& RESEARCH

Silver-containing alginate
fibres and dressings
Yimin Qin

Qin Y. Silver-containing alginate fibres and dressings. Int Wound J 2005;2:172—176.

ABSTRACT
Silver is a broad-spectrum antimicrobial agent that is gaining more and more importance in the wound-
management industry. By incorporating silver ions into alginate fibres, highly absorbent alginate wound dressings
with antimicrobial properties can be made. Laboratory studies have shown that by incorporating fine particles of
silver sodium hydrogen zirconium phosphate, the silver-containing alginate fibres can maintain the white physical
appearances while providing a sustained release of silver ions when in contact with wound exudates. Test results
have proven that these fibres are highly effective against bacteria.
Key words: Alginate fibre . Antimicrobial . Silver ions

SILVER AS AN ANTIMICROBIAL over time and generally appear to stimulate

Key Points
. silver has a long history as an
antimicrobial agent
. in recent years, silver has been
gaining importance in wound
management
. alginate dressings are also an
important dressing category of
modern wound management
. recent innovations have seen
the combination of alginate
with silver
. this combination provides a
moist wound healing dressing
with antimicrobial action
AGENT
Silver has a long history as an antimicrobial
agent (1,2), especially in the treatment of
burns. While metallic silver is relatively inac-
tive, silver ions are effective against a wide
range of bacteria. When low concentrations
of silver ions accumulate inside cells, they
can bind to negatively charged components
in proteins and nucleic acids, thereby effecting
structural changes in bacterial cell walls,
membranes and nucleic acids that affect via-
bility. Interestingly, although silver is a highly
effective antimicrobial agent, it has a limited
toxicity to mammalian cells (3). It was found
that in clean wounds in pigs, the use of silver-
containing dressings can increase the rate of
epithelialisation by 28%, indicating a benefi-
cial effect of silver ions in wounds, in addition
to its antimicrobial activity (4).
In recent years, silver has been gaining import-
ance in the wound-management industry as an
effective antimicrobial agent, and a number of
silver-containing wound dressings have been
developed. These function by the sustained
release of low concentrations of silver ions
Author: Y Qin, The Biochemical Materials Research and
Development Center, Jiaxing College, Jiaxing, Zhejiang
Province, P.R. China
Address for correspondence: The Biochemical Materials
Research and Development Center, Jiaxing College, 56 Yuexiu
Road South, Jiaxing 314001, Zhejiang Province, P.R. China
E-mail: yiminqin@hotmail.com
healing, as well as inhibiting microorganisms.
A number of laboratory studies have shown
the excellent antimicrobial performances of
the silver-containing wound dressings (5—9).
Human clinical studies have also shown
encouraging clinical benefits (10—13).
Alginate wound dressings are an import-
ant type of modern wound-management
materials. Since they are highly absorbent,
these dressings are mainly used on highly exud-
ing wounds where microbial infection is com-
mon. By incorporating silver ions into alginate
fibres, it is expected that a highly absorbent
wound dressing with good antimicrobial
properties can be obtained.
THE ADDITION OF SILVER INTO
ALGINATE FIBRES THROUGH
CHEMICAL REACTION
In the wound-management industry, a number
of silver compounds are used for antimicrobial
purposes. Aqueous silver nitrate solutions
have been used as a simple wound-cleansing
agent for over a long time. Since its introduc-
tion in 1968 (14), silver sulphadiazine (SSD) has
also become widely used in burn treatment.
Although it was first recommended as a topical
treatment for the prevention of pseudomonad
infections in burns, SSD has since been demon-
strated to possess broad-spectrum antibacter-
ial, antifungal and antiviral activity (15—17).

172 ß Blackwell Publishing Ltd and Medicalhelplines.com Inc 2005 . International Wound Journal . Vol 2 No 2

Since alginate is a polymeric acid, it can
form salt with silver ions. However, unlike
calcium alginate, which is highly insoluble in
water, when sodium alginate solution is
extruded into a silver nitrate solution, it is
difficult to form silver alginate fibre, mainly
because silver is a monovalent ion and solidi-
fication of the newly spun filament is slow
and difficult. A mixed solution of calcium
chloride and silver nitrate can be used to pro-
duce fibres that are a mixture of calcium
alginate and silver alginate. Table 1 sum-
marises the calcium and silver contents of
alginate fibres made with a mixed coagulation
bath containing calcium and silver ions (18).
In order to attach silver ions onto the alginate
fibres, calcium alginate fibres can be treated
with aqueous solutions of silver nitrate. The
silver ions in the solution exchange with the
calcium ions in the fibre, resulting in the forma-
tion of calcium alginate fibre containing silver
ions. These fibres are highly antimicrobial;
however, due to the oxidative power of the
silver ions, they are sensitive to light exposure
and can become dark-to-black in appearance.
Adding particles of water-insoluble silver
compounds to the alginate fibre is one way
to avoid oxidation and maintain the white
physical appearance that is highly desirable
for a biomedical material. Le et al. (18) devel-
oped a method to incorporate SSD into
alginate fibres by mixing the water-soluble
sodium sulphadiazine with sodium alginate
to form a spinning solution, which was then
extruded into a 2% calcium chloride solution
containing silver nitrate. During the fibre
forming process, sodium alginate reacts with
calcium ions to form the filament, whilst
sodium sulphadiazine reacts with silver ions
to form SSD, which is deposited inside the
fibre structure. Alternatively, after sodium
sulphadiazine and sodium alginate are
Table 1 Preparation conditions and properties of the calcium silver alginate fibre (18)
Sample
Alginate content of the spinning solution (%)
Coagulation duration (seconds)
Fibre silver content (%)
Fibre calcium content (%)
Ratio between silver/calcium
Fibre strength (cN/dtex)
Extension at break (%)
ß Blackwell Publishing Ltd and Medicalhelplines.com Inc 2005 . International Wound Journal . Vol 2 No 2
Silver-containing alginate fibres and dressings
dissolved to form a spinning solution, silver
nitrate is added to this solution before extru-
Key Points
sion. In this process, the SSD particles formed . the silver and alginate are com-
through the reaction between sodium sulpha- bined chemically
diazine and silver nitrate is dispersed in the . the alginate silver fibres are
highly antimicrobial
spinning solution. When extruded to form
. the fibres are sensitive to light
fibre, the SSD particles are embedded in the exposure becoming darker in
fibres. appearance
. different production techniques
THE ADDITION OF SILVER TO result in different fibres resistant
to light therefore discoloration
ALGINATE FIBRES THROUGH
BLENDING
As has been mentioned before, although silver
is a highly effective broad-spectrum anti-
microbial agent, it is also highly oxidative to
organic materials. Skin discoloration and irri-
tation associated with the use of silver nitrate
is well known. In order to protect the host
material from oxidation and discoloration,
some novel silver-containing compounds
have been developed in recent years, and
these have been made into fine particles that
can be blended with fibre forming polymers
during extrusion.
Alphasan RC5000 is a silver sodium hydro-
gen zirconium phosphate. This microbiologic-
ally active ingredient is a synthetic inorganic
polymer. Under a scanning electron micro-
scope, it resembles cube-shaped crystals, with
an average particle size of about one micron
(about the size of an average bacterium).
It consists of a three-dimensional, repeating
framework of sodium hydrogen zirconium
phosphate, with many equally spaced cavities
containing silver. Silver (at 3
8% by weight)
provides the main antimicrobial properties,
while the framework matrix acts to distribute
silver evenly (without clumping or pooling)
throughout the individual fibres where the
Alphasan particles are added.
When Alphasan RC5000 is mixed with
sodium alginate solution, the fine particles
Number 1 Number 2
6 6
30 600
5
12 7
30
4
98 6
18
1:03 1:18
1
09 1
15
10
5 8
9
173

Key Points
. silver is released into wound
exudate via three mechanisms
. firstly, there is an ionic
exchange in the fibres
. secondly, silver ions are che-
lated by protein molecules in
the exudate
. thirdly, special particles
attached to the fibres are
released
. the silver ions are slowly
released to provide antimicro-
bial activity
. the dressing’s activity is pro-
vided by the sustained release
of silver
174
Silver-containing alginate fibres and dressings
can be evenly distributed in the spinning solu-
tion under a high rate of shearing. Because the
particles are very fine, they can be suspended
uniformly while the solution is extruded to
form fibres. Since the sodium hydrogen zirco-
nium phosphate framework prevents the silver
ions from oxidising the alginate, this type of
silver-containing alginate fibre remains white
even after sterilisation through irradiation (19).
Figure 1 shows the photomicrograph of alginate
fibre with the Alphasan RC5000 particles
uniformly distributed inside the fibre structure.
RELEASE OF SILVER IONS FROM
SILVER-CONTAINING ALGINATE
FIBRES
When alginate fibres containing Alphasan
RC5000 particles are in contact with wound
exudates, the silver ions can be released into
the wound exudate by three mechanisms.
First, there is an ion exchange between the
silver ions in the fibre and the sodium and
calcium ions in the wound fluid. Second, sil-
ver ions can be chelated by protein molecules
in the wound fluid. Third, Alphasan particles
attached to the surface of the fibres can also be
detached from the fibres and get into the
wound exudate.
Table 2 summarises the results of the silver
ion concentration when alginate fibre contain-
ing 1% Alphasan RC5000 is placed in contact
with normal saline or human serum. It can be
seen that the silver ions are slowly released
into the solution, acting as an antimicrobial
agent. More silver ions can be seen to release
into human serum, suggesting the high silver-
binding abilities of the protein components in
the wound exudates.
Alphasan RC5000
particles
Figure 1. Photomicrograph of alginate fibre with the
Alphasan RC5000 particles uniformly distributed inside the
fibre structure. Magnification: 200.
ß Blackwell Publishing Ltd and Medicalhelplines.com Inc 2005 . International Wound Journal . Vol 2 No 2
Table 2 Silver concentrations in extract solutions (19)
Silver content of
Sample Duration of contact extract (mg/ml)
Normal saline
1 30 minutes 0
50
2 48 hours 0
40
3 7 days 1
32
Human serum
A 30 minutes 2
18
B 48 hours 2
74
C 7 days 3
74
In the test as summarised in Table 2, 1 g of
silver-containing fibres were placed in contact
with 40 ml of either solution A (aqueous solu-
tion containing 142 mmol of NaCl and
2
5 mmol of CaCl2) or human serum.
Analysis by atomic absorption spectrum
showed that 1 g fibre contained 0
17 mg of
silver ions. After 7 days, up to 3
74 mg/ml of
silver was present in the human serum
extract. The mass of silver ions released from
the dressing ¼ mass of solution  concentra-
tion of silver ¼ 40 ml  3
74 mg/ml ¼ 150
mg ¼ 0
150 mg. This means that 0
15/
0
17 ¼ 88% of the available silver is released
into the human serum.
THE ANTIMICROBIAL EFFECT OF
SILVER-CONTAINING ALGINATE
FIBRES
For alginate fibres, it is well known that when
they are in contact with wound exudate, the
calcium ions in the fibres exchange with
sodium ions in the fluid, and the fibres are
transformed from water-insoluble calcium
alginate into water-soluble sodium alginate,
resulting in the absorption of a large amount
of water by the fibres. In a wound dressing,
typically with a non woven structure, as the
fibres absorb water and swell, the spaces
between the fibres are closed and any bacteria
that is carried in the wound exudate is
trapped in the wound dressing. This can
help reduce the spreading of bacteria, giving
the alginate wound dressings bacteria static
properties.
The silver ions in the alginate fibre can
enhance its antimicrobial activities by the sus-
tained release of the broad-spectrum anti-
microbial silver ions. As Table 2 summarises,
 Silver-containing alginate fibres and dressings

Wound exudate with bacteria

Key Points
Non woven
alginate
with silver . silver can be released over 7
days
. the dressing has been shown to
Fibre swelling
provide 100% reduction of bac-
terial count within 5 hours for
Bacteria
trapped in the species tested
non woven . when tested against other
alginate
fibrous dressings, the silver algi-
nate proved more effective
Release of silver ions . silver has been shown to be
clinically safe in the treatment
Bacteria of wounds
Ag Ag Ag Ag killed with
Ag Ag
Ag Ag
Ag silver ions
Ag

Figure 2. The antimicrobial mechanism of the silver-containing alginate wound dressings.

silver ions can be released over a 7-day period. CLINICAL SAFETY OF THE
These ions can kill the bacteria that are trapped SILVER-CONTAINING ALGINATE
in the alginate wound dressing, thus making FIBRES
the dressings antimicrobial. Figure 2 shows In a review on the use of silver sulfadiazine in
the antimicrobial mechanism for the silver- burn wound treatment, Fuller (20) mentioned
containing alginate wound dressings. that silver is inert when deposited in human
Figures 3 and 4 show the antimicrobial tissues. It is normally present in mammalian
action of silver-containing alginate fibres tissue in concentrations <10 mg/dl. Serum
against Pseudomonas aeruginosa and Escherichia silver concentrations of up to 20 mg/dl are
coli. In both cases, there was a 100% reduction regarded as non toxic from the standard
in bacterial count within 5 hours when the point of the laboratory analysis for trace
fibres were placed in contact with solutions metals (21). In a study by Boosalis, it was
containing the two types of bacteria. found that the silver concentration in the
Interestingly, although the SorbsanTM alginate urine samples of those undergoing silver
fibres showed some antimicrobial activity sulfadiazine treatment is consistently higher
against E. coli, in the solution containing the during treatment, indicating the fact that
other alginate fibre and AquacelTM (made of there is a metabolic mechanism whereby
carboxymethyl cellulose), antimicrobial effect excess silver ions in the body can be excreted.
was not noted and there was increased rate of Other studies have also shown the systemic
bacteria growth in some cases. distribution and excretion of silver in urine (3).

Pseudomonas aeruginosa
Log percentage recovery

Escherichia coli
100 000
Log percentage recovery

10 000 1000
1000
100
100
10 10
1 1
0·1
0·01 0·1
0 20 40 60 80 0·01
Time (hours) 0 10 20 30 40 50 60 70 80
Time (hours)

Alginate+Ag Urgosorb Alginate+Ag Urgosorb

Sorbsan Aquacel Sorbsan Aquacel

Figure 3. The antimicrobial action of silver-containing algi- Figure 4. The antimicrobial action of silver-containing algi-
nate fibres against Pseudomonas aeruginosa (19). nate fibres against Escherichia coli (19).

ß Blackwell Publishing Ltd and Medicalhelplines.com Inc 2005 . International Wound Journal . Vol 2 No 2 175

Key Points
. silver exhibits antimicrobial
activity against a broad range
of microorganisms
. concerns exist regarding the
overuse of silver and any sub-
sequent resistance
176
Silver-containing alginate fibres and dressings
Exposure of wounds to low levels of silver ions
can therefore be considered as safe.
BACTERIAL RESISTANCE TO
SILVER IN WOUND CARE
Since ionic silver exhibits antimicrobial activity
against a broad range of microorganisms, silver
is now included in many commercially avail-
able health care products. The use of silver is
increasing rapidly in the field of wound care,
and a wide variety of silver-containing dres-
sings are now available. However, concerns
associated with the overuse of silver and the
consequent emergence of bacterial resistance
are being raised. The current understanding of
the biochemical and molecular basis behind
silver resistance has been documented in a
detailed review by Percival et al. (22).
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