Acta Biomaterialia 10 (2014) 4023–4042

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Acta Biomaterialia
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Review

Applications of biosynthesized metallic nanoparticles – A review

Adam Schröfel a,b,e,⇑, Gabriela Kratošová c, Ivo Šafařík a, Mirka Šafaříková a, Ivan Raška e, Leslie M. Shor b,d
a
Department of Nanobiotechnology, Institute of Nanobiology and Structural Biology of GCRC, Academy of Sciences, Ceske Budejovice, Czech Republic
b
Department of Chemical and Biomolecular Engineering, University of Connecticut, Storrs, CT, USA
c
Nanotechnology Centre, VSB-Technical University in Ostrava, Ostrava, Czech Republic
d
Center for Environmental Sciences & Engineering, University of Connecticut, Storrs, CT, USA
e
Charles University, Institute of Cellular Biology and Pathology, Prague, Czech Republic

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

Article history: We present a comprehensive review of the applications of biosynthesized metallic nanoparticles (NPs).
Received 16 January 2014 The biosynthesis of metallic NPs is the subject of a number of recent reviews, which focus on the various
Received in revised form 13 April 2014 ‘‘bottom-up’’ biofabrication methods and characterization of the final products. Numerous applications
Accepted 21 May 2014
exploit the advantages of biosynthesis over chemical or physical NP syntheses, including lower capital
Available online 9 June 2014
and operating expenses, reduced environmental impacts, and superior biocompatibility and stability of
the NP products. The key applications reviewed here include biomedical applications, especially antimi-
Keywords:
crobial applications, but also imaging applications, catalytic applications such as reduction of environ-
Biosynthesis
Metallic nanoparticles
mental contaminants, and electrochemical applications including sensing. The discussion of each
Nanomedicine application is augmented with a critical review of the potential for continued development.
Bioimaging Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Sensors

1. Introduction under standard conditions leads to many cost advantages, in terms

The unique properties of nanoscale materials have given rise to
tremendous research activity directed towards nanoparticle (NP)
fabrication, characterization and applications. In order to reveal
ever more favorable NP functionality, some researchers look to
nature for methods to produce NPs with novel properties or
enhanced function. Many organisms are known to form inorganic
materials either intra- or extracellularly. For example, iron-reduc-
ing bacteria have been known to reduce labile and/or toxic metals
into their zero-valent form [1]. The same or similar metal-reducing
capability used as an NP production method is called biosynthesis
[2]. As reviewed recently, many different prokaryotic and eukary-
otic organisms have been used to produce metallic NPs [3], and
biosynthesis of NPs has attracted increasing attention in the past
10 years [4] (see Fig. 1).
Among the key advantages that the biological approach has
over traditional chemical and physical NP synthesis methods is
the biological capacity to catalyze reactions in aqueous media at
standard temperature and pressure. Production in aqueous media
⇑ Corresponding author at: Charles University, 1st Faculty of Medicine, Institute
of Cellular Biology and Pathology, Prague, Czech Republic. Tel.: +420 777864404;
fax: +420 224917418.
E-mail address: adam.schrofel@gmail.com (A. Schröfel).
of both capital equipment and operating expenses, especially in the
purchase and disposal of solvents and other consumable reagents.
Biosynthesis can be implemented in nearly any setting and at any
scale [3]. In addition, extensive investment in biotechnology know-
how for optimized production of food, pharmaceuticals and fuels
also informs NP biosynthesis techniques. One important drawback
of NP biosynthesis methods is the requirement in some applica-
tions to purify the sample or to separate the NPs from the biolog-
ical material used in their synthesis.
The properties of biosynthesized materials may differ from
materials prepared by other methods. Biosynthesis can result in
forms that are difficult to make using other techniques, such as
alloys and wires. Biosynthesized NPs can also have enhanced
stability and biocompatibility and reduced toxicity, mainly due to
coating them with biogenic surfactants or capping agents. The
potential range of sizes, shapes and compositions of biosynthe-
sized NPs translates into a broad domain of existing and new nano-
material applications.
Applications of biosynthesized metal-based NPs range from
various biomedical purposes (e.g. antimicrobial coatings, medical
imaging and drug delivery) to catalytic water treatment and envi-
ronmental sensors. We have organized this review according to the
applications that use biosynthesized NPs. The chemical composi-
tion, form and organism used for the biosynthesis are also
described.

http://dx.doi.org/10.1016/j.actbio.2014.05.022
1742-7061/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
4024 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
Fig. 1. Light microscopy of gold nanoparticle biosynthesis inside the moss leaf. The
purple color indicates the presence of gold nanoparticles inside the cells (picture
taken and kindly provided by Markéta Bohunická).
2. Biomedical applications
Applications of metallic NPs in the biomedical fields are numer-
ous, and there is strong potential for continued growth in this area.
Metallic NPs are widely used for their antimicrobial functionality;
for example, silver NPs (AgNPs) have been incorporated into
wound dressings, bone cements and implants [5]. Gold NPs (AuNPs)
have medically relevant optical and anticancer properties. For
example, Alanazi et al. [6] describe how surface plasmon absorp-
tion and surface plasmon light scattering can be used for diagnostic
and therapeutic applications, and Patra et al. [7] describe the fab-
rication and application of AuNPs for targeted cancer therapy. As
described by Pankhurst et al. [8,9], magnetic NPs appear promising
for targeted drug delivery and hyperthermia applications.
2.1. Antimicrobial applications
The ongoing development of antimicrobial agents is important
due to the continuous selection of antibiotic resistance traits in
bacteria and other pathogens. Different metallic NPs, including
Fig. 2. Antimicrobial activity of AgNPs synthesized by S. hygroscopicus. (a) Candida albicans; (b) Bacillus subtilis; (c) Escherichia coli; (d) Enterococcus faecalis; (e) Salmonella
typhimurium; (f) Saccharomyces cerevisiae. Each plate shows (A) culture supernatant; (B) AgNO3 control; (C, D) synthesized AgNPs, respectively. Reprinted from Ref. [15] with
permission from Elsevier.
titanium, copper, magnesium and particularly silver and gold, are
known for their antimicrobial, antiviral and antifungal capabilities
[10]. These metallic NPs are actively investigated as disinfectants,
in food processing, and for use as additives in clothing and in med-
ical devices [11].
The following sections describe the key antibacterial, antiviral
and antifungal properties described in the literature for biosynthe-
sized NPs (Tables 1 and 2). However, due to the large number of
papers describing antimicrobial activity using slightly different
materials, endpoints or methods, in some cases only representative
examples are provided.
2.1.1. Antibacterial activity
AgNP exposure causes toxicity to bacteria, primarily from Ag
ions released into aqueous solution following partial oxidation
[5]. Ag ions and small NPs interact with the plasma membrane, dis-
turbing cellular functions, including permeability and respiration,
and ultimately leading to lysis. AgNP exposure can prevent DNA
replication and protein synthesis by binding to DNA or by denatur-
izing ribosomes [5].
The detailed mechanisms of AuNP antibacterial functionality
against Escherichia coli is described by Cui et al. [12]. AuNPs were
shown to collapse membrane potential, strongly inhibiting ATPase
activity and resulting in a decrease in cellular ATP levels. Another
consequence of AuNP exposure was inhibited binding of tRNA to
the ribosome subunit.
Bacterial susceptibility to antimicrobial agents can depend on
the cell wall structure. Bacteria are classified into two categories,
based on their cell wall structure: Gram-negative (G) bacteria
have a multi-layer cell wall and Gram-positive (G+) bacteria have
a single-layer cell wall. Antibacterial activity of biosynthesized
NPs has been studied for both types of bacteria.
A variety of biological materials have been used for the biosyn-
thesis of NPs with demonstrable antibacterial effects. These mate-
rials include fungal, bacterial and algal biomass, as well as extracts
of botanical materials, including leaves, bark, roots and tubers. One
of the first reports of antibacterial effects of biosynthesized NPs
was published by Vigneshwaran et al. [13]. These authors used
the edible mushroom Pleurotus sajor-caju for the synthesis of
AgNPs and performed successful antimicrobial testing against
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
Fig. 3. Probable anti-proliferative mechanism of AuNP. Reprinted from Ref. [54] with kind permission from Springer Science and Business Media.
Staphylococcus aureus (G+) and Klebsiella pneumoniae (G) bacteria.
Raheman et al. [14] reported the extracellular synthesis of AgNPs
by means of an endophytic fungus, Pestalotia sp., isolated from
leaves of Syzygium cumini and the antimicrobial properties of
AgNPs against S. aureus (ATCC-25923) and Salmonella typhi
(ATCC-51812). Synergistic effects were observed for combined
exposure to biosynthesized AgNPs and the commercially available
antibiotics gentamycin and sulphamethizole.
Antimicrobial properties of bacteria-biosynthesized NPs were
illustrated in two studies by Sadhasivam et al. [15,16]. Streptomy-
ces hygroscopicus cells were used for biosynthesis of Ag- and AuNPs
with antimicrobial properties against Bacillus subtilis, Enterococcus
faecalis, E. coli, Salmonella typhimurium, Staphylococcus epidermidis
and S. aureus (see Fig. 2).
An example of algae-based NP biosynthesis is described by
Merin et al. [17], where AgNPs with antibacterial properties were
synthesized by the microalgal strains Chaetocerus calcitrans, Chlorella
salina, Isochrysis galbana and Tetraselmis gracilis. These NPs showed
antimicrobial properties against K. pneumoniae, Proteus vulgaris,
Pseudomonas aeruginosa and E. coli, as measured using a clearing
zone assay. Venkatpurwar and Pokharkar [18] introduced a method
for synthesis of AgNPs using sulfated polysaccharides isolated from
the marine red alga Porphyra vietnamensis. The dose-dependent
effect of AgNPs synthesized in this study revealed strong antibacte-
rial activity against E. coli (G) and lesser effectiveness against
S. aureus (G+). The synthesis of antibacterial AuNPs using powder
or ethanolic extract from a marine alga Galaxaura elongata was
demonstrated by Abdel-Raouf et al. [19]. These authors also
performed spectroscopy experiments in order to identify the algal
compounds which may play a role as reducing agents or nanoparti-
cle capping agents.
4025
By far the most abundant studies on biosynthesized antibacterial
NPs are those using plant tissues and extracts as reducing agents. As
previously mentioned, biosynthesized NPs may require purification
to remove pathogenic or poisonous compounds, particularly for
materials intended for use in vivo. One approach to avoiding toxicity
concerns is to use only well-characterized and benign botanical
extracts for biosynthesis [20]. For example, green tea extract (pre-
pared from Camellia sinensis leaves) is a widely used reducing agent
used in the biosynthesis of NPs. Vaseeharan et al. [21] used tea
extract to prepare AgNPs with demonstrated antibacterial activity
against Vibrio harveyi. Other botanical extracts have been used for
biosynthesis of antimicrobial AgNPs. Stem callus extract of bitter
apple (Citrullus colocynthis) was used for AgNPs synthesis and dem-
onstrated activity against biofilm-forming E. coli, Vibrio paraheamo-
lyticus, Pseudomonas aeruginosa, Proteus vulgaris and Listeria
monocytogenes [22]. No activity was observed in the case of Proteus
mirabilis, Salmonella enteritidis or Staphylococcus aureus. Kaviya
et al. [23] studied biosynthesis of AgNPs using navel orange (Citrus
sinensis) peel extract and demonstrated antibacterial activity against
E. coli, Pseudomonas. aeruginosa and S. aureus. Finally, Nagajyothi and
Lee [24] used Chinese yam (Dioscorea batatas) rhizome extract for
the biosynthesis of antibacterial AgNPs.
Several reports have described synergistic antimicrobial effects
of phytosynthesized nanoparticles used in combination with anti-
biotics. Ghosh et al. [25] synthesized AgNPs prepared with tuber
extract of Dioscorea bulbifera, then measured synergistic antimicro-
bial potential using 22 types of commercially available antibiotics
and seven bacterial strains. For instance, they found an 11.8-fold
inhibition efficiency increase when streptomycin and AgNPS are
used in combination against E. coli compared with the inhibition
efficiency using streptomycin only.
4026 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042

Fig. 4. Optical images (right column) and reconstructed images from the intensity of Raman spectra with excitation at 514 nm (left column) and 633 nm (middle column), for
encapsulated cells before (top line) and after (second line) gold production and for free cells before (third line) and after (bottom line) gold production. Reproduced from Ref.
[70] by permission of The Royal Society of Chemistry.

Plant extracts have also been used for the biosynthesis of AuNPs
with antibacterial activity. Kumar et al. [26] used a deciduous tree
(Terminalia chebula) extract for the biosynthesis of AuNPs effective
against S. aureus and E. coli. MubarakAli et al. [27] used Mentha
piperita leaf extract for biosynthesis of AuNPs and AgNPs, and like-
wise demonstrated antimicrobial effects against S. aureus and
E. coli bacteria.
Biosynthesized metallic NPs that are immobilized on cotton
cloth have many important applications as material for wound
dressings. For example, Durán et al. [28] reported the extracellular
production of AgNPs mediated by the fungus Fusarium oxysporum.
Here, AgNPs were incorporated into cotton fabrics for inhibition of
S. aureus. However, one limitation of immobilized AgNPs in fabric
is the loss of the Ag ions, and sometimes the AgNPs, with washing.
El-Rafie et al. [29,30] demonstrated the use of immobilized
biogenic AgNPs on cotton fabric. In these studies, the AgNPs were
prepared with Fusarium solani and were applied to cotton fabrics
using an acrylate based binder. The cotton fabric showed a high
antimicrobial efficiency of approximately 90% against S. aureus
and E. coli after 20 washing cycles.
Tripathi et al. [31] examined biosynthesis of AgNPs using an
aqueous extract of Azadirachta indica leaves and their subsequent
immobilization on cotton cloth. These authors observed the bacte-
ricidal effect against E. coli and S. aureus with washing in distilled
water. Similarly, the biosynthesis of AgNPs in Eucalyptus citriodora Fig. 5. Electron micrograph of palladized cells of Shewanella oneidensis (kindly
and Ficus bengalensis leaf extracts and their loading into cotton provided by Simon de Corte).
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042 4027

fibers was reported by Ravindra et al. [32]. Cotton fibers were
immersed in the leaf extract containing AgNPs, kept on a shaker
for 24 h and then tested against E. coli using a modified disk diffu-
sion method.
Antibacterial effect against E. coli was also tested in AgNPs that
were prepared by means of the extract and powder of Curcuma
longa tubers [33], then immobilized on cotton cloth. AgNPs were
resuspended in water or in polyvinylidene fluoride (PVDF), then
sprayed over pre-sterilized cotton cloth. Cloth treated with NPs
in PVDF exhibited lower antibacterial activity but much longer
reusability. Recently, antimicrobial applications for biosynthesized
AgNPs incorporated into nonwoven fabrics have been demon-
strated. Yang and Li [34] prepared AgNPs using mango peel extract
and demonstrated the antimicrobial effectiveness of these nano-
particles immobilized on non-woven fabrics against E. coli,
S. aureus and B. subtilis.
Sundaramoorthi et al. [35] described a wound-healing applica-
tion for biosynthesized AgNPs, prepared extracellularly using the
fungus Aspergillus niger. The efficiency of the AgNPs was demon-
strated following excision in a rat model. The study supported both
the antimicrobial effects of Ag and the ability of AgNPs to modulate
cytokines involved in wound healing. Similarly, the medicinal
plant Indigofera aspalathoides was used for biosynthesis of AgNPs
tested in wound-healing applications following excision in animal
models [36].
Finally, biogenic AgNPs derived from Chrysanthemum morifoli-
um have been added to clinical ultrasound gel. In the study, the
gel was used on an ultrasound probe, and the bactericidal activity
and instrument sterility were evaluated [37].
2.1.2. Antifungal activity
Several studies have described the bacteria Aspergillus niger
antifungal activity of biosynthesized NPs. Gajbhiye et al. [38]
described the antifungal properties of biosynthesized NPs against
Phoma glomerata, P. herbarum, Fusarium semitectum, Trichoderma
sp. and Candida albicans in combination with fluconazol (a triazole
antifungal drug). AgNPs biosynthesized by another fungus, Alter-
naria alternata, enhanced the antifungal activity of fluconazole
against all tested strains except P. herbarum and F. semitectum. In
another study, mycelia-free water extracts of the fungal strain
Amylomyces rouxii were used for biosynthesis of AgNPs that were
effective against the bacteria Shigella dysenteriae type I, Staphylo-
coccus aureus, Citrobacter sp., E. coli, Pseudomonas aeruginosa and
Bacillus subtilis, and also against the fungi Candida albicans and
Fusarium oxysporum [39].
Antifungal activity of biosynthesized AuNPs has also been
described. Das et al. [40] synthesized AuNPs on the surface of the
fungus Rhizopus oryzae and demonstrated the growth inhibition
of G and G+ bacterial strains, as well as the fungi Saccharomyces
cerevisiae and C. albicans. AuNPs that inhibit the growth of
C. albicans have also been obtained following biosynthesis using
a banana peel extract [41].
2.1.3. Antiviral activity
Although viruses also represent serious problems in medicine
or agriculture, there have been relatively few reports on the antivi-
ral activity of biosynthesized NPs. Vijayakumar and Prasad [42]
described the antiviral activity of Ag NPs prepared intracellularly

Fig. 6. Electron micrographs of crystal morphologies and intracellular organization of magnetosomes found in various magnetotactic bacteria. The shapes of the magnetic
crystals include cubo-octahedral (a), elongated hexagonal prismatic (b, d, e, f) and bullet-shaped morphologies (c). The particles are arranged in one (a, b, c), two (e) or
multiple chains (d), or irregularly (f). The scale bar is equivalent to 100 nm. Reprinted from Schueler D, Frankel RB. Bacterial magnetosomes: microbiology, biomineralization
and biotechnological applications. Appl Microbiol Biotechnol 1999;52(4):464–473, with kind permission from Springer Science and Business Media.
4028 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042

Table 1
Antibacterial activity.

NP Organism used Activity against References

Ag Pleurotus sajor-caju Staphylococcus aureus, Klebsiella pneumonia Vigneshwaran et al. [13]
Ag Pestalotia sp. S. aureus, Salmonella typhi Raheman et al. [14]
Ag Streptomyces hygroscopicus Bacillus subtilis, Enterococcus faecalis, Escherichia coli, Salmonella Sadhasivam et al. [15]
typhimurium
Au S. hygroscopicus B. subtilis, E. faecalis, E. coli, S. typhimurium, S. epidermidis, S. aureus Sadhasivam et al. [16]
Ag Chaetocerus calcitrans, Chlorella salina, K. pneumoniae, Proteus vulgaris, Pseudomonas aeruginosa, E. coli Merin et al. [17]
Isochrysis galbana, Tetraselmis gracilis
Ag Porphyra vietnamensis S. aureus, E. coli Venkatpurwar and Pokharkar [18]
Au Galaxaura elongata E. coli, K. pneumonia, S. aureus, P. aeruginosa Abdel-Raouf et al. [19]
Ag Camellia sinensis Vibrio harveyi Vaseeharan et al. [21]
Ag Citrullus colocynthis E. coli, Vibrio paraheamolyticus, P. aeruginosa, P. vulgaris, Listeria Satyavani et al. [56]
monocytogens
Ag Citrus sinensis E. coli, P. aeruginosa, S. aureus Kaviya et al. [23]
Ag Dioscorea batatas B. subtilis, S. aureus, E. coli Nagajyothi and Lee [24]
Ag Dioscorea bulbifera Acinetobacter baumannii, Enterobacter cloacae, E. coli, Haemophilus Ghosh et al. [25]
influenzae, K. pneumoniae, Neisseria mucosa, Proteus mirabilis
Au Terminalia chebula S. aureus, E. coli Kumar et al. [20,26]
Au, Ag Mentha piperita S. aureus, E. coli MubarakAli et al. [27]
Ag Fusarium oxysporum S. aureus on cotton fabrics Durán et al. [28]
Ag Fusarium solani S. aureus, E. coli on cotton fabrics El-Rafie et al. [29,30]
Ag Azadirachta indica S. aureus, E. coli on cotton fabrics Tripathi et al. [31]
Ag Eucalyptus citriodora, Ficus bengalensis E. coli on cotton fabrics Ravindra et al. [32]
Ag Curcuma longa E. coli on cotton fabrics Sathishkumar et al. [33]
Ag Mangifera indica E. coli, S. aureus, B. subtilis on non-woven fabrics - Yang and Li [34]
Ag Aspergillus niger Wound healing activity Sundaramoorthi et al. [35]
Ag Indigofera aspalathoides Wound healing activity Arunachalam et al. [36]
Ag Chrysanthemum morifolium Bactericidal ultrasound gel He et al. [37]

Table 2
Antifungal, antiviral and anti-parasite activity.

NP Organism used Activity against References

Ag Alternaria alternata Phoma glomerata, Phoma herbarum, Fusarium semitectum, Trichoderma sp., Gajbhiye et al. [38]
C. albicans – combination w/fluconazole
Ag Amylomyces rouxii Candida albicans, Fusarium oxysporum Musarrat et al. [39]
Au Rhizopus oryzae Saccharomyces cerevisiae, C. albicans Das et al. [40]
Au Musa sp. C. albicans Bankar et al. [41]
Ag Aspergillus ochraceus M13 phage virus Vijayakumar and Prasad [42]
Ce Leptothrix discophora, Pseudomonas putida Bacteriophage UZ1 De Gusseme et al. [43]
Ag Lactobacillus fermentum Bacteriophage UZ1, application to NanoCeram filter De Gusseme et al. [44]
Ag Lactobacillus fermentum Bacteriophage UZ1, application to PVDF membrane De Gusseme et al. [45]
Ag Nelumbo nucifera Larvae of Anopheles subpictus, Culex quinquefasciatus Santhoshkumar et al. [46]
Ag Rhizophora mucronata Larvae of Aedes aegypti, Culex quinquefasciatus Gnanadesigan et al. [47]
Ag Lawsonia inermis Pediculus humanus capitis, Bovicola ovis Marimuthu et al. [48]
Ag Manilkara zapota Rhipicephalus microplus Rajakumar and Rahuman [49]

in Aspergillus ochraceus. In the study, AgNPs embedded in a carbo-
naceous matrix were obtained by heat treatment of the cells, and
the effectiveness against M13 phage was determined using the pla-
que count method.
In another study, De Gusseme et al. [43] described virus inhibi-
tion by zero-valent cerium produced by aqueous Ce(III) added to
Leptothrix discophora and Pseudomonas putida cultures. The as-
prepared cerium exhibited efficient antivirus activity against bac-
teriophage UZ1. In another study by the same researchers [44], Lac-
tobacillus fermentum bacteria were used both as a reducing agent
and as a scaffold for AgNPs. Their antiviral activity was determined
for murine norovirus 1 and bacteriophage UZ1. In another study,
the continuous antiviral capability of AgNPs embedded in Lactoba-
cillus cells was tested in an aqueous environment by depositing the
cells onto a NanoCeram electropositive filter. The study demon-
strated that the filter with cell-embedded NPs had remarkably
higher antiviral activity compared with the original filter. Similarly,
De Gusseme et al. [45] demonstrated the inactivation of UZ1
bacteriophages using a similar approach with cell-embedded NPs
on a PVDF membrane.
2.1.4. Anti-parasite applications
Biosynthesized NPs are effective against various disease-caus-
ing insects or parasites. Santhoshkumar et al. [46] compared larvi-
cidal activity of AgNPs biosynthesized using different lotus leaf
(Nelumbo nucifera) extracts. In the study, antilarval activity was
measured for the fourth instar larvae of Anopheles subpictus and
Culex quinquefasciatus, both well-known vectors for malaria and
lymphatic filariasis. A similar study by Gnanadesigan et al. [47]
evaluated AgNPs biosynthesized with mangrove (Rhizophora
mucronata) leaf extract against Aedes aegypti and C. quinquefascia-
tus larva.
In another study, the larvicidal properties of AgNPs biosynthe-
sized with henna (Lawsonia inermis) leaf extract was determined
for the human head louse Pediculus humanus capitis and the sheep
body louse Bovicola ovis [48]. The study determined lousicidal
activity using both a direct contact method (P. humanus) and an
impregnated filter paper method (B. ovis). Finally, the acaricidal
activity of an evergreen tree (Manilkara zapota) aqueous extract
and AgNPs synthesized by means of this extract were determined
against the cattle tick (Rhipicephalus microplus) [49].
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042 4029

2.2. Drug delivery and cancer treatment
Biosynthesized NPs can interact with and alter the function of
certain mammalian tissues. For example, metallic NPs can interfere
with the antioxidant defense mechanism, leading to accumulation
of reactive oxygen species, destruction of mitochondria and cell
apoptosis [50]. This effect can be targeted, because the in vivo
effects of metal NP exposure strongly depend on the capping
agent: the same AgNPs with different capping agents have been
reported to be both cytotoxic [50] and non-cytotoxic [51]. The
use of stable noble metal NPs as carriers may minimize the side
effect of conventional chemotherapeutic agents by the selective
delivery of anticancer agents to malignant cells without affecting
the normal cells. For instance, gold can be readily modified due
to its ability to bind strongly to thiols (–SH) and amines (–NH2).
Thus, covering the NP surface with biomolecules acting as chemo-
therapeutic and targeting agents is relatively straightforward [7].
With the selection of different capping agents, the cytotoxic activ-
ity of metallic NPs can be used for both drug delivery and cancer
cell targeting (Table 3). Whether the targeted delivery of NPs
themselves is therapeutic or the NPs act as carriers for some other
agent, biosynthesized NPs are becoming increasingly important in
nanomedicine.
2.2.1. Biocompatibility
Whenever NPs are used for in vivo applications, biocompatibil-
ity with normal tissue is an important consideration. Moulton et al.
[51] described the biosynthesis of AgNPs using tea leaf extract as a
reducing and capping agent. These authors exposed these NPs to
human keratinocytes and evaluated mitochondrial function to
assess cell viability and membrane integrity. The results showed
that AgNPs biosynthesized with tea leaf extract were nontoxic,
suggesting this method may be promising for future in vivo appli-
cations. The biocompatibility of tea-extract-biosynthesized AgNPs
may be attributed to the antioxidant effect of polyphenol and
flavonoid surfactants.
Kumar et al. [20] described the blood compatibility of AuNPs
synthesized with ginger (Zingiber officionale) extract. Upon contact
with human blood, these AuNPs were shown to be non-platelet
activating, and did not bring about the aggregation of other blood
cells. Moreover, they were highly stable under normal physiologi-
cal conditions compared to chemically synthesized NPs (citrate
capped), which tended to aggregate blood cells.
2.2.2. Anticancer NPs
Cytotoxicology studies against various cancer cell lines have
been described for biosynthesized NPs. Amarnath et al. [52] pub-
lished experiments using AuNPs synthesized using phytochemicals
present in grapes (Vitis vinifera). These AuNPs exhibited remark-
able affinity towards HBL-100 (human breast cancer cells), and
AuNP exposure resulted in HBL-100 apoptosis. Mishra et al. [53]
described AuNP biosynthesis by the supernatant, live cell filtrate
and biomass of the fungus Penicillium brevicompactum. In this
work, the cytotoxic properties of biosynthesized NPs were ana-
lyzed using mouse myoblast cancer C2C12 cells. In a different
study, guava and clove extracts were used to reduce Au and Ag
salts [54] (see Fig. 3). Although biosynthesized AuNPs exhibited
an anticancer effect on HEK-293, HeLa and HT-29 cancer cell lines,
AgNPs did not show any anticancer activity in this study.
In contrast, other reports have demonstrated anticancer effects
from AgNPs. Biosynthesis of anti-tumor AgNPs using Piper longum
leaf as a reducing and capping agent was reported by Jacob et al.
[55]. These NPs showed an excellent cytotoxic effect on HEp-2 can-
cer cell lines. Similarly, callus extract of Citrullus colocynthis was
use to form AgNPs which were effective against HEp-2 cells [56].
Similar efficiency against HeLa cells and a lymphoma mouse model
was observed for AgNPs biosynthesized using Melia azedarach, a
species of deciduous tree from the mahogany family [57]. A sophis-
ticated evaluation of AgNPs effect on cancerous cell lines was given
by Jeyaraj et al. [58]. The cytotoxicity effect of biogenic silver nano-
particles against human breast cancer cells in vitro was studied by
means of the MTT, acridine orange/ethidium bromide and Hoechst
methods and the COMET assay. Extracellular synthesis of copper
NPs was performed using stem latex of Euphorbia nivulia [50]. This
study concluded that copper NPs are toxic to A549 (human lung
carcinoma) cells in a dose-dependent manner.
Recently, the anti-metastatic activity of biologically synthesized
AuNPs was reported for the human fibrosarcoma cell line HT-1080
[59]. Although the biosynthesized AuNPs had no toxic effects on
HT-1080 cells in terms of cell viability, the study showed that
AuNPs inhibit cell migration of HT-1080 cells by interfering with
the actin polymerization pathway.
2.2.3. NP drug carriers
Magnetosomes are naturally occurring metallic nanoparticles
found in some species of magnetotactic bacteria. These chains
are membranous prokaryotic structures, and are composed of
approximately 20 magnetite crystals surrounded by a lipid bilayer.
Sun et al. [60] demonstrated the use of bacterial magnetosomes as
carriers for drug delivery applications. In the study, isolated and
cleaned bacterial magnetosomes from the magnetotactic bacte-
rium Magnetospirillum gryphiswaldense were loaded with the che-
motherapy drug doxorubicin (DOX), attached via amino groups.
The anticancer effect of DOX-loaded bacterial magnetosomes was
demonstrated using a cytotoxicity assay with HL60 and EMT-6 car-
cinoma cells. Inhibition of cancer cell proliferation and suppression

Table 3
Drug delivery and cancer treatment applications.

NP Organism used Application References

Ag Camellia sinensis Biocompatible Moulton et al. [51]
Au Zingiber officinale Blood compatibility Kumar et al. [20]
Au Vites vinefera Cytotoxic activity against HBL-100 cells Amarnath et al. [52]
Au Penicillium brevicompactum Cytotoxic activity against mouse mayo blast cancer cells Mishra et al. [53]
Au Guava Cytotoxic activity against HEK-293, HeLa, and HT-29 cells Raghunandan et al. [54]
Ag Piper longum Cytotoxic activity against Hep-2 cells Jacob et al. [55]
Ag Citrullus colocynthis (L.) Schrad Cytotoxic activity against HEp-2 cells Satyavani et al. [56]
Ag Melia azedarach Cytotoxic activity against HeLa cell lines and lymphoma mice model Sukirtha et al. [57]
Cu Euphorbia nivulia Anticancer efficiency against human lung carcinoma cells Valodkar et al. [50]
Ag Sesbania grandiflora Anticancer efficiency against human breast cancer cells Jeyaraj et al. [58]
Au Dysomsa pleiantha Cell migration of HT-1080 cell line blocking Karuppaiya et al. [59]
Fe3O4 Magnetospirillum gryphiswaldense Carriers for drug delivery applications Sun et al. [60]
Fe3O4 Magnetospirillum gryphiswaldense Biocompatibility of BM Li et al. [61]
Au Porphyra vietnamensis Carrier for drug delivery Venkatpurwar et al. [62]
4030 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042

of mRNA levels of the important oncogene c-myc suggest DOX-
loaded magnetosomes are promising for cancer therapy. Bacterial
magnetosomes are able to carry a large amount of drug, are easy
to prepare, and are more stable and more uniform compared with
artificial magnetic NPs. They are also biocompatible. Li et al. [61]
demonstrated the biocompatibility of purified and sterilized mag-
netosomes surrounded by a lipid/protein membrane to mouse
fibroblasts in vitro. Another drug delivery study employed porphy-
ran from the marine alga Porphyra vietnamensis as a reducing and
capping agent for the biosynthesis of AuNPs [62]. These NPs were
used as a carrier for DOX. The results demonstrated that AuNP-
bound DOX showed higher cytotoxicity to LN-229 (human glioma)
cells than unbound DOX. Spectroscopy revealed that hydrogen
bonds are involved in the DOX–AuNP conjugation.
2.3. Medical diagnostics and sensors
Biosynthesized NPs are also making important contributions to
medicine in the sensing and diagnostics areas (Table 4). These
materials have been successfully incorporated into chemical
sensors that can detect medically relevant compounds, including
peroxides and glucose. For example, eggshell membrane was used
as a reducing agent and scaffold in the biosynthesis of AuNPs [63].
The sensor showed a linear response to different glucose concen-
trations, with a detection limit of 17 lM. The same material was
used to measure the glucose content of human blood serum
samples, and analysis showed agreement with a standard routine
medical spectrophotometric test [64].
Hydrogen peroxide has been acknowledged as a diagnostic
marker of oxidative stress, playing an important role in asthma
or chronic obstructive pulmonary disease (COPD). Wang et al.
[65] constructed a hydrogen peroxide sensor based on biosynthe-
sized selenium NPs (SeNPs) prepared using the bacterial strain
Bacillus subtilis. The resulting SeNPs were spherical and could be
converted into one-dimensional trigonal wires (proteins excreted
from B. subtilis cells act as a template). A clean glassy carbon elec-
trode (GCE) was amended with a drop of a colloidal suspension of
SeNPs and a drop of the enzyme horseradish peroxidase. Cyclic vol-
tammetry studies confirmed that SeNPs enhanced the detection of
H2O2 resulting in an 80 nM detection limit). This material can
therefore be used, for instance, for the detection of hydrogen per-
oxide in the exhaled breath condensate of patients affected with
COPD (see Table 5).
Other authors have also used a GCE modified with biosynthe-
sized nanoparticles for electrochemical sensing. Zheng et al. [66]
synthesized Au–Ag alloy NPs using yeast cells and demonstrated
an enhanced electrochemical response for vanillin (from vanilla
beans and vanilla tea). With a linear range of 0.2–50 lM and a
detection limit of 40 nM, this sensor can be a simple and cheap
alternative to analytical instruments involving gas or liquid chro-
matography, and can be used to check the quality of food products.
Another possible medical application of biogenic AuNPs was
proposed and tested by MubarakAli et al. [67], who suggested that
the conjugation of DNA with biosynthesized nanoparticles can be
used for diagnosis of genetic disease.
2.4. Medical imaging applications
The optical properties of metallic nanocrystals have been of
interest for centuries. The incorporation of biosynthesis methods
has made possible the preparation of metal NPs with a range of
sizes, shapes and dielectric properties. Optical properties associ-
ated with metallic NPs include a high- or low-refractive index, high
transparency, novel photoluminescence properties, photonic crys-
tals and plasmon resonance [68]. Nanophotonics studies in the
field, where the light interacts with particles smaller than its wave-
length, lead to novel phenomena, such as localized surface plas-
mon resonance and a size-dependent semiconductor band gap
[69].
The biosynthesis AuNPs by silica-encapsulated Klebsormidium
flaccidum microalgae leads to the formation of a ‘‘living’’ biohybrid
material [70]. Researchers have used Raman spectroscopy for
in situ imaging of entrapped cells and have investigated the influ-
ence of the AuNPs on the photosynthetic system of the algae. The
coupling of Raman imaging and sol–gel encapsulation might allow

Table 4
Medical diagnostics and sensors.

NP Organism used Application References

Au Eggshell membrane Glucose sensor Zheng et al. [63]
Au Eggshell membrane Glucose sensor in human blood serum Zheng et al. [64]
Se Bacillus subtilis H2O2 sensor Wang et al. [65]
Au–Ag Saccharomyces cerevisiae Vanillin sensor Zheng et al. [66]
Au Different microalgae DNA conjugation MubarakAli et al. [67]

Table 5
Imaging and other medical applications.

NP Organism used Application References

Au Klebsormidium flaccidum Photosynthesis-based environmental biosensor Sicard et al. [70]
Ag Trichoderma viride NP photoluminescence Fayaz et al. [71]
Ag Parthenium hysterophorus NP photoluminescence Sarkar et al. [72]
Ag Coriandrum sativum leaf Optical limiting Sathyavathi et al. [74]
Te Bacillus selenitireducens Optical limiting Liao et al. [75]
Au Maduca longifolia Efficiency in absorbing infrared radiation Fayaz et al. [76]
Au Cymbopogon citratus Infrared absorbing optical coatings Shankar et al. [77]
CdTe Saccharomyces cerevisiae Biolabeling and bioimaging Bao et al. [78]
CdTe Escherichia coli Biolabeling and bioimaging Bao et al. [79]
CdS Brevibacterium casei Fluorescence emission Pandian et al. [80]
Au Psidium guajava Diabetes treatment –tyrosine phosphatase type PTP 1B inhibition Basha et al. [81]
Au, Ag Brevibacterium casei Anticoagulation activity Kalishwaralal et al. [82]
Au Solanum nigrum Free radical scavenging effect Muthuvel et al. [83]
Ag Trichoderma reesei HIV treatment Vahabi and Dorcheh [86]
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
for the development of photosynthesis-based biosensors (see
Fig. 4).
Blue orange light emission from biosynthesized AgNPs was
reported by Fayaz et al. [71]. Fungal-mediated AgNPs were
prepared using a Trichoderma viride filtrate. Photoluminescence
measurements after laser excitation showed an emission in the
range of 320–520 nm, making such AgNPs promising for future
labeling and imaging applications. A similar study was introduced
by Sarkar et al. [72] using Parthenium hysterophorus leaf extract for
AgNP biosynthesis.
An important problem of modern laser medicine is the exten-
sive exposure of vulnerable tissues outside of the operational field.
This problem can be solved by placing dyes that are capable of
reversible darkening of the radiation onto the surface of irradiated
tissues. This phenomenon is called optical radiation limiting [73].
AgNPs biosynthesized using Coriandrum sativum leaf extract were
found to exhibit strong reverse saturable absorption of laser irradi-
ation [74]. The authors measured nonlinear refraction and absorp-
tion coefficients using a Z-scan technique with laser pulses. These
results suggest AgNPs are capable of nonlinear optics. Similarly,
microbiologically formed nanorods prepared using Bacilus seleniti-
reducens and composed of elemental tellurium Te(0) have been
described elsewhere [75]. These TeNPs form unusual nanocompos-
ites when combined with an organic chemical host and exhibit
excellent broadband optical limiting at 532 and 1064 nm. In this
regard, they significantly exceeded the best commercial optical
limiters currently available. Their relative ease of biomanufactur-
ing combined with their unique properties makes these Te-based
nanocomposites particularly attractive for their immediate
employment as coatings in medicine or industry (e.g. to protect
eyes from damage caused by exposure to focused beams and
lasers).
Fayaz et al. [76] biosynthesized AuNPs using Maduca longifolia
extract and showed strong near-infrared absorption. Although
some applications are not directly medical in nature, such as
energy-saving window coatings, a similar technology can also be
applied for cancer hyperthermia coatings [77].
The same research team published two additional studies
describing cadmium telluride quantum dots (CdTeQDs) fabricated
via extracellular synthesis using Saccharomyces cerevisiae [78] and
Escherichia coli [79]. The authors evaluated the NP’s size-dependent
optical properties. CdTeQD were relatively small, capped with pro-
tein and highly soluble in water. The optical properties were stud-
ied in both cases using UV–visible spectroscopy and
spectrofluorimetry with photoluminescence emission from 488
to 551 nm. CdTeQDs functionalized with folic acid were used for
in vitro imaging of cancer cells, and were also found to be biocom-
patible in a cytotoxicity assay [79]. This study clearly shows the
capacity of biosynthesized QDs to be used in bioimaging and biola-
beling applications.
Finally, a study using Brevibacterium casei for the biosynthesis of
CdSNPs [80] showed that the NPs exhibited fluorescence emission
even after immobilization within a polyhydroxybutyrate matrix.
2.5. Other medical applications
Several studies have shown biosynthesized NPs to have poten-
tial applications for the treatment of other diseases, including dia-
betes and bleeding disorders. Biosynthesized AuNPs have been
shown to inhibit the enzyme tyrosine phosphatase type PTP 1B
in vitro [81]. Since PTP 1B has been found to dephosphorylate insu-
lin receptors, reducing its activity can enhance the activity of insu-
lin. AuNPs prepared by means of guavanoic acid from a leaf extract
of Psidium guajava showed a significant inhibitory effect, with an
IC50 of 1.14 lg ml1. Another study showed that biosynthesized
Au- and AgNPs produced and stabilized using Brevibacterium casei
4031
exhibited anticoagulation activity [82]. Exposure of the particles to
blood plasma for 24 h did not show any significant reduction in the
anticoagulation activity.
Free radical scavenging activity was demonstrated by Muthuvel
et al. [83]. Au-NPs biosynthesized by means of Solanum nigrum were
tested for the scavenging effect on 10 1-diphenyl-2-picrylhydrazyl
radical and hydroxyl radicals according to the method of Blois and
the deoxyribose method, respectively. The synthetic antioxidant
butyl hydroxyl toluene was used as a positive control, and biogenic
nanoparticles showed up to 60% inhibition efficiency for both radical
types [84,85]. Interestingly, Trichoderma reesei-produced AgNPs pre-
vent HIV-1 particles from binding to host cells [86].
Finally, Gopinath et al. [87] described enhanced mitotic cell
division and pollen germination activity caused by AuNPs synthe-
sized using Terminalia arjuna leaf extract. These studies demon-
strate the wide range of biomedically relevent effects possible by
exposure to biosynthesized NPs. Additional research will offer
new discoveries and insights into the use of biosynthesized NPs
as promising treatments for human diseases.
3. Environmental remediation applications
3.1. Metal biosorption, bioremediation and biorecovery
Oxidation–reduction processes are universally used for cellular
metabolism; therefore biomolecules with the ability to reduce or
oxidize other chemical compounds are abundant in any living cell.
Many microorganisms are able to bind and concentrate dissolved
metals as an active mechanism to detoxify their environment.
Other biological processes, and even dead biomass, simply couple
metal reduction with oxidation of an electron donor. Since the
product of cellular metal reduction is usually nanostructured, bio-
remediation of metals in solution and biosynthesis of metallic NPs
are in fact closely related processes [88]. In this section, we review
studies that describe biological metal removal and NP formation
via biologically mediated processes (see Table 6).
The biomass of algae, fungi, bacteria and yeasts, along with
some biopolymers and biowaste materials, are known to bind
and concentrate precious metals [89]. This so-called biosorption
process can represent a cost-effective alternative to the common
chemical methods for recovery of various dissolved metals from
aqueous solution. The mechanisms involved in binding and con-
centrating metals by microbes have been extensively studied in
natural environments [89].
Chakraborty et al. [90] demonstrated the ability of cyanobacte-
ria and algae to bind and concentrate Au and form AuNPs. The NP
formation process is specific to a particular genus, and they
described NP formation using the cyanobacterial strains Lyngbya
majuscula and Spirulina subsalsa, and the freshwater green alga Rhi-
zoclonium hieroglyphicum. AuNPs formation during biosorption by
the seaweed Fucus vesiculosus was reported by Mata et al. [91].
These authors described the pH dependence on NP formation and
discussed the stages of the bioreduction process.
Dead biomass of the macrofungus Pleurotus platypus was used
for biosorption of Ag in a study by Das et al. [92]. The fungal bio-
mass exhibited the highest Ag uptake of 46.7 mg g1 at pH 6.0 in
the presence of 200 mg l1 Ag(I) at 20 °C. These authors also
offered detailed kinetic and thermodynamic analysis of the bio-
sorption process. Zhang et al. [93] demonstrated the use of the
G facultative anaerobic bacteria Aeromonas SH10 to treat Ag in
waste water. In this study, biomass was shown to accumulate
Ag+ and [Ag(NH3)2]+ ions as AgNPs. The maximum uptake of
[Ag(NH3)2]+ was 0.23 g of Ag per g of cell dry weight.
An example of platinum recovery by polyethyleneimine (PEI)-
modified biomass was described by Won et al. [94]. In this study,
PEI was attached to the surface of E. coli biomass and the resulting
4032 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042

Table 6
Metal biosorption, bioremediation and biorecovery.

NP Organism used Application References

Au Lyngbya majuscula, Spirulina subsalsa, Rhizoclonium hieroglyphicum Bioaccumulation Chakraborty et al. [90]
Au Fucus vesiculosus Bioaccumulation, biorecovery Mata et al. [91]
Ag Pleurotus platypus Biosorption Das et al. [92]
Ag Aeromonas sp. SH10 Silver-containing waste water treatment Zhang et al. [93]
Pt Escherichia coli Biosorption, biorecovery by incineration Won et al. [94]
Au Sargassum sp. Biosorption, biorecovery by incineration Sathishkumar et al. [95]
Ag Saccharomyces cerevisiae As(V) bioaccumulation and removal Selvakumar et al. [96]
MnO2 Bacillus sp. (MTCC10650) Mn bioremediation Sinha et al. [97]

material was used to accumulate platinum from waste water. Sub-
sequent incineration of the modified biomass resulted in 98.7%
recovery of platinum from the ash. A similar study employed the
brown macroalga Sargassum sp. [95] for Au recovery and reported
an efficiency of greater than 90%.
Toxic concentrations of naturally occurring arsenic in drinking
water are a major public health problem in Southeast Asia.
Selvakumar et al. [96] described a promising solution to this prob-
lem through their development of an AgNP sorbent for As(V)
removal. In the study, the reducing capabilities of a novel yeast
strain of Saccharomyces cerevisiae was used to sequester the metal.
Finally, Sinha et al. [97] showed that a heavy-metal-resistant strain
of Bacillus sp. formed MnO2 NPs simultaneously with the remedia-
tion of manganese.
Hexavalent chromium compounds are dangerous toxins, while
Cr(III) ions and compounds are relatively non-toxic. Bare living
cells of Shewanella algae, Pseudomonas putida and Desulfovibrio vul-
garis have been shown to reduce Cr(VI) to Cr(III) [98]. Many other
studies rely on biosynthesized PdNPs to catalytically reduce chro-
mium. (See Section 3.4 on catalytic Cr(VI) reduction.)
3.2. Coupling biosorption with catalytic contaminant degradation
Due to their large surface area per weight, metallic NPs are
widely used for catalysis, and in particular for heterogeneous catal-
ysis. Metallic NPs offer selectivity, high activity and stability. The
major drawback of metallic NP catalysis is cost: the constituent
metals, including gold, platinum and palladium, are very expen-
sive, and their fabrication into nanoparticles is energy intensive.
Coupled biosynthetic approaches can generate catalytically active
NPs through biosorption of waste streams containing precious
metals. The coupling of biological metal removal with catalyst for-
mation has been described in recent reviews by De Corte et al. [99]
and Hennebel et al. [100]. These biosynthesized metallic NPs can
then be used for catalytic dehalogenation, organic oxidation or
metal reduction. Most environmental remediation applications of
biosynthesized catalyst employ palladium (Pd) NPs (see Table 7).
The following sections describe catalytic treatment of organic com-
pounds and metals using biosynthesized metallic NPs.
3.3. Catalytic degradation of organic pollutants
3.3.1. Catalytic dehalogenation
Palladium-based catalysts are able to dehalogenate aromatic
compounds. This reaction is very important for organic synthesis
in research and industry, and also for contaminant remediation.
Halogenated organic compounds dominate the priority list of per-
sistent, bioaccumulative and toxic (PBT) pollutants as designated
by the US Environmental Protection Agency. By definition, PBT
compounds do not break down naturally in the environment, so
enhanced processes to dehalogenate these compounds are of great
interest. Halogenated organic PBTs include several banned pesti-
cides, including chlordane, dichlorodiphenyltrichloroethane
(DDT), dieldrin and hexachlorobenzene, as well as polychlorinated
biphenyls (PCBs), compounds formerly used in electronic devices
and as coolants, lubricants and plasticizers.
Baxter-Plant et al. [101,100] described the dehalogenation of
chlorophenol (CP) and selected PCB congeners, including 4-chloro-
biphenyl, 2,4,6-trichlorobiphenyl, 2,3,4,5-tetrachlorobiphenyl and
2,20 ,4,40 ,6,60 -hexachlorobiphenyl, via palladized cells of G Desulf-
ovibrio bacteria. Biosynthesized PdNPs were obtained by the reduc-
tion of the palladium precursor in the presence of Desulfovibrio
desulfuricans, Desulfovibrio vulgaris and Desulfovibrio sp. Oz-7. As
described by Bunge et al. [103], reduction in the absence of cells
does not lead to the formation of PdNPs; rather, this process
requires an electron donor, such as formate (see Tables 8 and 9).
Shewanella oneidensis is another strain of bacteria that has been
used to biosynthesize PdNPs for dehalogenation of PCB and other
chlorinated organic compounds. De Windt et al. [104] described
PdNPs precipitated on the cell wall and inside the periplasmic
space of S. oneidensis and demonstrated the effective dehalogen-
ation of PCBs in water and sediment. Their study described in
detail bioreduction with different electron donors and varying frac-
tions of PdNPs associated with the biomass. They showed that the

Table 7
Catalytic dehalogenation.

NP Organism used Application References

Pd Desulfovibrio vulgaris, D. desulfuricans Dechlorination of CP and PCBs Baxter-Plant et al. [101]
Pd D. desulfuricans Dechlorination of CP and PCBs Baxter-Plant et al. [102]
Pd Shewanella oneidensis Dechlorination of chlorophenol and PCBs De Windt et al. [104]
Pd S. oneidensis Dechlorination of perchlorate and PCBs De Windt et al. [105]
Macaskie et al. [106]
Pd D. desulfuricans, Rhodobacter sphaeroides Dechlorination of (PCBs) and penta-CP Redwood et al. [107]
Pd S. oneidensis Dechlorination of lindane Mertens et al. [108]
Pd S. oneidensis Dechlorination of TCE, membrane reactor Hennebel et al. [109]
Pd S. oneidensis Dechlorination of TCE, fixed bed reactor Hennebel et al. [110]
Fe/Pd Camellia sinensis Dechlorination of TCE Smuleac et al. [111]
Pd D. desulfuricans Dehalogenation PCBs and polybrominated diphenyl ether Harrad et al. [112]
Pd D. desulfuricans Dehalogenation of flame retardant materials Deplanche et al. [113]
Pd S. oneidensis Deiodination of diatrizoate Hennebel et al. [114]
Pd S. oneidensis Dehalogenation of diatrizoate in microbial electrolysis cells De Gusseme et al. [115]
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042 4033

catalytic activity of biosynthesized PdNPs was 100 higher than
commercial palladium catalyst powder (see Fig. 5).
In a follow-on report, De Windt et al. [105] performed a detailed
assessment of the bioreduction process and its conditions. In par-
ticular, they investigated the factors influencing the particle size
and catalytic properties of PdNPs formed from a soluble palladium
precursor by S. oneidensis. Interestingly, the relatively large palla-
dium crystals formed on non-viable biomass exhibited high cata-
lytic efficiency towards hydrophobic molecules such as PCBs,
while the smaller PdNPs created on living bacterial cells showed
high catalytic activity towards perchlorate.
Macaskie et al. [106] extensively studied the catalytic dechlori-
nation of 2-chlorophenol, pentachlorophenol and various PCB
congeners by palladized cells of Desulfovibrio and Escherichia coli.
Redwood et al. [107] compared the efficiency of palladized D.
desulfuricans with Rhodobacter sphaeroides for catalytic dechlorina-
tion of PCBs and pentachlorophenol. Mertens et al. [108] demo-
strated the efficiency of palladized S. oneidensis for the catalytic
decomposition of the pesticide lindane. These authors also incor-
porated the catalytic material into a membrane bioreactor for the
continuous treatment of lindane-contaminated water.
Other studies have demonstrated the use of palladized cells for
dechlorination of the common groundwater contaminant trichlor-
ethylene (TCE). Hennebel et al. described two reactor geometries
for catalytic dechlorination of TCE by biosynthesized PdNPs: a
pilot-scale membrane reactor [109] and a fixed bed reactor with
PdNPs embedded in a polyurethane foam [110]. These authors
described the cumulative removal of 98% of TCE after 22 h, with
ethane as the predominant product, and a maximum removal rate
of 1.059 mg of TCE per g of biosynthesized PdNPs per day.
Other authors used Fe and Fe/Pd NPs biosynthesized with tea
extract (Camellia sinensis) then immobilized in polymer mem-
branes for the catalytic degradation of TCE [111]. These authors
found that the reaction rate constant was higher for the bimetallic
Fe/PdNPs. The biosynthesized NPs exhibited a lower reaction rate
than chemically synthesized FeNPs, though the reactivity of chem-
ically synthesized FeNPs diminished to less than 20% within four
cycles. By contrast, the reactivity of the green tea extract-synthe-
sized NPs was preserved throughout 3 months of repeated use
under conditions simulating a real water treatment system, possi-
bly due to a number of polyphenols that can act as capping agents.
Biosynthesized PdNPs can also catalytically dehalogenate bro-
minated organic compounds. Harrad et al. [112] demonstrated that
palladized D. desulfuricans is able to catalytically dehalogenate
polybrominated diphenyl ether (PBDE). Hydrophobic brominated
compounds such as PBDE are used as flame retardants in building
materials, textiles and plastics. Deplanche et al. [113] also used
palladized cells of D. desulfuricans for the catalytic dehalogenation
of flame retardants, including PBDE and tris-(chloroisopropyl)-
phosphate (TCPP), and compared their performance with chemi-
cally reduced palladium powder. The chemically reduced Pd was
more effective in debrominating PBDE, but the biosynthesized
PdNPs were five times more effective in TCPP dechlorination.
Two studies have demonstrated that biosynthesized NPs can
remediate diatrizoic acid (or diatrizoate), a radiocontrast agent.
Hennebel et al. [114] demonstrated that PdNPs encapsulated on
PVDF membranes effectively deiodinate diatrizoate in water. Sim-
ilarly, De Gusseme et al. [115] showed that biosynthesized PdNPs
contributed to higher dehalogenation rates of TCE and higher deio-
dination rates of diatrizoate when applied on the surface of a
graphite cathode. The presence of PdNPs on the cathode enhanced
the rate of diatrizoate removal by both direct electrochemical
reduction and catalytic reduction using the hydrogen produced
at the cathode of the microbial electrolysis cell.
3.3.2. Catalytic 4-nitrophenol degradation
The rapid development and use of synthetic pesticides, dyes,
explosives and pharmaceuticals in the middle of the last century

Table 8
Catalytic 4-nitrophenol degradation and catalytic treatment of other aqueous organic compounds.

NP Organism used Application References

Au Sesbania drummondii Reduction of 4-nitrophenol Sharma et al. [116]
Au Cacumen platycladi Reduction of 4-nitrophenol Huang et al. [117]
Ag Sepia esculenta Reduction of 4-nitrophenol Jia et al. [120]
Ag Breynia rhamnoides Reduction of 4-nitrophenol Gangula et al. [118]
Au B. rhamnoides Reduction of 4-nitrophenol Gangula et al. [118]
Pd/Au Cupriavidus necator Reduction of 4-nitrophenol Hosseinkhani et al. [119]
Ag Rhizopus oryzae Reduction of 4-nitrophenol Das et al. [121]
Fe C. sinensis Degradation of aqueous cationic and anionic dyes Shahwan et al. [122]
Au C. sinensis Reduction of methylene blue Gupta et al. [123]
ZnS Streptococcus thermophiles, Photocatalytic degradation of fuchsine Zhou et al. [124]
Lactobacillus bulgaricus,
Lactobacillus acidophilus
Ag Coccinia grandis Photocatalytic degradation of Coomassie Brilliant Blue G-250 Arunachalam et al. [125]
Pd Pseudomonas putida Removal of micropollutants (e.g. ibuprofen, diclofenac, mecoprop) Forrez et al. [126]

Table 9
Catalytic Cr(VI) reduction.

NP Organism used Application References

Pd E. coli mutant strains Reduction of Cr(VI) to Cr(III) Deplanche et al. [127]
Pd D. desulfuricans Reduction of Cr(VI) to Cr(III) Mabbett and Macaskie [128]
Pd Desulfovibrio vulgaris, Desulfovibrio desulfuricans Reduction of Cr(VI) to Cr(III) Humphries et al. [129]
Pd D. desulfuricans Reduction of Cr(VI) to Cr(III) Mabbett et al. [130]
Pd/MM* D. desulfuricans, Escherichia coli Reduction of Cr(VI) to Cr(III) Mabbett et al. [131]
Pd Serratia sp. (NCIMB) Reduction of Cr(VI) to Cr(III) Beauregard et al. [132]
Pd Clostridium pasteurianum Reduction of Cr(VI) to Cr(III) in aquifer environment Chidambaram et al. [133]
Pd E. coli, Desulfovibrio spp. Reduction of Cr(VI) to Cr(III) Macaskie et al. [148]
*
Mixed precious metals.
4034 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
has resulted in a legacy of toxic nitro-aromatic contamination in
soil and water. Technologies for catalytic removal of compounds
such a 4-nitrophenol (also known as p-nitrophenol or PNP) can
help restore impacted environments. Furthermore, the degradation
of PNP can be measured easily using widely available and inexpen-
sive optical methods such as UV–visible spectrophotometry. The
catalytic degradation of PNP has thus become a common test
system to evaluate the catalytic reduction capabilities of biosyn-
thesized NPs.
The first report of PNP reduction employing biosynthesized NPs
was published by Sharma et al. [116]. Seedlings of the plant Sesba-
nia drummondii were grown in a hydrogen tetrachloroaurate solu-
tion and stable AuNPs were subsequently formed in plant tissues.
This AuNP-rich plant tissue was used as an efficient catalyst for
PNP reduction in the presence of sodium borohydride.
Subsequently, others have used plant materials to biosynthesize
noble metal NPs for catalytic PNP reduction. Huang et al. [117] car-
ried out an extensive study using 21 species of traditional Chinese
herbs and medicinal plants. These plants were divided into four
groups, and their leaves, flowers, fruits were used for NP biosyn-
thesis by 30 min incubation in aqueous HAuCl4. Due to their mono-
dispersity and small size, AuNPs prepared using Cacumen platycladi
leaves were used to demonstrate catalytic PNP reduction. Gangula
et al. [118] used the stem extract of a medicinal plant Breynia
rhamnoides for fast (7 min) biosynthesis of AgNPs and AuNPs.
These authors found the conversion efficiency to be dependent
on the NP size, which is possibly controlled by the stem extract
concentration used for biosynthesis.
Bacteria have also been used for biosynthesis of bimetallic Pd/
AuNPs for PNP reduction. Hosseinkhani et al. [119] formed biosup-
ported Pd(0) and Au(0) NPs on the surface of Cupriavidus necator
cells. Bimetallic particles were subsequently formed following
the addition of either Au(III) or Pd(II) salt to the biosupported
NPs. Although the bimetallic NPs did not have a core–shell struc-
ture, they exhibited superior catalytic efficiency in PNP conversion
compared with monometallic NPs.
Catalytic PNP reduction has also been done using animal-derived
materials for the biosynthesis of NPs. Jia et al. [120] described AgNP
biosynthesis and immobilization using a cuttlebone-derived
organic matrix from the cuttlefish Sepia esculenta. The calcareous
matrix of the cuttlebone functioned as both a reducer and a scaffold
for AgNP formation. These researchers also described the reusabil-
ity of the composite material and the potential for separation of
NPs from the matrix. Das et al. [121] showed that the immobiliza-
tion of the biogenic AgNPs on the nanostructured silica leads to
their excellent hydrogenation catalytic efficiency. Protein extract
from Rhizopus oryzae was applied on the nanosilica and used for
AgNP biosynthesis. The resulting material was subsequently used
for catalytic hydrogenation of 4-nitrophenol.
3.3.3. Catalytic treatment of other aqueous organic compounds
Other organic compounds have been effectively reduced using
biosynthesized NPs. Iron and gold NPs have been used to catalyti-
cally remove dyes from aqueous solutions. In one study, FeNPs
biosynthesized by means of green tea extract were used as a
Fenton-like catalyst for the decolorization of aqueous solutions of
methylene blue and methyl orange dyes [122]. Compared with iron
NPs produced by the reduction of sodium borohydride, the biosyn-
thesized iron NPs exhibited faster dye removal and a greater extent
of dye removal. Gupta et al. [123] used green tea extract to biosyn-
thesize AuNPs for catalytic reduction of the dye methylene blue in
the presence of Sn(II) in both aqueous solution and micelles. The
authors showed that a small quantity of AuNPs decreases the acti-
vation energy for reduction of methylene blue, and complete
removal of dye could be achieved even at low temperature. Zhou
et al. [124] described the photocatalytic degradation of the
magenta dye fuchsine using PbS and ZnS hollow nanostructures
formed on two species of bacteria. Photocatalytic degradation of
the dye Coomassie Brilliant Blue G-250 in the presence of UV light
has also been shown by AgNPs prepared from the aqueous extract
of Coccinia grandis leaves [125].
Finally, Forrez et al. [126] used biosynthesized PdNPs in a mem-
brane reactor to remove micropollutants such as ibuprofen (>95%),
diclofenac (86%), mecoprop (81%) and triclosan (>78%) from the
secondary effluent of a sewage treatment plant. The authors
suggested that the removal mechanisms could include chemical
oxidation by PdNPs and/or biological removal by Pseudomonas
putida bacteria.
3.4. Catalytic Cr(VI) reduction
Another important environmental application for biosynthe-
sized NPs is the catalytic reduction of the powerful oxidant Cr(VI)
to the relatively non-toxic valence state Cr(III). Several recent stud-
ies have shown that PdNPs biosynthesized by various species of
bacteria, including E. coli, Desulfovibrio, Serratia and Clostridium,
can effectively catalyze the reduction of Cr(VI) to Cr(III) under both
batch and continuous flow conditions. For example, Deplanche
et al. [127] evaluated how three types of hydrogenases encoded
by E. coli influence the activity of biosynthesized catalyst for
Cr(VI)/Cr(III) reduction. This study also described the hydrogenase
involvement in Pd(II) reduction. Macaskie et al. [106] compared
E. coli and Desulfovibrio spp. for the biosynthesis of PdNPs for cat-
alytic Cr(VI)/Cr(III) reduction. Mabbett and Macaskie [128] used
Desulfovibrio desulfuricans for the biosynthesis of PdNPs for
Cr(VI)/Cr(III) reduction in waste water. These authors found that
the biosynthesized PdNPs were more efficient reduction catalysts
than either bare living D. desulfuricans biomass or chemically
reduced palladium. They proposed that the palladium catalyzes
the hemolytic cleavage of H2 and that the H⁄ radicals then donate
their electrons to reduce the Cr(VI).
Unlike the previous experiments, all of which were carried out
under batch conditions, Humphries et al. [129] reported a contin-
uous flow system for Cr(VI)/Cr(III) reduction. In this study, biosup-
ported PdNPs formed by Desulfovibrio vulgaris were immobilized in
agar and the effects of Pd concentration, Cr(VI) concentration and
process flow rate were investigated. This work built on a study
by Mabbett et al. [130], who had previously demonstrated a con-
tinuous flow system for Cr(VI)/Cr(III) reduction by PdNPs biosyn-
thesized by D. desulfuricans. Mabett et al. [131] subsequently
described the formation of a mixed metal catalyst biosynthesized
with D. desulfuricans and E. coli from a metal waste stream for
Cr(VI)/Cr(III) reduction.
Beauregard et al. [132] used a biofilm-forming bacterial species
Serratia sp. to mediate the adherence of bio-PdNPs to porous poly-
urethane foam. The foam was used as a scaffold for the catalyst and
supported the growth of the bacterium. Magnetic resonance imag-
ing was used to directly monitor Cr(VI)/Cr(III) reduction since
Cr(VI)aq is non-paramagnetic and Cr(III)aq is paramagnetic. Finally,
Chidambaram et al. [133] demonstrated successful Cr(VI) reduc-
tion experiments using PdNs biosynthesized by the bacterium
Clostridium pasteurianum. This study is unique because, unlike
the previous studies, the C. pasteurianum communities were grown
on aquifer material and catalytic reduction experiments were per-
formed in a natural aquifer environment. This study opens up the
potential for in situ Cr(VI) remediation via Pd(II) injection into the
aquifer.
3.5. Biosynthesized NPs to enhance membrane treatment processes
Technologies to reduce biofouling can greatly enhance the per-
formance of membrane-based water treatment processes. Zhang
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042 4035

et al. [134] showed that different amounts of biogenic AgNPs
formed by Lactobacillus fermentum prevented biofouling on polye-
thersulfone membranes. The membranes were used to remove
organophosphate pesticides and E. coli cells from a waste water
model. The authors measured the structure and performance of
the membrane and assessed biofouling using E. coli and P. aerugin-
osa bacteria both individually and in mixed culture. The nanofunc-
tionalized membrane coating exhibited good antibacterial activity
and prevented biofilm formation on the membrane surface during
the 9 week test.
4. Industrially important applications
4.1. Catalytic organic synthesis
Cheap specific catalysts for commercially important organic
synthesis reactions, including hydrogenation, cross-coupling reac-
tions and epoxidation, are extremely important in industry.
Biosynthesized palladium, gold and platinum catalysts have been
used successfully in several different organic synthesis pathways
(see Table 10).
Creamer et al. [135] used palladized cells of bacterial strains
Desulfovibrio desulfuricans (G) and Bacillus sphaericus (G+) for cat-
alytic hydrogenation of itaconic (or methylenesuccinic) acid. Com-
parisons performed in a stirred autoclave between biosynthesized
PdNPs and commercial graphite-supported catalysts displayed
similar activity. Bennett et al. [136] investigated the hydrogenation
and isomerization of 2-pentane using palladized D. desulfuricans in
a stainless steel Büchi reactor. They found that, although the rate of
2-pentane hydrogenation was lower for the biosynthesized Pd cat-
alyst than for the commercial Pd/Al2O3 catalyst, the selectivity was
similar. Wood et al. [137] used palladized Rhodobacter capsulatas
and Arthrobacter oxidans for the hydrogenation of 2-butyne-1,4-
diol. The biosynthesized PdNPs exhibited high selectivity during
partial hydrogenation to 2-butene-1,4-diol.
Creamer et al. [138] demonstrated the use of biosynthesized
PdNPs to catalyze non-aqueous hydrogenation. Desulfovibrio desul-
furicans and B. sphaericus produced palladium catalyst, which
catalyzed the hydrogenation of 4-azidoaniline hydrochloride to
1,4-phenylenediamine and 3-nitrostyrene to 1-ethyl-3-nitrobenzene
in methanol.
Unlike the aforementioned studies, Jia et al. [139] published a
method for PdNPs biosynthesis that does not require the H2 donor.
Biosynthetic PdNPs were formed by the reduction of palladium
chloride in a crude extract of Gardenia jasminoides. The authors
measured catalytic hydrogenation of p-nitrotoluene and demon-
strated a conversion of 100% at 5 MPa and 150 °C for 2 h, with a
selectivity of 26.3% for the product p-methyl-cyclohexylamine.
Reusability studies demonstrated that the catalyst retained its
activity over five cycles.
Biosynthesized NPs have been used to catalyze cross-coupling
reactions (i.e. C–C bond formation). Søbjerg et al. [140] showed
that palladized bacteria Cupriavidus necator, Pseudomonas putida
and Staphylococcus sciuri were effective catalysts for both the
Suzuki–Miyaura and Mizoroki–Heck reactions. In a follow-on
report, these authors described how biomass/Pd ratio and NPs
sizes influenced the hydrogenation of (E)-3-(4-methoxyphenyl)-
N-methylacrylamide and the reduction of 4-chloro-nitrobenzene
[141]. Finally, Gauthier et al. [142] demonstrated the formation
of catalyst for C–C bond formation was coupled to the recovery
of Pd from a waste stream using Cupriavidus necator cells.
In addition to palladium, biosynthesized gold and platinum NPs
have been used to catalyze other organic synthesis reactions. Du
et al. [143] used biosynthesized AuNPs to catalyze propylene epox-
idation. Negatively charged AuNPs were immobilized on a titanium
silicalite support using electrostatic attractive interactions in an
extract of Cacumen platycladi. These authors achieved a propylene
epoxide formation rate higher than previously described in other
reports. The authors proposed that the efficiency and selectivity
of biosynthesized catalysts could be influenced by residual biomol-
ecules. A more detailed investigation of the same catalyst by Zhan
et al. [144] described the optimum reaction parameters, including
the Si/Ti molar ratio, Au loading, immobilization pH and reaction
temperature, together with possible reaction mechanisms. Simi-
larly, AuNPs immobilized on a titanium silicalite support were
calcined and used for industrially important epoxidation of styrene
to styrene oxide [145]. This experimental setup enables a styrene
conversion of 92.7% and a styrene oxide selectivity of 90.4% under
optimal conditions.
Finally, biosynthesized PtNPs have been used to catalyze the
synthesis of the organic dye antipyrilquinoneimine from aniline
and 4-aminoantipyrine in acidic aqueous solution [146]. In this
report, honey-mediated platinum nanostructures were found to
be stable in water for more than 4 months.
4.2. Energy-related applications
The ability of different organisms to reduce and absorb precious
metal salts and form NPs has been used to enhance several aspects
of fuel cell performance. Biogenic NPs have been used to produce
H2 fuel, to catalyze chemical oxidation of the fuel and to improve
power recovery (Table 11).
Several investigators have used biosynthesized PdNPs for H2
production. Bunge et al. [103] used three species of bacteria (Cupri-
avidus necator, Pseudomonas putida and Paracoccus denitrificans)
to biosynthesize PdNPs for catalytic H2 production from

Table 10
Catalytic organic synthesis.

NP Organism used Application References

Pd D. desulfuricans, Bacillus sphaericus Hydrogenation of itaconic acid Creamer et al. [135]
Pd D. desulfuricans Hydrogenation of 2-pentane Bennett et al. [136]
Pd Rhodobacter capsulatus, Arthrobacter oxidans Hydrogenation of 2-butyne-1,4-diol Wood et al. [137]
Pd D. desulfuricans, B. sphaericus Hydrogenation, reduction and selective dehalogenation in non-aqueous solvents Creamer et al. [138]
Pd Gardenia jasminoides Hydrogenation of p-nitrotoluene Jia et al. [139]
Pd Cupriavidus necator, Pseudomonas putida Suzuki–Miyaura and Mizoroki–Heck reactions Søbjerg et al. [140]
Pd C. necator, Staphylococcus sciuri Suzuki–Miyaura, hydrogenation of (E)-3-(4-methoxyphenyl)-N-methylacrylamide Søbjerg et al. [141]
Pd C. necator, Staphylococcus sciuri 4-chloronitrobenzene reduction Søbjerg et al. [141]
Pd C. necator Catalysis of C–C bond formation Gauthier et al. [142]
Au Cacumen platycladi Propylene epoxidation Du et al. [143]
Au C. platycladi Propylene epoxidation Zhan et al. [144]
Au C. platycladi Styrene epoxidation Huang et al. [145]
Pt Honey Preparation of organic dye Venu et al. [146]
4036 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
hypophosphite. Wu et al. [147] biosynthesized PdNPs with garde-
nia extract on TiO2 supports to enhance photocatalytic H2 evolu-
tion from pure water. Macaskie et al. [148] provided a brief
overview of bacterial hydrogenase activity for several applications,
including waste decontamination, production of precious metal
nanocatalyst and biohydrogen production. These authors also
described how E. coli with modified hydrogenase and dehydroge-
nase regulation could be used to further enhance performance.
Biosynthesized NPs have been incorporated into fuel cells to
catalyze chemical reactions and have been used in electrode con-
struction. Yong et al. [149] bioaccumulated Pt and Pd as NPs using
Desulfovibrio desulfuricans and mixed the dried biomaterial with
activated carbon powder to create carbon paper used in a commer-
cial fuel cell system. Dimitriadis et al. [150] used yeast biomass
immobilized in polyvinyl alcohol (PVA) cryogels for the biorecov-
ery of platinum from aqueous solution, then directly incorporated
this PtNP–biomass–PVA material into a fuel cell. Another study
described four different concentrations of biomass-supported pal-
ladium NPs using Shewanella oneidensis as an electrode catalyst in a
polymer exchange membrane fuel cell [151].
Orozco et al. [152] studied the ability of PdNPs biosynthesized by
two different strains of E. coli to both produce hydrogen via fermen-
tation and convert the H2 into energy in a fuel cell. Both the parent
strain MC4100 and the mutant strain IC007 were coated with PdNPs
after the bioreduction of palladium precursor, then modified and
tested as anodes in a fuel cell. The mutant strain IC007 showed a
threefold greater power conversion compared with the parent
strain, but produced about half of the power of commercial Pd pow-
der or biosynthesized PdNPs made with D. desulfuricans.
Yong et al. [153] described the coupling of waste biorefining
with fuel cell power generation using biosynthesis to recover pre-
cious metals and form nanocatalysts. Palladium was biorecovered
from industrial processing waste and transformed into biosupport-
ed PdNPs using D. desulfuricans, E. coli and Cupriavidus metallidu-
rans. The study also described the biosynthesis and performance
of a mixed metal catalyst produced from the waste stream.
4.3. Electrodes and sensors
Fundamental electrochemical phenomena can be better under-
stood through nanoscale science and nanotechnology, and perfor-
mance of electrodes and sensors can be altered or enhanced
using biosynthesized nanoparticles. Several aspects of biosynthe-
sized metallic nanoparticles have been studied in detail, including
their surface chemistry, biological compatibility and electrical con-
ductivity. For nanoelectrochemical applications, special attention
has been paid to AuNPs because they provide a suitable substrate
for the immobilization of biomolecules without altering their
biological activity, and they provide excellent electron transfer
between the biomolecule and the electrode surface [154]. The
presence of capping agents and surfactants in biosynthesized AuN-
Ps can modulate electrode functionality and may enhance the
operating range or selectivity compared with conventional materi-
als (see Table 12).
Table 11
Energy-related applications.
NP Organism used
Pd Cupriavidus necator, Pseudomonas putida, Paracoccus denitrificans
Pd/TiO2 Gardenia jasminoides
Pd Escherichia coli
Pd Desulfovibrio desulfuricans
Pt Saccharomyces cerevisiae
Pd S. oneidensis
Pd E. coli
Pd D. desulfuricans, E. coli, Cupriavidus metallidurans
Several studies have examined the electrical transmission prop-
erties of biosynthesized NPs incorporated into electrodes. In one
study, dried whole plant extract from Scutellaria barbata was used
for the biosynthesis of AuNPs [155]. These AuNPs were applied to
a glassy carbon electrode (GCE), and the authors found enhanced
electrical transmission between the modified electrode and PNP.
Another study also demonstrated enhanced electrical transmission
using a GCE modified with AuNPs prepared from the flower extract
of Rosa damascene [156]. This study employed cyclic voltammetry
in a solution of 0.1 M KCl and 5.0 mM [Fe(CN)6]3-/4- to demonstrate
an increase in the electronic transmission rate for the modified
electrode. Sadhasivam et al. [16] performed cyclic voltammetry
studies using a three-electrode configuration employing AuNPs
biosynthesized by Streptomyces hygroscopicus. Platinum and Ag/
AgCl were used as counter and reference electrodes, respectively,
and electrochemically coated Cu2O on a Pt substrate (Cu2O–Pt)
with an AuNPs–methylene blue monolayer was employed as the
working electrode.
Various electrochemical sensing applications can make use of
the unique properties of biosynthesized NPs. Jha and Prasad
[157] introduced a biosynthetic method to prepare ferroelectric
BaTiO3 NPs using the bacterium Lactobacillus sp. The resulting
NPs were mixed with a PVDF solution then agitated and warmed
until the mixture became viscous. The process resulted in thin
nanocomposite sheets that exhibited significantly enhanced
dielectric properties. Torres-Chavolla et al. [158] biosynthesized
AuNPs using three species of actinomycetes, Thermomonospora
curvata, T. fusca and T. chromogena, and stabilized the NPs using
the cross-linker glutaraldehyde for enhanced biosensing applica-
tions. Shilov et al. [159] investigated different electrophysical char-
acteristics, such as cell zeta potential, surface conductivity,
electrophoretic mobility and the dispersion of cell conductivity,
of Candida albicans yeast cells with Ag precipitate prepared using
the reducer hydrazine.
Du et al. [160] introduced the bioreduction of Au by E. coli cells
and their application for direct electrochemical sensing of hemo-
globin. Biosynthesized AuNPs bound to the surface of the bacterial
cells were incorporated on a GCE. The authors performed cyclic
voltammetry measurements for different electrode configurations
on small samples of hemoglobin placed directly on the electrode
surface. The results showed a pair of redox peaks with a formal
potential of 0.325 V vs. an Ag/AgCl reference electrode. This study
demonstrated that biosynthesized nanocomposites can assist elec-
tron transfer between hemoglobin and the surface of a GCE.
Biosynthesized CdSNPs have also been used to fabricate a het-
erojunction with asymmetric electronic transfer properties [161].
Semiconducting wurtzite-type structured NPs were prepared using
Schizosaccharomyces pombe. Tin-doped indium oxide-coated glass
was covered by a thin film of spin-coated polyphenylene vinylene
and washed with S. pombe. While polyphenylene vinylene is a
p-type material, CdSNPs represent an n-type material. With added
Ag contacts, the resulting diode had a forward current of
75 mA cm2 at 10 V and experienced breakdown at approximately
15 V in reverse mode.
Application References
Hydrogen production from hypophosphite Bunge et al. [103]
Photocatalytic H2 evolution from pure water Wu et al. [147]
Biohydrogen production Macaskie et al.[148]
fuel cell electrode Yong et al. [149]
Pt biorecovery, fuel cell electrode Dimitriadis et al.[150]
Fuel cell electrode Ogi et al. [151]
Fuel cell electrode Orozco et al. [152]
Waste biorefining, fuel cell electrode Yong et al. [153]
 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042 4037

Table 12
Electrodes and sensors.

NP Organism used Application References

Au Scutellaria barbata Direct electrochemistry of 4-NP Wang et al. [155]
Ag, Au Rosa damascena Modified glassy carbon electrode Ghoreishi et al. [156]
BaTiO3 Lactobacillus sp. Nanocomposite with significantly enhanced dielectric properties Jha and Prasad [157]
Au Thermomonospora curvata, T. fusca, T. chromogena Applications in enhanced biosensors Torres-Chavolla et al. [158]
Au Escherichia coli Direct electrochemistry of hemoglobin Du et al. [160]
CdS Schizosaccharomyces pombe Construction of ideal diode Kowshik et al. [161]
Au Black tea Capacitors construction Uddin et al. [162]
Au, Ag Solanum lycopersicum Metallic ion detection Bindhu and Umadevi [163]

Biogenic AuNPs in polyvinyl alcohol–KH2PO4 films were used
by Uddin et al. [162] to ameliorate the percolative behavior of
these nanocomposite films and to generate high dielectric permit-
tivity at room temperature. The performance of the material is
promising for use in capacitors.
The unique optical properties of metallic nanoparticles can be
also used for chemical sensing. AuNPs and AgNPs reduced using
extract from the tomato Solanum lycopersicum were used for detec-
tion of metallic ions, including Fe3+ and Cu4+, in water based on
subtle changes in their surface plasmon resonance spectra [163].
5. Applications for magnetically responsive NPs
Magnetotactic bacteria have a natural ability to synthesize
magnetite NPs (MNPs), which are useful for various applications
(Table 13). Only certain NP forms are synthesized spontaneously
by magnetotactic bacteria [164,163] (see Fig. 6). The biological syn-
thesis of magnetically responsive NPs is well established, and their
use in various medical, environmental and industrial applications
has been reviewed [166–166].
The yield and properties of MNPs can be manipulated and opti-
mized to suit a particular purpose. Kundu et al. [169] described
changes in magnetosome size, number, and alignment with bio-
synthesis performed in the presence of Zn and Ni salts. Other
investigators have described the formation of zinc–ferrite NPs by
Thermoanaerobacter strain TOR-39 [170]. Coker et al. [176]
described improvement of magnetic properties of biosynthesized
magnetic NPs. In the study, FeCo-oxyhydroxides were created by
adding CoCl2.6H2O to FeCl3 precursor and then treating them with
Geobacter sulfurreducens culture. The resulting cobalt ferrite
(CoFe2O4) NPs exhibited dramatically enhanced magnetic proper-
ties compared with simultaneously produced magnetite MNPs.
Staniland et al. [171] described controlled cobalt doping of mag-
netosomes in vivo, where an estimated cobalt content of between
0.2 and 1.4% resulted in a 36–45% increase in the coercive field. Roh
et al. [172] also reported Co, Cr, Mn and Ni doping of magnetite
biosynthesized extracellularly by Thermoanaerobacter ethanolicus
and a psychrotolerant Shewanella sp. In a follow-up report, these
authors described how the process is amenable to large-scale pro-
duction and can produce magnetic particles at a fraction of the cost
of traditional chemical synthesis [173].
Telling et al. [174] employed MNPs to catalyze Cr(VI) reduction
(see also Section 3.4). MNPs were biosynthesized by Geobacter sul-
furreducens and the reduction of Cr(VI) to Cr(III) at sites within the
magnetic spinel surface were studied using X-ray absorption and
X-ray magnetic circular dichroism. The same group also investi-
gated the use of biosynthesized magnetites produced by G. sulfur-
reducens for recovery of metal contaminants from water [175].
MNPs produced by the bacterial reduction of powdered schwert-
mannite (an iron-oxyhydroxysulfate mineral) were found to be
more efficient at reducing Cr(VI) than ferrihydrite (an oxyhydrox-
ide mineral), ‘‘gel’’-derived biomagnetite and commercial nano-
scale Fe3O4.
One key advantage of MNPs is the ease of collection and recov-
ery. Magnetic properties can also ensure that particles remain dis-
persed and distributed throughout a reaction vessel. Coker et al.
[176] employed MNPs synthesized by G. sulfurreducens as a bio-
magnetic support for palladium nanocatalyst. The Pd-MNPs were
used to catalyze the C–C bond-forming Mizoroki–Heck reaction,
coupling iodobenzene to ethyl acrylate or styrene. Crean et al.
[177] used a similar approach for the continuous removal of Cr(VI).
6. Biosynthesis of unique formulations and geometries
The properties and potential applications of nanoscale materials
are determined by their chemical composition, crystal structure,
particle size and particle shape. Several studies have described
the biosynthesis of NPs with unique compositions and/or physical
forms that will modulate performance in a range of applications
(Table 14).
NPs with certain chemical compositions have been difficult to
synthesize using conventional chemical methods. Ahmad et al.
[178] described fungal biosynthesis of transparent p-type conduct-
ing oxide CuAlO2 NPs with Humicola sp. In this case, traditional
chemical synthesis is challenging because high temperatures are
necessary for overcoming reaction barriers, but low temperatures
are necessary for maintaining the Cu(1+) valence. Ankamwar et al.
[179] introduced a biosynthetic approach using transmetallation

Table 13
Application enhancements using magnetically responsive NPs.

NP Organism used Application References

Fe3O4 Thermoanaerobacter sp. TOR-39 Magnetite substituted with Zn Yeary et al. [170]
CoFe2O4 Geobacter sulfurreducens Enhanced magnetic properties of biosynthesized composite Coker et al. [176]
Fe3O4 Magnetospirillum gryphiswaldense, Magnetospirillum Cobalt doping of magnetosomes Staniland et al.
magnetotacticum [171]
Fe3O4 Thermoanaerobacter ethanolicus, Shewanella sp. Magnetite substituted with Co, Ni, Cr, Mn Roh et al. [172]
Fe3O4 Thermoanaerobacter sp. TOR-39 Magnetite substituted with Co, Ni, Cr, Mn, Zn and rare earth Moon et al. [173]
metals
Fe3O4 G. sulfurreducens Cr(VI) remediation Telling et al. [174]
Fe3O4 G. sulfurreducens Cr(VI) and Tc(VII) remediation Cutting et al. [175]
Fe3O4 G. sulfurreducens Magnetically recoverable Pd nanocatalyst Coker et al. [176]
Fe3O4 G. sulfurreducens Cr(VI) remediation Crean et al. [177]
4038 A. Schröfel et al. / Acta Biomaterialia 10 (2014) 4023–4042
Table 14
Unique formulations and geometries.
NP Organism used
CuAlO2 Humicola sp.
Au, Ag Emblica officinalis
Au–Ag–Cu Brassica juncea
Au–Ag Fusarium oxysporum
Au–Ag Fusarium semitectum
Au–Pd Escherichia coli
Au Tamarindus indica
PbS, ZnS Streptococcus thermophilus,
Lactobacillus bulgaricus, Lactobacillus acidophilus
Au Hansenula anomala
reactions. AgNPs and AuNPs phytosynthesized using Emblica offici-
nalis fruit extract were transferred into methanol solution using a
cationic surfactant, and transmetallation was carried out between
AgNPs and chloroaurate ions in chloroform.
The creation of metal alloys by casting requires heavy equip-
ment and high temperatures. Bottom-up biosynthesis of Au–Ag–Cu
alloys by Brassica juncea seed was introduced by Haverkamp
et al. [180]. Similar studies reported bimetallic Au–Ag alloy biosyn-
thesis employing the fungus Fusarium [181,180]. Deplanche et al.
[183] likewise introduced a hybrid two-step method for the pro-
duction of core–shell Pd–Au NPs by means of E. coli cells.
NP biosynthesis can also result in NPs with various useful
shapes. Ankamwar et al. [184] described the phytosynthesis of
Au nanotriangles using tamarind (Tamarindus indica) leaf extract.
The authors measured the electrical conductivity of these triangu-
lar NPs in different organic solvents, and suggested a possible
chemical vapor sensor application. The biosynthesis of Ag nano-
plates was described by Xie et al. [185], who employed the green
alga Chlorella vulgaris. Hollow structures created for various photo-
catalytic applications were described in a paper by Zhou et al.
[124], who coated empty bacterial cells with PbS and ZnS NPs.
The authors chose bacteria with spherical (Streptococcus thermo-
philus) and rod-like shapes (Lactobacillus bulgaricus, L. acidophilus).
Although the photocatalytic activity of the resulting hollow nano-
structures had been described previously, the authors described
additional uses, including as electromagnetic wave absorbers,
ultraviolet shielding materials and photocatalysts for solar cells.
Sathish Kumar et al. [186] biosynthesized Au NPs by means of
the yeast Hansenula anomala and its extract. These AuNPs were fur-
ther stabilized by the addition of two different types of poly(amido
amine) dendrimers. The authors demonstrated the use of these
AuNPs as bioink for rubber stamps.
7. Future outlook of biosynthesized NPs
This review highlights the key medical, environmental and
industrial applications of biosynthesized NPs. The natural machin-
ery used by all biological systems to execute redox reactions with
specificity, in aqueous solution, and under conditions of standard
temperature and pressure provides a powerful strategy for produc-
ing a wide range of nanosized materials, often at a fraction of the
cost of traditional chemical synthesis. Biosynthesized NPs are
frequently attached to a biological carrier or scaffold, and many
feature biogenic capping materials that enhance the compatibility
and stability of the NPs under environmental conditions. Capping
agents are specific to the particular organisms used for biosynthe-
sis, so a wide range of interesting properties can be achieved.
Biosynthesized NPs have been used in nearly every field where
traditional NPs have been employed. One of the challenges of bio-
genic NPs is the separation of the NPs from the biological material.
In addition, contamination from biological cells can be a problem
Application References
Difficult-to-synthesize NPs Ahmad et al. [178]
Phase transfer, transmetallation Ankamwar et al. [179]
Alloy Haverkamp et al. [180]
Alloy Senapati et al. [181]
Alloy Sawle et al. [182]
Core/shell Au/Pd NPs Deplanche et al. [183]
Nanotriangles, vapor sensing Ankamwar et al. [184]
Hollow nanostructures; light harvesting and photocatalytic properties Zhou et al. [124]
Bio-ink Sathish Kumar et al. [186]
especially in medical applications, due to the potential introduc-
tion of allergens or pathogens.
Considering the volume and growth in NP biosynthesis research
in recent years, the field appears to be on the threshold of much
more widespread and intensive research into applications. Mean-
while, further research and development of the underlying biosyn-
thesis methods themselves and the creation of novel biosynthetic
NP forms is anticipated.
Acknowledgements
This book chapter was supported by the Grant Agency of the
Czech Republic (grant number P302/12/G157) by the Charles
University in Prague (projects UNCE 204022 and Prvouk/1LF/1). This
publication is also supported by the project ‘‘BIOCEV – Biotechnol-
ogy and Biomedicine Centre of the Academy of Sciences and Charles
University’’ (CZ.1.05/1.1.00/02.0109), from the European Regional
Development Fund, project CZ.2.16/3.1.00/24010 from the European
Regional Development Fund and grant NSF 1242167.
Appendix A. Figures with essential colour discrimination
Certain figures in this article, particularly Figs. 1–4 are difficult
to interpret in black and white. The full colour images can be found
in the on-line version, at doi:http://dx.doi.org/10.1016/j.actbio.
2014.05.022).
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