].Pack. Sci. Tech. Vol. 12 No.5 (2003)

Property Improvement of Fish Water Soluble Protein
Films by Dialdehyde Starch (DAS) and / or Sodium
Dodecyl Sulfate (SDS) Treatments
Patricia Yuca HAMAGUCHP, Yusuke SHIKU*, and Munehiko TANAKA**
Transparent biodegradable films were successfully prepared from fish water soluble proteins(FWSP) in our laboratory, but FWSP films generally have the inferior mechanical and water
vapor barrier properties. The objective of this study was to improve physical properties of FWSP
u si n g t re at me nt s wi th dia l de hy de star c h ( DAS) and/or sodi um dodecy l sulf a te ( SD S) . Fi l mforming solution containing 3% FWSP from blue marlin (Makaira mazara) flesh was mixed withDAS (2.5, 5. 7.5 and 10% of FWSP) or SDS (10, 20, 30 and 40% of FWSP) or the combination of
DAS with SDS (2.5/40, 5/40, 7.5/40 and 10/40% of FWSP) prior to pH adjustment to 10.5.
Glycerol at a level of 50% of FWSP was used as a plasticizer. Film forming solution was cast anddried at 25 C, 50% relative humidity for 24 h. Increasing DAS concentration enhanced tensile
strength (TS) of FWSP films, while increasing SDS concentration improved elongation at break(EAB). Optimum ratios of DAS/SDS were 5/40 or 7.5/40%, which increased EAB by 82 or 56 %with decreasing water vapor permeability (WVP) by 41 or 26%, respectively. Thus,
biodegradable FWSP films with various strength and flexibility were successfully prepared by
combining DAS with SDS.
Keywords : Biodegradable film, Fish water soluble proteins, Sodium dodecyl sulfate,
Dialdehyde starch

1.

Introduction

The interest of biopolymer films has increased during the last decade, because they areenvironmentally friendly alternatives to synthetic, non-biodegradable films. Although it is not
feasible to entirely replace synthetic packaging films, biopolymer films have the potential toreduce and replace synthetic films in some applications. Basically, biodegradable/edible films
are prepared with polysaccharides, proteins, and lipids. Among these materials, proteins havebeen extensively utilized for the development of biodegradable/edible films because of theirrelative abundance, film-forming ability, and nutritional qualities.
Effluents from seafood processing plants have become a crucial issue due to the presence of alarge amount of organic matters. Furthermore, the cost of waste water treatment represents amajor expenditure for processors. Recovery of water soluble proteins from effluents and their___________________________________________________________________________________________*Department of Food Science and Technology, Tokyo University of Fisheries, Minato, Tokyo 108-8477, Japan**Corresponding author : Tel : 03-5463-0611. Fax : 03-5463-0627. E-mail: mune@tokyo-u-fish. ac.jp- 2 7 1 -

Property Improvement of Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecyl Sulfate (SVS) Treatments

reutilization as the novel products should be a promising means to reduce the cost of waste
water treatment and expand potential for the utilization of seafood by-products. In ourlaboratory, fish water soluble proteins (FWSP) were used for the preparation of biodegradable
films 1) . However, FWSP films generally have the inferior mechanical and water vapor barrier
properties to synthetic films.
Various physical, chemical and enzymatic treatments have been used to modify properties ofprotein films. Such treatments mainly promote cross-linking within protein film network. To
enhance tensile strength of films aldehydes such as formaldehyde, glutaraldehyde, and glyoxal
were added into film-forming solutions. Aldehydes can promote inter- and intramolecularcross-linking in proteins2). In particular, the ɛ-amino group of lysine is considered the primary
reactive site between protein and aldehyde. Cross-linking with formaldehyde, glutaraldehydes.
and glyoxal has been reported for protein films from collagen, gelatin, corn zein, and soy
protein isolate 3 ) . However, the inherent toxicity of the aldehydes restricts their use inedible/biodegradable films.
Dialdehyde starch (DAS) is a polymeric aldehyde obtained by reacting native starch withperiodic acid 4) . The cross-linking effect of DAS on various proteins such as soy protein
isolate 3 ) , collagen 5 ) , casein 6 , 7 ) , wheat gluten 8 ) , and corn zein 9 ) has been documented. In
contrast to low molecular weight aldehydes, DAS has low toxicity to rats by oral, dermal, andrespiratory routes of introduction 10) . On the other hand, ionic surfactants such as sodium
dodecyl sulfate (SDS) are powerful denaturing and dissociating agents for proteins 11,12 ) .
Strength reduction and even re-solubilization of protein gels in SDS buffers have beenreported 13-15). Therefore, an incorporation of DAS and/or SDS into protein based film forming
solutions would affect the structure and properties of protein films.
The objective of this study was to improve selected various properties (tensile strength,
elongation at break, water vapor permeability, film solubility, color, light transmission,transparency, and protease digestibility) of FWSP films using treatments with DAS or SDS in
separate and a combination of DAS with SDS in different ratios.

2. Materials and Methods

2.1 Preparation of film forming solution
FWSP were extracted from the flesh of blue marlin Makaira mazara according to Iwata et al1)
Freeze-dried powders were dissolved in distilled water at the protein content of 3% and pH wasadjusted to 10.5. After glycerol was added as a plasticizer at 50% (w/w) of FWSP, the film
forming solutions were heated at 70°C for 15 min and air bubbles were removed by a Hybrid- 2 7 2 -

J.Pack.Sci. Tech. Vol.12 No.5 (2003)

Mixer (HM-500, Kyence, Tokyo). In addition to the control films prepared in this manner,other films were prepared by adding DAS at 2.5, 5, 7.5, or 10%, SDS at 10, 20, 30, or40% and
DAS/SDS at 2.5/40, 5/40, 7.5/40, or 10/40% (w/w) of FWSP prior to pH adjustment. All
reagents used in this study were purchased from Wako Pure Chemical Ind., Tokyo.

2.2 Preparation of FWSP films
The prepared film forming solutions were cast by pipetting 4 ml onto a rimmed silicone plate(50×50 mm) placed on a level surface and dried in a ventilated oven (Environmental Chamber
Model HllOK-30DM, Seiwa Riko Co., Tokyo) at 25 C and 50% relative humidity (RH).
After the water was evaporated, resulting films were manually peeled off. All film samples
were conditioned for 3 days in the Environmental Chamber maintained at 25°C and 50% RH.
Synthetic polymer films for household wrap such as low density polyethylene (LDPE,), oriented
polypropylene (OPP), polyethylene terephthalate (PET), and polyvinylidene chloride werepurchase from Tokyu Hands Department Store (Tokyo) in June, 2002 and their mechanicalproperties, water vapor permeability, and light transmission were also determined forcomparison.

2.3 Film thickness
Film thickness was measured using a micrometer (Dial Pipe Gauge, Peacock Co., Tokyo) tonearest 0.005 mm at 8 random locations around the film. Precision of thickness measurement
w a s± 5 % .

2.4 Mechanical property
Tensile strength (TS) and percentage elongation at break (EAB) were determined using a
Texture Analyzer (TA.XT2 Stable Micro System, UK) operated according to the ASTM
standard method D 882-22 (ASTM, 1989). Two rectangular strips (width 20 mm; length 45mm) were cut from each FWSP film to measure the mechanical properties. Initial grip
separation and mechanical crosshead speed were set at 30 mm and 0.5mm・s-1, respectively. TS(MPa) was calculated by dividing the maximum load (N) necessary to pull the sample film apartby the cross-sectional area (m2). Average thickness of the film strip was used to estimate thecross-sectional area of the sample. Percentage EAB was calculated by dividing film elongation
at the moment of rupture by the initial grip length of sample and multiplied by 100%. A totalof 10 samples were tested for each film type.

- 2 7 3 -Properly improvement of Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecvl Sulfatc iSDS) Treatments

2.5 Water vapor permeability (WVP)

WVP was measured using a modified ASTM method reported by Gontard et al 16). FWSP film
was sealed on a glass permeating cup containing silica gel (0%RH) with silicone vacuum grease
and a plastic band to hold the film in place. The cups were placed at 30°C in a desiccator with
distilled water (100% RH). The cups were weighed at 1 h intervals over 12 h periods and WVPof the films was calculated as follows : WVP=w・x・A-1-t-1・ (P2-P1)-1, where w is the weight gain(g), x is film thickness (m), A is the area of exposed film(m2), t is time of gain(s), and (P?-Pi)
is the vapor pressure differential across the film (Pa). This entire procedure was repeated
twice, for a total of 10 tests on each film type.

2.6 Film solubility in water
Film solubility in water which was defined as the percentage of dry weight solubilized after 24 h
immersion in water was determined according to Gontard et al16). The percentage of initial dry
matter of each film was determined by drying at 105°C for 24 h. Film samples weighing 0.13 to0.14 g were immersed in 10 ml of distilled water containing 0.02 % sodium azide. After
immersion for 24 h at 30°C with continuous gentle agitation, undissolved films were removed
and dried at 105°C for 24 h to determine the loss of dry matter. Total protein content wasdetermined using a Bio-Rad DC Protein Assay (Lowry method, Bio-Rad Lab., USA).

2.7 Protease digestibility
Ground film (50 mg) was suspended in 50 ml of enzyme solution (α-chymotrypsin 40 mg/rnl in
40 mM Tris-HCl buffer, pH 7.6). The protease-substrate suspension was incubated at 37°C for
120 min17). Hydrolysis was terminated on a 5 ml aliquot by heating in boiling water for 3 min.
After standing at room temperature for 30 min, the precipitate was removed by centrifugation(2,000×g for 15 min). The amount of protein in the supernatant was determined by a Bio-Rad
DC Protein Assay method.

2.8 Color measurement
Color values of FWSP films were measured using CIE L*, a*, b* color system. Following
spectral scanning, the values of L* (lightness), a* (redness), b* (yellowness) of all films wered e t e r mi n e d b y a S p e c t r u m C o l o r S e n s o r C L R - 7 1 0 0 F ( S h i ma d z u C o . , K y o t o ) . C o l o rmeasurements of each type of film were replicated ten times.

2.9 Light transmission and transparency
The ultraviolet and visible light barrier properties of the films were measured at selected- 2 7 4 -

J . P a c k . Sc i . T e c h . V o l . 1 2 N o . 5 ( 2 0 0 3 )wavelengths from 200 to 800 nm using a UV-Visible Recording Spectrophotometer UV-160(Shimadzu Co., Kyoto). The transparency of film was measured by a modified method of
ASTM method D 1746-92 (ASTM, 1987)18). The transparency of the films was calculated asfollows : transparencyA600/x or (-log T600)/x, where A600 is absorbance at 600 nm, where T600
is transmittance at 600 nm and x is film thickness (mm).

2.10 Electrophoresis
Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) was performed
according to the method of Laemmli19). A 4.5% stacking gel and a 10% separating gel wereused. Prior to SDS-PAGE, the samples were heated at 100°C for 3 min in the presence of two
different dissolving solutions ; 8 M urea, 2% SDS, 20 mM Tris-HCl (pH 8.8.) with or without
2% mercaptoethanol. Electrophoresis was performed at constant current 10 mA for 30 min
and 20 mM for 1.5 h. Gels were stained with 0.05% Coomassie Brilliant Blue R-250 inisopropanol/acetic acid/water (25 : 10: 65%, v/v/v) and were destained in isopropanol/acetic
acid/water (10 : 7: 83%, v/v/v). The standard protein mixture (Sigma Chemical Co., USA)
ranged in molecular mass from 14.2 to 205 kDa.

2.1 1 Statistical analysis
Statistical analysis on a completely randomized experimental design was performed using theGeneral Linear Models procedure in SPSS computer program (SPSS Statistical software,USA). One-way analyses of variance (ANOVA) were carried out and mean comparisons wererun by Duncan's multiple range tests 20)

3. Results and discussion

3.1 Mechanical properties
Table 1 summarizes the mechanical properties of FWSP films treated with DAS and/or SDS
together with some synthetic polymer films for household wrap. TS of FWSP films increased
and EAB decreased significantly when DAS was incorporated in the film solution at 2.5 to 10%(w/w) of FWSP. DAS is a polymeric aldehyde which can cross-link between protein
molecules21). Fig. 1 depicts SDS-PAGE patterns of FWSP films in the absence and presence of
mercaptoethanol. FWSP films treated with 7.5 and 10% DAS could not be dissolved in thefilm dissolving solution, suggesting a strong structural film formation induced by DAS at higher
concentration. It is obvious from Fig. 1 that the cross-linking effect of DAS resulted inincreased film TS and decreased EAB. However, the effect of DAS on the mechanical- 2 7 5 -Property Improvement of Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecyl Sulfate (SDS) Treatments

Fig. 1. SDS-PAGE patterns of fish water soluble protein films treated with dialdehyde starch DAS).
A: containing mercaptoethanol, B: not containing mercaptoethanol
Ml : high molecular weight standard, M2: low molecular weight standard
a-c: DAS films(0, 2.5, 5 %), d-f: DAS films (0, 2.5, 5 %)Table 1. Tensile strength (TS), elongation at break (EAB), water vapor permeability (WVP), filmsolubility (FS), and protease digestibility(PD) of fish water soluble protein (FWSP) films treated with different
levels of dialdehyde starch (DAS), sodium dodecyl sulfate (SDS), and DAS combined with SDS, together withsynthetic polymer films for household wrap.
TS
Control (FWSP)DAS(%) 2.5
5.0
7.5
10
SDS(%)

10
20
30
40
DAS/SDS (%) 2.5/40
5/40
7.5/401 0/40(MPa)
4.8 1±0.93
4.97±0.45
5.20±0.80
6.39±1.74
6.77±1.02
3.16±1.13
3.13±0.40
3.45±0.77
3.51±1.08
4.08±1.16
5.44± 1.06
5.18±0.93
4.29±1.12

Synthetic polymer films
for household wrap
Low density polyethylene 1 6.5±0.9
Oriented polypropylene
50.7±8.2
Polyethylene terephthalate 81.6±3.2
Polyvinylidene chloride
65.6±10.8

EAB
-10

WVP
g・m-1・s-1・Pa-1)

(×10
(%)
81±27
1.73±0.1283±36
1.67±00871±29
l.5l±0.2441±16
1.39±0.0925±8
1.25±0.1479±27
1.86±0.26
1 03±261.67±0.49
123±291.32±0.28
1 59±261.12±0.19124±260.92±0. 1 8
1 47±201.02±0.28
126±111.08±0.1482±191.024=0.24

>1000
73±27
1 9±6
1 8±5

0.020±0.006
0.03 8±0.035
0. 198±0.015
0. 002±0.000- 2 7 6 -

FS

PD

(%)
1 9.2±0.2
21.1±1.222.8±0.7
19.7±1.0
20.5±0.3
92.4±8.4
95.4±1.8
99.0±2.0
1 00±0.0
58.0±8.7
54. 1±3.4
61.7±12.0
40.8±9.5

(%)
66.4
61.9
59.8
56.8
52.6
52.6
52.1
48.5
46.0
58.8
64.0
55.7
51.6

0
0
0
0

J.Pack.Sci. Tech. Vol. 12 No.5 (2003)

properties of protein films seems to be dependent on proteins used and the moisture content offilms3,21,22).
On the other hand, the addition of SDS in the film solution reduced TS of FWSP films, but its
reduction was independent on SDS concentration up to 40% (Table 1). It is well-known thatcovalent bonds including disulfide bonds as well as hydrogen bonds and hydrophobic
interactions are attributed to the formation of protein films 23,24) . Since SDS, powerful ionicsurfactants, can denature and dissociate proteins, the TS reduction of FWSP films by SDS is
expected. It is agreeable with other reports on whey protein isolate film25) and soy protein
isolate film26). This was also confirmed by the SDS-PAGE patterns of the films treated with
SDS, where there were no polymerized protein bands observed (data not shown). In contrast
to TS, EAB of FWSP films increased significantly by the addition of SDS and its increment was
proportional to SDS concentration up to 40% (Table 1). This could be due to the unfolding of
the protein molecules induced by SDS as pointed out by Rhim et al 2 6 ) . SDS disruptshydrophobic interactions in proteins, resulting in the linear orientation of protein molecules in
FWSP films and the reduction of film EAB.
From the above results, it is clear that DAS and SDS work in different ways toward themechanical properties of FWSP films. Therefore, we tried to examine the effect of DAS andSDS combination on the mechanical properties of the film. In this experiment, theconcentration of SDS was fixed to 40% and DAS concentration was altered from 2.5% to 10%.
The results are also given in Table 1. The maximum TS and EAB were obtained by the
combination of 5/40% and the increased ratio of DAS above 5% brought about the gradualreduction of the mechanical properties.
Any FWSP films prepared had smaller TS than synthetic polymer films for household wrap
examined in this study. PET film had the strongest strength among the tested synthetic films,
followed by polyvinylidene chloride, OPP, and LDPE films. On the other hand, most of FWSP
films, especially those treated with SDS, were more flexible than synthetic polymer films forhousehold wrap except LDPE.

3.2 Water vapor permeability
WVP of FWSP films decreased with increasing amount of DAS (Table 1). This is agreeablewith the result reported by Rhim et al. on soy protein isolate 3) Although the bulky structureof DAS molecule should increase the diffusion of water vapor through the films, WVP of
FWSP films was reduced by the increased incorporation of DAS. The reason for thisphenomenon cannot be explained at this moment. SDS incorporation in the film solutions also
decreased WVP (Table 1). This is likely due to the hydrophobic portions of SDS molecules,- 2 7 7 -

Property Improvement of Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecyl Sulfate (SDS) Treatments

which reduce the rate of sorp tion and diffusio n o f water vapo r mo lecu les th roug h the fil mstructures as pointed out by Rh im et al 2 6 ) . Generally, protein films have poor water vapor
barrier property, limiting their use as packaging materials. The reduction of WVP by SDS isd e s i r a b l e f o r t h e f u nc t i o n a l i t y o f F W S P f i l ms . T h e c o mb i n a t i o n o f D A S a n d S D S b r o u g h t
about the significant decrease in WVP of FWSP films, but the level of WVP did not vary withthe ratio of DAS incorporated (Table 1 ). Ho wever, th e WVP values o f FWSP films treatedwith DAS and/or SDS were two or three orders of magnitude greater than those of synthetic
p o l y me r f i l ms f o r h o u s e h o l d w r a p e x a mi n e d i n t h i s s t u d y ( T a b l e 1 ) .

3.3 Film solubility and protease digestibility
Film solubility can be viewed as a measure of the water resistance and the integrity of a film 3) .
According to the studies on soy protein isolate3) and egg white27), their film solubilities
decreased with increasing amount of added DAS due to the cross-linking treatments which can
improve moisture resistance of protein films. However, the film solubility of FWSP films was
not affected by the addition of DAS in this study (Table 1). Control FWSP film itself had lower
film solubility than soy protein isolate film3) and egg white film27). On the contrary, theincorporation of SDS in FWSP markedly increased the film solubility and the film with 40%
SDS was completely dissolved in water. The large solubility of the FWSP films with SDS wasprobably attributed to the weaker structure of such films as evidenced by their smaller TS andlarger EAB values compared with control films (Table 1). All of synthetic polymer films usedin this study were not dissolved in the distilled water as shown in Table 1.
Protein digestibility of FWSP films was determined by α-chymotrypsin hydrolysis at 37°C after
2 hours (Table 1). Hydrolysis of the films by α-chymotrypsin increased with time andplateaued out towards the end of the digestion period (data not shown). The addition of DAS
a n d /o r S D S s lo w ed d o wn th e d ig e st ion at t he be ginn ing , but d id no t a pp a re nt l y a ff e c t t h eprotein digestibility of films, implying that neither DAS nor SDS interfered with the protein
digestion of FWSP films by α-chymotrypsin.

3

.

4

C

o

l

o

r

Color value was recorded as L* (lightness, 0=black, 100=white), a* (-a*=greenness, +a* =redness), and b* (-b* =blueness, +b* =yellowness). Addition of DAS in FWPS film
solutions up to 7.5% caused yellowness as indicated by a drastic increase in +b* values (Table2). Furthermore, the films containing DAS had lower -a* values (increased greenness). Thiswas visually perceived as browning of the films 3) . DAS level of 7.5% of FWSP appears to be asaturation point in the FWSP-DAS reaction. The yellow/brown color associated with protein-- 2 7 8 -

J.Pack. Sci. Tech. Vol. 12 No.5 (2003)

aldehyde interaction is mostly due to the various intermediate or final products of the Maillard
reaction and this result is agreeable with other reports on several protein films 3,21,27-29) . On theother hand, SDS addition to FWSP film solutions did not affect L* and a* values of the films,
but their + b* value (increased yellowness) increased with increasing amount of SDS used
( T a b l e 2 ) . T h i s i n c r e a s e d y e l l o w n e s s o f S D S - c o n t a i n i n g F W S P f i l ms w a s n o t r e ma r k a b l e
e n o u g h t o c o n s i d e r v i s u a l l y d e t r i m e n t a l . T h e F W S P f i l m s t r e a t e d w i t h a c o mb i n a t i o n o f
DAS/SDS tended to have yellow color, because the effect of DAS was more significant thant h a to f

S D S .

Table 2. L*, a*, b* color values of cast films from fish water soluble proteins (FWSP) treated withdifferent levels of dialdehyde starch (DAS), sodium dodecyl sulfate (SDS), and DAS combined with
SDS.

L*

a*

b*

Control (FWSP)

95.6O±0.84- 1.42±0.22

3.46±0.68

DAS(%)

2.5

95.12±0.25-2.50±0. 14

7.07±0.43

595.25±0.25-3.28±0.20

9.64±0.67

7.5

94.23±0.28-5.23±0.38

18.33±1.79

1094.24±0.36-5.06±0.54

1 8.05±2.43

1095.42±1.12-2. 1 6±0.34

5.72±1.12

20

95.69±0.49-2.48±0.39

6.93± L3330

95.68±0.25-2.66±0.22

7.40±0.78

40

98.34±0.50-2.70±0.47

7.44±1.79

DAS/SDS(%) 2.5/40

95.29±0.59-3.70±0.43

13.20±2.27

5/40

95. 12±0.68-3.60±0.36

14.55±2.30

7.5/4095.32±0.31-4.00±0.23

15.02±I.41

1 0/4094.55±1.75-4.35±0.45

17. 19±3.30

SDS(%)

3.5 Light transmission and transparency
Table 3 lists the light transmission at selected wavelengths for the FWSP films as influenced by
DAS and/or SDS concentrations in comparison to some synthetic polymer films. The control
FWSP film had excellent barrier properties to UV light in the 200-280 nm region regardless ofcomposition, suggesting that FWSP films can prevent the lipid oxidation induced by UV light in- 2 7 9 -

Property Improvement ol Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecyl Sultate (SDS) Treatments

Table 3. Light transmission (%) and transparency (absorbance/mm) of cast films from fish water soluble
protein (FWSP) treated with different levels of dialdehyde starch (DAS), sodium dodecyl sulfate (SDS),
and DAS combined with SDS, together with synthetic polymer films for household wrap.

Control (FWSP)DAS (%) 2.5
5.0
7.5
10
SDS (%) 10
20
30
40
DAS/SDS (%) 2.5/40
5/40
7.5/401 0/40Synthetic polymer films forhousehold wrap
Low density polyethylene
Oriented polypropylene
Po lyethylene terephthalate
Polyvinyl idene chloride

200

280

350

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3

55.4
49.7
40.2
16.7
15.1
65.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3

Wavelength (nm)
400 500 600 800 Transparency
74.5 79.9 81.7 83.5
2.7
71.7 80.1 82.3 83.3
2.3
67.4 81.2 84.0 85.5
1.9
49.8 76. 1 82.2 84.5
2.4
49.0 75.7 82.0 84.0
2.7
72.6 77.9 79.5 80.6
2.6
26.1 29.5 39.0 51.0
11.1
16.3 29.0 37.6 51.5
17.0
25.8 34.9 42.1 51.5
13.0
18.0 34.8 46.5 61.9
10.4
18.4 34.9 46.5 61.6
9.8
18.7 43.0 55.8 68.9
5.8
20.8 39.5 50.5 63.2
7.2

13.1
4.6
0.3
0.3

67.5
81.0
0.3
79.1

79.9
86.2
68.3
83.8

83.4
87.9
73.6
86.6

85.6
88.8
82.1
87.5

86.9
89.1
83.5
90.0

83.6
89.6
84.9
84.9

3.1
1.7
1.5
4.6

the food systems. This result is in the agreement with other studies30). It is interesting to notethat the SDS-containing films blocked most light in the UV-visible range form 200 to 800 nm.
On the other hand, synthetic polymer films for household wrap did not prevent the passage of
UV light above 280 nm except PET film.
The control FWSP film showed a transparency of 2.7 (Table 3), indicating that the film is fairly
transparent. The transparency of FWSP films was not affected by the addition of DAS,
whereas the addition of SDS made the FWSP film semitransparent. The transparency of FWSP
film and DAS-containing films was fairly close to that of synthetic films for household wrap
examined in this study (Table 3). Those data obtained in this study seem to indicate that the
FWSP films treated with DAS/or SDS are clear enough to be used as see-through packaging or
coating materials 3 1 ) .

4. Conclusion
In general, increasing DAS concentration enhanced TS of FWSP films, while increasing SDS
concentration improved EAB. Optimum ratios of DAS/SDS were 5/40 or 7.5/40% which
increased EAB by 82 or 56% with decreasing WVP by 41 or 26%, respectively. Thus,
biodegradable FWSP films with various strength and flexibility were successfully prepared by- 2 8 0 -

J.Pack.Sci. Tech. Vol.12 No.5 (2003)

combining DAS with SDS. Continuing interest in increasing food quality, reducing use oflimited resources, and reducing the environmental impact of synthetic polymers will likely
result in increased use of edible/biodegradable films in the future. To achieve this potential,
advances in information, properties, and economics of edible/biodegradable protein films arenecessary.

5. Acknowledgment
This study was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of
Education, Culture, Sports, Science and Technology of Japan (No. 13556032).

6. References
1) K. Iwata. S. Ishizaki, A. Handa and M. Tanaka, Fisheries Sci., 66, 372 (2000).
2) A. F. S. A. Habeeb and R. Hiramoto, Arch. Biochem. Biophys., 126, 16 (1968).
3) J. W. Rhim, A. Gennadios, C. L. Weller, C. Cezeirat and M. A. Hanna. Ind. Crops &Products, 8, 195 (1998).
4) V. F. Pfeifer, V. E. Sohns, H. F. Conway, E. B. Lancaster, S. Dabic and E. L. Griffin Jr.,
Ind. Eng. Chem., 52, 201 (1960).
5) Y. Nayudamma, K. T. Joseph and S. M. Bose, J. Am. Leather Chem. Assoc, 56, 548(1961).
6) F. P. Weakley, M. L, Ashby and C. L. Mehtretter, J. Food Prod., 13, 51 (1963).
7) A. J. Ernst, M. E. Carr, F. P. Weakley, B. T. Hofreiter and C. L. Mehtretter,TAPPI, 45,646(1962).
8) A. K. Chatterji andL. K. Arnold, J. Polym. Sci.A, 3, 3857 (1965).
9) K. E. Spencer, J. L. James and A. L. Ponetto III, J. Environ. Polymer Degrad., 3, 69(1995).
10) R. H. Wilson, Proc. Soc. Exp. Biol. Med., 102, 735 (1959).
11) A. Graveland, P. Bongers and P. Bosveld, J. Sci. Food Agric, 30, 71 (1979).
12) J. C. Cheftel, J. L. Cug and D. Lorent, "Food Chemistry" (Ed. By O. R. Fennema),Marcel Dekker, p. 245 (1985).
13) N. Kitabatake and E. Doi, Food Rev. Int., 9, 445 (1993).
14) D. J. McClements, F. J. Monahan and J. E. Kinsella, J. Texture Studies, 24, 411 (1993).
15) A. Kiosseoglou, G. Doxastakis, S. Alevisopoulos and S. Kasapis, J. Food Sci. Technol.,
3 4 , 2 53 (19 99 ) .
16) N. Gontard, S. Guilbert and J. L. Cuq, J. Food Sci., 57, 190 (1992).

281 -Property Improvement of Fish Water Soluble Protein Films by Dialdehyde Starch (DAS) and/or Sodium Dodecyl Sulfate (SDS) Treatments17) M. Yildirim and N. S. Hettiarachchy, J. Food Sci., 63, 248 (1998).
18) J. H. Han and J. D. Floros, J. Plastic Film & Sheet, 13, 287 (1997).
19) U. K. Laemmli, Nature, 227, 680 (1970).
20) R. D. D. Stell and J. H. Torrie, "Principles and procedure of statistic : A biometricalapproach", McGraw-Hill, p.862 (1980).
21) J. W. Rhim, A. Gennadios, A. Handa, C. L. Weller and M. A. Hanna, J. Agric. Food
Chem., 48, 4937 (2000).
22) C. A. Hall, S. L. Cuppett and P. Dussault, J. Agric. Food Chem., 46, 1303 (1998).
23) Y. M. Stuchell and J. M. Krochta, J. Food Sci., 59, 1332 (1994).
24) W. S. Choi and J. H. Han, J. Food Sci., 66, 319 (2001).
25) P. Fairley, F. J. Monahan, J. B. German and J. M. Krochta, J. Agric. Food Chem., 44,438(1996).
26) J. W. Rhim, A. Gennadios, C. L. Weller andM. A. Hanna, Ind. Crops &Prod., 15, 199(2002).
27) A. Gennadios, A. Handa, G. W. Froning, C. L. Weller and M. A. Hanna, J. Agric. Food
Chem., 46, 1297 (1998).
28) Y. Nayudamma, K. T. Joseph and S. M. Bose, Am. Leather Chem. Assoc. J., 56, 548(1961).
29) F. B. Weakley, C. L. Mehltretter and C. E. Rist, TAPPI, 44, 456 (1961).
30) M. A. Fang, I. J. Britt, S. Yada and D. G. Dalgleish, J. Food Sci., 67, 188 (2002).
31) W. S. Choi and J. H. Han, J. Food Sci., 67, 1399 (2002).
(原稿受付2003年7月9日)(審査受付2003年8月12日)-282~