applied Polymer Science, 105,
1597e1604.


Alvarez-Ch

avez, C. R., Edwards, S., Moure-Eraso, R., & Geiser, K. (2012). Sustain-
ability of bio-based plastics: general comparative analysis and recommenda-
tions for improvement. Journal of Cleaner Production, 23(1), 47e56.
Arancibia, M. Y., Lo
pez-Caballero, M. E., Go
mez-Guille
n, M. C., & Montero, P. (2014).
Release of volatile compounds and biodegradability of active soy protein lignin
blend films with added citronella essential oil. Food Control, 44, 7e15.
Atare
s, L., De Jesús, C., Talens, P., & Chiralt, A. (2010). Characterization of SPI-based
edible films incorporated with cinnamon or ginger essential oils. Journal of Food
Engineering, 99(3), 384e391.
Bai, H., Xu, J., Liao, P., & Liu, X. (2013). Mechanical and water barrier properties of
soy protein isolate film incorporated with gelatin. Journal of Plastic Film and
Sheeting, 29(2), 174e188.
Behera, A. K., Avancha, S., Basak, R. K., Sen, R., & Adhikari, B. (2012). Fabrication and
characterizations of biodegradable jute reinforced soy based green composites.
Carbohydrate Polymers, 88(1), 329e335.
Calabria, L., Vieceli, N., Bianchi, O., Boff de Oliveira, R. V., do Nascimento Filho, I., &
Schmidt, V. (2012). Soy protein isolate/poly(lactic acid) injection-molded
biodegradable blends for slow release of fertilizers. Industrial Crops and Prod-
ucts, 36(1), 41e46.
Chabba, S., Matthews, G. F., & Netravali, A. N. (2005). “Green” composites using
cross-linked soy flour and flax yarns. Green Chemistry, 7(8), 576e581.
Chabba, S., & Netravali, A. N. (2004). “Green” composites using modified soy protein
concentrate resin and flax fabrics and yarns. International Journal Series A Solid
Mechanics and Material Engineering, 47(4), 556e560.
Chen, G., & Liu, H. (2008). Electrospun cellulose nanofiber reinforced soybean
protein isolate composite film. Journal of Applied Polymer Science, 110(2),
641e646.
Chen, L., Remondetto, G. E., & Subirade, M. (2006). Food protein-based materials as
nutraceutical delivery systems. Trends in Food Science & Technology, 17(5),
272e283.
Chen, P., & Zhang, L. (2006). Interaction and properties of highly exfoliated soy
protein/montmorillonite nanocomposites. Biomacromolecules, 7(6), 1700e1706.
Chiellini, E., Barghini, A., Cinelli, P., & Ilieva, V. I. (2008). Overview of environmen-
tally compatible polymeric materials for food packaging. In E. Chiellini (Ed.),
Environmentally compatible food packaging (pp. 371e395). Woodhead Publish-
ing Limited.
Chien, K. B., & Shah, R. N. (2012). Novel soy protein scaffolds for tissue regeneration:
material characterization and interaction with human mesenchymal stem cells.
Acta Biomaterialia, 8(2), 694e703.
Cho, S. Y., Lee, S. Y., & Rhee, C. (2010). Edible oxygen barrier bilayer film pouches
from corn zein and soy protein isolate for olive oil packaging. Food Science and
Technology, 43(8), 1234e1239.
Cho, S. Y., Park, J. W., Batt, H. P., & Thomas, R. L. (2007). Edible films made from
membrane processed soy protein concentrates. Food Science and Technology,
40(3), 418e423.
Choi, S. G., Kim, K. M., Hanna, M. A., Weller, C. L., & Kerr, W. L. (2003). Molecular
dynamics of soy-protein isolate films plasticized by water and glycerol. Journal
of Food Science, 68, 2516e2522.
190 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Ciannamea, E. M., Stefani, P. M., & Ruseckaite, R. A. (2014). Physical and mechanical
properties of compression molded and solution casting soybean protein
concentrate based films. Food Hydrocolloids, 38, 193e204.
Das, P. R., Prava, S., Rudra, D., Nanda, M., Dash, H., Nanda, P. K., et al. (2011). Spectral,
thermal, morphological and mechanical properties of soy-protein isolate
modified with urea. International Journal of Research in Pharmacy and Chemistry,
1(4), 754e764.
Dash, S., & Swain, S. K. (2013). Effect of nanoboron nitride on the physical and
chemical properties of soy protein. Composite Science and Technology, 84,
39e43.
Deepa, B., Abraham, E., Cherian, B. M., Bismarck, A., Blaker, J. J., Pothan, L. A.,
et al. (2011). Structure, morphology and thermal characteristics of banana
nano fibers obtained by steam explosion. Bioresource Technology, 102(2),
1988e1997.
Denavi, G., Tapia-Bla
cido, D. R., Anon, M. C., Sobral, P. J. A., Mauri, A. N., &
Menegalli, F. C. (2009). Effects of drying conditions on some physical properties
of soy protein films. Journal of Food Engineering, 90, 341e349.
Echeverría, I., Eisenberg, P., & Mauri, A. N. (2014). Nanocomposites films based on
soy proteins and montmorillonite processed by casting. Journal of Membrane
Science, 449, 15e26.
Espitia, P. J. P., Du, W. X., Avena-Bustillos, R. D. J., Soares, N. D. F. F., & McHugh, T. H.
(2014). Edible films from pectin: physical-mechanical and antimicrobial prop-
erties e a review. Food Hydrocolloids, 35, 287e296.
Fagundes, C., Palou, L., Monteiro, A. R., & Pe
rez-Gago, M. B. (2014). Effect of anti-
fungal hydroxypropyl methylcellulose-beeswax edible coatings on gray mold
development and quality attributes of cold-stored cherry tomato fruit. Post-
harvest Biology and Technology, 92, 1e8.
Fang, Q. H., Zhou, D., Han, W. C., Gao, Y., Wang, N., & Yang, F. (2012). Preparation of
soy protein isolate modified by glutaric dialdehyde and its application in rubber
composite. Key Engineering Materials, 501, 208e214.
Farahnaky, A., Dadfar, S. M. M., & Shahbazi, M. (2014). Physical and mechanical
properties of gelatineclay nanocomposite. Journal of Food Engineering, 122,
78e83.
Fei, X., Jia, M., Du, X., Yang, Y., Zhang, R., Shao, Z., et al. (2013). Green synthesis of silk
fibroin-silver nanoparticle composites with effective antibacterial and biofilm-
disrupting properties. Biomacromolecules, 14(12), 4483e4488.

lix, M., Martín-Alfonso, J. E., Romero, A., & Guerrero, A. (2014). Development of
Fe
albumen/soy biobased plastic materials processed by injection molding. Journal
of Food Engineering, 125, 7e16.
Fernandes, E. M., Pires, R. A., & Reis, R. L. (2013). Bionanocomposites from
lignocellulosic resources: properties, applications and future trends for
their use in the biomedical field. Progress in Polymer Science, 38(10e11),
1415e1441.
Friesen, K., Chang, C., & Nickerson, M. (2014). Incorporation of phenolic, compounds
rutin and epicatechin, into soy protein isolate films: mechanical, barrier and
cross-linking properties. Food Chemistry, 172, 18e23.
Galus, S., & Lenart, A. (2013). Effect of oxidized potato starch on the physicochemical
properties of soy protein isolate-based edible films. Food Technology and
Biotechnology, 51(3), 403e409.
Galus, S., Mathieu, H., Lenart, A., & Debeaufort, F. (2012). Effect of modified starch or
maltodextrin incorporation on the barrier and mechanical properties, moisture
sensitivity and appearance of soy protein isolate-based edible films. Innovative
Food Science & Emerging Technologies, 16, 148e154.
Garrido, T., Etxabide, A., Pen ~ alba, M., de la Caba, K., & Guerrero, P. (2013). Prepa-
ration and characterization of soy protein thin films: processingeproperties
correlation. Materials Letters, 105, 110e112.
Ghanbarzadeh, B., Oleyaei, S. A., & Almasi, H. (2014). Nano-structured materials
utilized in biopolymer based plastics for food packaging applications. Critical
Reviews in Food Science and Nutrition, 00.
Ghavidel, R. A., Davoodi, M. G., & Adib, A. F. (2013). Effect of selected edible coatings
to extend shelf-life of fresh-cut apples. International Journal of Agriculture and
Crop Sciences, 6(16), 1171e1178.
Ghidelli, C., Mateos, M., Rojas-Argudo, C., & Pe
rez-Gago, M. B. (2014). Extending the
shelf life of fresh-cut eggplant with a soy proteinecysteine based edible coating
and modified atmosphere packaging. Postharvest Biology and Technology, 95,
81e87.
Gonza
lez, A., & Alvarez Igarzabal, C. I. (2013). Soy protein e poly (lactic acid) bilayer
films as biodegradable material for active food packaging. Food Hydrocolloids,
33(2), 289e296.
Gonza
lez, A., & Alvarez Igarzabal, C. I. (2014). Nanocrystal-reinforced soy
protein films and their application as active packaging. Food Hydrocolloids, 43,
777e784.
Gonza
lez, A., Strumia, M. C., & Alvarez Igarzabal, C. I. (2011). Cross-linked soy
protein as material for biodegradable films: synthesis, characterization and
biodegradation. Journal of Food Engineering, 106(4), 331e338.
Goy, R. C., Britto, D., & Assis, O. B. G. (2009). A review of the antimicrobial activity of
chitosan. Polimeros, 19, 241e247.
Guerrero, P., & de la Caba, K. (2010). Thermal and mechanical properties of soy
protein films processed at different pH by compression. Journal of Food Engi-
neering, 100(2), 261e269.
Guerrero, P., Garrido, T., Leceta, I., & de la Caba, K. (2013). Films based on proteins
and polysaccharides: preparation and physical e chemical characterization.
European Polymer Journal, 49, 3713e3721.
Guerrero, P., Leceta, I., Pen ~ alba, M., & de la Caba, K. (2014). Optical and mechanical
properties of thin films based on proteins. Materials Letters, 124, 286e288.
Guerrero, P., Nur Hanani, Z. A., Kerry, J. P., & de la Caba, K. (2011). Characterization of
soy protein-based films prepared with acids and oils by compression. Journal of
Food Engineering, 107(1), 41e49.
Guerrero, P., Retegi, a., Gabilondo, N., & de la Caba, K. (2010). Mechanical and
thermal properties of soy protein films processed by casting and compression.
Journal of Food Engineering, 100(1), 145e151.
Guerrero, P., Stefani, P. M., Ruseckaite, R. A., & de la Caba, K. (2011). Functional
properties of films based on soy protein isolate and gelatin processed by
compression molding. Journal of Food Engineering, 105(1), 65e72.
Gupta, P., & Nayak, K. K. (2014). Characteristics of protein-based biopolymer and its
application. Polymer Engineering and Science. http://dx.doi.org/10.1002/
pen.23928.
Gurgel, M., Vieira, A., Altenhofen, M., Oliveira, L., & Beppu, M. M. (2011). Natural-
based plasticizers and biopolymer films: a review. European Polymer Journal,
47(3), 254e263.
Hong, S. I., Choi, W. Y., Cho, S. Y., Jung, S. H., Shin, B. Y., & Park, H. J. (2009). Me-
chanical properties and biodegradability of poly-ε-caprolactone/soy protein
isolate blends compatibilized by coconut oil. Polymer Degradation and Stability,
94(10), 1876e1881.
Hsieh, J. F., Yu, C. J., Chang, J. Y., Chen, S. T., & Tsai, H. Y. (2014). Microbial
transglutaminase-induced polymerization of b-conglycinin and glycinin in
soymilk: a proteomics approach. Food Hydrocolloids, 35, 678e685.
Huang, X., & Netravali, A. N. (2006). Characterization of nano-clay reinforced
phytagel-modified soy protein concentrate resin. Biomacromolecules, 7(10),
2783e2789.
Huang, X., & Netravali, A. (2007). Characterization of flax fiber reinforced soy pro-
tein resin based green composites modified with nano-clay particles. Compos-
ites Science and Technology, 67(10), 2005e2014.
Huang, X., & Netravali, A. (2009). Biodegradable green composites made using
bamboo micro/nano-fibrils and chemically modified soy protein resin. Com-
posites Science and Technology, 69(7e8), 1009e1015.
Ifuku, S., & Saimoto, H. (2012). Chitin nanofibers: preparations, modifications, and
applications. Nanoscale, 4(11), 3308e3318.
Iman, M., Bania, K. K., & Maji, T. K. (2013). Green jute-based cross-linked soy flour
nanocomposites reinforced with cellulose whiskers and nanoclay. Industrial and
Engineering Chemistry Research, 52, 6969e6983.
Insaward, A., Duangmal, K., & Mahawanich, T. (2014). Mechanical, optical, and
barrier properties of soy protein film as affected by phenolic acid addition.
Journal of Agricultural and Food Chemistry. http://dx.doi.org/10.1021/jf504016m.
Kaewprachu, P., & Rawdkuen, S. (2014). Mechanical and physico-chemical proper-
ties of biodegradable protein-based films: a comparative study. Food and
Applied Bioscience Journal, 2(1), 14e29.
Kalman, D. (2014). Amino acid composition of an organic brown rice protein
concentrate and isolate compared to soy and whey concentrates and isolates.
Foods, 3(3), 394e402.
Khalsa, A., Kim, J. T., & Netravali, A. N. (2009). Sisal fiber reinforced Green composite
using soy flour resin modified with sorbitol, agar and NB416 microfibers. Ma-
terials Research, 10e20.
Kim, J. T., & Netravali, A. N. (2010a). Mechanical and thermal properties of sisal
fiber-reinforced green composites with soy protein/gelatin resins. Journal of
Biobased Materials and Bioenergy, 4(4), 338e345.
Kim, J. T., & Netravali, A. N. (2010b). Mechanical, thermal, and interfacial properties
of green composites with ramie fiber and soy resins. Journal of Agricultural and
Food Chemistry, 58(9), 5400e5407.
Kim, J. T., & Netravali, A. N. (2011). Development of aligned-hemp yarn-rein-
forced green composites with soy protein resin: effect of pH on mechanical
and interfacial properties. Composites Science and Technology, 71(4),
541e547.
Kokoszka, S., Debeaufort, F., Hambleton, A., Lenart, A., & Voilley, A. (2010). Protein
and glycerol contents affect physico-chemical properties of soy protein isolate-
based edible films. Innovative Food Science & Emerging Technologies, 11(3),
503e510.
Kumar, R., Choudhary, V., Mishra, S., & Varma, I. (2008). Banana fiber-reinforced
biodegradable soy protein composites. Frontiers of Chemistry in China, 3(3),
243e250.
Kumar, A. P., Depan, D., Singh Tomer, N., & Singh, R. P. (2009). Nanoscale particles for
polymer degradation and stabilizationdTrends and future perspectives. Prog-
ress in Polymer Science, 34(6), 479e515.
Kumar, S., & Gupta, S. K. (2012). Applications of biodegradable pharmaceutical
packaging materials: a review. Middle-East Journal of Scientific Research, 12(5),
699e706.
Kumar, P., Sandeep, K. P., Alavi, S., & Truong, V. D. (2011). A review of experimental
and modeling techniques to determine properties of biopolymer-based nano-
composites. Journal of Food Science, 76(1), E2eE14.
Kumar, P., Sandeep, K. P., Alavi, S., Truong, V. D., & Gorga, R. E. (2010a). Effect of type
and content of modified montmorillonite on the structure and properties of
bio-nanocomposite films based on soy protein isolate and montmorillonite.
Journal of Food Science, 75(5), N46eN56.
Kumar, P., Sandeep, K. P., Alavi, S., Truong, V. D., & Gorga, R. E. (2010b). Preparation
and characterization of bio-nanocomposite films based on soy protein isolate
and montmorillonite using melt extrusion. Journal of Food Engineering, 100(3),
480e489.
Kumar, R., & Zhang, L. (2009). Aligned ramie fiber reinforced arylated soy protein
composites with improved properties. Composites Science and Technology, 69(5),
555e560.
 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
La Mantia, F. P., & Morreale, M. (2011). Green composites: a brief review. Composites
Part A: Applied Science and Manufacturing, 42(6), 579e588.
Lee, J., & Kim, K. M. (2010). Characteristics of soy protein isolate-montmorillonite
composite films. Journal of Applied Polymer Science, 118, 2257e2263.
Li, Y., Jiang, Y., Liu, F., Ren, F., Zhao, G., & Leng, X. (2011). Fabrication and charac-
terization of TiO2/whey protein isolate nanocomposite film. Food Hydrocolloids,
25(5), 1098e1104.
Liu, W., Misra, M., Askeland, P., Drzal, L. T., & Mohanty, A. K. (2005). “Green” com-
posites from soy based plastic and pineapple leaf fiber: fabrication and prop-
erties evaluation. Polymer, 46(8), 2710e2721.
Liu, W., Mohanty, A. K., Askeland, P., Drzal, L. T., & Misra, M. (2004). Influence of
fiber surface treatment on properties of Indian grass fiber reinforced soy protein
based biocomposites. Polymer, 45(22), 7589e7596.
Li, S., Wei, Y., Fang, Y., Zhang, W., & Zhang, B. (2013). DSC study on the thermal
properties of soybean protein isolates/corn starch mixture. Journal of Thermal
Analysis and Calorimetry, 115(2), 1633e1638.
Lodha, P., & Netravali, A. N. (2005a). Characterization of Phytagel® modified soy
protein isolate resin and unidirectional flax yarn reinforced “green” composites.
Polymer Composites, 26(5), 647e659.
Lodha, P., & Netravali, A. N. (2005b). Characterization of stearic acid modified soy
protein isolate resin and ramie fiber reinforced “green” composites. Composites
Science and Technology, 65(7e8), 1211e1225.

pez-Carballo, G., Higueras, L., Gavara, R., & Herna
Lo
ndez-Mun ~ oz, P. (2013). Silver
ions release from antibacterial chitosan films containing in situ generated silver
nanoparticles. Journal of Agricultural and Food Chemistry, 61(1), 260e267.
Lu, Y., Weng, L., & Zhang, L. (2004). Morphology and properties of soy protein isolate
thermoplastics reinforced with chitin whiskers. Biomacromolecules, 5(3),
1046e1051.
Maruthi, Y., Sudhakar, H., Rao, U. S., Babu, P. K., Rao, K. C., & Subha, M. C. S. (2014).
Blend membranes of sodium alginate and soya protein for pervaporation
dehydration of isopropanol. Advances in Polymer Science and Technology, 4(2),
12e21.
Mekonnen, T., Mussone, P., Khalil, H., & Bressler, D. (2013). Progress in bio-based
plastics and plasticizing modifications. Journal of Materials Chemistry A, 1(43),
13379e13398.
Min, Z., Ding-yu, L., Bi, Z., Min, Z., Ding-yu, L., Bi, Z., et al. (2011). Influence of nano-
SiO_x on the property of soy protein isolate films. Food Science and Technology.
Mincea, M., Negrulescu, A., & Ostafe, V. (2012). Preparation, modification, and ap-
plications of chitin nanowhiskers: a review. Recent Advances in Material Science,
30, 225e242.
Mishra, R. K., Ramasamy, K., Lim, S. M., Ismail, M. F., & Majeed, A. B. A. (2014).
Antimicrobial and in vitro wound healing properties of novel clay based bio-
nanocomposite films. Journal of Materials Science. Materials in Medicine, 25(8),
1925e1939.
Mitra, B. (2014). Environment friendly composite materials: biocomposites and
Green composites. Defence Science Journal, 64(3), 244e261.
Mohanty, A. K., Tummala, P., Liu, W., Misra, M., Mulukutla, P. V., & Drzal, L. T.
(2005). Injection molded biocomposites from soy protein based bioplastic
and short industrial hemp fiber. Journal of Polymers and the Environment,
13(3), 279e285.
Monedero, F. M., Fabra, M. J., Talens, P., & Chiralt, A. (2010). Effect of calcium and
sodium caseinates on physical characteristics of soy protein isolateelipid films.
Journal of Food Engineering, 97(2), 228e234.
Nam, S., & Netravali, A. N. (2006). Green composites. II. Environment-friendly,
biodegradable composites using ramie fibers and soy protein concentrate
(SPC) resin. Fibers and Polymers, 7(4), 380e388.
Nandane, A. S., & Jain, R. (2014). Study of mechanical properties of soy protein based
edible film as affected by its composition and process parameters by using RSM.
Journal of Food Science and Technology, 1e6.
Narine, S. S., & Kong, X. (2005). Vegetable oils in production of polymers and
plastics. Bailey's Industrial Oil and Fat Products, 6, 279e306.
Nayak, P. (2011). Synthesis and characterization of soy protein Isolate/MMT nano-
composite film for the control release of the drug ofloxacin. World Journal of
Nano Science and Engineering, 01(02), 27e36.
Nishinari, K., Fang, Y., Guo, S., & Phillips, G. O. (2014). Soy proteins: a review
on composition, aggregation and emulsification. Food Hydrocolloids, 39,
301e318.
Nur Hanani, Z. A., Roos, Y. H., & Kerry, J. P. (2014). Use and application of gelatin as
potential biodegradable packaging materials for food products. International
Journal of Biological Macromolecules, 71, 94e102.
Ojijo, V., & Sinha Ray, S. (2013). Processing strategies in bionanocomposites. Progress
in Polymer Science, 38(10e11), 1543e1589.
Ortega-Toro, R., Jime
nez, A., Talens, P., & Chiralt, A. (2014). Effect of the incorpora-
tion of surfactants on the physical properties of corn starch films. Food Hy-
drocolloids, 38, 66e75.
Ozcalik, O., & Tihminlioglu, F. (2013). Barrier properties of corn zein nanocomposite
coated polypropylene films for food packaging applications. Journal of Food
Engineering, 114(4), 505e513.
Petersen, K., Væggemose Nielsen, P., Bertelsen, G., Lawther, M., Olsen, M. B.,
Nilsson, N. H., et al. (1999). Potential of biobased materials for food packaging.
Trends in Food Science & Technology, 10(2), 52e68.
Pradhan, N. K., Das, M., Palve, Y. P., & Nayak, P. L. (2012). Synthesis and character-
ization of soya protein isolate/Cloisite 30B (MMT) nanocomposite for controlled
release of anticancer drug curcumin. International Journal of Research in Phar-
maceutical and Biomedical Sciences, 3(4), 1513e1522.
191
Rachtanapun, P., & Suriyatem, R. (2012). Moisture sorption isotherms of soy protein
isolate/carboxymethyl chitosan blend films. Journal of Agricultural Science and
Technology A, 2, 50e57.
Rahman, M. M., Netravali, A. N., Tiimob, B. J., & Rangari, V. K. (2014). Bioderived
“green” composite from soy protein and eggshell nanopowder. ACS Sustainable
Chemistry & Engineering, 2(10), 2329e2337.
Reddy, N., & Yang, Y. (2011). Completely biodegradable soyproteinejute bio-
composites developed using water without any chemicals as plasticizer. In-
dustrial Crops and Products, 33(1), 35e41.
Rhim, J. W., Gennadios, A., Weller, C. L., & Hanna, M. A. (2002). Sodium dodecyl
sulfate treatment improves properties of cast films from soy protein isolate.
Industrial Crops and Products, 15(3), 199e205.
Rhim, J.-W., Park, H.-M., & Ha, C. S. (2013). Bio-nanocomposites for food packaging
applications. Progress in Polymer Science, 38(10e11), 1629e1652.
Rhim, J. W., Wu, Y., Weller, C. L., & Schnepf, M. (1999). Physical characteristics of a
composite film of soy protein isolate and propyleneglycol alginate. Journal of
Food Science, 64(1), 149e152.
Routray, M., Rout, S. N., Mohanty, G. C., & Nayak, P. L. (2013). Preparation and
characterization of soy protein isolate films processed by compression and
casting. Journal of Chemical and Pharmaceutical Research, 5(11), 752e761.
Saenghirunwattana, P., Noomhorm, A., & Rungsardthong, V. (2014). Mechanical
properties of soy protein based “green” composites reinforced with surface
modified cornhusk fiber. Industrial Crops and Products, 60, 144e150.
Shameli, K., Bin Ahmad, M., Zargar, M., Yunus, W. M. Z. W., Ibrahim, N. A.,
Shabanzadeh, P., et al. (2011). Synthesis and characterization of silver/mont-
morillonite/chitosan bionanocomposites by chemical reduction method and
their antibacterial activity. International Journal of Nanomedicine, 6, 271e284.
Shan, H., Lu, S. W., Jiang, L. Z., Wang, L. K., Liao, H., Zhang, R. Y., et al. (2014). Gelation
property of alcohol-extracted soy protein isolate and effects of various reagents
on the firmness of heat-induced gels. International Journal of Food Properties.
Silva, S. S., Goodfellow, B. J., Benesch, J., Rocha, J., Mano, J. F., & Reis, R. L. (2007).
Morphology and miscibility of chitosan/soy protein blended membranes. Car-
bohydrate Polymers, 70(1), 25e31.
Silva, S. S., Oliveira, J. M., Benesch, J., Caridade, S. G., Mano, J. F., & Reis, R. L. (2013).
Hybrid biodegradable membranes of silane-treated chitosan/soy protein for
biomedical applications. Journal of Bioactive and Compatible Polymers, 28(4),
385e397.
Silva, N. H. C. S., Vilela, C., Marrucho, I. M., Freire, C. S. R., Pascoal Neto, C., &
Silvestre, A. J. D. (2014). Protein-based materials: from sources to innovative
sustainable materials for biomedical applications. Journal of Materials Chemistry
B, 2(24), 3715e3740.
Siqueira, G., Bras, J., & Dufresne, A. (2010). Cellulosic bionanocomposites: a review
of preparation, properties and applications. Polymers, 2(4), 728e765.
Sirvio€ , J. A., Kolehmainen, A., Liimatainen, H., Niinim€ aki, J., & Hormi, O. E. O. (2014).
Biocomposite cellulose-alginate films: promising packaging materials. Food
Chemistry, 151, 343e351.
Song, F., Tang, D., Wang, X., & Wang, Y. (2011). Biodegradable soy protein isolate-
based materials: a review. Biomacromolecules, 12(10), 3369e3380.
Song, Y., & Zheng, Q. (2014). Ecomaterials based on food proteins and poly-
saccharides. Polymer Reviews, 54(3), 514e571.
Song, X., Zhou, C., Fu, F., Chen, Z., & Wu, Q. (2013). Effect of high-pressure ho-
mogenization on particle size and film properties of soy protein isolate. In-
dustrial Crops and Products, 43, 538e544.
Su, J., Huang, Z., Yang, C., & Yuan, X. (2008). Properties of soy protein isolate/poly
(vinyl alcohol) blend “Green” films: compatibility, mechanical properties, and
thermal stability. Journal of Applied Polymer Science, 110, 3706e3716.
Su, J. F., Huang, Z., Yuan, X. Y., Wang, X. Y., & Li, M. (2010). Structure and properties
of carboxymethyl cellulose/soy protein isolate blend edible films crosslinked by
Maillard reactions. Carbohydrate Polymers, 79(1), 145e153.
Su, J. F., Huang, Z., Zhao, Y. H., Yuan, X. Y., Wang, X. Y., & Li, M. (2010). Moisture
sorption and water vapor permeability of soy protein isolate/
poly(vinyl alcohol)/glycerol blend films. Industrial Crops and Products, 31(2),
266e276.
Su, J. F., Yuan, X. Y., Huang, Z., & Xia, W. L. (2010). Properties stability and biodeg-
radation behaviors of soy protein isolate/poly (vinyl alcohol) blend films.
Polymer Degradation and Stability, 95(7), 1226e1237.
Swain, S. K., Priyadarshini, P. P., & Patra, S. K. (2012). Soy protein/clay bio-
nanocomposites as ideal packaging materials. Polymer-Plastics Technology and
Engineering, 51(12), 1282e1287.
Tai, J., Chen, K., Yang, F., & Yang, R. (2014). Heat-sealing properties of soy protein
isolate/polyvinyl alcohol film made compatible by glycerol. Journal of Applied
Polymer Science, 131(11).
Taylor, P., Song, Y., & Zheng, Q. (2014). Ecomaterials based on food proteins and
polysaccharides. Polymer Reviews, 54, 514e571.
Teng, Z., Luo, Y., & Wang, Q. (2013). Carboxymethyl chitosan-soy protein complex
nanoparticles for the encapsulation and controlled release of vitamin D3. Food
Chemistry, 141(1), 524e532.
Tian, H. (2011). Processing and properties of soy protein/silica nanocomposites
fabricated in situ synthesis. Journal of Composite Materials, 46(4), 427e435.
Tian, H., Wu, W., Guo, G., Gaolun, B., Jia, Q., & Xiang, A. (2012). Microstructure and
properties of glycerol plasticized soy protein plastics containing castor oil.
Journal of Food Engineering, 109(3), 496e500.
Tian, H., Xu, G., Yang, B., & Guo, G. (2011). Microstructure and mechanical properties
of soy protein/agar blend films: effect of composition and processing methods.
Journal of Food Engineering, 107(1), 21e26.
192 R.R. Koshy et al. / Food Hydrocolloids 50 (2015) 174e192
Tian, H., Zhang, L., Wu, Q., Wang, X., & Chen, Y. (2010). Creation of hydro-
phobic materials fabricated from soy protein and natural rubber: surface,
interface, and properties. Macromolecular Materials and Engineering, 295,
451e459.
Unalan, I. U., Cerri, G., Marcuzzo, E., Cozzolino, A., & Farris, S. (2014). Advances
nanocomposite films and coatings using inorganic nanobuilding blocks (NBB):
current applications and future opportunities in the food packaging sector.
Royal Society of Chemistry, 4, 29393e29428.
Vasconcellos, F. C. S., Woiciechowski, A. L., Soccol, V. T., Mantovani, D., & Soccol, C. R.
(2014). Antimicrobial and antioxidant properties of -conglycinin and glycinin
from soy protein isolate. International Journal of Current Microbiology and
Applied Sciences, 3(8), 144e157.
Verbeek, C. J. R., & van den Berg, L. E. (2010). Extrusion processing and properties of
protein-based thermoplastics. Macromolecular Materials and Engineering,
295(1), 10e21.
Wang, Y., Cao, X., & Zhang, L. (2006). Effects of cellulose whiskers on prop-
erties of soy protein thermoplastics. Macromolecular Bioscience, 6(7),
524e531.
Wang, X., Chang, P. R., Li, Z., Wang, H., Liang, H., Cao, X., et al. (2011). Chitosan-
coated cellulose/soy protein membranes with improved physical properties and
hemocompatibility. BioResources, 6(2), 1392e1413.
Wang, X., & Chi, Y. (2012). Microwave-assisted phosphorylation of soybean protein
isolates and their physicochemical properties. Czech Journal of Food Science,
30(2), 99e107.
Wang, X., Shi, N., Chen, Y., Li, C., Du, X., Jin, W., et al. (2012). Improvement in
hemocompatibility of chitosan/soy protein composite membranes by heparin-
ization. Bio-Medical Materials and Engineering, 22, 143e150.
Wang, X. Y., & Su, J. F. (2014). Biodegradation behaviours of soy protein isolate/
carboxymethyl cellulose blend films. Materials Science and Technology, 30(5),
534e539.
Wang, Z., Sun, X., Lian, Z., Wang, X., Zhou, J., & Ma, Z. (2013). The effects of ultra-
sonic/microwave assisted treatment on the properties of soy protein isolate/
microcrystalline wheat-bran cellulose film. Journal of Food Engineering, 114(2),
183e191.
Wang, L., Xiao, M., Dai, S., Song, J., Ni, X., Fang, Y., et al. (2014). Interactions between
carboxymethyl konjac glucomannan and soy protein isolate in blended films.
Carbohydrate Polymers, 101, 136e145.
Wang, Z., Zhang, N., Wang, H., Sui, S., Sun, X., & Ma, Z. (2014). The effects of
ultrasonic/microwave assisted treatment on the properties of soy protein
isolate/titanium dioxide films. Food Science and Technology, 57(2),
548e555.
Wang, Z., Zhou, J., Wang, X., Zhang, N., Sun, X., & Ma, Z. (2014). The effects of ul-
trasonic/microwave assisted treatment on the water vapor barrier properties of
soybean protein isolate-based oleic acid/stearic acid blend edible films. Food
Hydrocolloids, 35, 51e58.
Wang, S.-Y., Zhu, B.-B., Li, D. Z., Fu, X. Z., & Shi, L. (2012). Preparation and charac-
terization of TIO2/SPI composite film. Materials Letters, 83, 42e45.
Wihodo, M., & Moraru, C. I. (2013). Physical and chemical methods used to enhance
the structure and mechanical properties of protein films: a review. Journal of
Food Engineering, 114(3), 292e302.
Wu, R. L., Wang, X. L., Wang, Y.-Z., Bian, X. C., & Li, F. (2009). Cellulose/soy protein
isolate blend films prepared via room-temperature ionic liquid. Industrial &
Engineering Chemistry Research, 48(15), 7132e7136.
Xu, W., Liu, B., Yang, H., Liu, K., Jia, S., & Chen, F. (2012). Effect of g-irradiation on the
physicochemical properties of mixed soy protein isolate/starch material. African
Journal of Biotechnology, 11(28), 7238e7246.
Yang, S., Madbouly, S. A., Schrader, J. A., Srinivasan, G., Grewell, D., McCabe, K. G.,
et al. (2014). Characterization and biodegradation behavior of bio-based pol-
y(lactic acid) and soy protein blends for sustainable horticultural applications.
Green Chem.
Yu, L., Ramaswamy, H. S., & Boye, J. (2013). Protein rich extruded products prepared
from soy protein isolate-corn flour blends. LWT e Food Science and Technology,
50(1), 279e289.
Yuan, B., Ren, J., Zhao, M., Luo, D., & Gu, L. (2012). Effects of limited enzymatic
hydrolysis with pepsin and high-pressure homogenization on the functional
properties of soybean protein isolate. LWT e Food Science and Technology, 46(2),
453e459.
Yuan, Y., Sun, Y.-E., Wan, Z.-L., Yang, X.-Q., Wu, J.-F., Yin, S.-W., et al. (2014). Chitin
microfibers reinforce soy protein gels cross-linked by transglutaminase. Journal
of Agricultural and Food Chemistry, 62(19), 4434e4442.
Yuan, Y., Wan, Z.-L., Yin, S.-W., Yang, X.-Q., Qi, J.-R., Liu, G.-Q., et al. (2013). Char-
acterization of complexes of soy protein and chitosan heated at low pH. LWT e
Food Science and Technology, 50(2), 657e664.
Yue, H.-B., Cui, Y.-D., Shuttleworth, P. S., & Clark, J. H. (2012). Preparation and
characterisation of bioplastics made from cottonseed protein. Green Chemistry,
14(7), 2009.
Zhang, S., Li, F., & Yu, J. Y. (2011). Novel cellulose/SPI blend bio-fibers prepared
via direct dissolving approach. Journal of Engineered Fibers and Fabrics, 6(1),
31e37.
Zhang, H., & Mittal, G. (2010). Biodegradable protein-based films from plant Re-
sources: a review. Environmental Progress and Sustainable Energy, 29(2),
203e220.
Zhang, M., Song, F., Wang, X.-L., & Wang, Y.-Z. (2012). Development of soy protein
isolate/waterborne polyurethane blend films with improved properties. Colloids
and Surfaces. B, Biointerfaces, 100, 16e21.
Zhang, Y.-N., & Zhao, X.-H. (2013). Study on the functional properties of soybean
protein isolate cross-linked with gelatin by microbial transglutaminase. Inter-
national Journal of Food Properties, 16(6), 1257e1270.
Zhao, S., Yao, J., Fei, X., Shao, Z., & Chen, X. (2013). An antimicrobial film by
embedding in situ synthesized silver nanoparticles in soy protein isolate. Ma-
terials Letters, 95, 142e144.
Zheng, H., Ai, F., Chang, P. R., Huang, J., & Dufresne, A. (2009). Structure and prop-
erties of starch nanocrystal-reinforced soy protein plastics. Polymer Composites,
30, 474e480.
Zheng, H., Tan, Z., Zhan, Y. R., & Huang, J. (2003). Morphology and properties of soy
protein plastics modified with chitin. Journal of Applied Polymer Science, 90,
3676e3682.
Zheng, H., Zhou, Z., Chen, Y., Huang, J., & Xiong, F. (2007). pH-sensitive alginate/soy
protein microspheres as drug transporter. Journal of Applied Polymer Science,
106, 1034e1041.
Zhong, Z., Sun, X. S., & Wang, D. (2007). Isoelectric pH of polyamideeepichlorohydrin
modified soy protein improved water resistance and adhesion properties.
Journal of Applied Polymer Science, 103(4), 2261e2270.
Zolfi, M., Khodaiyan, F., Mousavi, M., & Hashemi, M. (2014). The improvement of
characteristics of biodegradable films made from kefiran-whey protein by
nanoparticle incorporation. Carbohydrate Polymers, 109, 118e125.