Advances in Colloid and Interface Science 166 (2011) 119135

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Advances in Colloid and Interface Science

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 / c i s

Silver polymeric nanocomposites as advanced antimicrobial agents: Classication,

synthetic paths, applications, and perspectives
Panagiotis Dallas a, 1, Virender K. Sharma b, Radek Zboril a,
a
Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University, Slechtitelu 11, 783 71 Olomouc, Czech Republic
b
Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901, USA

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

Available online 31 May 2011 Utilization of metallic nanoparticles in various biotechnological and medical applications represents one of
the most extensively investigated areas of the current materials science. These advanced applications require
Keywords: the appropriate chemical functionalization of the nanoparticles with organic molecules or their incorporation
Silver nanoparticle in suitable polymer matrices. The intensied interest in polymer nanocomposites with silver nanoparticles is
Polymer nanocomposite due to the high antimicrobial effect of nanosilver as well as the unique characteristics of polymers which
Antimicrobial agent
include their excellent structural uniformity, multivalency, high degree of branching, miscellaneous
Composite material
Nanobiotechnology
morphologies and architectures, and highly variable chemical composition. In this review, we explore
several aspects of antimicrobial polymer silver nanocomposites, giving special focus to the critical analysis of
the reported synthetic routes including their advantages, drawbacks, possible improvements, and real
applicability in antibacterial and antifungal therapy. A special attention is given to green synthetic routes
exploiting the biopolymeric matrix and to the methods allowing preparing magnetically controllable
antimicrobial polymers for targeting to an active place. The controversial mechanism of the action of silver
against bacteria, fungi and yeasts as well as perspectives and new applications of silver polymeric
nanocomposites is also briey discussed.
2011 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2. Antimicrobial silver systems applications, mechanisms of antimicrobial action, nanoparticles vs. ionic silver . . . . . . . . . . . . . . . 120
3. Synthesis of silver nanocomposites after entrapment and subsequent reduction of silver cations . . . . . . . . . . . . . . . . . . . . . . 122
3.1. Engineering polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
3.2. Carbohydrates and biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.3. Dendrimers as templates and hosts for silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4. One-step formation of nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.1. Silver cations as initiators for the polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.2. Polymer as a reductant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
5. Smart syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
5.1. Thin lm formation after photocatalytic reduction of silver cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
5.2. Layer by layer assemblies, magnetically controllable silverpolymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . 130
5.3. Non-chemical directions for the synthesis of composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
6. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

Corresponding author. Tel.: + 420 585634947; fax: + 420 585634958.

E-mail address: zboril@prfnw.upol.cz (R. Zboril).
1
Present address: Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853-1501, USA.

0001-8686/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2011.05.008
120 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
1. Introduction
Polymer nanocomposites have attracted considerable attention
in recent years and have become key materials in modern nanotech-
nologies. This interest arises as a result of their unprecedented per-
formance, improved properties compared to the constituent's parts,
design exibility, lower life-cycle costs, and uniquely large applica-
bility of nanocomposites in various industrial elds. For example,
it is remarkable that current market forecasts estimate the use of
nanocomposites to reach 45 million kilograms in 2011 ($500800 M)
with an annual growth rate of 24% [13].
Polymer nanocomposites are advanced functional materials com-
posed of nanoparticles dispersed inside the polymeric matrix [410]
and/or coated by polymer, thus forming a core-shell structure [1114].
As a result, the produced material combines the suitable properties of
both partners [15]. Among the numerous nanoparticles that have been
used as polymer functionalizing agent, silver nanoparticles represent
the most sought-after (nano)material. This is mainly due to their
unique electric [1620], optical [2123], catalytic [2426], and,
particularly, antimicrobial properties [27,28], which are well estab-
lished and extensively investigated mainly in colloidal systems.
Nevertheless, numerous practical applications of silver nanoparticles
require their entrapment on various substrates and matrices [2934].
From this point of view, polymers are the materials of the rst choice
because of their specic morphology, chemical and structural nature
with the long polymeric chains allowing incorporation and ne
dispersion of nanoparticles. Additionally, the suitable functional groups
of polymers can be used as targeted reactive sites for the controlled
one-step synthesis of nanoparticles [3537]. In order to fully exploit the
properties of silver nanocomposites, they should be well dispersed on
the surface of the polymer host without the formation of large
aggregates, which otherwise dramatically reduce the antimicrobial
effect of silver. For the same reason, the size of the nanoparticles should
be as small as possible with a narrow size distribution. The sufciently
high loading and free surface of nanoparticles allowing an antimicrobial
action are other important factors affecting the real applicability of
silver polymeric nanocomposites.
In this critical review, we will focus on the silver nanocomposites
with a polymeric matrix, while the colloid silver systems, well
explored in various review papers [38], will remain out of our dis-
cussion. Several synthetic routes toward silver polymeric nanocom-
posites will be critically discussed just from the viewpoints of the
aforementioned crucial parameters (particle size, size distribution,
degree of particle agglomeration, silver content, interaction of
silver surface with polymer host), which determine the antimicrobial
efciency of these polymeric nanocomposites. The current knowledge
on the microbial action of silver will also be briey reviewed. In the
main part, different approaches enabling the incorporation of silver
nanoparticles in polymer matrices or hosts toward advanced nano-
composites are presented and classied. The strategies allowing
the control of the size, shape, and size distribution of silver nano-
particles are emphasized. Similarly, the magnetically controllable
silver composites and the processes enabling covalent immobilization
of silver nanoparticles on polymer surface are highlighted [39].
2. Antimicrobial silver systems applications, mechanisms of
antimicrobial action, nanoparticles vs. ionic silver
Elemental silver and silver salts are well known as antimicrobial
agents in curative and preventive health care for centuries [40].
Concerning its action against microbes, it is remarkable that it possesses
both an oligodynamic effect and a bactericidal impact. Legendary
examples include the use of diluted solutions of silver salts in the
prophylactic treatment of newborn eye infections and in the treatment
of burn wounds [4146]. Although silver salts and complexes are
effective antimicrobial agents, their use may result in unwanted
adsorption of ions in epidermis cells and sweat glands [47,48]. Thus,
the silver nanoparticles seem to be stronger candidates compared to
the silver cation salts and complexes. Moreover, unlike pharmaceutical
antibiotics, which may destroy benecial enzymes, colloidal silver
leaves these benecial enzymes intact. Notably, comparing to all other
available antimicrobial agents, silver is probably the most powerful
antimicrobial agent that exhibits a strong toxicity toward a broad range
of microorganisms, and simultaneously a remarkably low human
toxicity [49,50]. Colloidal silver has been proven to be relatively safe for
humans, plants and all multi-celled living matter. The observed toxicity
has been assigned to the oxidation of surface ions toward silver cations
that can affect basic cellular functions in mammalian cells [51] or due to
the uptake of very small particles from the cells. The later has been
demonstrated from studies of silver particles with a size of about 10 nm
against J774 A1 macrophages [52]. From that viewpoint, the immobi-
lization of silver on polymer substrates seems advantageous since it will
not allow the direct uptake of the particles from mammalian cells.
Currently, silver-containing agents are regularly used in clinical wound
dressings (e.g., silver sulfadiazine) as well as in the coatings of
biomedical materials (e.g., silver impregnated catheters). While being
relatively nontoxic to human cells, silver possesses antimicrobial
properties for a broad spectrum of bacterial strains that are found in
industrial processes as well as in the human body. Because of these
characteristics, silver in various forms is ideally suited for a wide range
of applications in consumer, industrial, and medical products [5360].
The most widely spread application lies in the coatings used in
impregnated catheters [6170]. This is very important since contam-
inated and infected catheters are a major source of nosocomial
infections, and are responsible for N40% of all episodes of nosocomial
sepsis in acute-care hospitals. Previous attempts with antibiotics as well
as surface modications with, for example, hydrogel proved to be of
little value in preventing the contamination of indwelling catheters
[71]. The urinary tract is the most common site of nosocomial infections
in intensive care units. Catheter-associated infections result from an
ascending bacterial colonization within the glycocalyx-enclosed biolm
on the inner and outer surface of the catheter [7277]. Consequently,
the development of silver-impregnated catheters that prevent bacteria
colonization is a valuable contribution in the medical eld and an
example of the application of nanoscience in crucial and important
aspects of everyday life.
The antimicrobial activity of the silver salts and complexes (ionic
silver) is generally based on the bonding of metallic ions in various
biomacromolecular components. Cationic silver targets and binds
to negatively charged components of proteins and nucleic acids,
thereby causing structural changes and deformations in bacterial cell
walls, membranes, and nucleic acids [7885]. In fact, silver ions are
generally well known to interact with a number of electron donor
functional groups like thiols, phosphates, hydroxyls, imidazoles,
indoles, and amines [86]. Accordingly, it is believed that silver ions
that bind to DNA block transcription while those that bind to cell
surface components interrupt bacterial respiration and adenosinetri-
phosphate (ATP) synthesis [8792]. Other reports suggest that silver
ions block the respiratory chain of microorganisms in the cytochrome
oxidase and nicotinamide adenine dinueocleotide (NADH) succinate-
dehydrogenase region, the later being an enzyme complex in bacterial
cells [93]. Very early reports have mentioned the inhibition of oxidation
of succinate, glycerol, glucose, and other molecules due to silver ions in
Escherichia coli [94]. The mechanism of the antimicrobial activity of
silver nanoparticles has not fully been understood. Three most common
mechanisms proposed are: (i) gradual release of free silver ions,
followed by disruption of ATP production and DNA replication,
(ii) silver nanoparticles direct damage to cell membranes, and
(iii) silver nanoparticles and silver ion generation of reactive oxygen
species [95103]. Several studies insist that the mode of antimicrobial
action of silver nanoparticles is similar to that of silver ions [95102]. It
has been suggested that it is important to have an ion ow from the
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135 121

silver component toward the bacteria. Kumar et al. [95] have

made substantial research efforts toward the investigation of ion
release from silver/polyamide composites. The concentration of the
silver ions released to the aqueous medium was measured by anodic
stripping voltammetry (ASV). ASV is an electrochemical method
applied for trace element detection and the identication of the
identity and concentration of analytes in aqueous and non-aqueous
media. It was performed by applying a deposition potential that is more
negative than the deposition potential of the species to be determined.
In this step, the electrolytic deposition of the reducible species onto an
inert electrode (working electrode) surface occurs at a constant
potential. The second step consists of the application of an anodic
(positive-going) potential scan to oxidize (strip) the reduced metal
back into solution at a potential characteristic of the species under
concern. Kumar et al. [95] studied the ion release from 1 g of an Ag/
polyamide composite in 100 ml of an aqueous environment. The ion
release was constantly increasing with time and the authors studied the
data according to the two dual sorption theory. According to this
theory, there are two different physical mechanisms that affect mass
transfer: (i) diffusion and (ii) embedding (intermolecular forces
between the penetrant molecules and the polymer specimen). While
the diffusion process is fast the embedding process is slow.
Micromolar levels of Ag + ions, i.e., 0.1 ppb, have also been reported
to uncouple respiratory electron transport from oxidative phosphory-
lation [104], inhibit enzymes, or interfere with the membrane
permeability to protons and phosphate [105107]. In addition, higher
concentrations of Ag + ions have been shown to interact with
cytoplasmic components and nucleic acids as previously mentioned
[108,109] and the presence of organic acids has been recently found to
alter the solubility, aggregation, and, consequently, the antimicrobial
activity of silver nanoparticles [110].
The dissolution of citrate-stabilized and poly(vinylpyrrolidone)-
stabilized silver nanoparticles in water was studied by dialysis for up
to 125 days at 5, 25, and 37 C. The particles slowly dissolve into ions
on a time scale of several days. However, in all cases, a limiting value
of the released silver was observed, i.e., the particles did not
completely dissolve. In some cases, the nanoparticles released up to
90% of their weight. Formal kinetic data were computed. Rate and
degree of dissolution depended on the functionalization as well as on
the storage temperature. The release of silver led to a considerably
increased toxicity of silver nanoparticles which had been stored in
dispersion for several weeks toward human mesenchymal stem cells
due to the increased concentration of silver ions. Consequently, aged
(i.e., immersed) silver nanoparticles are much more toxic to cells
than freshly prepared silver nanoparticles [111].
Some group of authors emphasized a possible important role of
electrostatic interactions between negatively charged bacterial cells
and positively charged nanoparticles [112,113]. On the other hand,
negatively charged silver particles have been reported by Sondi et al. Fig. 1. TEM image of E. coli cell treated with 50 g cm 3 of silver nanoparticles in liquid Luria
Bertani (LB) medium for 1 h (a) and enlarged view of the membrane of this cell (b). The TEM
[114] to interact with building elements of the bacterial mem-
images clearly reveal that the nanoparticles were accumulated in the membrane and/or
brane, causing structural changes and degradation and nally, cell penetrated the cell. Fig. reproduced from Ref. [114] with permission, Elsevier.
death. The exact mechanism of interaction between these particles
and the constituents of the outer membrane of E. coli unfortunately
remains unresolved. Interestingly, Sondi et al. [114] demonstrated
the existence of silver in the membranes of treated bacteria by It is clear that treated bacteria show signicant changes as well as
Transmission Electron Microscopy (TEM) analysis (Fig. 1). Elemental damages in its membranes something that is recognized by the
analysis performed by Energy Dispersive X-Ray Spectrometry formation of marks on their surfaces. A similar effect was described
(EDX) conrmed the incorporation of silver into the cell membrane by Klabunde and co-workers [115] when E. coli bacteria were treated
structure; consequently, the authors established the penetration with highly reactive metal oxide nanoparticles like MgO. The authors
of the cell membranes of bacteria by silver nanoparticles as an showed that these materials were very effective against Gram-
explanation for the possible mechanism causing the antimicrobial positive and Gram-negative bacteria as well as spores. Zeta-potential
effect. Further electron microscopic studies from the same group measurements show an attractive interaction between the MgO
revealed that the majority of silver nanoparticles were localized not nanoparticles and bacteria and spore cells, which is conrmed by
only inside the membranes of treated E. coli cells, but some of them confocal microscopy images. Atomic Force Microscopy (AFM) studies
even penetrated into the cells probably interacting with the internal illustrate considerable changes in the cell membranes upon treat-
components of the cell (Fig. 2). ment, resulting in the death of the cells.
122 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
Fig. 2. Scanning electron micrographs of native E. coli cells (a) and cells treated with
50 g cm 3 of silver nanoparticles in liquid LB medium for 4 h (b) indicating the
presence of silver nanoparticles inside the cell itself. The cells seem to be affected from
the penetration of the silver particles. Fig. reproduced from Ref. [114] with permission,
Elsevier.
From that perspective, it might be interesting to analyze briey the
outer membrane of E. coli cells: it is predominantly constructed from
tightly packed lipopolysaccharide (LPS) molecules, which provide an
effective permeability barrier [116119]. Amro and co-workers [120]
have shown that metal depletion may cause the formation of
irregular-shaped pits in the outer membrane and changed membrane
permeability, which is caused by progressive release of LPS molecules
and membrane proteins. We may speculate that a similar mechanism
causes the degradation of the membrane structure of E. coli during
treatment with silver nanoparticles.
The antifungal activity of stabilized silver nanoparticles has been
also extensively studied by Panacek et al. [121]. The minimum
inhibitory concentration (MIC) of silver nanoparticles was found to be
21 mg/L, below the cytotoxic level for human broblasts [119].
In recent years, some other studies on antifungal activity of silver
nanoparticles have been reported [122,123].
An interesting study revealed a size-dependent interaction of silver
nanoparticles with HIV-1 virus [124]. The work suggested that the
exposed sulfur-bearing residues of the glycoprotein knobs would be
attractive sites for silver nanoparticle interaction. Consequently, the
nanoparticles interact with the HIV-1 virus via preferential binding to
the gp120 glycoprotein knobs and silver inhibits the virus from binding
to host cells, as demonstrated in vitro. Leonard and coworkers [125]
reported that the gp120 subunit has nine disulde bonds. These exposed
disulde bonds would be the most attractive sites for nanoparticles to
interact with the virus. Recent studies have also reported mode of
actions of silver nanoparticles against HIV-1 [126,127].
A few studies on the generation of reactive oxygen species (ROS)
from silver nanoparticles have been reported [110]. Electron spin
resonance (ESR) evidence was given to demonstrate the formation of
radicals from silver nanoparticles [101]. The radical scavengers
were also utilized to show the radical contribution to the antimicro-
bial activity against E. coli [102]. The ROS radicals can damage the
membrane protein to cause the toxicity to bacterial strains [103].
Understanding the role of dissolved oxygen in performing antimicro-
bial experiments may provide evidence for responsible species
causing toxicity by silver nanoparticles. Additionally, more extensive
investigations directed to a better understanding of the interactions
between bacterial components and silver nanoparticles, with empha-
sis on both size (i.e., reactive surface area) and crystallinity (i.e.,
surface reactivity) should shed light on the mode of action of these
nanomaterials as bactericidal agents. Particularly, the biochemical
and molecular aspects of the action should be more addressed.
3. Synthesis of silver nanocomposites after entrapment and
subsequent reduction of silver cations
The most frequently used approach to prepare dispersion of silver
nanoparticles attached in polymer matrices involves the entrapment
of silver cations from polymer chains followed by reduction
with common reducing agents. This method presents two advantages
compared to the simple mixing of the two components and the
polymerization in the presence of pre-synthesized silver nanoparti-
cles. Firstly, the template role of the host macromolecular chains
for the synthesis of nanoparticles helps improve the dispersion of
nanoparticles inside the polymeric matrix, and also partially prevents
the formation of aggregates. Secondly, the template role that the
polymer chains play, leads to reduced size of nanoparticles with a
narrow size distribution and well dened shape.
3.1. Engineering polymers
Various common, engineering polymers have been used for the
immobilization of silver nanoparticles toward composite materials
with antimicrobial activity. For example, the incorporation of silver
into nylon 6,6 has been carried out by ultrasound irradiation with the
addition of ethyleneglycol as a reducing agent [128]. Perkas et al. [128]
demonstrated that the interaction of silver with amide groups of
nylon results in their well dispersion and stability within the
matrix. However, their composite synthesized through ultrasound
irradiation included only 1% wt. of silver, an amount not signicantly
high for antimicrobial activity. In any case, the interaction of metallic
silver with functional organic groups in order to achieve improved
dispersion inside the polymer matrix is worthwhile.
A great attention in the polymer market is targeted to polyurethanes,
due to their numerous applications in furniture, automobiles, con-
struction materials, coatings, adhesives, medical applications, etc. [129].
The high mechanical and chemical resistance and high rubber-like
elasticity have made thermoplastic polyurethanes (TPUs) suitable for a
number of medical applications like catheters, etc. [129]. In the work by
Shah et al., a composite from polyethyleneglycol-polyurethane-TiO2
was decorated with silver nanoparticles and showed excellent activity
against E. coli and Bacillus subtilis [130]. Another interesting aspect of
this work is that TiO2 facilitated the photoreduction of AgNO3 to metallic
silver nanoparticles inside the polymer matrix.
Silver nanoparticles/poly (methyl methacrylate)/poly (vinyl alco-
hol) nanocomposites have been synthesized using radical-mediated
dispersion polymerization, and the procedure is illustrated in Fig. 3
[131]. Kong et al. [131] used poly (methyl methacrylate) (PMMA), a
highly transparent and well-known polymer, widely available and easy
to be synthesized in a large scale. As such, the incorporation of silver
nanoparticles in it will open the gates to new semi-transparent
antimicrobial coatings. The process involves silver ions dissolved in
aqueous PVA solution and the hydroxyl group of PVA was coordinated
with silver ion. Again, this coordination makes the synthesis to be
targeted in specic reaction sites and not random. Azobisisobutyroni-
trile (AIBN), as a reductant and radical initiator, was added to the Ag+/
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
Fig. 3. Synthesis of silver nanoparticles/polymer nanober using the radical-mediated dispersion polymerization: (a) photograph image of Ag+/PVA aqueous solution, (b) TEM
image of Ag/PVA linear assembly, and (c) TEM image of Ag/PMMA nanober indicating the ultra-small silver nanoparticles attached on the polymer nanober. Fig. reproduced from
Ref. [131] with permission, American Chemical Society.
PVA aqueous solution. Subsequently, Ag/PVA complexes were linearly
assembled in the shear ow and more tightly assembled because of the
dipoledipole interaction of silver nanoparticle surface. The carboxyl
group of methyl methacrylate (MMA) can form a hydrogen bond with
the hydroxyl group of PVA which is coated on silver nanoparticles.
When MMA monomer was injected into the reaction medium and then
polymerized for 24 h, the silver nanoparticles/PMMA nanobers could
be obtained. Interestingly, the TEM images of these nanobers reveal
that silver nanoparticles are embedded in the PMMA polymer
nanobers (Fig. 3). As such, their surface is exposed in a high percent
and this consequently results in high antimicrobial activity as
evidenced from the minimum inhibitory concentration values obtained
in various bacterial strains. Furthermore, all materials used in this
synthesis are common and of low-cost allowing numerous potential
applications. Similarly, porous PMMA/Ag spheres have also shown
good antimicrobial activity, despite the fact that the silver nanoparticles
are mostly encapsulated within the polymer chains [131,132].
An excellent hydrophilic environment is important in antimicro-
bial applications because water is necessary to facilitate the release of
silver ions from the encapsulated silver complex in the polymer
matrix. It is also envisaged that the material will maintain a moist
environment around the wound bed, as it is known that good
hydration is essential for optimal wound healing. Tecophilic is a
polymer that belongs to the family of hydrophilic polyether-based
thermoplastic aliphatic polyurethanes [133]. It is a medical grade
polymer, and most importantly it is capable of absorbing water
content up to 150% of the weight of its dry resin, which is a
signicantly high amount. Tecophilic has been chosen as a host for
encapsulating an imidazole silver complex since it can be electrospun
from ethanol and exhibits excellent hydrophilic properties. The
123
formation of silver nanoparticles was achieved inside the polymer
matrix, when the electrospun ber was exposed to water. The authors
used TEM to reveal the gradual formation of the nanoparticles inside
the ber over a small time period. The exposure of the as-spun bers
to water makes the silver complex decomposing and releasing silver
ions (Fig. 4), which aggregate into silver particles at nanoscale
measurement. The bactericidal and fungicidal effects of the nano-
composite were studied by using a modied Kirby Bauer technique.
The composite and the pure electrospun Tecophilic ber as a control
were placed on a lawn of organisms in an agar plate and incubated
overnight at 35 C. Both Gram-positive and Gram-negative pro-
karyotes were tested (E. coli, Pseudomonas aeruginosa, Staphylococcus
aureus). The fungi used were Candida albicans, Aspergillus niger, and
Saccharomyces cerevisiae. The bactericidal activity showed a zone of
inhibition within and around the ber after an overnight incubation
of the agar plate at 35 C [133].
3.2. Carbohydrates and biopolymers
In the previous paragraph, we discussed some important examples
of common, plastic polymer nanocomposites. The biopolymers
represent another important group, mostly due to their almost
unlimited supply, low cost, and biocompatibility [134]. From that
viewpoint and taking into account the fact that the application of
silver nanocomposites are mostly toward biomedical treatment,
hydrogels and carboxymethylcellulose carbohydrates have denitely
emerged as strong challengers in this eld.
Vimala et al. [135] report the preparation of semi-interpenetrating
hydrogel networks (SIHNs) based on cross-linked poly(acrylamide).
The cross-linked polymer was prepared through a redox polymerization
124 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135

Fig. 4. TEM images showing the release of silver nanoparticles by exposing bers consisting from the silver(I)-imidazole cyclophane gem-diol and tecophilic to water vapor
environment. In the TEM images, we can clearly see the release of the particles when comparing: (a) as-spun ber, (b) bers in water vapor environment for 0.5 h, and (c) bers in
water vapor environment for 65 h. By exposing the bers in water the silver complex decomposed and released silver ions which formed metallic nanoparticles. Fig. reproduced from
Ref. [133] with permission, American Chemical Society.

of N,N-methylenebisacrylamide (MBA) in the presence of different
carbohydrate polymers: gum acacia (GA), carboxymethylcellulose
(CMC), and starch (SR). They reduced silver cations inside the network
using sodium borohydride (NaBH4). The characteristic amide and
hydroxyl groups of the organic network were proposed to enhance the
stability of the silver nanoparticles inside the matrix, however their size
distribution was broad. Their antimicrobial properties were tested
against E. coli. It is important to note here that even if the polymer
polyacrylamide is completely safe for humans, the acrylamide monomer
is toxic.
Furthermore, highly stable and uniformly distributed silver
nanoparticles have been obtained with hydrogel networks as
nanoreactors via in situ reduction of silver nitrate (AgNO3) using
sodium borohydride (NaBH4) as a reducing agent. However, the
antimicrobial activity was not high, obviously due to the limited ion
release from the capped and protected silver nanoparticles.
Hydrogelsilver nanocomposites have been synthesized by a
synthetic route involving the formation of silver nanoparticles
within swollen poly(acrylamide-co-acrylic acid) hydrogels. The
silver ions were reduced with citrate, dening a completely green
and environmentally friendly approach toward the synthesis of
new antimicrobial agents [136]. This is very important since this
method avoids the use of toxic organic solvents, harsh reduction
agents, and high temperature. The formation of silver nanoparticles
was conrmed by TEM and their characteristic surface plasmon
resonance (SPR) absorption at the UVvisible spectrum which was
centered at 406 nm. TEM images of hydrogelsilver nanocompo-
sites showed almost uniform distribution of nanoparticles through-
out the gel networks. Most of the particles, as revealed from the
particle-size distribution curve, were 2430 nm in size. The
nanocomposites demonstrated excellent antimicrobial effects
against E. coli strains. The antimicrobial activity was proved to be
dependent on the size of the nanoparticles, the amount of silver
nanoparticles, and amount of monomer acid present within the
hydrogelsilver nanocomposites.
Various other hydrogel composites have also been synthesized and
tested, e.g., composites in which colloidal silver hydrosols were rstly
prepared in the presence of an amphiphilic block copolymer, the
commercially available poly(oxyethylene)-poly(oxypropylene)-poly
(oxyethylene) also known as Pluronic F-68, and then mixed
with aqueous solution of alpha-cyclodextrin [137141]. A complete
analysis from rheology, X-ray diffraction, and SEM conrmed the
formation of the supramolecular-structured hydrogels hybridized with
silver nanoparticles. The colloidal stability of the resultant silver
hydrosol, its gelation kinetics in the presence of a-cyclodextrin as
well as the viscoelastic properties of the resultant hybrid hydrogel were
investigated under various concentrations of the used block copolymer.
It was found that the used block copolymer could act not only as the
effective reducing and stabilizing agents for the preparation of the silver
hydrosol but also as an effective guest molecule for the supramolecular
self-assembly with a-cyclodextrin resulting in a promising green and
biocompatible silver nanocomposite even if the authors did not studied
the antimicrobial activity of their nanocomposite. Particularly, the
supramolecular-structured hydrogels based on the inclusion complex
formation of cyclodextrins with the polymer chains are important due
to the fact that cyclodextrins as the host molecules are water-soluble
and capable of selectively including a wide range of guest molecules by
their internal hydrophobic cavities as such these silver biopolymer
nanocomposites are promising candidates in numerous biological
applications.
Very important members in this class of nanocomposites are the
biodegrable cellulose matrices [131,142150]. Very efcient and
green antimicrobial cellulose nanocomposites were synthesized by
reduction of the silver cations under UV radiation [131]. Two different
coatings were employed, namely bacterial cellulose and vegetable
cellulose. Interestingly, Scanning Electron Microscopy (SEM) analysis
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
conrmed a homogeneous distribution of silver nanoparticles form-
ing a compact lm at the cellulose surface. The authors demonstrate
that mechanical stirring of these nanocomposites in water did
not alter signicantly the load of the bers. This observation was
conrmed by quantifying the Ag load before and after the washing
treatment. The explanation, according to the authors, is that the Ag
nanoparticles become strongly attached to the cellulosic bers, which
is directly related to the strong electrostatic interactions between the
negatively charged Ag nanoparticles and the positively charged bers
surface. The application of the layer-by-layer assembly approach
to bacterial cellulose (BC) membranes is also possible; however, the
internal nanostructure of BC membranes makes this substrate
more attractive for the incorporation of the Ag nanoparticles inside
its particular nanobrillar structure.
Cu, Ag, Fe and even In metal nanocomposites with biodegrable
carboxymethylcellulose have been studied by Nadagouda et al. [142]
and may nd medical and technological applications in various elds
such as in antimicrobial and antifungal coatings, food packaging,
and biomedical devices. Their composites are easily synthesized
and dene another group of green antimicrobial agents. In general,
nanocomposites of cellulose and its derivatives are gaining impor-
tance because of their value-added applications in science and
technology, for example, in nanocomposites of cellulose based
electrolytes, high-performance composite materials, organoclay-
exfoliated cellulose with improved mechanical properties, nanocom-
posites with good tensile strength, biomedical applications, and as
host materials. Consequently, present innovations are more focused
on understanding the structureproperty relationships and adapta-
tion of these cellulose-derived products for specic newer applica-
tions that result in a decreased use of chemicals. Among cellulosic
ethers, carboxymethyl celluloses (CMCs) are very important de-
rivatives of cellulose; they have good solubility, high chemical
stability, and are toxicologically innocuous [143150].
Through a similar view, dextrose and poly(-glutamic acid)
nanocomposites have been tested in various bacterial strains [151].
The concept is that the carbohydrates play a template role for the
entrapment of silver cations through carboxylate units and lately the
metal cations are reduced to silver nanoparticles by various reducing
agents. In these composites there has also been performed a
cytotoxicity test based on the L929 broblasts. The broblasts were
incubated in different Ag + or polyglutamic acid/Ag composites in
different concentrations and the cell lysis and cell monolayer
destruction were observed with optical microscopy (Fig. 5).
Similarly, ne colloidal silver has been in situ deposited onto
functionalized porous poly(ethylene glycol dimethacrylate) [poly-
(EGDMA)] microspheres. The effectiveness of the silver deposition has
been investigated through an examination of the surface character-
istics of poly(EGDMA) microspheres. The results reported by Kim et al.
[152] demonstrate that the control of the surface area and surface
functionality (in this study, a hydroxyl group) of poly(EGDMA)
microspheres is an important factor that practically determines the
degree of deposition of colloidal silver. X-ray analysis has shown that
silver nanoparticles are dispersed evenly on inner and outer surfaces.
Preservation testing has shown that silver-containing poly(EGDMA)
microspheres have powerful antimicrobial properties over various
bacterial strains and, as such, may found applications as preservatives.
Finally, an important application of silver/polymer nanocompo-
sites in a crucial industrial eld lies in the lms and coatings for food
packaging. These packaging lms require biocompatible polymers
with specic properties. The biopolymer-based lms and coatings
should very well act as barriers against moisture, oxygen, avor,
aroma, and oil, thereby improving food quality and enhancing the
shelf life of food products [153]. Furthermore, they may also provide
physical protection to foods, reducing bruising, and breakage, thus
improving food integrity. Furthermore, biopolymer lms are excellent
vehicles for incorporating a wide variety of additives, such as
125
antioxidants, antifungal agents, antimicrobials, colors, and other
nutrients which are important in the food preservation [154,155]. In
particular, biopolymer-based antimicrobial lms have been attracting
much attention from the food industry with their potential applica-
tion for a very large variety and number of foods including meat,
sh, poultry, cereals, cheese, fruits, and vegetables [156158]. The
promising candidates in this eld are the chitosan-based nanocom-
posite lms that have been proved to be exible and free-standing
[159,160]. Chitosan is a natural polysaccharide, a derivative of chitin
that comes from the shells and exoskeletons of some crustacea. This
biopolymer is nontoxic, biodegradable, and biocompatible, and, as
such, denes a very strong candidate for all the above mentioned
applications. The authors demonstrated that nanocomposite lms
were as tough and as smooth-surfaced as cellophane. Besides the
antimicrobial properties they measure the mechanical behavior, e.g.,
tensile strength. The increase in toughness of hybrids containing
evenly distributed nanoparticle layers in a polymer matrix has been
frequently observed with various nanocomposites. Chitosan, a natural
saccharidic polybase composed of (beta 14)-linked glucosamine
residues interspersed with residual N-acetylglucosamine moieties.
However, the limitations of such polysaccharide are connected with
its pH-dependent solubility (limited to low pH only, as a polycation),
immiscibility with other oppositely charged polyelectrolytes, and lack
of cell specic molecular signals. To overcome these problems, a
lactose-substituted chitosan, 1-deoxylactit-1-yl chitosan, short-
named as Chitlac can be used. Chitlac is a highly branched polymer
devoid of pH limitations as to aqueous solubility; it is both bio-
compatible and bioactive, owing to the terminal galactose unit on
the side chain [161,162]. In addition, at neutral pH, the moderately
cationic Chitlac can give rise to soluble binary mixtures with alginate,
an anionic polysaccharide composed of (1f4)-linked R-L-guluronic
acid and -d-mannuronic acid.
This branched polysaccharide has been also recently used for the
fabrication of silver antimicrobial composites. Travan et al. [162]
prepared a Chitlac (1-deoxylactit-1-yl chitosan) membrane starting
from a highly deacetylated chitosan (residual acetylation degree:
11.3%). They prepared the silver nanoparticles by reducing silver ions
with ascorbic acid in Chitlac solutions (Fig. 6). For the preparation
of alginate-Chitlac hydrogels (AC-Gel), an in situ calcium release
approach was used. Briey, a Chitlac solution was added to an
alginate solution and the mixture was blended with an inactivated
form of Ca 2+ (CaCO3, 15 mM) followed by the addition of the slowly
hydrolyzing D-glucono--lactone (GDL). This gelling solution was
poured into well tissue culture plates. Finally, the gels were washed
with CaCl2 5 mM solution to remove residual GDL [162]. Conse-
quently, a generalized overview of all these different strategies that
have been followed to prepare hydrogelsilver nanocomposites is
the following: (i) polymerization of the monomer in the presence of
a functionalized proper initiator metal nanoparticles; (ii) surfactant-
free emulsion polymerization to encapsulate metal nanoparticles
within larger spherical hydrogel particles; and (iii) mixing a colloidal
solution of metal nanoparticles with aqueous polymer solution,
followed by solvent evaporation or precipitation in a bad solvent.
However, the optimized procedures do not involve use of organic
solvents, other toxic reagents, and harsh synthesis conditions that
may limit the potential of hydrogel/silver nanocomposites for
biomedical applications.
3.3. Dendrimers as templates and hosts for silver nanoparticles
As we have already mentioned, the main target in the synthesis of
nanocomposite materials is to keep an easy and efcient approach for
the production of long-term-stable silver nanoparticle dispersions
with a narrow size distribution and in addition, if possible, to
synthesize water soluble and biocompatible nanomaterials that can
be used in biological systems.
126 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135

Fig. 5. The cell morphology of L929 broblasts observed by optical microscopy after treatment with (a) silver ion solution and (b) polyglutamic acid-silver composites of different
concentrations. Fig. reproduced from Ref. [151] with permission, Elsevier B.V.

Dendrimers have appeared as ideal candidates to fulll these
requirements due to their symmetry and canonical structure, their
functional units, and monodispersity. Perfect dendrimers are mono-
dispersed macromolecules with a regular symmetric and dened
branched architecture. They are constructed from ABn monomers
(n usually 2 or 3) in contrast to standard AB monomers leading to
linear polymers. The synthesis of dendrimers is based on iterative
sequences of reaction steps. Each additional iteration step leads to a
branched material with controlled increase of the number of terminal
functional groups and molecular weight.
Especially, amphiphilic-modied hyperbranched polyethylenei-
mines or PAMAM (poly amido amine) dendrimers with core/shell
architecture have been successfully used as macromolecular tem-
plates and carriers [163166]. The PAMAM dendrimers hold great
promise as templates for metal composite nanoparticles because of
their low toxicity and highly regular, branched, three-dimensional
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135 127

Fig. 6. (a,b) TEM images of silver nanoparticles dispersed in Chitlac, a natural saccharidic polybase, at different magnications; (c) silver nanoparticle size distribution histogram
based on the TEM image in Fig. 6a; the mean particle size is 33.6 7.6 nm; (d) TEM image of silver nanoparticles formed on the polymeric chains of Chitlac (Chitlac 2 g/L, AgNO3
1 mM, C6H8O6 0.5 mM). Chitlac chains have been stained with a mixed solution of lead citrate (5 g/L) and uranyl acetate (5 g/L); (e) schematic representation of the polymeric chains
of Chitlac providing the nitrogen atoms for the coordination and stabilization of silver nanoparticles. Fig. reproduced from Ref. [162] with permission, American Chemical Society.

structure allowing them to host inorganic nanoclusters and form
stable dendrimer complexes and nanocomposites. In general, the
procedures follow the reduction of silver cations with NaBH4 and
the template role of the dendrimers ensures well dispersed silver
nanoparticles with a relatively small size distribution [167].
Extensive studies have already shown that dendrimer-encapsulated
silver nanoparticles do have antimicrobial activity [168]. The bonding
is achieved through a well known mechanism of interaction for
noble metals: e.g., catalytic palladium nanoparticles were prepared in
the lm of linear poly(ethyleneimine) (PEI) and silver, platinum, and
palladium nanoparticles were successfully encapsulated within poly
(propyleneimine) dendrimers [169]. All of these polymers possessed
some strong electron-donating centers, such as amino or carboxylate
groups, which facilitate metalpolymer complex formation. In these
works, the preparation of polymer/metal nanoparticles often involved
some tedious steps and extra reducing agents were required, including
sodium borohydride (NaHB4), formaldehyde, sodium citrate, hydrazine,
ascorbic acid, glucose, and solvents like N,N-dimethylformamide
(DMF), ethylene glycol, etc.
Interestingly, these materials cannot be used only as effective
antimicrobial agents but also as markers for cell labeling with the aid of
dendritic polymers. For example, the work presented by Lesniak et al.
[169] demonstrates the synthesis of water-soluble, biocompatible,
uorescent, and stable silver/dendrimer nanocomposites that can be
used for in vitro cell labeling. They employed amino-, hydroxyl-, and
carboxyl-terminated ethylenediamine core generation 5 poly(ami-
doamine) dendrimers in order to prepare aqueous silver(I) dendrimer
at the biologic pH of 7.4. Firstly, a silver(I) dendrimer complex was
formed and it was later converted into dendrimer nanocomposites
by irradiating the solutions with UV light to reduce the bound Ag +
cations to zero-valent Ag metallic silver nanoparticles which were
immediately trapped in the dendrimer network, resulting in the
formation of silver/dendrimer nanocomposites. In Fig. 7, the TEM
images show the dispersion and location of the PAMAM-Ag composite
128 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135

Fig. 7. Representative TEM images of cells incubated with silver/dendrimer nanocomposites (DNCs) for 1 h at 37 C. Images a and b: NIH3T3 cell showing DNCs located on the surface
of the cell and randomly dispersed single particles in the cytoplasm, respectively; Images c and d: U937 cell viewing the agglomerates of DNCs located on the surface of the cell and
trapped in the phagocytic or endocytic vesicles. Fig. reproduced from Ref. [169] with permission, American Chemical Society.

in cells [169]. Furthermore, the authors studied the cytotoxicity of
dendrimers and related silver nanocomposites were evaluated using
an XTT colorimetric assay of cellular viability. The cellular uptake of
nanoparticles was examined by TEM. The dendrimer nanocomposites
are uorescent, and their surface charge, cellular internalization,
toxicity, and cell labeling capabilities are determined by the surface
functionalities of dendrimer templates. As such, these dendrimer
nanocomposites exhibit potential application as cell biomarkers due
to their uorescence properties and also the presence of ultra-small
silver nanoparticles will provide them with antimicrobial activity.
4. One-step formation of nanocomposites
4.1. Silver cations as initiators for the polymerization
The use of silver cations as oxidizing agents and initiators of
polymerization in polymer chemistry is well known, particularly in
the eld of conductive polymers, such as pyrrole [170173] or aniline
[174]. Herein, it has been widely used in order to replace iron nitrate
as an oxidizer and initiator and it is simultaneously reduced to zero-
valent metallic silver nanoparticles. In the resulting composites, the
nanoparticles are dispersed either on the surface of the polymer
particles or they are embedded inside the polymer matrix, depending
on the orientation of the macromolecular chains. The oxidation
potential of Ag(I) (E = 0.8 V, compared to 0.77 V for the Fe 3+/Fe 2+
couple) makes it ideal for all these smart, one-step, and targeted
synthetic routes toward the promotion of oxidative polymerization
and synthesis of nanocomposites. The basic advantages of these
reactions are the absence of extra reduction agents, the mild reaction
conditions, and the targeted synthesis of nanoparticles. These result
in a better dispersion of silver nanoparticles inside the polymer
matrix. Here, the polymers play various roles; they act as stabilizers,
templates, or protecting agents against agglomeration.
A very interesting route similar to the polymerization of pyrrole was
proposed by Kong et al. [175,176]. The authors employed rhodamine
as the polymer host and silver cations as initiators. In this process,
silver nanoparticle-embedded polyrhodanine nanobers were synthe-
sized by a chemical oxidation polymerization (Figs. 8 and 9). As in the
case of pyrrole, silver ions were reduced to silver nanoparticles by
oxidizing rhodanine monomer and they were simultaneously com-
plexed with rhodanine due to coordinative interactions, resulting in
the formation of silver nanoparticle-embedded polyrhodanine nano-
bers. The synthesized silver/polyrhodanine nanober was found to
have the excellent antimicrobial activity against the following bacteria:
Gram-negative E. coli, Gram-positive S. aureus, and C. albicans. The
modied KirbyBauer test demonstrated that the silver/polyrhodanine
nanober had better antimicrobial efciency than silver sulfadiazine,
probably due to the exposed surface of silver [151]. Furthermore, the
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
Fig. 8. Formation mechanism of silver/polyrhodanine composites in ethanol solution through an oxidative polymerization of rhodamine monomers. Fig. reproduced from Ref. [176]
with permission, Wiley.
nanocomposites can also be used for detecting metal ions, because
rhodanine molecule has metal-binding functional groups such as
thioamide and amide [177].
In conclusion, the simultaneous reduction of silver cation and the
oxidative polymerization of various monomers is a route with many
advantages. Of note worthy are the ne dispersion and low size of the
resulting nanoparticles. The disadvantage, however, is that the
number of monomers that can be used is quite limited and most of
them do not allow the polymerization with silver cations as initiator,
thus restricting their potential applications.
4.2. Polymer as a reductant
In order to overcome the disadvantage of the limited number of
monomers that can be used in a redox polymerization, the alternative
route is to employ polymers with functional groups that will enable
the reduction of cations and simultaneously entrap nanoparticles on
their surfaces.
Of particular interest due to the commercial availability and their
interesting properties are the well-studied matrices like SiO2 zeolites
[178180]. The work of Kim et al. [178180] involves the synthesis
of AgSiO2 nanocomposites synthesized by one-pot solgel method at
room temperature. Their purpose is to prevent the aggregation of
Ag nanoparticles, which leads to a deterioration in its antimicrobial
property. They focused their study on the thermal behavior of Ag
nanoparticles formed on the surface of SiO2 nanoparticles and the
antimicrobial properties of the nanocomposites have been proven
to decrease with increasing temperature. Their synthetic route
involves a simple deprotonation of hydroxyl silane in the following
three steps: (i) deprotonation of hydroxyl ligand in SiOH (SiOH +
B SiO + BH); (ii) electrophilic metal attack (SiO + Ag + SiO
Ag); and (iii) the growth of Ag nanoparticles on the surface of SiO2
(see Fig. 10).
Novel polymeric organicinorganic hybrids have also been used
toward that direction. For example, in a previous work, we employed
the active amine units of novel hollow polymeric cornet-like
structures toward this direction [181]. This novel polymer consists
of a phosphotriazine central core and aromatic diamine units that
129
substitute the reactive chlorine anions and are connected forming
a 3-D polymeric network. During the polymerization process, the
polymer forms hollow cornet-like microstructures due to the free
space that is left as a result of the in- and out-of-place direction of
the substitution sites of the phosphotriazine cores (Fig. 11). The
protonated amine units on the surface are active and can be used for
the reduction of noble metal cations, e.g., silver or gold. As such, the
synthesis is targeted and the silver nanoparticles are nely dispersed
and attached on the surface of the polymer and their ultrasmall
size results in a signicantly high antimicrobial activity as tested
in numerous bacterial strains and yeasts (see Table 1) [181]. No
additional reducing agents, mild conditions, very high antimicrobial
and antifungal activity and also a very light weight material due to
its hollow nature are the advantages of this process.
Also, pure and alkylated linear poly(ethyleneimine) (PEIs) have
been reported to act as both reductants and stabilizers to prepare
metallic nanoparticles [182184]. However, the stabilizing ability
for metallic nanoparticles of pure linear PEI was not satisfactory
due to its chain aggregation. This often resulted in the coagulation
of metallic nanoparticles. As for alkylated linear PEI, its stabilizing
ability was greatly improved. However, self-reduction was com-
pleted over a long period of time. As a new sort of polymers with
quasispherical branched architecture and special solution/melting
properties, hyperbranched polymers have received more and more
attention, and have been widely applied as rheological additives,
drug carriers, self-assembly precursors. Tiller and coworkers
adopted the amphiphilically modied hyperbranched PEI to stabilize
silver nanoparticles toward environmentally friendly antimicrobial
nanocomposites [185]. They further used the network lm based
on the hyperbranched PEI containing double bonds to load silver
nanoparticles. Here, Li[HBEt3] or ascorbic acid was used as a
reducing agent.
In these works, the hyperbranched polymers did show some
fascinating advantages in preparing polymer/metal nanocomposites,
such as the quasispherical branched structure with many inner cavities
and almost nonexistence of chain entanglements. Nevertheless, without
exception, extra reducing agents were needed in these systems in
order to achieve efcient and complete reduction.
130 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
Fig. 9. (a) TEM images of the silver/polyrhodanine composite and (b) comparison of
its FT-IR spectrum with the FT-IR of the monomer. Fig. reproduced from Ref. [175] with
permission, American Chemical Society.
Thus, a new kind of stabilizer, i.e., an amine-terminated hyper-
branched poly(amidoamine) (HPAMAM-NH2) has been used to
produce antimicrobial silver nanocomposites (Fig. 12) [186]. More
importantly, this hyperbranched polymer was found to serve as a
highly effective self-reducing agent. The advantages of this method are
as follows: (i) no extra reducing agent was needed; (ii) the process
was conducted at room temperature, under normal pressure, and in
aqueous solution, thus, it is a green route; and (iii) the obtained silver
nanoparticles have several excellent properties, including long-term
dispersion stability, small particle sizes, and a narrow size distribution
controlled by the amount and a good antimicrobial activity as tested
in E. coli, S. aureus, B. subtilis, and K. mobilis. The activity was enhanced
with increasing silver concentration. The bacterial inhibition ratio
of the HPAMAM-NH2/Ag nanocomposites reached up to 95% at a
silver concentration of 2.7 g/mL. Besides, pure HPAMAMNH2 also
showed some limited antimicrobial ability with the inhibitation
ratio less than 10%.
5. Smart syntheses
5.1. Thin lm formation after photocatalytic reduction of silver cations
All the methods that we have previously discussed involve the
reduction of the metal cations either by common reducing agents or
by the monomers or the polymer itself. Another simple and green
Fig. 10. Scheme describing the mechanism of formation of Ag nanoparticles on the
surface of SiO2 nanoparticle, with and without catalyst, and schematic diagram of
chemical structure of AgSiO2 nanocomposite. Fig. reproduced from Ref. [179] with
permission, American Chemical Society.
methodology is based on the photoreduction of silver nitrate using
bare titania and polyvinyl alcohol (PVA)-capped colloidal titanium
dioxide nanoparticles/nanotubes under UVvis light with a wave-
length of 365 nm. The resulting silver nanoparticles had an average
particle size around 15 nm. The antimicrobial efciency of all
nanocomposites was investigated on E. coli using standard procedures
and the metal-metal oxide nanocomposites are shown to be very
efcient toward destroying these Gram-negative bacteria [187].
5.2. Layer by layer assemblies, magnetically controllable silverpolymer
composites
All the above mentioned nanocomposites are static. They may
be dispersed in a solvent or attached on a solid surface. However,
their place for acting is restricted. In this regard, more advanced
nanocomposites, e.g., magnetically modied, should be synthesized
and applied.
Lee et al. [188] have developed a very efcient route toward
magnetically directed multilayers incorporating nanoparticles. They
used polyacrylamide (PAM) and polyacrylic acid for the construction
of the multi-layered assembly which have been proved to be very
effective in many Gram-negative and Gram-positive bacteria.
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
Fig. 11. TEM and SEM images of the hollow cornet-like polymeric matrix synthesized by the reaction of phosphonitrilic chloride and 1,4 phenylenediamine in reuxing toluene. The
silver nanoparticles were covalently attached by reduction of silver nitrate by the amine units of the polymer matrix and can be seen homogeneously decorating the hollow polymer.
Fig. reproduced from Ref. [181] with permission, Wiley.
In general, the layer-by-layer assembly is a powerful tool for the
construction of functional composite materials with improved
properties. It is one of the most efcient and popular methods toward
functional thin lms. In this direction, a similar path was followed
by Li et al. [189]. They presented the construction of a two-level
antimicrobial coating with both release-killing and contact-killing
capabilities (Fig. 13) [189]. Using a combination of an aqueous layer-
by-layer deposition technique, nanoparticle surface modication
chemistry, and nanoreactor chemistry, they constructed thin lm
coatings with two distinct layered functional regions: a reservoir for
the loading and release of bactericidal chemicals and a nanoparticle
surface cap with immobilized bactericides. This results in dual-
functional bactericidal coatings bearing both chemical-releasing
bacteria-killing capacity and contact bacteria-killing capacity. These
dual-functional coatings showed very high initial bacteria-killing
efciency due to the release of silver ions and retained signicant
antimicrobial activity after the depletion of embedded Ag because of
the immobilized quaternary ammonium salts. This tendency to form
nanoparticles at interfaces when using nanoreactor chemistry has
been observed previously [190]. Furthermore, the reduction of silver
cations can also be carried out in the dry phase by using hydrogen
gas as a reductant. In the solid state reduction, the nanoparticles
exhibit fewer tendencies to accumulate at interfaces. In the wet-phase
reduction, the multilayers are swollen with water, presumably
providing more mobility to the nanoparticles or silver atoms that
ultimately form the nanoparticles.
Table 1
Minimum inhibition concentration (MIC) values for the phoshonitrilic/diamine
nanocomposites synthesized by Dallas et al. [181].
Bacterial strain MIC (g/L) Yeasts
Enterococcus faecium (VRE) 0.177 Candida albicans
Staphylococcus aureus (MRSA 0.350 Candida tropicalis
Escherichia coli CCM 3954 0.088 Candida parapsilosis
Pseudomonas aeruginosa CCM 3955 0.044
Staphylococcus epidermidis 0.044
Klebsiella pneunomoniae (ESBL) 0.177
131
The Kotov group has found that sufcient number of layers of the
polyelectrolyte poly-(diallyldimethylammonium chloride) (PDDA)
and montmorillonite can lead to a free-standing lm with mechanical
properties similar to those of nacre and lamellar bone [191]. In
previous studies, the Tsukruk group has demonstrated that incorpo-
ration of Au NPs in the polyectrolyte lms also resulted in free-
standing lms with excellent mechanical properties and unique
potential applications [192,193]. The study of the Kotov group
demonstrates an antimicrobial coating for such structures using a
multifunctional layer-by-layer assembly of PDDA, montmorillonite,
and biocompatible, starch-coated silver NPs prepared using a green
synthesis strategy. Film homogeneity and deposition were monitored
using AFM and UVvis spectrometry, and lm stability was analyzed
using ICP-MS. Cell culture testing was also performed with E. coli and
mammalian cells to observe bactericidal activity and cytocompat-
ibility. Such antimicrobial coatings could prove effective for a variety
of biomedical devices and help realize the potential bioapplications of
these high strength nacre-like composites. The composite possesses
strong antimicrobial characteristics as well as biocompatibility with
human osteoblasts.
Recently, our group incorporated organophilic magnetic iron
oxide nanoparticles in a phosphazene-based matrix (Fig. 14) and
by exploiting the amine groups on the surface of the polymer they
created a magnetically controllable antimicrobial agent with prom-
ising targeted disinfection and bactericidal effect and subsequent
removal by a magnet [39]. The material had a saturation magnetiza-
tion of nearly 6 Am 2/kg, enough to be attracted by a simple magnet.
This can be particularly useful in the case that the antimicrobial
agent should be later removed from the infected point and con-
sequently reused for other disinfection purposes. The material can
MIC (g/L) be also targeted and directed by an external magnetic eld. This can
be of particular importance in the case of disinfection of the poorly
0.044
0.177
accessible areas. Prucek et al. recently expanded this process by using
0.088 the polyacrylic acid as a biocompatible spacer between magnetic iron
oxides and the silver nanoparticles [194]. Such magnetically control-
lable antimicrobial colloid would be well applicable even in the
case of targeted applications in biomedicine.
132 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135

Fig. 12. The synthesis of polyamidoamine (HPAMAM-NH2) dendrimers and their silver nanocomposites. The dendrimers were synthesized through the reaction of N,N-methylene
bisacrylamide and 1-(2-aminoethyl)piperazine. The silver nanoparticles are formed though a one-step reduction by the amine units of the dendrimers. Fig. reproduced from
Ref. [186] with permission, American Chemical Society.

5.3. Non-chemical directions for the synthesis of composites
A brief demonstration of non-chemical fabrication of silver/polymer
antimicrobial composites will be done in this paragraph. Silver/
polyethylene oxide (PEO) composites are well known and effective
antimicrobial agents [195198]. PEO (or polyethylene glycol, PEG) is
used for its hydrophilic behavior in water and biological media. It
exhibits non-fouling behavior against the adhesion of cells, bacteria,
proteins, and other biological systems. Consequently, the syntheses of
Ag nanoparticles that are embedded in polymers by low-temperature
plasma techniques were widely studied recently [199], but the
fabrication of the combination of Ag target and electrode sputtering
with the simultaneous polymerization of PEO for Ag/PEO or PEO-like
nanocomposites in radio frequency plasma-enhanced chemical
vapor deposition (rf-PECVD) seemed inefcient because of poisoning
electrodes that not only limit the deposition rate but also obtain a
monotonic lm. Interestingly, Piedade et al. fabricated composites
where the (111) crystal plains of silver, surfaces with less tendency
to absorb reactive species, are preferentially oriented [199201].
For silver deposition, meanwhile, magnetron sputtering had been
commonly used for the synthesis of Ag nanoparticles. Because of the
easy oxidation and aggregation of Ag nanoparticles during sputtering,
the deposition process is performed in only a relatively low-pressure
chamber [202,203] but it is still difcult, for example, to obtain particles

Fig. 13. Scheme showing the design of a two-level antimicrobial material with quaternary ammonium salts and silver. Initially the layer-by-layer (LbL) deposition of a reservoir made
of bilayers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) takes place. (a) A bilayer of PAH and SiO2 nanoparticles is added to the top. (b) SiO2 nanoparticles
are modied with a quaternary ammonium silane (OQAS). (c) Silver cations are loaded inside the coating using the available unreacted carboxylic acid groups in the LbL multilayers.
Fig. reproduced from Ref. [189] with permission, American Chemical Society.
 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135 133

Fig. 14. Top: the synthesis of the magnetically controllable antimicrobial agent. Schematic representation of the redox reaction between the polymer and the silver cations for the
synthesis of silver nanoparticles; the maghemite nanoparticles are the spheres in the lower part of the scheme and are incorporated inside the polymer matrix. Bottom: TEM image
indicating the attachment of silver nanoparticles on the surface of the polymer and the entrapment of magnetic nanoparticles inside the polymer mass. Fig. reproduced from ref. [39]
with permission, Wiley.

with a small diameter. However, Mejia et al. [204] recently prepared an
Ag/textile composite through sputtering where the silver nanoparticles
had an average size of 4.7 nm with a very good size distribution. XPS
analysis showed the presence of oxidized silver cations on the surface.
Chen et al. [205] present a magnetron sputtering method to prepare a
nanocomposite of embedded silver nanoparticles in simultaneously
polymerized, polyethylene oxide (PEO) lm. They employed X-ray
diffraction (XRD) in order to show that the silver nanoparticles had
tunable growth in a preferential (111) facet, and transmission electron
microscopy reveals that diameters of silver could also be controllable in
the range of 510 nm by varying the processing parameters, such as the
working pressure and the target-to-substrate distance. The antimicro-
bial activities tests demonstrate that nanocrystalline silver in the Ag/
PEO composite fabricated by this method has a markedly efcient effect
against E. coli and S. aureus [205].
6. Outlook
The constantly expanding eld of silver nanocomposites has been
proven to become of signicant importance mainly due to their well
proved antimicrobial properties and a great potential for applications
as antimicrobial coatings and agents. Among the many experimental
routes that have been proposed, all appear to have some advantages
as well as drawbacks. In general, the goal is to identify the method
that allows the preparation of composites with biocompatible,
biodegradable, and non-toxic matrix, synthesized through non-toxic
monomers and precursors with well attached silver nanoparticles
exhibiting a low mean diameter and narrow size distribution. Notably,
the nanocomposites that combine these features with high silver wt.%
loading have achieved MIC values comparable to those of neat silver
nanoparticles.
Let briey summarize advantages and drawbacks of selected
synthetic routes and produced silver-bearing polymeric nanocompo-
sites. Engineering polymers have restricted applications in biomedicinal
elds mainly due to their limited biocompatibility. Silver containing
carbohydrates and biopolymers including hydrogels and carboxymeth-
ylcellulose have a relatively large potential due to their biocompatibility,
low cost and green approach. However, the complicated organic
reactions and the necessity to use apply extra reducing agent represent
drawbacks of some of these synthetic routes. Dendrimers as hosts for
silver nanoparticles constitute water soluble and biocompatible
nanomaterials that can be used in biological systems and that allow to
achieve the narrow size distribution of silver nanoparticles.
The advanced synthetic routes do not use any extra reducing
agents and exploit the polymers with suitable functional groups (e.g.,
NH2) for one-step reduction of silver nanoparticles, which can be
even covalently bound to the matrix. These green one step procedures
when the polymer acts simultaneously as a reductant and matrix for
the formed silver nanoparticles, may be recognized, in our opinion, as
the most sophisticated approaches with a high application potential,
mainly if biocompatible polymer is used. The polymers with dened
and controllable morphology that will molecularly mediate the
assembly of nanoparticles and their interparticle interactions repre-
sent also an important target for the polymer chemists. Finally,
magnetically controllable silver polymeric composites, which enable
the targeted transport and consequent antimicrobial action of
nanosilver in required place, seem to be of a great importance. The
magnetically drivable silver nanoparticles with biocompatible
134 P. Dallas et al. / Advances in Colloid and Interface Science 166 (2011) 119135
polymer are of a particular interest due to their possible in vivo
applications and evaluation of their targeted antimicrobial effect
compared to that of common antibiotics.
Anyhow, there are also scientic gaps in this eld related mainly to
mechanisms of antifungal activity and antivirotic activity of silver
polymer composites. As already stated, an application of NTA may
allow to examine the movement of particle in the studied system to
have better knowledge on the action of silver nanoparticles on the
bacterial species. Similarly, the toxicity against human cell, general
risks related to the release of silver ions are described only marginally
for silver-based polymeric composites. The long-term efciencies of
the silver polymeric composites representing an important practical
aspect have not been reported at all and should be addressed much
more in future.
Acknowledgments
The authors gratefully acknowledge the support by the Operational
Program Research and Development for Innovations European
Social Fund (Project No. CZ.1.05/2.1.00/03.0058 of the Ministry of
Education, Youth and Sports of the Czech Republic). This work has also
been supported by the Projects of the Ministry of Education of the
Czech Republic (Projects Nos. 1M6198959201 and MSM6198959218).
The authors would like to acknowledge Dr. A. Panacek for his useful
comments.
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