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Sharma, V. K., Yngard, R. A. & Lin, Y. Silver nanoparticles: Green synthesis

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 Advances in Colloid and Interface Science 145 (2009) 83–96

Contents lists available at ScienceDirect

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 nanoparticles: Green synthesis and their antimicrobial activities

Virender K. Sharma ⁎, Ria A. Yngard, Yekaterina Lin
Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, Florida 32901, USA

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

Available online 17 September 2008 This review presents an overview of silver nanoparticles (Ag NPs) preparation by green synthesis approaches
that have advantages over conventional methods involving chemical agents associated with environmental
Keywords: toxicity. Green synthetic methods include mixed-valence polyoxometallates, polysaccharide, Tollens,
Silver colloid nanoparticles irradiation, and biological. The mixed-valence polyoxometallates method was carried out in water, an
Environmentally friendly synthesis
environmentally-friendly solvent. Solutions of AgNO3 containing glucose and starch in water gave starch-
Irradiation
Silver-titanium dioxide nanoparticles
protected Ag NPs, which could be integrated into medical applications. Tollens process involves the reduction
Antibacterial of Ag(NH3)+2 by saccharides forming Ag NP films with particle sizes from 50–200 nm, Ag hydrosols with
particles in the order of 20–50 nm, and Ag colloid particles of different shapes. The reduction of Ag(NH3)+2 by
HTAB (n-hexadecyltrimethylammonium bromide) gave Ag NPs of different morphologies: cubes, triangles,
wires, and aligned wires. Ag NPs synthesis by irradiation of Ag+ ions does not involve a reducing agent and is
an appealing procedure. Eco-friendly bio-organisms in plant extracts contain proteins, which act as both
reducing and capping agents forming stable and shape-controlled Ag NPs. The synthetic procedures of
polymer-Ag and TiO2–Ag NPs are also given. Both Ag NPs and Ag NPs modified by surfactants or polymers
showed high antimicrobial activity against Gram-positive and Gram-negative bacteria. The mechanism of the
Ag NP bactericidal activity is discussed in terms of Ag NP interaction with the cell membranes of bacteria.
Silver-containing filters are shown to have antibacterial properties in water and air purification. Finally,
human and environmental implications of Ag NPs to the ecology of aquatic environment are briefly
discussed.
© 2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2. Silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3. Green synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.1. Polysaccharide method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2. Tollens method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.3. Irradiation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.4. Biological method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.5. Polyoxometalates method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4. Ag NPs and their incorporation into other materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.1. Silver-doped hydroxyapatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.2. Polymer-silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.2.1. Poly(vinyl alcohol)-silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.3. Silver nanoparticles on TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5. Antimicrobial activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.1. Studies: mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.2. The battle against infection: Ag NPs and their incorporation into the medical field . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.2.1. Ag NPs and HIV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3. Antibacterial water filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.4. Antimicrobial air filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

⁎ Corresponding author. Tel.: +1 321 674 7310; fax: +1 321 674 8951.
E-mail address: vsharma@fit.edu (V.K. Sharma).

0001-8686/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2008.09.002
84 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

6. Implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6.1. Human Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6.2. Environmental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
7. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

1. Introduction Colloidal silver is of particular interest because of distinctive proper-

ties, such as good conductivity, chemical stability, catalytic and
The application of nanoscale materials and structures, usually antibacterial activity [31]. For example, silver colloids are useful
ranging from 1 to 100 nanometers (nm), is an emerging area of substrates for surface enhanced spectroscopy (SERS), since it partly
nanoscience and nanotechnology. Nanomaterials may provide solu- requires an electrically conducting surface [19,32,33]. Also, the
tions to technological and environmental challenges in the areas of exposure of silver ions to light reduces them into 3–5 atoms clusters
solar energy conversion, catalysis, medicine, and water treatment of silver, which catalyzes a gain of ∼ 108 atoms in latent image to be
[1,2]. This increasing demand must be accompanied by “green” visible [34].
synthesis methods. In the global efforts to reduce generated Chemical reduction is the most frequently applied method for the
hazardous waste, “green” chemistry and chemical processes are preparation of silver nanoparticles (Ag NPs) as stable, colloidal
progressively integrating with modern developments in science and dispersions in water or organic solvents [35,36]. Commonly used
industry. Implementation of these sustainable processes should adopt reductants are borohydride, citrate, ascorbate, and elemental hydro-
the 12 fundamental principles of green chemistry [3–7]. These gen [37–45]. The reduction of silver ions (Ag+) in aqueous solution
principles are geared to guide in minimizing the use of unsafe generally yields colloidal silver with particle diameters of sever-
products and maximizing the efficiency of chemical processes. Hence, al nanometers [36]. Initially, the reduction of various complexes with
any synthetic route or chemical process should address these Ag+ ions leads to the formation of silver atoms (Ag0), which is followed
principles by using environmentally benign solvents and nontoxic by agglomeration into oligomeric clusters [46]. These clusters
chemicals [3]. eventually lead to the formation of colloidal Ag particles [46]. When
Nanomaterials often show unique and considerably changed the colloidal particles are much smaller than the wavelength of visible
physical, chemical and biological properties compared to their light, the solutions have a yellow color with an intense band in the
macro scaled counterparts [8]. Synthesis of noble metal nanoparticles 380–400 nm range and other less intense or smaller bands at longer
for applications such as catalysis, electronics, optics, environmental, wavelength in the absorption spectrum [19,32,33]. This band is
and biotechnology is an area of constant interest [9–15]. Gold, silver, attributed to collective excitation of the electron gas in the particles,
and copper have been used mostly for the synthesis of stable with a periodic change in electron density at the surface (surface
dispersions of nanoparticles, which are useful in areas such as plasmon absorption) [47–49].
photography, catalysis, biological labeling, photonics, optoelectronics Previous studies showed that use of a strong reductant such as
and surface-enhanced Raman scattering (SERS) detection [16,17]. borohydride, resulted in small particles that were somewhat mono-
Additionally, metal nanoparticles have a surface plasmon resonance disperse, but the generation of larger particles was difficult to control
absorption in the UV–Visible region. The surface plasmon band arises [50,51]. Use of a weaker reductant such as citrate, resulted in a slower
from the coherent existence of free electrons in the conduction band reduction rate, but the size distribution was far from narrow
due to the small particle size [18,19]. The band shift is dependent on [37,38,52]. Controlled synthesis of Ag NPs is based on a two-step
the particle size, chemical surrounding, adsorbed species on the reduction process [51]. In this technique a strong reducing agent is
surface, and dielectric constant [20]. A unique characteristic of these used to produce small Ag particles, which are enlarged in a secondary
synthesized metal particles is that a change in the absorbance or step by further reduction with a weaker reducing agent [37]. Different
wavelength gives a measure of the particle size, shape, and studies reported the enlargement of particles in the secondary step
interparticle properties [20,21]. Moreover, functionalized, biocompa- from about 20–45 nm to 120–170 nm [53–55]. Moreover, the initial sol
tible and inert nanomaterials have potential applications in cancer was not reproducible and specialized equipment was needed [39]. The
diagnosis and therapy [22–26]. The target delivery of anticancer drugs syntheses of nanoparticles by chemical reduction methods are
has been done using nanomaterials [22]. With the use of fluorescent therefore often performed in the presence of stabilizers in order to
and magnetic nanocrystals, the detection and monitoring of tumor prevent unwanted agglomeration of the colloids.
biomakers have been demonstrated [24,25]. The green synthesis of Ag NPs involves three main steps, which
Generally, metal nanoparticles can be prepared and stabilized by must be evaluated based on green chemistry perspectives, including
physical and chemical methods; the chemical approach, such as (1) selection of solvent medium, (2) selection of environmentally
chemical reduction, electrochemical techniques, and photochemical benign reducing agent, and (3) selection of nontoxic substances for the
reduction is most widely used [27,28]. Studies have shown that the Ag NPs stability [7]. Based on this approach, we have reviewed the
size, morphology, stability and properties (chemical and physical) of green-chemistry type Ag NP synthesis processes. The synthesis of
the metal nanoparticles are strongly influenced by the experimental polymer-Ag NPs and Ag NPS on TiO2 are also summarized because of
conditions, the kinetics of interaction of metal ions with reducing their industrial and environmental importance. Finally, antimicrobial
agents, and adsorption processes of stabilizing agent with metal activities of Ag NPs with some examples of mechanism are presented.
nanoparticles [21,22]. Hence, the design of a synthesis method in Implications of Ag NPs to human health and environment are briefly
which the size, morphology, stability and properties are controlled has discussed.
become a major field of interest [29].
3. Green synthesis
2. Silver nanoparticles
3.1. Polysaccharide method
Silver is widely known as a catalyst for the oxidation of methanol
to formaldehyde and ethylene to ethylene oxide [30]. In the United In this method, Ag NPs are prepared using water as an
States, more than 4 × 106 tons of silver were consumed in 2000. environmentally benign solvent and polysaccharides as a capping
 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96 85

agent, or in some cases polysaccharides serve as both a reducing and a

capping agent. For instance, synthesis of starch-Ag NPs was carried
out with starch as a capping agent and β-D-glucose as a reducing agent
in a gently heated system [7]. The starch in the solution mixture avoids
use of relatively toxic organic solvents [56]. Additionally, the binding
interactions between starch and Ag NPs are weak and can
be reversible at higher temperatures, allowing separation of the
synthesized particles.
In a case of dual polysaccharide function, Ag NPs were synthesized by
the reduction of Ag+ inside of nanoscopic starch templates, Fig. 1. The
extensive network of hydrogen bonds in the templates provides surface
passivation or protection against nanoparticle aggregation [7,57]. Also,
Ag NPs were synthesized by using negatively charged heparin as a
reducing/stabilizing agent by heating a solution of AgNO3 and heparin to
70 °C for ∼8 h [58]. TEM images of these Ag NPs revealed an increase in
particle size with increased concentrations of both, AgNO3 and heparin
[58]. Furthermore, changes in heparin concentration varied Ag NP size
and morphology suggesting that heparin must behave as a nucleation
Fig. 2. Concentration of free Ag+ ions and silver–ammonia complexes versus the
controller and stabilizer [58]. The Ag NPs were highly stable and showed ammonia concentration. The total [silver] = 0.001 M.
no signs of aggregation after two months [58].
In another study, stable Ag NPs (10–34 nm) were synthesized by
autoclaving a solution of AgNO3 and starch (capping/reducing agent) glucose and the lowest ammonia concentration, 0.005 M, resulted in
at 15 psi and 121 °C for 5 min [59]. The Ag NPs were stable in solution the smallest average particle size of 57 nm with an intense maximum
for three months at ∼ 25 °C. Smaller Ag NPs (≤10 nm) were produced of the surface plasmon absorbance at 420 nm. Furthermore, a
by mixing two solutions of AgNO3 containing starch, a capping agent, simultaneous increase in particle size and polydispersity was detected
and NaOH solutions containing glucose, a reducing agent, in a with an increase in [NH3] from 0.005 M to 0.2 M [63].
spinning disk reactor with a reaction time of less than 10 min [60]. To gain further insight on the effect of ammonia, it is important to
Importantly, starch-protected nanoparticles can be easily integrated know the chemical speciation of Ag(I) in the studied system. Both, Ag
into systems for biological and pharmaceutical applications.

3.2. Tollens method

The Tollens synthesis method gives Ag NPs with a controlled size in

a one-step process [61–64]. The basic Tollens reaction involves the
reduction of Ag(NH3)+2(aq), a Tollens reagent, by an aldehyde, Eq. (1).

AgðNH3 Þþ
2 ðaqÞ þ RCHOðaqÞ→AgðsÞ þ RCOOHðaqÞ ð1Þ

In the modified Tollens procedure, Ag+ ions are reduced by

saccharides in the presence of ammonia, yielding Ag NP films with
particle sizes from 50–200 nm, Ag hydrosols with particles in the
order of 20–50 nm, and Ag NPs of different shapes [62,63]. Ag(NH3)+2 is
a stable complex ion resulting from ammonia's strong affinity for Ag+,
therefore the ammonia concentration and nature of the reductant
must play a major role in controlling the Ag NP size [63].
To better understand the synthesis process lets consider this
example. A research study on the saccharide reduction of Ag+ ions by
the modified Tollens process revealed that the smallest particles were
formed at the lowest ammonia concentration [63]. Specifically,

Fig. 3. Log-normal size distribution of silver nanoparticles at different pH for glucose

Fig. 1. Typical TEM image of starch silver nanoparticles. The scale bar corresponds to and maltose in 0.005 M ammonia concentration (reproduced from [66] with permission
20 nm (reproduced from [7] with permission from the American Chemical Society). from the American Chemical Society).
86 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

(NH3)+ and Ag(NH3)+2 are produced in the reaction solution as shown stabilized by two surfactants, sodium dodecyl sulfate-SDS and
in Eqs. (2) and (3), where the formation constants are log β1 = 3.367 polyoxyethylenesorbitane monooleate-Tween 80, and a polymer,
and log β2 = 7.251, respectively [65]. polyvinylpyrrolidone-PVP 360 [67,68].
A modified Ag mirror reaction (Tollens reaction) is an example of a
Agþ þ NH3 ⇆AgðNH3 Þþ logβ1 ¼ 3:367 ð2Þ synthesis route yielding Ag NPs of different shapes. Ag NPs of various
morphologies with b10 nm diameters were synthesized in water by
Agþ þ 2NH3 ⇆AgðNH3 Þþ
2 logβ2 ¼ 7:251 ð3Þ adjusting the concentrations of n-hexadecyltrimethylammonium
bromide (HTAB) and the Tollens reagent, Ag(NH3)+2, at 120 °C
The concentrations of the possible Ag species using formation [69,70]. TEM images of Ag NPs obtained by this method are shown
constants expressed in Eqs. (2) and (3) as a function of [NH3] are in Fig. 4.
displayed in Fig. 2. A decrease in [Ag+] in the presence of NH3 results in
a decrease in the reduction rate to Ag(s), Eq. (1), and thus is reflected 3.3. Irradiation method
in the particle size. Initially this would lead to a decrease in the
formation of stable Ag nuclei. In the latter stage of particle growth, the Ag NPs can be successfully synthesized by using a variety of
limited presence of nuclei would lead to larger particles. irradiation methods. For example, laser irradiation of an aqueous
Likewise, Ag NPs of controllable sizes were synthesized by solution of Ag salt and surfactant can fabricate Ag NPs with a well-
reduction of [Ag(NH3)2]+ with two monosaccharides (glucose and defined shape and size distribution [71]. No reducing agent is required
galactose) and two disaccharides (maltose and lactose) [66]. The in this method. Additionally, laser was applied in a photo-sensitization
synthesis was carried out at various ammonia concentrations (0.005– technique for the synthesis of Ag NPs using benzophenone [72]. Here,
0.20 M) and pH conditions (11.5–13.0) resulting in average particle low laser powers at short irradiation times gave Ag NPs of ∼ 20 nm,
sizes of 25–450 nm. As anticipated, the average particle size increased while an increased irradiation power gave nanoparticles of ∼ 5 nm.
with increasing [NH3]. A maximum particle size was reached at the The formation of Ag NPs by this photo-sensitization technique was
concentration of 0.035 M for disaccharides and 0.20 M for mono- also achieved using a mercury lamp [72]. In the visible light irradiation
saccharides. The difference in structure of monosaccharides and studies, photo-sensitized growth of Ag NPs using thiophene as a
disaccharides influences the particle size with disaccharides giving on sensitizing dye [73] and Ag NP production by illumination of Ag(NH3)+
average smaller particles than monosaccharides at pH 11.5 (e.g. Fig. 3). in ethanol has been carried out [74].
Furthermore, particles obtained at pH 11.5 were smaller than those at Synthesis procedures using microwave irradiation has also been
pH 12.5. Polydispersity also decreased by lowering the pH (Fig. 3). employed. Microwave radiation of a carboxymethyl cellulose sodium
Maltose gave Ag NPs with the most narrow size distribution and the and silver nitrates solution produced uniform Ag NPs that were stable
smallest average size of 25 nm. To extend shelf life, Ag NPs were for two months at room temperature [75]. The microwave irradiation

Fig. 4. TEM images of silver nanoparticles: (a) cubes; (b) triangles; (c) wires; (d) an alignment of wires. (reproduced from [70] with permission from the American Chemical Society).
 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96 87

of a AgNO3-ethylene-glycol-H2[PtCl6]-poly(vinylpyrrolidone) solution olens, gave Ag NPs after 24 h [96]. The reaction time was reduced to 2 h
gave Ag NPs of different shapes within 3 min. [76]. Recently, the use of by heating the reaction mixture just below the boiling point [98].
microwave radiation to synthesize nearly monodisperse Ag NPs using Secreted proteins in spent mushroom substrate reduced Ag+ to give
basic amino acids as reducing agents and soluble starch as a protecting uniformly distributed Ag-protein (core–shell) NPs with an average
agent has been shown [77]. size of 30.5 nm [99]. A vegetable, Capsicum annuum L., was used to also
Ionizing radiation can reduce Ag+ ions in Ag NPs synthesis [78–83]. synthesize Ag NPs [100].
In one study, Ag NPs of N10 nm were produced in supercritical ethane Studying the synthesis of Ag NPs with isolated/purified bioor-
at 80 °C and 80–120 bar with methanol as a solvent [78]. The solvated ganics may give better insight into the system mechanism.
electrons reduced the Ag+ ions and a characteristic plasmon absorp- Glutathione (γ-Glu-Cys-Gly-) as a reducing/capping agent can
tion was detected within 1–10 s after the ionization pulse. produce water-soluble and size tunable Ag NPs that easily bind to
Furthermore, radiolysis has been applied in the Ag NP production. The model protein (bovine serum albumin) — attractive for medical
radiolysis of Ag+ ions in ethylene glycol was studied [82]. Here, the applications [101]. Tryptophan residues of synthetic oligopeptides at
formation of Ago was observed at 350 nm (k (Ag+ +e−solv)=2.8×109 M− 1 s− 1) the C-terminus were identified as reducing agents giving Ag NPs
and the surface plasmon band appeared slowly at 400 nm with a [102]. Furthermore, Ag NPs were successfully synthesized by
coalescence cascade k = 2 × 106 M− 1 s− 1 [82]. Furthermore, Ag NPs Vitamin E in the Langmuir–Blodgett technique, by biosurfactants,
supported on silica aerogel were synthesized using gamma radiolysis such as sophorolipids, [103–105] and by L-Valine-based oligopep-
[83]. The Ag clusters were stable in the 2–9 pH range and started tides with chemical structures, Z-(L-Val)3-OMe and Z-(L-Val)2-L-Cys
agglomeration at pH N9 [83]. In another work, oligochitosan as a (S-Bzl)-OMe [106]. The sulfur content in the Z-(L-Val)2-L-Cys(S-Bzl)-
stabilizer was used in preparation of Ag NPs by gamma radiation OMe controls the shape and size of Ag NPs, which suggests the
synthesizing 5–15 nm stable Ag NPs in a 1.8–9.0 pH range [79]. interaction between the Ag+ ion and the thioether moiety of the
Gamma radiation in acetic water solution containing AgNO3 and peptide [106]. Oleic acid has also been used in environmentally-
chitosan gave particles with an average diameter of 4–5 nm [80]. Ag friendly synthesis of organic-soluble Ag NPs [107].
NPs of different size (60–200 nm) have also been synthesized by Several microorganisms have been utilized to grow Ag NPs
irradiating a solution, prepared by mixing AgNO3 and poly-vinyl-alcohol, intracellularly or extracellularly [108–114]. For instance, Ag containing
with 6 MeV electrons [84]. The variation of electron fluence nanocrystals of different compositions were synthesized by Pseudo-
from 2 × 1013–3 × 1015 e cm− 2 produced Ag NPs of narrow size distribu- monas stutzeri AG259 bacterium [108]. In Fusarium oxysporum fungus,
tion (60–10 nm) [84]. the reduction of Ag+ ions was attributed to an enzymatic process
The pulse radiolysis technique has been applied to study the involving NADH-dependent reductase [113]. The white rot fungus,
reactions of inorganic and organic species in Ag NP synthesis [85–87]. Phanerochaete chrysosporium, also reduced Ag+ ion to form Ag NPs; a
This technique was successfully applied to understand the factors protein was suggested to cause the reduction [114]. Possible involve-
controlling the shape and size of Ag NPs produced by a common ment of proteins in synthesizing Ag NPs was observed in filamentous
reduction method using citrate ions [88]. Interestingly, the citrate ion cyanobacterium, Plectonema boryanum UTEX 485 [115]. Moreover, Ag+
functioned as a reductant, a complexant, and a stabilizer. Recently, a reduction by culture supernatants of Klebsiella pneumonia, Escherichia
pulse radiolysis study was performed to demonstrate the role of coli (E. coli), and Enterobacter cloacae (Enterobaceteriacae) produced
phenol derivatives in the formation of Ag NPs by the reduction of Ag+ rapid formations of Ag NPs [116].
ions with dihydroxybenzene [89].
In a morphology conversion study, suspensions of Ag nanospheres 3.5. Polyoxometalates method
were converted to triangular Ag nanocrystals, so called nanoprisms, in
high yield using photoinduced electron transfer [90]. This photo- Polyoxometalates, POMs, have the potential of synthesizing Ag NPs
induced method was extended to demonstrate synthesis of relatively because they are soluble in water and have the capability of undergoing
monodisperse nanoprisms with desired edge lengths of 30–120 nm stepwise, multielectron redox reactions without disturbing their
[91]. With the use of dual-beam illumination, the nanoparticle growth structure [117–119]. For example, Ag NPs were synthesized by
process could be controlled. illuminating a deaerated solution of POM/S/Ag+ (POM: [PW12O40]3−,
[SiW12O40]4−; S:prpan-2-ol or 2,4-dichlorophenol) [119]. In this method
3.4. Biological method POMs serve both as a photocatalyst, a reducing agent, and as a stabilizer
[119]. In another study, one-step synthesis and stabilization of Ag
Extracts from bio-organisms may act both as reducing and capping nanostructures with MoV–MoVI mixed-valence POMs in water at room
agents in Ag NPs synthesis. The reduction of Ag+ ions by combinations temperature has been demonstrated [120]. This method did not use a
of biomolecules found in these extracts such as enzymes/proteins, catalyst or a selective etching agent.
amino acids, polysaccharides, and vitamins [92,93] is environmentally Ag NPs of different shape and size can be obtained using different
benign, yet chemically complex. An extensive volume of literature POMs in which the POMs serve as a reductant and a stabilizer.
reports successful Ag NP synthesis using bioorganic compounds. For instance, a salt, Ag2SO4, and POMs, (NH4)10[MoV)4(MoVI)2O14
For example, the extract of unicellular green algae Chlorella vulgaris (O3PCH2PO3)2(HO3PCH2PO3)2]-15 H2O and H7[β-P(MoVI)4(MoVI)8O40],
was used to synthesize single-crystalline Ag nanoplates at room were reacted. After several minutes of mixing a characteristic SPR band
temperature [94]. Proteins in the extract provide dual function of Ag+ at 400 nm for Ag NPs appeared and the location of the peak was not
reduction and shape-control in the nanosilver synthesis. The carboxyl significantly affected by the initial concentration of Ag2SO4 (Fig. 5a)
groups in aspartic and/or glutamine residues and the hydroxyl groups in [120]. The Ag NPs obtained were spherical and quasi-monodispersed
tyrosine residues of the proteins were suggested to be responsible for with a diameter of ∼38 nm (Fig. 5b), the particle size distribution was
the Ag+ ion reduction [94]. Carrying out the reduction process by a quantitatively displayed in a histogram (Fig. 5c). The single Ag NP in
simple bifunctional tripeptide Asp-Asp-Tyr-OMe further identified the Fig. 5d has a Ag-POM core-shell structure with a ∼2 nm thick POM layer.
involvement of these residues. This synthesis process gave small Ag
nanoplates with low polydispersity in good yield (N55%) [94]. 4. Ag NPs and their incorporation into other materials
Plant extracts from live alfalfa, the broths of lemongrass, geranium
leaves and others have served as green reactants in Ag NP synthesis The unique properties of Ag NPs have been extended into a broader
[95–97]. The reaction of aqueous AgNO3 with an aqueous extract of range of applications. Incorporation of Ag NPs with other materials is an
leaves of a common ornamental geranium plant, Pelargonium grave- attractive method of increasing compatibility for specific applications.
88 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

Fig. 5. (a) SPR spectra of Ag nanoparticles obtained from different molar ratios, (b) a representative TEM image of Ag nanoparticles obtained from the mixture with γ) 4, (c) size
histogram of Ag nanoparticles of about 200 NPs counted from TEM image showing the distribution of Ag NPs, and (d) a magnified Ag nanoparticle. (reproduced from [70] with
permission from the American Chemical Society).

4.1. Silver-doped hydroxyapatite evaporation method since the polymer solvent is evaporated from the
reaction mixture after NP dispersion. However, this often leads to
There is interest in inorganic-inorganic hybrid nanocomposites inhomogeneous distribution of the particles in the polymer. One
materials because of their industrial and medical applications [121– solution is the in situ synthesis of metal particles in the polymer
124]. Recently, one-step synthesis of anisotropic Ag nanocrystals was matrix, which involves the dissolution and reduction of metal salts or
achieved by reducing aqueous Ag+ ion by the electron transfer from complexes into the matrix [138,143]. Or, another approach is a system
the surface of hydroxyapatite (HA) [125]. The hydroxyl group in this in which simultaneous polymerization and metal reduction occur.
process acted both as a reducing and a binding agent to give highly For example, the in situ reduction of Ag+ ions in poly(N-vinyl-2-
oriented flat rod and needle-like Ag NPs [125]. A microwave process pyrrolidone) (PVP) by microwave irradiation produced particles with
was also applied to synthesize nanosize Ag-substituted HA with a narrow size distribution [144] and Ag NPs incorporated in acacia, a
length of 60–70 nm and width of 15-20 nm [126]. natural polymer, had been made under mild condition [145]. Or, a
conventional heating method to polymerize acrylonitrile simulta-
4.2. Polymer-silver nanoparticles neously reduces Ag+ ions resulting in homogeneous dispersal and
narrow size distributions of the Ag NPs in the silver-polyacrylonitrile
Nanocomposite materials consisting of metallic nanoparticles (Ag-PAN) composite powders [138]. Further, size-controlled synthesis
incorporated in or with polymers have attracted much attention of a Ag nanocomplex was recently achieved in the reduction of AgNO3
because of their distinct optical, electrical and catalytic properties, by a UV-irradiated argine-tungstonsilicate acid solution [146]. Other
which have potential applications in the fields of catalysis, bioengi- various metal-polymer nanocomposites have been prepared by these
neering, photonics, and electronics [47,127–130]. Polymers are reduction methods, such as poly(vinyl alcohol)-Ag, Ag-polyacryla-
considered a good host material for metal nanoparticles as well as mide, Ag-acrylonitrile (Ag-PAN), Ag2Se-polyvinyl alcohol, Ag-poly-
other stabilizing agents such as citrates, organic solvents (THF or THF/ imide, Au-polyaniline, and Cu-poly(acrylic acid) [143,147]. Due to its
MeOH), long chain alcohols, surfactants, and organometallics growing importance in a multitude of industries, let's explore poly
[9,131,132]. The organic solvents are though not as environmental (vinyl alcohol)-Ag synthesis and applications in more detail.
benign.
Different chemical and physical methods exist to prepare metal- 4.2.1. Poly(vinyl alcohol)-silver nanoparticles
polymer composites [46,133,134–142]. A successful preparation of Poly(vinyl alcohol) (PVA) is a biologically friendly polymer since it
nanoparticles is determined by the ability to produce particles with is water soluble and has extremely low cytotoxicity [148]. This allows
uniform distributions and long stability, given their tendency to a wide range of potential biomedical applications. It is frequently used
rapidly agglomerate in aqueous solution [130,133]. The main fabrica- as a stabilizer due to its optical clarity, which enables investigation of
tion approach is to disperse previously prepared particles in the the nanoparticle formation [149,150]. PVA is classified into grades of
polymer matrix [141,142]. This method is often referred to as the partially (85–89%) and fully (97–99.5%) hydrolyzed polymers (Fig. 6).
 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96 89

out. The TEM images of these nanocomposites are given in Fig. 8. The
reactants, TiO2 particles and TiO2 nanotubes, were well dispersed in
their reaction mixtures having a ∼ 25 nm particle size and a ∼20 nm
nanotube diameter with a length of ∼ 250 nm, respectively (a and b).
In the images of the resulting 5 wt.% Ag–TiO2 nanocomposites, the Ag
on the TiO2 nanoparticles was difficult to visualize (c) yet Ag on the
TiO2 nanotubes was clearly evident (d). Next, in-situ PVA-capped TiO2
nanoparticles, ∼ 20 nm particle size, and PVA-capped TiO2 nanotubes
were prepared (e and f). Photoreduction on these nanocomposites
Fig. 6. Structure of fully hydrolyzed and partially hydrolyzed PVA. products caused Ag aggregation into fairly large colloids. The Ag in
PVA-capped Ag–TiO2 particles formed Ag clusters of sizes ∼ 15 nm (g),
while Ag on the PVA-capped Ag–TiO2 nanotubes gave larger, ∼ 40 nm,
PVA is widely used in various industries such as textile, paper, food Ag particle sizes (h). This work reports that low concentration of
packaging, pharmacy, and cosmetics [151]. Introduction of nanosized colloidal Ag–TiO2 nanoparticles and nanotubes were effective in
Ag into PVA provides antibacterial activity, which is highly desired in destroying E. coli and B. subtilis [182].
textiles used in medicine, clothing and household products [151].
However, this can significantly affect the properties of the polymer 5. Antimicrobial activities
due to the high surface to bulk ratio of Ag NPs. [150–153].
Different methods including solvent evaporation, electron radia- Silver is known for its antimicrobial properties and has been used
tion, UV light, thermal annealing, in situ chemical reduction, and for years in the medical field for antimicrobial applications and even
sonochemical have been proposed to synthesize PVA-Ag NPs [154– has shown to prevent HIV binding to host cells [178,183–186].
166]. And a variety of morphologies were obtained under different Additionally, silver has been used in water and air filtration to
preparation conditions. In the solvent evaporation methods, the eliminate microorganisms [187–189].
synthesis of PVA-Ag NPs was achieved by first reducing Ag salt with
NaBH4, followed by the mechanical dispersion of the Ag colloids into 5.1. Studies: mechanism
the dissolved polymer, and then the solvent was evaporated resulting
in final structure [154]. The initial average particle size of 5 nm with The mechanism of the bactericidal effect of silver and Ag NPs
narrow size distribution increased to 20 nm with a broad surface remains to be understood. Several studies propose that Ag NPs may
plasmon absorption band after the dispersion [154]. This particle attach to the surface of the cell membrane disturbing permeability
agglomeration during the incorporation into the PVA matrix resulted and respiration functions of the cell [67]. Smaller Ag NPs having the
in significant changes in the thermal and mechanical properties of the large surface area available for interaction would give more bacter-
polymer [154]. The electron and UV radiation preparation methods icidal effect than the larger Ag NPs [67]. It is also possible that Ag NPs
involve irradiation of a Ag+ doped polymer film which gives PVA-Ag not only interact with the surface of membrane, but can also penetrate
composites [159–161]. In thermal methods, the annealing time and inside the bacteria [190].
temperature vary the morphologies of the PVA-Ag NPs [165,166]. For In one study, the Ag NPs obtained in the reduction of the Ag(NH3)+2
instance, hydrogels of PVA-PVP (poly(N-vinyl pyrolidone) containing complex cation by four saccharides with narrow size distribution were
Ag NPs were prepared by repeated freezing–thawing treatment [167]. tested as antimicrobial agents (Table 1) [66]. Table 1 shows that Ag NPs
The hydrogels have unique properties because of their three- synthesized using disaccharides, maltose and lactose, have a higher
dimensional hydrophilic polymer networks, which provide a wide antibacterial activity than those synthesized using monosaccharides,
range of pharmaceuticals and medical applications [168]. Using in situ glucose and galactose. The sizes of the colloidal Ag particles were
chemical reduction, our laboratory had recently synthesized Ag NPs of smaller for disaccharide than monosaccharide and thus may be
controlled size by the modified Tollens process with PVA as a stabilizer responsible for the observed antibacterial activity. The 25 nm-sized Ag
and reductant [169]. Briefly, one drop of 0.02 M NaOH was added to NPs synthesized via reduction by maltose (see Table 1) showed the
2 ml of 1 mM AgNO3, followed by 3 drops of 0.2 M NH4OH and 0.25 ml highest activity and were comparable to the effects of ionic silver in
1% aqueous PVA solution. Gentle heating for 2 min resulted in a yellow certain bacteria strains. Galactose had the largest Ag NPs particles,
colored mixture. The visible spectrum showed a maximum at 422 nm, 50 nm, and gave the lowest antimicrobial effect [66].
indicating the formation of PVA-Ag NPs (Fig. 7).

4.3. Silver nanoparticles on TiO2

Silver/TiO2 surfaces have advantageous properties such as visible

light photocatalysis, biological compatibility, and antimicrobial activ-
ity [170–176]. Aqueous reduction, photochemical, liquid phase
deposition, and sol–gel methods can be applied to synthesize Ag
NPs on TiO2 surfaces [177–182]. Ag NPs with a narrow size distribution
were synthesized by simple aqueous reduction from silver ions in
different molar ratios of TiO2 suspensions and a reducing agent, NaBH4
[178]. One of the photochemical reduction methods involves loading
Ag NPs with ∼ 3–5 nm diameters onto the surface of TiO2 nanotubes
first using the liquid deposition approach followed by UV [179] or by
femtosecond laser irradiation [181].
In another photoreduction example, Ag–TiO2 nanocomposites and
PVA-capped colloidal Ag–TiO2 nanocomposites have been prepared to
investigate their antibacterial activity in E. coli and Bacillus subtilis
[182]. Photoreduction of AgNO3 at 365 nm wavelength using bare TiO2 Fig. 7. The surface-plasmon absorbance spectrum of Ag NPs formed in the Tollens-PVA
and PVA-capped colloidal TiO2 nanoparticles/nanotubes was carried solution (λmax = 422 nm).
90 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

Fig. 8. TEM images of (a) TiO2 nanoparticles, (b) TiO2 nanotubes, (c) Ag–TiO2 nanoparticles, (d) Ag–TiO2 nanotubes, (e) PVA-capped TiO2 nanoparticles, (f) PVA-capped TiO2
nanotubes, (g) Ag on PVA-capped TiO2 nanoparticles, and (h) Ag on PVA-capped TiO2 nanotubes (reproduced from [182]) with permission from the American Chemical Society).
 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96 91

Table 1 NPs prepared with surfactant templates, and Ag NPs in a carbon

Minimum inhibition concentrations and minimum bactericidal concentrations of Ag matrix [195,200,201]. The strong interaction between negatively
particles prepared via reduction of [Ag(NH3)2]+ by various reducing saccharides at an
ammonia concentration of 0.005 mol L− 1 (data were taken from [66] with permission
charged bacterial wall and HPAMAM-NH2 macromolecules [202–
from the American Chemical Society) 204] can possibly decrease the distance between the Ag NPs and
bacteria. This process could facilitate the release of active Ag into the
Bacteria Minimum inhibition and bactericidal concentrations
bacteria resulting in a synergistic antibacterial effect of the HPAMAM-
(μg/mL)⁎
NH2/Ag nanocomposites [199].
Saccharide (Ag NP size) Glucose Galactose Maltose Lactose Conta Contb
(44 nm) (50 nm) (25 nm) (35 nm) In proteomic and biochemical studies, nanomolar concentrations
Enterococcus faecalis – – 13.5 54.0 6.75 –
of Ag NPs have killed E. coli cells within minutes possibly due to
CCM 4224 immediate dissipation of the proton motive force [205]. This action is
Staphylococcus aureus 6.75 54.0 6.75 6.75 6.75 – similar to that found for antimicrobial activities of Ag+ ions [206]. For
CCM 3953 example, low concentrations of Ag+ ion result in massive proton
Escherichia coli CCM 3954 27.0 – 3.38 27.0 1.69 –
leakage through the Vibrio cholerae membrane [206]. This proton leak
Pseudomonas aeruginosa 27.0 – 6.75 13.5 0.84 –
CCM 3955 might be happening from either any Ag+-modified membrane protein
Pseudomonas aeruginosa 13.5 27.0 3.38 13.5 0.84 – or any Ag+-modified phospholipids bilayer. The phenomenon causes
Staphylococcus epidermidis1 13.5 6.75 1.69 6.75 0.84 – deenergization of the membrane and consequently cell death [206].
Staphylococcus epidermidis2 6.75 54.0 1.69 6.75 1.69 – Importantly, the determined effective concentration of Ag NPs was at
Staphylococcus aureus MRSA 27.0 54.0 6.75 27.0 6.75 –
Enterococcus faecium (VRE) – – 13.5 54.0 3.38 –
nanomolar levels while Ag+ ions were effective at micromolar levels
Klebsiella pneumoniae 27.0 – 6.75 54.0 3.38 – [205]. Ag NPs thus seem to be more efficient than Ag+ ions in
(ESBL-positive) performing antimicrobial activities. Picomolar levels of Ag NPs, on the
1
(Methicillin-susceptible); 2 (methicillin-resistant); “–” growth inhibition of bacteria other hand, have been used as nanoprobes in membrane penetration
unsubstantiated. studies and did not create significant toxicity to the cells [207].
⁎ MIC and MBC of silver sols had same values. Moreover, the role of Ag+ ion in the antibacterial activity of Ag NPs was
a
Control sample containing all initial reaction components without reducing recently studied by partially oxidizing Ag NPs [208]. The oxygen can
saccharides.
b
Control sample containing all initial reaction components without silver nitrate.
easily oxidize nano-Ag [78,209] to yield partially oxidized nano-Ag
with chemisorbed Ag+ ions [208]. The antibacterial activities of Ag NPs
against E. coli depended on the chemisorbed Ag+ ions (surface
Enhanced antibacterial activities have been reported in Ag NPs oxidation) and particle size.
modified by surfactants, as SDS and Tween 80, and polymers, as PVP The effect of shape on the antibacterial activity of Ag NPs has only
360 [67]. The results are presented in Fig. 9. The antibacterial activity recently been reported [210]. The Ag NPs of different shapes
was significantly enhanced for most of the species when Ag NPs were (triangular, spherical, and rod) were tested against E. coli [210]. The
modified with SDS (Fig. 9). However, the antibacterial effect of Tween surfaces of untreated and treated bacterial cells were investigated by
80 modified Ag NPs was not significant (Fig. 9). SDS provides more energy-filtering transmission electron microscopy (EFTEM). The {111}
stability to Ag NPs than Tween 80; resulting in a higher antibacterial facets have high-atom-density, which is favorable for the reactivity of
activity. Additionally, SDS is an ionic surfactant and may have the
ability to penetrate or disrupt the cell wall, particularly of gram-
positive strains [67,191]. Comparatively, Tween 80 is a non-ionic
surfactant and may not be making contact with the cell wall [67]. The
antibacterial activities of PVP modified Ag NPs were significant
because the polymer is most effective in stabilizing particles against
aggregation [67].
In another work, the effect of Ag NPs on bacterial growth of E. coli,
Vibria cholera, P. aeruginosa, and Syphillis typhus has been studied
using a high angle annular dark field (HAADF) scanning transmission
electron microscopy (STEM) technique Fig. 10 [42,190]. Fig. 10 (b) and
(c) demonstrate that this technique can identify presence of Ag NPs as
small as ∼ 1 nm. No significant bacterial growth was observed at Ag
NPs concentrations above 75 μg/mL. Some noticeable damage to the
cell membrane by Ag NPs could be seen (Figs. 10 (b) and 9 (e)). The
damage to cell may be caused by interaction of Ag NPs with
phosphorous- and sulfur-containing compounds such as DNA. Silver
tends to have a high affinity for such compounds [192,193]. Ag+ ions
strongly interact with the available –SH groups of the biomolecule to
inactivate the bacteria [194,195]. Furthermore, the antibacterial
activity of Ag+ ion under anaerobic conditions was found less potent
than in oxygen rich environment [195]. Such interactions in the cell
membrane would prevent DNA replications [195,196], which would
lead to bacterial death [195,197,198].
Involvement of interaction of Ag NPs with bacteria has also been
shown in a study of amine-terminated hyperbranched poly(amidoa-
mine) (HPAMAM-NH2)/Ag nanocomposites [199]. The nanocompo-
sites had an average particle size of 15–4 nm and the antibacterial
activity was tested against S. typhus, E. coli, B. subtilis, and Klebsiella
Fig. 9. A plot of minimum inhibition concentration (MIC) of the Ag NPs prepared by the
mobilis [199]. The bacterial activity was inhibited up to 95% by low
modified Tollens process with D-maltose and consequently modified by addition of SDS,
concentrations of the HPAMAM-NH2/Ag nanocomposite, 2.7 μg/mL, Tween 80, and PVP 360 in concentration of 1% (w/w). (Data were taken from [67] with
and this was comparable to inhibition observed in Ag-doped TiO2, Ag permission from the American Chemical Society).
92 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

Fig. 10. (a) bacteria grown on agar plates at different concentrations of Ag NPs. Upper left, E. coli; upper right, S. typhus; bottom left, P. aeruginosa, and bottom right, V. cholerae. 0 μg mL− 1
(upper left), 25 μg mL− 1 (upper right), 50 μg mL− 1 (bottom left) and 75 μg mL− 1 (bottom right). HAADF STEM images that show the interaction of the bacteria with the Ag NPs:
(b) E. coli, (c) S. typhus, (d) P. aeruginosa, and (e) V. cholerae. The inset correspond to higher magnification images. (reproduced from [190] with permission from the Institute of Physics).

Ag [211]. A triangular nanoplate has a high percentage of {111} facets coccus, Staphylococcus aureus, Candida albicans, Staphylococci, and
whereas spherical and rod-shaped Ag NPs predominantly have {100} Pseudomonas aeruginosa and also show significant in vitro antimicro-
facets along with a small percentage of {111} facets [211]. bial activity [212]. Silver aerosol NPs were efficient as antimicrobial
agents against B. subtilis [213]. Polymethylmetacrylate (PMMA) bone
5.2. The battle against infection: Ag NPs and their incorporation into the cement loaded with Ag NPs has shown clinical use [183]. Supple-
medical field mentation of Ag NPs with antibiotics as penicillin G, amoxicillin,
erythromycin, clindamycin, and vancomycine against E. coli and S.
In hospitals, infection is the most common complication and cause aureus has been examined [214]. The presence of Ag NPs increased the
of death in patients. Therefore, antibacterial effects of Ag have been antibacterial activities of antibiotics for both strains [214]. Addition-
incorporated into various medical applications. Plastic catheters ally, Ag NPs-embedded paints demonstrated killing of both Gram-
coated with Ag NPs prevent biofilm formation from E. coli, Entero- positive human pathogens and Gram-negative bacteria [215].
 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96 93

5.2.1. Ag NPs and HIV and reduce the risk of water related diseases such as diarrhea and
Recently, a study revealed the potential cytoprotective activity of dehydration [218,219]. Ag NPs on polyurethane foam were stable and
Ag NPs toward HIV-1 infected cells [216]. The activity of Ag NPs were not washed away by water flow, possibly due to its interaction
towards HIV-1 infected Hut/CCR5 cells was investigated using with the nitrogen atom of polyurethane [220]. The foam was tested
terminal uridyl-nucleotide end labeling (TUNEL) assay after a three with an E. coli load of 105 CFU mL− 1 at a flow rate of 0.5 L min− 1. Within
day treatment [216]. The percentage of aproprotic cells were seconds, the output count of E. coli in the effluent was below the
determined as 49%, 35%, and 19% for vehicle control, 5 μM Ag, and detection limit [220]. Also, few studies have been conducted on Ag
50 μM Ag, respectively. Ag NPs might inhibit the replication in Hut/ containing carbon filters for their ability to reduce bactericidal activity
CCR5 cells causing HIV-associated apoptosis [216]. Size dependent [221–223]. Bacteria and fungi were tested and strong lethal activity
interaction of Ag NPs with HIV-1 virus has also been demonstrated against E. coli, Saccharomyces cerevisiae, and Pichia pastoris was
[217]. Ag NPs preferentially binds to gp120 glycoprotein knobs of HIV- observed within a few seconds [221]. The use of reactive oxygen
1 virus. In the vitro study, it was further shown that this interaction species (ROS), a scavenger, and Ag+ ion, a neutralizing agent, suggested
caused the virus not to bind with the host cell [217]. a role of ROS in the strong bactericidal activity of carbon filter
supporting silver [222].
5.3. Antibacterial water filter Colloidal-Ag-impregnated ceramic filters were recently tested for
household water treatment in the laboratory [224]. The filters removed
According to the World Health Organization (WHO), point-of-use ∼97.8%–100% of the E. coli. Initially, Ag concentrations in the effluent
treatment has the potential to improve the microbial quality of water filter water were greater than 0.1 mg L− 1, but decreased to b0.1 mg L− 1
after ∼200 min. Overall, the findings suggest the use of the ceramic filters
as an effective and sustainable point-of-use water treatment technology.

5.4. Antimicrobial air filter

Bioaerosols are airborne particles of biological origins, which are

capable of causing acute and chronic diseases [225]. Generally,
bioaerosols accumulate on ventilating, heating, and air-conditioning
systems with a tendency to multiply under humid conditions [226].
Activated carbon fiber (ACF) filters are widely used for removal of
hazardous gaseous pollutants from the air. However, ACF filters
themselves become a source of bioaerosols because bacteria prefer-
entially adhere to carbon solid materials [227,228].
The antimicrobial effect of Ag particles coated onto an ACF filter
was recently tested [229,230]. Ag-deposited ACF filters were effective
for the removal of bioaerosols. The results of the test filters on E. coli
and B. subtilis are shown in Fig. 11. The ACF/Ag-10, ACF/Ag-20, and
ACF/Ag-30 represent samples prepared with metal solution at
deposition times of 10, 20, and 30 min, respectively without using
electric current [230]. The colony ratios (C/Co) of both E. coli and B.
subtilis increased with time suggesting multiplication of bacteria on
the pristine ACF filters [230]. However, the colony ratios decreased for
Ag-containing ACF filters; the decrease was sharper for B. subtilis than
for E. coli species (Fig. 11). Due to low resistivity of B. subtilis, inhibition
took place in about 10 min [230]. Comparatively, E. coli was fully
inhibited after 60 min using a Ag-containing ACF filters [230].

6. Implications

6.1. Human Health

Nanoparticles may have different effects on human health

relative to bulk material from which they are produced [15].
Increase in biological activity of nanoparticles can be beneficial,
detrimental or both. Many nanoparticles are small enough to have
an access to skin, lungs, and brain [15,231,232]. Currently, no
sufficient information is available on the adverse effects of
nanoparticles on human health [233], but studies are forthcoming
to address this subject [234–239]. Exposure of metal-containing
nanoparticles to human lung epithelical cells generated reactive
oxygen species, which can lead to oxidative stress and cellular
damage [240,241]. Nanoparticles and reactive oxygen production
have an established link in vivo [242,243]. A study on toxic effects of
Ag NPs was done on zebrafish as a model due to its fast development
and transparent body structure [244]. The results showed a
Fig. 11. Antimicrobial effects of the test filters on E. coli (a) and B. subtilis (b). C0 and C
deposition of particles on organs and severe developmental effects
are colony count at contact time 0 and t minutes, respectively. (reproduced from [230] [244]. Similar results of Ag NPs toxicity were observed during
with permission from the American Chemical Society). zebrafish embryogenesis [245].
94 V.K. Sharma et al. / Advances in Colloid and Interface Science 145 (2009) 83–96

6.2. Environmental approaches for the surface modification were provided resulting in
different particle morphologies. Surfactants and polymers modified
The increasing use of consumer nanotechnological products may Ag NPs have advantages in antibacterial activities; however their
result in an increased release of NPs into the aquatic environment antibacterial actions are not fully understood. The techniques to
[246–248]. Though regulation exists for protecting aquatic species measure transport of Ag NPs in vivo in real time scales are needed to
from soluble forms of toxic metals, it is critical to understand the make headways in observing particle interactions. Some progress was
toxicity of metallic nanoparticles [249–252]. The studies on the effect made in a recent study [254] and more such studies should occur in
of Ag NPs on biological species are forthcoming [253–256]. As the future. This will also determine the effect of Ag NPs on important
discussed previously, proteomic analysis (2-DE and MS identification) aquatic species and reveal their environmental consequences.
was conducted to observe the mode of the antibacterial effect of Ag The increasing use of Ag NPs in consumer products will increase
NPs against E. coli [253]. An accumulation of envelope protein their release to the environment and any advancement in nanotech-
precursors due to Ag NPs occurred, which suggests the dissipation nology would thus require assessment of environmental risks
of proton motive force [253]. Furthermore, the proteomic data associated with these particles [15,258]. The ecotoxic studies on the
indicate that Ag NPs destabilized the outer membrane, which resulted exposure of Ag NPs need an analytical technique that can distinguish
in a collapse of the plasma membrane potential and depletion of nano-Ag metal from the dissolved Ag+ species under environmental
intracellular ATP levels [253]. conditions. Such techniques are becoming more available, but their
Single-NP probes (individual Ag NPs) were developed to study real applications at relatively low concentrations are still limited
time transport, biocompatibility, and toxicity of Ag NPs in the early [259,260].
development of zebrafish embryos [254]. It was found that single Ag
NPs with an average diameter of 11.6 ± 3.5 nm were transported in and Acknowledgment
out of embryos through chorion pore canals. The Brownian diffusion,
3 × 10− 9 cm2 s− 1, inside the chorionic space was determined [254]. The We wish to thank three anonymous reviewers for their useful
biocompatibility and toxicity of Ag NPs were exhibited by observing comments that greatly improved this paper.
single Ag NPs inside embryos at each development stage. The types of
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