MATERIALS AND INTERFACES

Value-Added New Materials from Byproduct of Corn Based Ethanol Industries:

Blends of Plasticized Corn Gluten Meal and Poly(E-caprolactone)
Dinesh Aithani and Amar K. Mohanty*
School of Packaging, Michigan State UniVersity, 130 Packaging Building, East Lansing, Michigan 48824
This study attempts to explore the value-added applications of corn gluten meal (CGM), the inexpensive
byproduct from corn based ethanol industries. The byproducts, CGM, was plasticized using glycerol/ethanol
mixture, denatured by the addition of guanidine hydrochloride (GHCl), and then blended with poly(-
caprolactone), PCL, a synthetic commercial biodegradable polymer. Extrusion followed by injection molding
was adopted to fabricate the newly blended green materials. The processing conditions affected the performance
of the blends. The GHCl modified corn gluten meal was characterized by IR spectroscopy. The developed
materials were characterized through their thermomechanical, tensile, and Izod impact strength measurements.
The effects of processing conditions on properties of blends were investigated. One of the promising outcomes
of this research was that the GHCl modified corn gluten meal based bioplastic, on blending with PCL had a
substantially higher percent elongation. Scanning electron microscopy (SEM) analysis revealed better
compatibility of PCL with GHCl modified plasticized CGM. The percent elongation and impact strength of
the blended material was found to be higher than high-density polyethylene (HDPE).
1. Introduction
Biodegradable polymers are getting increasing attention
recently due to their possible environmental benefits and societal
attractions. The utilization of agricultural products in plastic
applications is considered an interesting way to reduce surplus
farm production and to develop nonfood applications.
1
Plastics
account for 11.3 wt % of the total waste generation in United
States,
2
and the major portion of this waste is from the packaging
stream. Biodegradable polymers can provide environmental
benefits through degradation on disposal by living organisms
as a contrast to traditional polymers such as polyethylene (PE)
and polypropylene (PP), etc., that stick with the environment
for many years after disposal.
3
The use of some biodegradable
materials could make use of renewable resources and can
maintain neutrality with respect to the release of carbon
dioxide.
4,5
Biodegradable plastic can be a very good choice for
packaging of items used for a short period of time, and when
disposed of, they can be degraded in a suitable composting
environment unlike conventional plastics. The use of biodegrad-
able plastic can also avoid the recycling of plastics, which are
undesirable due to soiling by food or other biological sub-
stances.
3
The ethanol production from corn is done by two different
processes, i.e., dry milling and wet milling. One of the major
byproducts obtained from wet milling industries is corn gluten
meal (CGM). Similarly one of the major byproducts obtained
from dry milling ethanol industries is distillers dried grains
with solubles (DDGS). These byproducts from corn based
ethanol industries are mostly used for animal feeds. But
extensive research can find the value-added applications of such
byproducts in making biodegradable plastics. The plasticization
of corn gluten meal (CGM) is reported
6
to exhibit thermoplastic
type behavior. Corn gluten meal mainly consists of proteins
(60%) and hydrophobic amino acids (10% leucine) with the
remaining components mainly being moisture, fiber, and lipids.
7
The high demand for the production of bioethanol, a better
substitute for the ethanol produced from nonrenewable sources,
means increased generation of CGM. The current use of CGM
is mainly as animal feed, but extensive research is directed
toward finding additional value-added applications for CGM.
One of the growing avenues is the design and engineering of
CGM-based biodegradable plastics which would compete with
the petroleum based products on the basis of cost and perfor-
mance. The production of CGM from renewable and abundant
resources has attracted attention in the field of packaging due
to its biodegradability.
8
Poly(-caprolactone) (PCL) is an aliphatic polyester. It is one
of the important biodegradable polymers gaining interest due
to its technological properties and inherent biocompatibility.
9-12
It is well-known for its biodegradability and is often used for
packaging, plant containers, and medical devices.
13,14
It is
semicrystalline in nature with a melting point of around 60 C
15
and a glass transition temperature (T
g
)
16
in the range of -65 to
-60 C. PCL can be blended with a variety of other polymers
to improve their properties.
17
Blending a natural polymer with
polyester is one way to reduce cost and to improve the
biodegradability of the resulting polymeric blend.
16
Therefore,
blending of a petroleum-based biodegradable polymer (PCL)
with a compatible natural biodegradable material like CGM may
provide an alternative packaging material with lower cost and
environmentally friendly properties. Recently, several studies
have been made on CGM based biodegradable materials. Wu
et al.
18
have successfully extruded and compression molded a
CGM-wood fiber composite into sheets and injection molded
* To whom correspondence should be addressed. Tel.: +1-517-355-
3603. Fax: +1-517-353-8999. E-mail: mohantya@msu.edu.
6147 Ind. Eng. Chem. Res. 2006, 45, 6147-6152
10.1021/ie0513200 CCC: $33.50 2006 American Chemical Society
Published on Web 07/27/2006
the same into pots. CGM, glycerol, urea, and an organic acid
were used to prepare compression molded thermoplastic by
Nobuhiro et al.
19
The interaction of CGM with polar and
amphiphilic plasticizers has been studied by Gioia et al.
20
The uniqueness of the present investigation includes the
plasticization along with the denaturization of CGM that
imparted a much improved percent elongation to the blends.
This newly developed green plastic shows potential as a
substitute for polyethylene on the basis of specific performance
with an added advantage of biodegradability.
2. Experimental Details
2.1. Materials. The commercial corn gluten meal, a byproduct
of corn based ethanol industries with protein content of 60%,
was supplied by Cargill Inc., Minnesota. A commercial grade
PCL (TONE 787) with a melting point of 60 C was obtained
from Union Carbide Corp. Glycerol (99.9% purity), ACS grade
from J. T. Baker, and ethanol, 190 proof ACS grade from
Pharmco, were used. Guanidine hydrochloride was supplied by
Acros Organic, New Jersey.
2.2. Preparation of Blends. A microscale extruder with
injection molder, called a microcompounding instrument (DSM
Research, The Netherlands), was used for blending. It consists
of twin vertical co-rotating screws, with a length of 150 mm,
L/D of 18, and a maximum capacity of 15 cm
3
. The blending
was accomplished by plasticizing CGM with glycerol and
ethanol (denoted as plasticized CGM or CGMP) followed by
chemical modification with guanidine hydrochloride (GHCl).
The CGMP was made by weighing the CGM and glycerol/
ethanol separately and then adding glycerol/ethanol slowly into
the CGM while mixing to ensure uniformity of distribution. The
specified ratio of CGMP and GHCl was weighed and melt
blended using the DSM microcompounding instrument. The
GHCl modified CGMP was dried at 60 C for 5 h in a vacuum
oven before blending with PCL. Blending of GHCl modified
CGMP with PCL was followed by injection molding to prepare
samples for dynamic mechanical analysis (DMA) and tensile
testing. The blended material was drawn and injection molded
on a DSM injection molder at 120 C and 100 psi pressure.
The mold temperature was set at 40 C.
2.3. Characterization. 2.3.1. Infrared Spectroscopy. The
infrared spectrum was measured using a Perkin-Elmer FT-IR
spectrophotometer. An ATR attachment was used to measure
the IR spectrum for the CGMP before and after chemical
modification in order to observe the chemical changes that
occurred in the structure. The IR spectrum of GHCl was also
obtained.
2.3.2. Dynamic Mechanical Analyzer. The storage modulus
of the blend was measured using a Model Q800 dynamic
mechanical analyzer (DMA) from TA Instruments, using a
single-cantilever clamp and multifrequency strain mode. Mea-
surements were made at 1 Hz and 15 m amplitude over the
temperature range of 30-60 C at the heating rate of 2 C/
min.
2.3.3. Tensile Testing. The tensile testing was done on
Universal Test System load frame according to ASTM D638.
The tensile samples were made by injection molding im-
mediately after extrusion from the DSM. A load cell of 1000
lb capacity was used for the testing, with a cross-head speed of
2 in./min for tensile tests.
2.3.4. IZOD Impact Testing. The samples were notched
using a TMI notching cutter (model TMI 22-05, Testing
Machine Inc., Amityville, NY), and the impact strength was
measured using a TMI IZOD impact strength tester (model 43-
02). A 5 lb pendulum was used for impact measurement. ASTM
D 256 was followed for the testing.
2.3.5. Scanning Electron Microscopy. The fractured surfaces
were coated with gold thin films and examined in a JEOL 6300
field emission scanning electron microscope (FESEM) at an
accelerating voltage of 10 kV.
3. Results and Discussion
One of the promising ways to find value-added applications
of inexpensive byproduct like CGM is the development of CGM
based biodegradable plastics. In this piece of research work we
look forward to the use of CGM without any purification in
order to make it more cost-effective with an overall target of
finding new value-added materials. Zein, an alcohol soluble
protein, can be extracted from CGM through solvent extraction.
Polymers derived purely from zein are very expensive and have
found limited applications.
21
The brittle nature of the corn protein based materials
necessitates the use of plasticizers. Glycerol has been extensively
studied as a plasticizer.
18,22
The plasticization effect of glycerol
is attributed to its small size which helps in its insertion and
positioning within the protein network
23,24
and thereby reducing
the intermolecular forces and increasing the mobility of protein
chains.
25
The use of ethanol aids the processing of CGM.
18
The
glycerol/ethanol (3:1) mixture was used for better plasticization
of CGM system. The GHCl was used to break down the protein
structure in order to make it more flexible and compatible with
the other components of the polymer system.
Various studies have been done on the interaction of GHCl
with proteins, which revealed the induction of denaturation and
unfolding of the protein structure.
26-28
Denaturation is the
alteration of secondary, tertiary, or quaternary structures in the
protein molecules. The GHCl forms cross-link at different
locations in the side chains and on the backbone of the protein
Table 1. Modulus of PCL Blends with GHCl Modified CGMP
Processed at 150 rpm and Temperatures of 120 and 150 C at the
Ratio of PCL:CGMP:GHCl ) 50:37.5:12.5 (wt %)
storage modulus (MPa)
processing
temp, C at 30 C at 40 C at 50 C
120 88 ( 10.77 75 ( 9.43 49 ( 5.52
150 87 ( 3.17 74 ( 2.57 48 ( 1.73
Table 2. Modulus of PCL Blends with GHCl Modified CGMP
Processed at 150 C and Different Processing Speeds of 75 and 150
rpm at the Ratio of PCL:CGMP:GHCl ) 50:37.5:12.5 (wt %)
storage modulus (MPa)
processing
speed, rpm at 30 C at 40 C at 50 C
75 170 ( 31.64 148 ( 29.27 105 ( 22.28
150 87 ( 3.17 74 ( 2.57 48 ( 1.73
Figure 1. Percentage elongation of PCL blends with modified CGMP
processed at 150 C and different processing speeds of 75 and 150 rpm.
6148 Ind. Eng. Chem. Res., Vol. 45, No. 18, 2006
molecule by means of hydrogen bonding and van der Waals
interactions.
28
This phenomenon is likely responsible for the
improvement of mechanical properties of the protein blends.
In melt processing technique it is important to optimize the
processing conditions in order to get the best performing
materials. The processing conditions, i.e., the temperature and
processing speed, play important roles in determining the final
properties of the blend. To analyze the effect of processing
conditions, a blend containing PCL:CGMP:GHCl at the ratio
of 50:37.5:12.5 on a weight basis were processed at 120 and
150 C, keeping the processing speed constant. The mechanical
properties (modulus) of the resulting blends were evaluated
using DMA. The blend processed at 150 C shows more
consistency in results than the blend processed at 120 C, which
is evident from the standard deviation results (Table 1). The
superior consistency of modulus data obtained at the higher
temperature as contrasted with that obtained from lower
temperature is taken as the basis for the more optimized
condition of processing used under the present investigations.
On the basis of these results, the processing temperature of 150
C was used versus 120 C in the subsequent studies.
To study the effect of extruder screw speeds on blend
properties, the blends were prepared at 150 C using two
different screw speeds. Speeds of 75 and 150 rpm were used
during processing. The storage modulus of the blend was
reduced by about 50% with an increase in processing speed
(Table 2). The material blended at 75 rpm had large average
standard deviations in its storage modulus. The material blended
at 150 rpm exhibited a much improved percent elongation and
reduced storage modulus (Figure 1) in contrast to their
counterparts blended at 75 rpm. On the basis of these results,
e.g., considering the low standard deviation in modulus data
and much superior elongation data at 150 rpm in contrast to
those at 75 rpm, the processing speed of 150 rpm was chosen
in contrast to 75 rpm for further studies. Such observations were
attributed to inconsistent mixing at lower screw speeds, or higher
orientation is generated at higher speed due to higher shear rate.
The GHCl modified corn gluten meal based bioplastics were
characterized by using IR spectroscopy. A peak shift was
observed in GHCl modified CGMP bioplastic at 1651 cm
-1
(Figure 2) in contrast to CGMP bioplastic (e.g. unmodified
CGMP) at 1624 cm
-1
. This peak shift is attributed to hydrogen
bonding.
29
Researched by Dunbar et al.
28
as well supports the
formation of a hydrogen bond during the interaction of GHCl
with protein.
Blends of PCL and zein have shown poor mechanical
properties in previous research.
16
These results were attributed
to incompatibility between the components of the system. In
this present study, we used plasticized CGM as well as GHCl
Figure 2. IR spectroscopy of CGMP before and after chemical modification with GHCl: A ) GHCl; B ) GHCl:CGMP ) 25:75 (wt %); C ) CGMP.
Figure 3. Effect of GHCl on tensile strength of PCL blends (ratio
PCL:CGMP:GHCl): (A) 100:0:0; (B) 50:37.5:12.5; (C) 50:42.5:7.5; (D)
50:45:5; (E) 50:50:0.
Figure 4. Effect of GHCl on percentage elongation of PCL blends (ratio
PCL:CGMP:GHCl): (A) 100:0:0; (B) 50:37.5:12.5; (C) 50:42.5:7.5; (D)
50:45:5; (E) 50:50:0.
Ind. Eng. Chem. Res., Vol. 45, No. 18, 2006 6149
modified CGMP as the blending partners for PCL in order to
study the effectiveness of GHCl in designing new biodegradable
plastics. Such developed biodegradable plastic blends exhibit
some useful properties that can be targeted in certain plastic
applications as a substitute for high-density polyethylene
(HDPE).
The tensile strength of PCL was reduced upon blending with
CGMP (Figure 3) as expected. The effect of GHCL on the
percent elongation of the blends is represented in Figure 4. The
percent elongation of PCL decreased when blended with CGMP
but showed significant improvement when blended with GHCl
modified CGMP. As apparent from Figure 4 the percent
elongation was not proportional to the percentage of added
GHCl. The elongation of the blend first increased with increas-
ing GHCl content from 5 to 7.5% and then decreased with
further addition of GHCl content up to 12.5%. Therefore, 7.5%
GHCl was considered the optimum amount under the present
experimental conditions investigated. The higher elongation of
the blend from PCL and GHCL modified CGMP is attributed
to optimum hydrogen bonding at a specific concentration of
GHCL. Higher concentration of GHCl beyond this optimum
amount might have caused phase separation under the present
experimental conditions. The stress-strain curve in Figure 5
shows the effect of GHCl in the blend. The higher area under
the curve for the blend that was modified with GHCl indicates
higher plastic character in contrast to its counterpart not modified
with GHCl.
The PCL-CGMP blended with 7.5% GHCl was found to
be better in comparison to the other composition. This composi-
tion was compared to one of the injection molded grade HDPE.
30
The percent elongation of this blend was 450%, while HDPE
has a percent elongation of 320% (Figure 6). This blend was
also found to have higher impact strength in contrast to HDPE
(Figure 6).
The storage modulii of PCL and its blends with CGMP as
well as with GHCl modified CGMP (with varying content of
GHCl) were measured using DMA at 30, 40, and 50 C (Figure
7). The PCL as well as all of the blends exhibited decreasing
modulus values with an increase of temperature from 30 to 50
C. As expected, the modulus of the PCL decreased on blending
with CGMP as well as GHCl modified CGMP bioplastics. In
the comparative study to observe the effect of GHCl proportion
in the GHCl modified CGMP, it was observed that 7.5% of
GHCl resulted in an optimized modulus and percent elongation
values (Figures 3, 4, and 7) of the resulting biodegradable
blends.
The blend morphology is closely related to its mechanical
properties. In our investigations of blend compositions and their
mechanical property evaluations, we found that GHCl modified
CGMP was superior to the unmodified counterpart. Blends with
PCL:CGMP:GHCl in the ratio of 50:42.5:7.5 and 50:50:0 were
selected and the fractured surfaces of these compositions were
examined using scanning electron microscopy (SEM) in order
to reveal the morphology of the blend with and without GHCl.
The morphological analysis revealed that the blend without
GHCl contained cavities, which must have created in the fracture
region during the spontaneous separation of the PCL and CGMP
regions due to the weak interfacial adhesion between PCL and
CGMP. The presence of GHCl in the blend enhanced the
interfacial adhesion by means of the secondary forces and
Figure 5. Stress-strain curves for PCL blends with and without GHCl (ratio
PCL:CGMP:GHCl): (A) 50:50:0; (B) 50:42.5:7.5.
Figure 6. Comparison of percent elongation and impact strength of PCL,
PCL blend, and HDPE (HDPE data from ref 30): (A) PCL:CGMP:GHCl,
100:0:0; (B) PCL:CGMP:GHCl, 50:42.5:7.5; (C) HDPE.
Figure 7. Storage modulus of PCL and its blends.
6150 Ind. Eng. Chem. Res., Vol. 45, No. 18, 2006
exhibited quite a high degree of homogeneity, which was a sign
of increased compatibility between PCL and CGMP phases
(Figure 8).
In the current research, using a unique chemical modification
of CGMP with GHCl followed by blending with PCL has
resulted in a new biodegradable plastic composition having a
tensile strength of 10 MPa and a percent elongation of 462%
(Table 3). The newly developed biodegradable plastic shows
immense potential for plastic film applications. In a separate
investigation, the content of PCL was increased by 10% in the
blend system. A comparison of some properties of the two
blends is shown in Table 3.
The blend with 7.5% GHCl was found to be the best in the
overall properties under the present experimental conditions.
To further improve the properties of this blend so that it can be
compared with some other synthetic plastics, the percentage of
PCL was increased from 50 to 60%. The resulting blend with
60% PCL showed improvement in its mechanical properties as
shown in Table 3 and Figure 9. The tensile strength, percent
elongation, and modulus improved by 70, 29, and 28%,
respectively.
Figure 8. SEM photomicrographs of the blends (ratio PCL:CGMP:GHCl): (A, B) 50:42.5:7.5 (scale bars are 50 and 10 m, respectively); (C, D) 50:50:0
(scale bars are 50 and 10 m, respectively).
Figure 9. Storage modulus of PCL and its blends.
Table 3. Comparison of Properties between 50 and 60% PCL Based
Blend
blend composition
tensile strength
(MPa)
%
elongation
50:50 PCL:(GHCl-modified CGMP) 10 ( 1.61 462 ( 33.3
60:40 PCL:(GHCl-modified CGMP) 17 ( 1.13 598 ( 15.6
Ind. Eng. Chem. Res., Vol. 45, No. 18, 2006 6151
4. Conclusion
The main motivation of the present investigations was to
design novel green biodegradable plastics with the maximum
permissible content of CGM, thereby finding value-added
application of the byproducts of corn based ethanol. In the
current research we developed injection molded biodegradable
plastic from the blends of corn gluten meal based bioplastic
and PCL. The choice of the ratio of components, the melt
processing temperature, and the screw speed of the extruder
affected the overall properties of the resulting biodegradable
polymer blends. The uniqueness of the present investigation is
the chemical modification with GHCl, which has resulted in a
biodegradable plastic having a high percent elongation, which
shows potential applications for biodegradable packaging.
Among the different blends tested, the blend with 7.5% GHCl
produced the best results under present experimental conditions.
Further increase in the PCL content, i.e., from 50 to 60% in
the final blend, improved the overall mechanical properties of
the blend. The morphological analysis revealed increased
homogeneity between PCL and CGM phases in the presence
of GHCl.
Acknowledgment
We are thankful to Mr. Tom Guinan, Cargill Inc., MN, for
donating corn gluten meal samples. The authors are also thankful
to Michigan State University for start-up funding to A.K.M.
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Accepted June 8, 2006
IE0513200
6152 Ind. Eng. Chem. Res., Vol. 45, No. 18, 2006