56 J. Agric. Food Chem.

2011, 59, 56–61

DOI:10.1021/jf103164r

Reducing the Brittleness of Zein Films through

Chemical Modification
KE SHI, YUPING HUANG, HAILONG YU, TUNG-CHING LEE, AND QINGRONG HUANG*
Department of Food Science, Rutgers University, 65 Dudley Road,
New Brunswick, New Jersey 08901, United States

Zein protein is a major coproduct of biofuel from corn. To reduce the brittleness of zein films, a new
type of zein-based biomaterial, was synthesized by chemical modification of zein with lauryl chloride
through an acylation reaction. The final products were confirmed by 1H NMR, FT-IR analysis, and
SDS-PAGE. Thermal analysis detected no microphase separation in the synthesized polymer
matrix. As the content of lauryl moiety increased, the glass transition temperatures of modified zein
decreased by as large as 25.8 °C due to the plasticization effect of the lauryl moiety. In addition,
mechanical and surface properties of cast films from acylated zein were also investigated. The
elongation at break of modified zein sheet was increased by about 7-fold at the high modification
level with some loss of mechanical strength. The surfaces of modified zein films were as uniform as
unmodified zein film but more hydrophobic, further suggesting that no microphase separation happened
during the film formation process. This work indicated the potential of these new biomaterials in the
development of biodegradable food packaging materials and delivery systems.

KEYWORDS: Zein films; mechanical properties; chemical modification

INTRODUCTION multivalent carboxylic acids etc., to zein has been commonly used
Zein, an alcohol-soluble protein enriched in the endosperm of to increase the mechanical strength and reduce the water perme-
corn, is a main coproduct of the bioethanol industry. The com- ability. However, such an approach often showed little or even
mercial R-zein contains two main components with apparent negative effects on the flexibility (11-17). Wu et al. (18) used
molecular weights of 19 kDa (Z19) and 22 kDa (Z22). Although polycaprolactone (PCL) to modify zein, where the hydrophobic
zein has a long history of being used as a coating material for chain of PCL not only cross-linked the zein molecule but also
candies, medical tablets and paper (1), other applications of zein served as plasticizers and thus significantly increased the elasticity
are still limited mainly due to the undesirable properties of the of zein sheets. On the other hand, palmitic chloride was used to
zein-based materials (2-4). Like many other proteins, zein, acylate the zein in order to improve the thermoprocessability and
without plasticizers, forms brittle films with poor flexibility that water resistance. However, the study did not clarify whether the
cannot withstand industrial processing. Some low molecular modification improved the intrinsic mechanical properties of zein or
weight molecules, such as some polyols and fatty acids, could the byproduct such as palmitic acid played a role as plasticizer (19).
be used as plasticizers to improve the mechanical properties of In this paper, we aimed to obtain zein derivatives with im-
zein films (1). However, phase separation as a result of immisci- proved film properties through chemical modification by lauryl
bility between zein and these plasticizers is difficult to avoid, chloride, which would introduce hydrophobic alkyl chains onto
which usually leads to instability of the mechanical properties and zein molecules. The success of the synthesis was confirmed by
often heterogeneous surfaces. Another disadvantage of using combined 1H NMR, FT-IR analysis, and SDS-PAGE, and our
polyol plasticizers is that they exacerbate the sensitivity of zein- characterization indicated increased flexibility and hydrophobic-
based materials to moisture (5-7). Thus, new efforts are needed ity of zein derivative films with no sign of phase separation.
to improve the water resistance and mechanical properties of
zein-based materials. MATERIALS AND METHODS
Chemical modification allows an extensive exploration to the
Materials. The R-zein of biochemical-grade purity was obtained from
novel functionalities and applications of synthetic polymers. The
Wako Pure Chemical Industries, Ltd. (Tokyo, Japan). Deuterated di-
methods could also be used on biopolymers to generate new methyl sulfoxide (DMSO-d6) was purchased from Sigma-Aldrich Inc.
biomaterials to substitute synthetic polymers (8-10). Cross- (St. Louis, MO). Lauryl chloride (99%, Acros Organics), triethylamine
linking agents have often been used to improve the properties (TEA), dimethyl sulfoxide (DMSO), hydrochloric acid, ethanol (95%),
of protein films. In many reported studies, the addition of cross- and glycerol were obtained from Fisher Scientific, Inc. (Pittsburgh, PA).
linkers, such as formaldehyde, glutaraldehyde, transglutaminase, Pluronic F127 was from BASF Corporation (New Jersey). Milli-Q water
was used throughout the experiment.
*To whom correspondence should be addressed. Tel: (732)-932- Modification by Acylation Reactions. Acylation of zein was
7193. Fax: (732)-932-6776. E-mail: qhuang@aesop.rutgers.edu. performed as previously described (19) with some modifications.

pubs.acs.org/JAFC Published on Web 12/02/2010 © 2010 American Chemical Society

Article J. Agric. Food Chem., Vol. 59, No. 1, 2011 57
TEA (3, 9, or 15 mmol) and lauryl chloride (1, 3, or 5 mmol) per gram of
zein were added to a 5% w/v solution of zein in DMSO dropwise at
ambient temperature while stirring. The resultant solution was heated to
65 °C under stirring for 3 h. Subsequently, the reaction mixture was poured
into water, acidified to pH 5-6 using HCl in order to neutralize the extra
TEA and to facilitate its removal through dialysis. The product, acyl zein,
was separated by centrifugation, and washed with water three times before
lyophilization. The powder obtained was dissolved in 80% ethanol and
dialyzed against 80% ethanol for one week, and then dialyzed against
water for another 24 h, followed by lyophilization. The lauryl-substituted
zein molecules were named zein-C12-1, zein-C12-3 and zein-C12-5,
respectively, according to the amount of lauryl chloride per gram of zein.
If the average molecular weight of zein was assumed to be 20 kDa, the
initial molar ratio of lauryl chloride to zein was 20:1, 60:1, and 100:1,
respectively.
1
H NMR Spectroscopy. The 1H NMR spectra were acquired using a
Varian VNMRS 500 MHz spectrometer. The 1H solution spectra of zein
and modified zein were recorded in DMSO-d6 at 25 °C.
ATR-FTIR Spectroscopy. The attenuated total reflection Fourier
transform infrared spectra were collected under ambient conditions, using
a Thermal Nicolet Nexus 670 FT-IR spectrometer (Thermo Electron
Corp., Madison, WI) with a Smart MIRacle horizontal attenuated total
reflectance Ge crystal accessory. Each spectrum was averaged by 128 scans
with 4 cm-1 resolution.
Sodium Dodecyl Sulfate Polyacrylamide Gel Electrophoresis
(SDS-PAGE). Each sample was dissolved in sodium dodecyl sulfate/
nonreducing sample buffer to 1 mg/mL solution, and then heated at 95 °C
for 5 min. Each sample solution (5 μL) or protein marker was loaded onto
sodium dodecyl sulfate polyacrylamide gel with 5% stacking gel and 15%
separating gel. The gel was run in a BioRad Mini-Protean II system under Figure 1. SDS-PAGE of pure zein and modified zein. The protein marker
90 V for about 2 h. The gel was then stained with Coomassie blue (20) and was run in the first lane, with the molecular weights labeled.
photographed by a monochrome gel documentation system.
Differential Scanning Calorimetry (DSC). DSC analyses were per- 25% Pluronic F127 and 12.5% glycerol based on the weight of zein or
formed on a DSC 823E thermal analyzer (Mettler-Toledo Inc., Columbus, modified zein and then dried in a vacuum oven at 50 °C for 48 h. Yellow
OH) supplied with liquid nitrogen and compressed nitrogen gas. Approxi- and transparent sheets were obtained from each sample. The zein sheets
mately 5 mg of each sample was packed into an aluminum crucible with lid were denoted as ZS, ZS1, ZS3 or ZS5, where ZS stands for zein sheet, and
and heated from 32 to 140 °C at a rate of 10 °C/min. The sample was then ZS1, -3, and -5 stand for sheets made from different amount of acylated
cooled to -120 °C at a rate of 30 °C/min in order to remove any prior zein. Dumbbell-shaped specimens with dimensions of 40  10  (0.05-
thermal history within the sample. Subsequently, the thermogram was 0.30) mm3 were cut from the central region of the sheets and stored in 50%
obtained by heating the sample to 210 °C at a rate of 10 °C/min. Glass relative humidity desiccators under ambient temperature for more than
transition temperature (Tg, the midpoint of the glass transition) and the 30 days before conducting tensile tests. Mechanical properties were
melting temperature (Tm, the lowest point of each melting peak) were measured on a TA.XT2 texture analyzer (Texture Technologies Corp.,
automatically analyzed from the thermogram by the STARe software New York) with an initial grip distance of 20 mm and a test speed of 6 mm/min.
accompanied with the instrument. Triplicate readings were taken.
Film Surface Properties. Zein films were prepared by a spin-casting RESULTS AND DISCUSSION
method as described previously with some modifications (21). Sample
solutions were prepared by dissolving zein or modified zein into glacial Preparation and Structure of Acylated Zein. According to
acetic acid (0.1% and 1%, w/v), and then heating at 70 °C for 30 min. Zein Gianazza et al. (22), about 8.2% of the amino acids of zein were
films were prepared by spin coating the solutions onto precleaned silicon either serine or threonine, while 26.6% amino acids were any of
(Si) wafers, using a Laurell model WS-400A-6NPP/LITE spin coater glutamic acid/glutamine/aspartic acid/asparagine. The hydroxyl
(Laurell Technologies Corp., North Wales, PA) at 4000 rpm for 80 s. Clear group and the amino group could potentially serve as the sites to
and homogeneous zein films were obtained and dried at 50 °C in a vacuum form ester or amide bonds in the acylation reaction. However,
oven overnight to remove the residual solvent. The zein films prepared here due to the limitation of protein conformation, some of the hy-
were denoted as ZFm-n, where m indicated the level of lauryl chloride
droxyl and amino groups may be buried inside the protein and,
added in the reaction, and n indicated the concentration of protein solution
used for film preparation. For example, the film ZF5-0.1 was prepared thus, are not accessible to reactions. In the present study, acylated
from 0.1% (w/v) zein-C12-5 in acetic acid solution. zein molecules were synthesized with three different amounts of
The surface morphology images of zein films were collected by tapping lauryl chloride. To ensure complete removal of unreacted lauryl
mode atomic force microscopy (TP-AFM) on a NanoScope IIIA Multi- chloride (or its hydrate laurylate acid), the products underwent
mode AFM (Veeco Instruments Inc., Santa Barbara, CA) under ambient extensive dialysis.
conditions. SDS-PAGE analysis of the modified zein was used to reveal
The surface hydrophilicity was represented by the static water contact the modification extent upon adding different amounts of lauryl
angle measured on a VCA Optima XE Dynamic Contact Angle Analyzer chloride (Figure 1). The two major bands at 19 kDa (Z19) and
(AST Products Inc., Billerica, MA) at ambient conditions. The images 22 kDa (Z22) represented the two main components in R-zein
were recorded by a CCD camera immediately after the water droplets were
(23). Because the samples were run in a nonreducing condition,
deposited onto the zein film surface. The water contact angles were
determined using the associated software provided by the manufacturer. the bands at around 39 kDa should be the respective dimeric
At least six measurements were averaged for each sample. forms of Z19 and Z22 (24). The bands at around 11 kDa and 14 kDa
Mechanical Properties Measurement. Zein sheets were prepared by were also suggested to be two β-zein components (25). On the
solvent casting in Teflon Petri dishes using solutions consisted of 20% zein, SDS-PAGE gel, modified zein would shift to higher molecular
zein-C12-1, zein-C12-3, or zein-C12-5 in acetic acid (HAc) plasticized by weights. Interestingly, after modification at the two higher levels
58 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Shi et al.

Figure 2. 1H NMR spectra of (a) zein, (b) zein-C12-1, (c) zein-C12-3 and
(d) zein-C12-5.

of lauryl chloride, three bands appeared at the position between

19 kDa and 22 kDa. Without further analysis, it is not clear what
forms of zein the three aggregates comprised. In spite of the Figure 3. FT-IR spectra of (a) lauryl chloride, (b) zein, (c) zein-C12-1,
sequence homology, the reactivity and surface hydrophobicity of (d) zein-C12-3 and (e) zein-C12-5.
the two subunits were found to be different on the basis of
reversed-phase HPLC analysis (24). The molecular conforma- respectively (Figures 2b-2d), which suggested more alkyl chains
tions of the two subunits of zein (Z19 and Z22) were also thought in the molecule of modified zein and further indicated that the
to be different (26). Thus, it is possible that the lowest band came lauryl groups were grafted to the molecule of zein as expected.
from the modified Z19 component. According to our previous By combining the results of SDS-PAGE and 1H NMR
experience, the Z19 component was more accessible to chemical analysis, we found that, at the initial lauryl chloride to zein molar
modification than the Z22. The addition of 12-carbon alkyl ratio of 20:1, zein was only slightly acylated, and at the ratio of
chains would lead the denatured protein to adopt different 60:1 and 100:1, acylation occurred to a similar extent, suggesting
thermodynamic conformation in SDS-PAGE gel compared to the possible saturation of the reaction groups on zein surface.
the pure protein. In addition, other studies suggested that the Moreover, the FTIR spectra of the zein samples also revealed
hydrophobic interactions, exceeding the down effects from the the difference in molecular structures between modified and pure
lost positive charges, enhanced the binding of SDS with protein zein. The FTIR spectrum of lauryl chloride (Figure 3a) contained
modified with long alkyl-chain (27,28). This could result in higher a sharp peak at 1798 cm-1 which is associated with the CdO
density of positive charge on acylated protein molecules which stretching in the CO-Cl group (29). Another sharp peak at
would migrate faster than a pure protein with the same molecular 720 cm-1 represented the vibrations of alkyl chain with at least four
weight in electrophoresis. Thus, low-degree modified Z19 aggre- methylene groups (30). The three adjacent peaks at 2958, 2923,
gate may appear to separate from original Z19 bands, even and 2854 cm-1 were assigned to the vibrations of the methylene
though the molecular weight did not change significantly. group, the symmetric and asymmetric vibrations of the methylene
Modified zein binds less staining dye per unit mass than group, respectively (31). After modification, the newly formed
unmodified zein. Therefore, it is not appropriate to use a densitom- ester and amide groups intensified the absorption of the amide I
etry method to calculate the unmodified zein contents, which can band (stretching vibrations of the CdO bond of the amide) at
only be roughly estimated if there is more than 12% modified zein around 1650 cm-1 and the amide II band (bending vibrations
in zein-C12-1 (18). This value increases to more than 24% in both of the N-H bond) at 1544 cm-1. The vibrations of attached
zein-C12-3 and zein-C12-5, regardless of the amount of lauryl hydrocarbon chains gave rise to those bands in the 2800-
chloride added. 3000 cm-1 range and the bands at 1447 cm-1 and 720 cm-1.
1
H NMR spectra of zein and its derivatives also confirmed the Besides acylating the protein, lauryl chloride could also react
successful grafting of lauryl groups onto zein molecule. In com- with water and form fatty acid. The fatty acid could function as a
parison with the 1H NMR spectrum of zein (Figure 2a), the ratio plasticizer and interfere with other characterizations. The free
of the number of H in CH2 (δ 1.21) to that in CH3 (δ 0.83) fatty acid could be detected from the FTIR spectrum as a
significantly increased from 0.26:1 to 0.32:1, 0.47:1 and 0.51:1, shoulder peak at 1700-1800 cm-1, as seen in the previous study
Article J. Agric. Food Chem., Vol. 59, No. 1, 2011 59

Figure 4. DSC thermograms for lauryl chloride, zein, and modified zein.

Table 1. Glass Transition Temperatures of Zein and Modified Zein Samples Figure 5. Tapping mode atomic force microscopy (TP-AFM) images of
Measured by DSC films prepared from zein 0.1% and 1% solutions (ZF-0.1, ZF-1) and from
glass transition temperature (°C) zein-C12-5 0.1% and 1% solutions (ZF5-0.1, ZF5-1). Each image size is
500 nm  500 nm, and the z scale is 50 nm.
sample T 1g T 2g

zein 94.4 ( 2.1 173.6 ( 0.3 Table 2. Surface Water Contact Angles of Zein and Modified Zein
zein-C12-1 81.1 ( 2.2 177.2 ( 1.3 sample water contact angle (°)
zein-C12-3 74.7 ( 1.6 169.8 ( 0.6
zein-C12-5 68.8 ( 1.0 167.7 ( 0.3 ZF 75.6 ( 1.1
ZF1 78.5 ( 0.5
ZF3 86.4 ( 0.3
on modifying soy proteins with palmitic acid chloride (19). In
ZF5 86.0 ( 1.0
Figure 3, the absence of absorption bands at around 1798 cm-1
confirmed the effective removal of the fatty acid by the dialysis
procedure (32). chains did not shift to a lower wavelength compared to the
Thermal Properties. DSC is conventionally used to study the spectrum obtained for our modified zein (31).
plasticizer compatibility with biopolymer and the effectiveness of Film Surface Properties. The surface properties are believed to
plasticization. The DSC thermograms of lauryl chloride, zein and be important for the barrier properties of films, where homo-
modified zein were shown in Figure 4, and the glass transition geneous and smooth surface is usually preferred. In our previous
temperature data were summarized in Table 1. Previously, Sessa study, it was observed that the spin-cast zein films from acetic acid
solutions bear smooth and featureless surfaces (21). However, a
et al. reported that the Japanese white zein had a lower Tg than
heterogeneous surface is often observed on biopolymer films that
Freeman zein, at around 158 °C (15, 33), whereas Wu et al. also
are simply plasticized with fatty acids, due to the instability of the
performed DSC on Showa zein and found two Tg at 180.1 and
emulsions formed between fatty acids and biopolymers, resulting
200.1 °C, potentially attributed to the two zein subfractions (18).
in phase separation afterward. For this reason, cast zein films
The zein used in this study could be from the same manufacturer plasticized by fatty acids often show granules on the top of the
as their zein. However, the zein thermograms obtained here were film surface (6, 7, 34). AFM tapping mode images shown in
quite different. Two distinct glass transition processes were Figure 5 revealed that chemical modification by lauryl chloride
observed, with Tg at 94.4 and 173.6 °C, which may be attributed did not create any visible aggregates or pattern, and the film
to the two components in R-zein, Z19 and Z22, respectively. The surfaces maintained as uniform as the untreated zein.
differences in glass transition temperatures among zein may be Water permeability and moisture sensitivity of protein-based
due to the different origins of zein. materials were also directly affected by surface and overall
Table 1 summarizes the glass transition temperatures of zein hydrophobicity (35). Water surface contact angle, representing
and modified zein samples measured by DSC. After modification, the surface hydrophobicity, was also measured on the zein and
the lower Tg decreased from 94.4 to 68.8 °C, by about 25.8 °C, modified zein films. Table 2 contained static water contact angles
while the higher Tg (i.e., 173.6 °C) only decreased by about 5 °C. of films prepared by zein and its derivatives. Films cast from
This also suggested that the reaction showed certain preference unmodified zein showed relatively large water surface contact
between various components in zein, and was consistent with the angles, due to its hydrophobic nature. Meanwhile, water contact
SDS-PAGE and 1H NMR studies (see above): compared to Z22, angles of modified zein films were further slightly increased, due
Z19 is more reactive in acylation. to the increased surface hydrophobicity through the acylation
Pure lauryl chloride had a melting point at 10.4 °C. Modified reaction, implying possible decreased water permeability and
zein did not show any endothermic peak at that temperature, moisture sensitivity.
indicating that there was no microcrystal in the samples formed Mechanical Properties. Plasticized with Pluronic F127 and
by lauryl chains. The FT-IR spectra also confirmed this, because glycerol, zein and acylated zein were cast into films and their
the absorption in the 2800-3000 cm-1 range derived from the mechanical properties were measured. As shown in Table 3, the
vibration of methylene groups in ordered long hydrocarbon elongation at break of zein-C12-5 was about 7 times that of the
60 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Shi et al.
Table 3. Mechanical Properties of Cast Films Prepared from Pure Zein and permeability, surface energy and microstructure properties of zein
Modified Zein films. LWT;Food Sci. Technol. 2007, 40, 1191-1197.
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