Some properties of alginate gels derived from algal sodium
alginate
H. Kakita & H. Kamishima
Originally published in the Journal of Applied Phycology, Vol 20, No 5, 93–99.
DOI: 10.1007/s10811-008-9317-5 # Springer Science + Business Media B.V. 2008
Abstract Alginic acid in soluble sodium alginate turns to
insoluble gel after contact with divalent metal ions, such as
calcium ions. The sodium alginate character has an effect
on the alginate gel properties. In order to prepare a suitable
calcium alginate gel for use in seawater, the effects of
sodium alginate viscosity and M/G ratio (the ratio of D-
mannuronate to L-guluronate) on the gel strength were
investigated. The wet tensile strengths of gel fibers derived
from high viscosity sodium alginate were higher than those
from low viscosity sodium alginate. The tensile strength
increased with diminishing sodium alginate M/G ratio.
Among the gel fibers tested, the gel fiber obtained from a
sodium alginate I-5G (1% aqueous solution viscosity =
520 mPa·s, M/G ratio=0.6) had the highest wet tensile
strength. After 13 days treatment in seawater, the wet
tensile strength of the gel fiber retained 36% of the original
untreated gel strength. For sodium alginates with similar
viscosities, the seawater tolerance of low M/G ratio alginate
was greater than that of the high M/G ratio one. This study
enables us to determine a suitable calcium alginate gel for
use in seawater.
Keywords Alginic acid . Brown algae . Gel property .
Polysaccharide . Seawater . Seaweed
H. Kakita (*) : H. Kamishima
AIST Shikoku, National Institute of Advanced
Industrial Science and Technology,
Hayashi,
Takamatsu, Kagawa 761-0395, Japan
e-mail: h-kakita@aist.go.jp
Borowitzka et al. (eds.), Nineteenth International Seaweed Symposium. DOI: 10.1007/978-1-4020-9619-8_13
Introduction
Seaweed can produce several polysaccharides (e.g., alginic
acid, agar, and carrageenan) which differ from those of
terrestrial plant origin. Most alginic acid is commercially
prepared from brown algae, such as Laminariales and
Fucales species, and used as a food viscosity stabilizer,
textile printing glue, dental impression agent and sizing
agents (Gacesa 1988). Alginic acid, an acidic polysaccha-
ride, is a linear copolymer of D-mannuronate (M) and L-
guluronate (G) and is composed of homo-polymer blocks
of M and G, and a hetero-polymer block (Haug et al.
1967a). The main characteristics of alginic acid are as
follows: (1) high viscosity solution and spin tolerant; (2)
ability to form gels in the presence of certain divalent (or
multivalent) cations, particularly calcium ions; (3) adhesive
and biocompatible properties; and (4) ability to entrap other
materials in the gel. These characteristics may help to
develop new industrial materials.
Because the ratio of D-mannuronate to L-guluronate (M/
G ratio) in the sodium alginate molecule affects the
properties of calcium alginate gel (Haug et al. 1967b), the
selection of suitable sodium alginates as raw materials fit
for each purpose is important. For example, alginates rich
in L-guluronate form strong but brittle gels, whereas those
rich in D-mannuronate are weaker but more flexible
(Penman and Sanderson 1972; Rees 1972).
We have already reported that a calcium alginate gel
derived from sodium alginate I-7 (1% aqueous solution
viscosity = 784 mPa·s, M/G ratio=1.3) was useful as a
carrier of microorganisms in seawater (Li et al. 1994, 1995,
1996). For the efficient degradation of oil spilled on the sea
93
94
surface, the alginate carrier was prepared incorporating both
a marine oil-degrading yeast, Candida sp., and nutrients. In
a biodegradation test in a flask with n-tetradecane as an oil
component, this model system degraded up to 61% of the
initial oil within 14 days at 20°C. But during the 14-day
biodegradation test, the calcium alginate carriers decom-
posed. Improvement of alginate gel strength therefore still
remains necessary.
To select a suitable calcium alginate gel for use in
seawater, the wet tensile strengths of calcium alginate gel
fibers derived from various sodium alginates were investi-
gated with variations in the sodium alginate M/G ratio (0.4–
1.3) and viscosity at 1% aqueous solution (16–994 mPa·s).
We also evaluated the seawater tolerance of the gel fibers
derived from various sodium alginates. In this paper, we
describe a suitable calcium alginate gel fiber for use in
seawater.
Materials and methods
The six sodium alginate samples [I-S (1% aqueous
solution viscosity = 994 mPa·s, M/G ratio=1.3), I-7
(784 mPa·s, M/G ratio=1.3), I-5 (583 mPa·s, M/G
ratio = 1.3), I-3 (354 mPa·s, M/G ratio = 1.3), I-1
(133 mPa·s, M/G ratio=1.3), and SI-L (16 mPa·s, M/G
ratio=1.3)] were purchased from Kimica (Tokyo, Japan).
The two sodium alginate samples [I-5M (565 mPa·s, M/G
ratio=1.3) and I-5G (520 mPa·s, M/G ratio=0.6)] were
kindly provided by Dr Hisashi Yamaguchi of Kimica.
The four sodium alginate samples [350-M (370 mPa·s,
M/G ratio=1.0), 150-M (171 mPa·s, M/G ratio=0.9), 350-
G (350 mPa·s, M/G ratio=0.5), and 150-G (135 mPa·s,
M/G ratio = 0.4)] were purchased from Kibun Food
Chemifa (Tokyo, Japan). Other reagents were of analyt-
ical grade.
Sodium alginate viscosity measurements
Viscosity measurements were made at 20°C on the sodium
alginate solutions by means of a rotating cylinder viscom-
eter, Model LVDV-I (Brookfield, Mass., U.S.A.). A range
of alginate concentrations up to 2.5% w/v was used.
Sodium chloride was used in all cases to adjust the ionic
strength (Smidsrød et al. 1973). The final concentration of
sodium chloride was adjusted to 0.1 M NaCl. In order to
evaluate [η] values, (ln η)/c values against the alginate
concentration (c) were plotted, and [η] values were
determined from the intercept (Smidsrød 1970; Johnson et
al. 1997). Molecular weights (Mw) were calculated using
the formula: [η]=2.0×10−5MW, where [η] is the intrinsic
viscosity and MW is the molecular weight (Smidsrød and
Haug 1968).
Borowitzka et al. (eds.)
Preparation of calcium alginate gel fibers
Five percent sodium alginate aqueous solutions (dope) were
prepared by mixing sodium alginate powder in distilled
water, followed by degassing with a centrifuge or vacuum
pump. The dopes were extruded from a 0.84-mm (or 1.14-
mm) diameter nozzle of an air-dispenser Model
ML5000XII (Musashi Engineering, Tokyo, Japan) into a
0.5 M calcium chloride solution (as a coagulation reagent)
at 30∼200 kPa at room temperature. The extruded gel fibers
were stretched up to 1.4-fold length of original gel length
and then washed with water.
Gel fiber strength measurements
The wet tensile strength of the gel fiber was measured with
a tensile tester Model Autograph 100A (Shimazdu, Kyoto,
Japan), according to Japan Industrial Standard L1069.
Measurement conditions were as follows: (1) fiber diame-
ter, 20 mm; (2) speed, 20 mm/min; (3) temperature, 20±
2°C. The wet tensile strength (g d−1) was defined as the
minimum load (g) which caused a gel fiber to break,
applied by a tensile tester / denier (d). One denier (d) is
defined as dry weight of a fiber 9,000 m in length.
Effects of sodium alginate viscosity and M/G ratio on gel
fiber strength
First, in the viscosity experiment, the wet tensile strengths
of calcium alginate gel fibers were compared, using six
sodium alginates (viscosity; 16, 133, 354, 583, 784, and
994 mPa·s, M/G ratio=1.3) as raw materials. Then the wet
tensile strength of gel fiber prepared from a high M/G ratio
alginate (viscosity; 565 mPa·s, M/G ratio = 1.3) was
compared with that with a low M/G ratio (viscosity;
520 mPa·s, M/G ratio = 0.6). Finally, the wet tensile
strengths of gel fiber derived from five sodium alginates
[variations in viscosity (135, 171, 350, 370, and 520 mPa·s)
and M/G ratio (0.4, 0.5, 0.6, 0.9, and 1.0)] were measured.
For each experiment, six replicates of each gel fiber were
measured.
Seawater tolerance of alginate gel fiber
The seawater tolerance of gel fiber prepared from a high M/G
ratio alginate (I-5M; viscosity; 565 mPa·s, M/G ratio=1.3)
was compared with that with a low M/G ratio (I-5G; viscosity;
520 mPa·s, M/G ratio=0.6). Five grams of gel fibers were
immersed four times for 1 h each in 40 mL of soaking solution
(either distilled water or seawater). The soaking solution was
renewed each time. Finally the gel fibers were stored in the
soaking solution. After soaking for 5 days, the wet tensile
Nineteenth International Seaweed Symposium
strength of each gel fiber (three replicates per fiber) derived
from I-5M and I-5G alginates was measured.
In another experiment, the time-course (pre-soaking, and
at 2 days, and 13 days) of the decrease in wet tensile strength
of alginate gel fiber treated with seawater was measured. A
low M/G ratio alginate I-5G (viscosity; 520 mPa·s, M/G
ratio=0.6) was used as the raw material. In this experiment,
five replicates of each gel fiber were measured.
To clarify the effect of additional calcium ions on the wet
tensile strength of gel fiber soaked in seawater, calcium
alginate gel fibers derived from I-5G (1% aqueous solution
viscosity; 520 mPa·s, M/G ratio; 0.6) and I-S (994 mPa·s,
M/G ratio; 1.3) were treated with various calcium concen-
trations in seawater for 5 days. After soaking, the wet tensile
strengths of gel fibers (four replicates each) were measured.
Statistics
The data concerning gel fiber strength were analyzed by
one-way ANOVA followed by Tukey’s multiple compari-
son test (Winer et al. 1991) or t test.
Results
The viscosity of sodium alginate at a constant M/G ratio
(M/G ratio=1.3) had a significant effect on the wet tensile
strength of calcium alginate gel fiber (n=6, F=79.249, p<
0.001). The optimum sodium alginate viscosity (1%
aqueous solution) for the wet tensile strength of calcium
alginate gel fiber was 354–994 mPa·s (I-3, I-5, I-7, and I-S).
The wet tensile strength ranged from 0.166 g d−1 at
16 mPa·s (SI-L) to 0.494 g d−1 at 994 mPa·s (I-S) (Fig. 1).
0.6
c
c
-1
c
c
0.4 b
a
0.2
SI-L I-1 I-3 I-5 I-7 I-S
0
0 100 200 300 400 500 600 700 800 900 1000
Viscosity (mPa s) of 1% sodium alginate
Fig. 1 Effect of sodium alginate viscosity on wet gel fiber strength.
The wet tensile strengths of calcium alginate gel fibers prepared from
alginates with different viscosity but constant M/G ratio (M/G ratio=
1.3) [SI-L (1% aqueous solution viscosity; 16 mPa·s), I-1(133 mPa·s),
I-3 (354 mPa·s), I-5 (583 mPa·s), I-7 (784 mPa·s), I-S (994 mPa·s)].
Extrusion nozzle diameter: 0.84 mm. Wet tensile strengths of alginate
gel fibers were measured according to Japan Industrial Standard
L1069. Each data point is the mean of six replicates (mean ± SE).
Bars marked with the same letter are not significantly different
according to Tukey’s multiple comparison test (p=0.05)
95
0.8
-1
*
0.6
0.4
0.2
0
I-5M I-5G
Sodium alginate
Fig. 2 Effect of M/G ratio on gel fiber strength. The wet tensile
strengths of calcium alginate gel fibers derived from alginates with
different M/G ratios but constant viscosity [I-5M (1% aqueous
solution viscosity; 565 mPa·s, M/G ratio; 1.3) and I-5G (520 mPa·s,
M/G ratio; 0.6) ]. Extrusion nozzle diameter: 0.84 mm. Wet tensile
strengths of alginate gel fibers were measured according to Japan
Industrial Standard L1069. Each data point is the mean of six
replicates (means ± SE). *The wet tensile strength of gel fiber derived
from low M/G ratio alginate (I-5G) was statistically different to that of
gel fiber from high M/G ratio alginate (I-5M)
At similar viscosities (520 and 565 mPa·s), the M/G ratio
in the sodium alginate molecule also had a significant effect
on the wet tensile strength of gel fibers (n=6, t=4.404, p<
0.005). Gel fiber strength derived from M/G ratio 0.6 (I-5G;
1% aqueous solution viscosity = 520 mPa·s, M/G ratio=
0.6) was stronger than that derived from M/G ratio 1.3 (I-
5M; 1% aqueous solution viscosity = 565 mPa·s, M/G ratio=
1.3) (Fig. 2).
The wet tensile strength of each alginate gel fiber
derived from five sodium alginates (150-G, 350-G, 150-
M, 350-M, and I-5G) was measured (Fig. 3). Variations in
sodium alginate had a significant effect on the wet tensile
strength of calcium alginate gel fibers (n=6, F=14.671,
p<0.001). Wet tensile strengths varied from 0.396 g d−1
(150-M; 1% aqueous solution viscosity = 171 mPa·s, M/G
ratio=0.9) to 0.647 g d−1 (I-5G; 520 mPa·s, M/G ratio=
0.6). The strength of the alginate gel fibers, in order of
derivation, were I-5G = 350-G (350 mPa·s, M/G ratio=0.5) >
150-G (135 mPa·s, M/G ratio=0.4) = 350-M (370 mPa·s, M/G
ratio=1.0) > 150-M.
These results suggested that the wet tensile strengths of
gel fibers derived from high viscosity sodium alginates
were higher than those from low viscosity ones. The results
also suggested that the tensile strength increased with
decreasing sodium alginate M/G ratio. From these results,
we selected I-5G sodium alginate as a raw material for
alginate gel fibers in the subsequent experiment in this
paper.
Soaking alginate gel fibers in seawater for 5 days had a
significant effect on their wet tensile strengths [I-5M (n=3,
t=25.829, p<0.001) and I-5G (n=3, t=11.193, p<0.001)]
(Fig. 4). Although the wet tensile strength of the gel fiber
derived from high M/G ratio alginate (I-5M) decreased with
96
Wet tensile strength (g d-1) c
0.8
b I-5
0.6
350
-G
0.4
150
-G
0.2
0 100
0.4 0.5 0.6
M/G ratio
Fig. 3 Wet tensile strengths of alginate gel fibers derived from five
sodium alginates, 150-G (1% aqueous solution viscosity; 135 mPa·s,
M/G ratio; 0.4), 350-G (350 mPa·s, 0.5), 150-M (171 mPa·s, 0.9),
350-M (370 mPa·s, 1.0), and I-5G (520 mPa·s, 0.6). Extrusion nozzle
diameter: 1.14 mm. Wet tensile strengths of alginate gel fibers were
measured according to Japan Industrial Standard L1069. Each data
point is the mean of six replicates (mean). Bars marked with the same
letter are not significantly different according to Tukey’s multiple
comparison test (p=0.05)
5 days seawater treatment to 19% of the original untreated
gel strength, the wet tensile strength of the gel fiber derived
from low M/G ratio alginate (I-5G) retained 44% of the
original untreated gel strength. For sodium alginates with
similar viscosities, the seawater tolerance of low M/G ratio
alginate was greater than that of the high M/G ratio one.
Alginate gel fibers subjected to seawater treatment for 2
days underwent significant change in their wet tensile
strengths (n=5, F=242.000, p<0.001) (Fig. 5). There was
no statistical difference in gel fiber strength between 2 days
and 13 days of seawater soaking (n=5, t=1.433, p>0.05).
After 2 days in seawater, the wet tensile strength of the gel
fiber derived from low M/G ratio alginate (I-5G) decreased
to 41% of the original untreated gel strength (Fig. 5). But
0.5
-1
0.4
* (n=4, t=2.198, p>0.05). There was also no statistical
0.3
0.2
0.1
0 difference in wet tensile strength between gel fibers
DW
I-5M
Fig. 4 Effect of M/G ratio on seawater tolerance of gel fiber. The wet
tensile strengths of calcium alginate gel fibers derived from alginates
with different M/G ratios but constant viscosity [I-5 M (1% aqueous
solution viscosity; 565 mPa·s, M/G ratio; 1.3) and I-5G (520 mPa·s,
M/G ratio; 0.6) ]. Extrusion nozzle diameter: 1.14 mm. Gel fiber wet
weight: 5 g. Soaking solution volume: 40 ml. Soaking solution
renewal:, 1 h×4 on first day. Storage time: 5 days. Wet tensile
strengths of alginate gel fiber were measured according to Japan
Industrial Standard L1069. Each data point is the mean of three
replicates (mean ± SE). *Significant statistical difference. SW
Seawater, DW distilled water
Borowitzka et al. (eds.)
0.6
-1
c a
b 0.4
G
a 350
b
-M 600 b
0.2
150 500
-M 400
300
200
0
0.7 0.8 0.9 1.0 0 2 13
Seawater immersion time (days)
Fig. 5 The time-course of wet tensile strength of gel fiber immersed
in seawater. The wet tensile strengths of calcium alginate gel fibers
derived from I-5G (1% aqueous solution viscosity; 520 mPa·s, M/G
ratio; 0.6)] with seawater immersion for 0, 2, and 13 days. Extrusion
nozzle diameter: 0.84 mm. Gel fiber wet weight: 5 g. Soaking solution
volume: 40 ml. Soaking solution renewal: 1 h×4 on first day. Wet
tensile strengths of alginate gel fibers were measured according to
Japan Industrial Standard L1069. Each data point is the mean of five
replicates (mean ± SE). Bars marked with the same letter are not
significantly different according to Tukey’s multiple comparison test
(p=0.05)
even after 13 days of seawater soaking, the gel fiber
strength remained at 36% at the original untreated gel
strength.
The concentration of calcium chloride in seawater had a
significant effect on the wet tensile strength of alginate gel
fiber (n=4, F=46.591, p<0.001).
After the gel fibers had been treated for 5 days with
seawater, their wet tensile strengths decreased to 42% (gel
fiber derived from sodium alginate I-5G) and 19% (gel
fiber derived from sodium alginate I-S) of the original
untreated gel strengths. There was no statistical difference
in wet tensile strength between gel fibers (derived from
sodium alginate I-5G) treated with distilled water and those
*
treated with seawater containing 0.03 M calcium chloride
difference in wet tensile strength between gel fibers
(derived from sodium alginate I-S) treated with distilled
water and those treated with seawater containing 0.05 M
calcium chloride (n=4, t=0.773, p>0.05). Tukey’s multiple
comparison test indicated that there was no statistical
SW DW SW
I-5G (derived from sodium alginate I-S) treated with distilled
Sodium alginate water and those treated with seawater containing 0.04 M
calcium chloride (Fig. 6), but the t test result indicated a
significant statistical difference (n=4, t=2.614, p<0.05).
Gel fiber (derived from I-5G) in seawater containing 0.005
M calcium chloride could retain 53% of the original
untreated gel strength. From these results, adding 0.03 M
calcium chloride seems to be enough to maximize the
original gel fiber strength in seawater (for I-5G sodium
alginate). For I-S sodium alginate, adding 0.05 M calcium
chloride was necessary.
Nineteenth International Seaweed Symposium
Wet tensile strength (g d-1)
0.5
c, d
e ,f
0.4
0.3 b, c a
0.2
b binding of calcium ions to alginate with increased concen-
0.1
0
0 10 20 30 40
Calcium concentration (mM) in SW
Fig. 6 Effect of calcium ions on the wet tensile strength of gel fiber
soaked in seawater. Calcium alginate gel fibers derived from I-5G (1%
aqueous solution viscosity; 520 mPa·s, M/G ratio; 0.6) and I-S
(994 mPa·s, M/G ratio; 1.3) were treated in solutions with various
calcium ion concentrations. Gel fiber wet weight: 5 g. Soaking
solution volume: 40 ml. Soaking solution renewal: 1 h×4 on first day.
Storage time;:5 days. Unfilled bar calcium alginate gel fibers derived
from I-5G. Filled bar calcium alginate gel fibers derived from I-S.
After soaking for 5 days, the wet tensile strengths of gel fibers were
measured. Solutions included distilled water, seawater, seawater
containing 0.005 M calcium chloride, seawater containing 0.03 M
calcium chloride, seawater containing 0.04 M calcium chloride, and
seawater containing 0.05 M calcium chloride. The wet tensile
strengths of alginate gel fibers were measured according to Japan
Industrial Standard L1069. Each data point is the mean of four
replicates (mean). Bars marked with the same letter are not
significantly different according to Tukey’s multiple comparison test
(p=0.05). SW Seawater, DW distilled water
Discussion
Under a constant sodium alginate M/G ratio of 1.3, the
extent of sodium alginate viscosity in the range of about
16–994 mPa·s was proportional to the strength of calcium
gel fiber. But in the high viscosity region above 354 mPa·s
(I-3, I-5, I-7, and I-S), sodium alginate viscosity had no
significant effect on the wet tensile strength of sodium
calcium gel fiber (Fig. 1). Molecular weight (Mw) was
calculated using the formula: [η]=2.0×10−5MW. Molecular
weights of sodium alginates tested were as follows: SI-L;
59×103, I-1; 136×103, I-3; 182×103, I-5; 206×103, I-7;
241×103, and I-S; 255×103. The correlation coefficient (r=
0.846) between the sodium alginate viscosities and the
calcium gel fiber strengths was smaller than that (r=0.962)
between the sodium alginate molecular weights and the
fiber strengths. Thus, we infer that sodium alginate
molecular weight was an influential factor in gel fiber
strength. Because sodium alginate monomer (i.e. sodium
mannuronate or guluronate) has a molecular weight of
about 216, SI-L, I-1, I-3, I-5, I-7, and I-S corresponded to
about 270, 630, 840, 950, 1,120, and 1,180 polymerization
degrees, respectively. Therefore, we infer that an alginate
with more than an 800 polymerization grade alginate (under
a constant sodium alginate M/G ratio of 1.3) was needed to
make a high strength gel fiber, although other parameters
such as percentage and configuration of uronic acid blocks
97
(GG-block, MM-block, and GM-block) also influence the
d, e e polymer properties.
d,e
f The influence of alginate molecular weight on the
binding of calcium ions to alginate has been reported. Fang
et al. (2007) revealed three distinct successive steps in the
1000
900
800
tration of calcium ions. The first step is the interaction of
700
600
calcium ions with a single guluronate unit to form
50 DW
500 monocomplexes. The second step is the propagation and
formation of egg-box dimers via pairing of these mono-
complexes. The third step is the lateral association of the
egg-box dimers, generating multimers. They also clarified
that the third step has different association modes depend-
ing on the molecular weight of the alginate.
The influence of the percentage and configuration of
uronic acid blocks (GG-block, MM-block, and GM-block)
on the binding of calcium ions to alginate has also been
reported. Donati et al. (2005) reported that the frictional
force between the calcium–alginate gel network chains
increases with increasing length of the alternating mannur-
onate–guluronate (MG) sequences. Li et al. (2007) reported
that MG block or short G blocks in calcium–alginate
junction zones contribute gel bond stability.
Gel fiber derived from low M/G ratio alginate was
stronger than that from high M/G ratio alginate (Figs. 2, 3).
The C-2 hydroxyl groups in the M (mannuronic acid) block
are transformed from an equatorial conformation to an axial
one, which reduces the flexibility of the polymer chain. But
the whole structure is like cellulose in its conformation. In
contrast, the G (guluronic acid) block has the axial–axial
form of glycosides, which leads to a less flexible buckle-
type ribbon structure. Because its molecular model illus-
trates the existence of large voids between the helices, the
G-block has a higher affinity for cation ligands and causes a
new configuration of the polymer chains which are brought
together by the cations. As the arrangement of the model, in
which cations are arrayed in the voids full of oxygen
molecules between the chains, resembles an egg box
holding eggs, it is named the ‘egg box’ structure (Rees et
al. 1982). Braccini and Pérez (2001) developed a novel
molecular modeling procedure and demonstrated that the
popular “egg-box model” can still be referred to in the case
of polyguluronate in alginates. The small-angel x-ray
scattering profiles of the alginate gels depend on the
alginate concentration, calcium ion concentration, and the
alginate composition (Stokke et al. 2000). The small-angle
x-ray scattering study also revealed that high-G alginates
(proportion of guluronic acid residues fractions; 0.68) give
alginic acid gels of a higher aggregate density compared to
domains composed of loosely packed shorter junction
zones in intermediate-G alginates (proportion of guluronic
acid residues fractions; 0.50) or low-G alginates (proportion
of guluronic acid residues fractions; 0.39) (Draget et al.
98
2003). We presume that low M/G ratio alginate could
produce strong gel fibers because the guluronic acid
polymer (poly-guluronic acid) adopts an egg-box structure,
which is able to capture metal ions (calcium ions) and form
a rigid gel.
The wet tensile strengths of both gel fibers derived from
I-5M and I-5G were decreased by seawater treatment
(Fig. 4). The percentage of the residual strength (44% of
the original untreated gel strength) of the gel fiber derived
from I-5G (G block rich alginate) was higher than that
(19% of the original untreated gel strength) derived from
I-5M (M block rich alginate). The concentrations of ions in
typical seawater (salinity 34.5‰) are: sodium, 455 mM;
magnesium, 52.5 mM; calcium, 10.2 mM; potassium, 9.2
mM; strontium, 0.15 mM (Lyman and Fleming 1940). We
think that after calcium alginate gel fibers were immersed in
seawater, sodium ions, which are the great majority of
chemical components in seawater, replaced the calcium ions
of alginate gel fibers, and gel fiber strength decreased. The
high calcium ion capacity of G block rich alginate (i.e. I-5G)
seems to be the reason for its high tolerance of seawater.
We used a microorganism carrier (a calcium alginate gel)
prepared from an M block rich alginate I-7 alginate (1%
aqueous solution viscosity = 784 mPa·s, M/G ratio=1.3) in
our previous study. For preparation of gel fibers for use in
seawater, G block rich alginates may be a more suitable raw
material than M block rich ones. The change to G block
rich alginate (i.e. I-5G) from M block rich alginate (i.e. I-7)
causes the fiber strength improvement which was an
unsolved problem in our previous study.
The results from the study of the time course of the fiber
strength decrease on storage with seawater suggest that the
fiber strength decrease was due to ion exchange from
calcium ions to sodium ions, because the storage period
(between 2 days and 13 days) in seawater had no significant
effect on the wet tensile strength of alginate gel fiber (n=5,
t=1.433, p>0.05) (Fig. 5).
To maximize the original gel fiber strength in seawater,
an M block rich alginate (I-S) needed additional 0.05 M
calcium ions (Fig. 6). In contrast, a G block rich alginate
(I-5G) needed just 0.03 M calcium ions. We infer that the
result arose from the difference in the calcium ion
capacities of alginates.
Among the gel fibers tested those derived from G block
rich alginate I-5G (1% aqueous solution viscosity = 520
mPa·s, M/G ratio=0.6) seem to be the best alginate gel fiber
for use in seawater, because the gel fibers had the highest
wet tensile strength and seawater tolerance.
This study provided some information on which to base
the selection of a suitable alginate gel fiber for use in
seawater. The development of alginate gel products for use
in seawater would lead to extension of alginate application
fields and contribute to the seaweed industry.
Borowitzka et al. (eds.)
We conclude that this study enabled us to identify a
suitable alginate gel fiber for use in seawater. A high
viscosity sodium alginate with low M/G ratio seems to be
the best raw material for deriving alginate gel fiber for use
in seawater. Additional calcium ions were useful for
preventing gel decomposition in seawater, a 0.03 M
calcium chloride concentration being enough to maximize
the original untreated gel strength in seawater.
Acknowledgements We gratefully acknowledge Dr Hisashi Yamaguchi
of Kimica (Tokyo, Japan) for providing the sodium alginates (I-5G and
I-5M). We are grateful to Mr Hideki Obika of AIST Shikoku for much
helpful advice. We thank Ms. Satoko Tsukuda for her technical assistance.
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