Materials Letters 64 (2010) 2435–2437

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Novel agarose and agar fibers: Fabrication and characterization

Xuxu Bao ⁎, Kenichiro Hayashi, Yuan Li, Akira Teramoto, Koji Abe
Department of Functional Polymer Science, Faculty of Textile Science and Technology, Shinshu University, Tokida 3-15-1, Ueda city 386-3485, Nagano, Japan

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

Article history: In this study, natural agarose and agar polysaccharides were successfully developed to novel fibrous form for
Received 15 May 2010 the first time via wet-spinning. Dimethyl sulfoxide (DMSO)/H2O = 9:1(v/v) mixture was used as an
Accepted 4 August 2010 appropriate solvent which was amenable to the wet-spinning process that produced continuous agarose and
Available online 7 August 2010
agar fibers in ethanol coagulation bath. Results of SEM investigation, swelling ratio and tensile test suggested
that the smooth and homogeneous agarose fibers had considerable water swelling capacity (400–500%) and
Keywords:
tensile strength (30–50 MPa). The agar fiber showed better water swelling capacity than the agarose fiber;
Agarose
Agar
however the existence of agaropectin leads to its flexibility flaws. These results demonstrate that the agarose
Wet-spinning fiber fabricated in this study is a good candidate material for wound-dressing applications.
Fiber technology © 2010 Elsevier B.V. All rights reserved.
Mechanical properties

1. Introduction porosity, high surface-to-volume ratio and most importantly, analogy

Agarose, a natural polysaccharide obtained from red algae, is a
linear polymer based on the 3, 6-anhydro-α-L-galactopyranose unit.
It has been extensively used in food and cosmetic industries for a
hundred years [1]. During the last few decades, various forms of the
agarose-based systems have been developed for the applications in
pharmaceutical industries and medical research, i.e. Z.X. Xue et al. [2]
developed agarose hydrogel and agarose/chitosan porous micro-
spheres to serve as a potential carrier for controlled drug release. Due
to the soft tissue-like mechanical properties, biocompatibility and
osteogenesis ability, agarose/gelatin conjugate made by Sakai et al. [3]
and agarose/hydroxyapatite gel composites made by Watanabe et al.
[4] have been successfully explored as promising candidates for tissue
engineering in recent years.
Agar is a gelatinous substance derived from red algae. It consists of
a mixture of agarose and agaropectin. Agaropectin is a heterogeneous
mixture of smaller molecules which have similar structures with
agarose but slightly branched and sulfated. Due to the similar
chemical and physical properties with agarose, agar has also been
widely studied and applied in the biomedical field because of its good
biocompatibility, biodegradability, nontoxicity, availability and low
cost [5].
Since agarose and agar have good biocompatibility and excellent
moisturizing capacity, they have been widely used as wound-dressing
materials in the form of gel or film [6]. Among various material types,
fibrous materials are more desirable for tissue regeneration applica-
tions (i.e. wound healing) than the other types, because of their high
⁎ Corresponding author. Tel.: + 81 0268 21 5490; fax: + 81 0268 21 5336.
E-mail address: baqiaobaoxu@hotmail.com (X. Bao).
in architecture to natural extracellular matrix [7].
However, to the best of our knowledge, very little effort has been
devoted to fabricate agarose or agar fibers. In this study, novel fibers
made from natural polysaccharides (agarose and agar) used for
wound-dressing were developed. Dimethyl sulfoxide (DMSO)/
H2O = 9:1(v/v) mixture was used as an appropriate solvent for
agarose and agar wet-spinning. Agarose and agar with different
molecular weight were used to explore the process of fabricating
desirable fibers for wound-dressing applications.
2. Experimental
2.1. Fabrication
Agarose (molecule weight 100–200 kDa, denoted as AG1)
was purchased from FUNAKOSHI Co. Ltd. Japan. Agarose (molecule
weight 200–300 kDa, denoted as AG2) and agar (molecule weight
200–300 kDa, denoted as AR1; 500–600 kDa, denoted as AR2) were
provided by INA Food Industry Co. Ltd. Japan. To prepare spinning
dopes, AG1, AG2, AR1 and AR2 were dissolved respectively in 10 ml of
DMSO/H2O = 9:1(v/v) mixture with corresponding concentrations:
120 mg/ml, 100 mg/ml, 70 mg/ml and 40 mg/ml.
Fig. 1 shows the original facility for wet-spinning process. Spinning
dope was pumped into the ethanol bath through stainless steel needle
(18G) at a speed of 4.5 ml/h at room temperature. The distance from
the needle to the collector was fixed at 50 cm. Using an original roller
system (EYELA, Japan), the resulting fibers were collected at the speed
of 50.6 m/h. The fibers wound in the roller were immersed in ethanol
for additional 2 h and then washed by distilled water for overnight
and dried at room temperature.

0167-577X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2010.08.008
2436 X. Bao et al. / Materials Letters 64 (2010) 2435–2437

morphological structure is the difference of volumetric mass transfer

Fig. 1. Original facility for wet-spinning process.
2.2. Characterization
The fibers were cut into pieces with appropriated length and
coated with Pt for 90 s using a sputter coater (HITACHI, Japan). The
morphologies of the fibers were examined by SEM (S-2380N,
HITACHI, Japan).
For swelling capacity test, the fibers with the same weight (Wd)
were preconditioned at room temperature at 55% relative humidity
for 24 h. Preconditioned fibers were placed into 20 ml of deionized
water at room temperature for 2 h; the swollen samples were
weighted (Ws) after removing excess surface water with filter
paper. Swelling ratio of each sample was calculated as follows:
rate between solvent and coagulation bath. The circular shape means
that the volumetric mass transfer rate of coagulant inward the
filament is faster than that of solvent outward the coagulant by very
rapid coagulation. As a result, the pressure inside as-spun filament
was maintained during the coagulation process which makes a
circular and smooth morphology possible [8].
AR2 fiber showed a nonuniform circular cross-section and a rough
surface morphology. It is because high molecular weight agar had low
dissolubility in mixture solvent that probably leads to undissolvable agar
particles. The average fiber diameter counted from 50 means by ImageJ
(NIH, U.S.) was AG1:123±8 μm; AG2:117 ± 12 μm; AR1:86 ± 5 μm;
AR2: 74 ± 9 μm. The average fiber diameter showed a decreased
tendency as the concentration of spinning dopes decreased.
The morphological structures are closely related to mechanical and
physical properties of wet-spun filament. Generally, the filament with
uniform structure shows excellent mechanical properties superior to
nonuniform structure [9].
Since moisture absorption of a wound dressing is an important
factor in its performance [10], swelling ratios of the agarose and agar
fibers were investigated to estimate the hydrophilicity of each kind of
wet-spun fiber.
After immersion for 2 h in water, AG1 and AG2 fibers showed
similar swelling ratio as 400%. Molecular weight differences had no
significant effect on the swelling ratio of agarose fibers. Compared to
agarose fibers, agar fibers showed higher swelling ratio (AR1, 700%;

Swelling ratio ð%Þ = ðWs −Wd Þ = Wd × 100%:

Mechanical properties in terms of the stress and elongation at

break of the fibers were measured according to the ISO2062 (E)
standard test method using a Universal Testing Machine (ORIENTEC
Ltd, Co, Japan). The load cell, the gauge length and the strain rate were
10 N, 50 mm and 10 mm/min, respectively. The fibers with initial
lengths of 80 mm were preconditioned at room temperature at
55% relative humidity for 24 h. During the measurements, both
the ambient temperature and the relative humidity were recorded
(20 ± 2 °C and 55 ± 5%). The stress and the elongation at the breaking
point were recorded. The tensile modulus was obtained from the
slope of the plot.

3. Results and discussion

In this study, a preliminary investigation was performed on the

spinnability of agarose and agar. Unfortunately, they seemed quite
difficult to be processed into fibers due to their insolubility in most
common organic solvents. In most cases, the solvent for agarose was
only confined to hot water which was not recognized as a suitable
solvent for wet-spinning under room temperature [7].
Nevertheless, we firstly found that the DMSO/H2O = 9:1(v/v)
mixed solvent could be used for dissolving both agarose and agar.
Moreover, we worked out the most suitable concentration of spinning
dope as follows: AG1, 120 mg/ml; AG2, 100 mg/ml; AR1, 70 mg/ml;
AR2, 40 g/ml.
Before spinning, the dopes of agarose were transparent while the
agar dopes were transparent with a light brown color, though the
solutions became opaque white in the ethanol coagulation.
SEM images of the cross-section and longitudinal-section of the
agarose and agar fibers were shown in Fig. 2. Very fine, non-porous
and dense filaments with smooth surfaces and circular cross-sections Fig. 2. Scanning electronic microscope images of the cross-section and longitudinal-
were obtained from AG1, AG2 and AR1 spinning dopes. In wet- section of the agarose and agar fibers. a, b, c and d means AG1, AG2, AR1 and AR2; 1:
spinning process, the most important factor that essentially affects the cross-section, 2: longitudinal-section.
 X. Bao et al. / Materials Letters 64 (2010) 2435–2437 2437

Table 1
Mechanical properties of agarose fiber, agar fiber and various representative wound-
dressings.

Material/format Tensile Elastic Elongation

strength modulus at break
[MPa] [MPa] [%]

AG1 fiber (Mw: 100~200 kDa) 32.7 ± 2.7 576 ± 53 47.0 ± 2.0
AG2 fiber (Mw: 200~300 kDa) 50.8 ± 2.4 807 ± 44 62.8 ± 7.5
AR1 fiber (Mw: 200~300 kDa) 28.3 ± 3.1 551 ± 51 12.7 ± 1.4
AR2 fiber (Mw: 500~600 kDa) 36.0 ± 5.5 692 ± 68 10.7 ± 2
Electrospun gelatin mat [11] 1.6 ± 0.6 490 ± 52 17.0 ± 4.4
Electrospun collagen mat [12] 11.4 ± 1.2 N.A. N.A.
Resolut LT regenerative membrane 11.7 N.A. 20
(Gore). Glycolide fiber mesh coated
with an occlusive PDLGA membrane
[13]
Fig. 3. Swelling ratio of agarose and agar fibers. Kaltostat (ConvaTec) Calcium/sodium 0.9 1.3 ± 0.2 10.8 ± 0.4
alginate fleece [14]
AR2, 500%). Since agaropectin contained in agar was a heterogeneous
mixture of smaller branched and sulfated molecules, the agar fiber
showed better hydrophilicity than the agarose fiber. Moreover, the weak mechanical properties. Moreover, since mechanical and
molecular weight was an impact on the agar fiber swelling ratio: physical properties are closely related to morphological structure,
higher molecular weight agar fiber (AR2) showed relatively low AR2 fibers with highest molecular weight yet nonuniform structure
swelling ratio. This is mainly due to the long-chain molecules (Fig. 2 d1, d2) showed lowest elongation at break.
interwoven with each other making it difficult to form a network
structure which is conducive to water absorption (Fig. 3). 4. Conclusion
The mechanical properties of a wound dressing are important
factors in its performance, whether it is typically used to protect Continuous agarose and agar fibers have been produced for the
cutaneous wounds or as an internal wound support, for surgical tissue first time using a wet-spinning process in DMSO/H2O solvent. With
defects, i.e., in the clinical setting, appropriate mechanical properties this simple spinning process, the obtained agarose fibers with
of dressing materials are needed to ensure that the dressing will not homogeneous appearance showed desirable swelling ratio, tensile
be damaged by handling. strength, modules and breaking elongation. Agar fibers were also
As shown in Fig. 4, the agarose fibers showed plastic deformation fabricated; AR1 fiber had a uniform appearance, while AR2 had a
of the specimens occurs while the agar fiber showed a typical brittle nonuniform circular cross-section, rough surface morphology and
fracture, after an initial elastic deformation. As illustrated in Table 1, brittleness deformation. All the fibers showed considerable swelling
AG1, AG2, AR1, and AR2 fibers demonstrated higher tensile strength ratio. Based on these results, we considered that agarose fibers could
and elastic modulus than most of the representative wound-dressing be a potential material for wound-dressing or other biomedical
materials currently used or studied. Among which, the tensile applications.
strength for AG2 is 50.8 MPa, 4.5 times higher tensile strength than
electrospun collagen mat [12]; elongation at break is 62.8%, 3.7 times Acknowledgement
higher than electrospun gelatin mat [11]; the elastic modulus is
807 MPa, almost 1.6 times higher than the electrospun gelatin mat This work was supported by Grant-in-Aid for Global COE program
[11]. AG2 fibers of higher molecular weight (200–300 kDa) showed by the Ministry of Education, Culture, Sports, Science, and Technology.
better tensile properties than AG1 fibers which happen to AR2 fibers
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Fig. 4. Stress–strain curves of wet-spun agarose and agar fibers.