Sensors and Actuators B 191 (2014) 31–36

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Sensors and Actuators B: Chemical

journal homepage:www.elsevier.com/locate/snb

Silver nanoparticles based selective colorimetric sensor for Cd2+, Hg2+ and Pb2+
ions: Tuning sensitivity and selectivity using co-stabilizing agents

V. Vinod Kumar, Savarimuthu Philip Anthony ∗

School of Chemical & Biotechnology, SASTRA University, Thanjavur 613401, Tamil Nadu, India

article info abstract

Article history: N-(2-hydroxybenzyl)-valine (VP) and N-(2-hydroxybenzyl)-isoleucine (ILP) organic ligands have been utilized as reducing
Received 27 August 2013 Received in and surface functionalizing agents in the synthesis of silver nanoparticles (AgNPs) with metal ion interacting functionality.
revised form 19 September 2013 VP and ILP metal interacting ligands functionalized AgNPs exhib-ited selective colorimetric sensing of toxic Cd2+ , Hg2+ and
Accepted 22 September 2013 Available
Pb2+ metal ions in aqueous solution at ppm level. The colorimetric sensitivity and metal ion selectivity of VP- and ILP-
online 30 September 2013
AgNPs were modulated by incorporating co-stabilizing agents. Importantly, ILP functionalized AgNPs selectively detected
Cd2+ ions in the polluted ground water samples also.
Keyword:
© 2013 Elsevier B.V. All rights reserved.
Colorimetric sensor
Toxic metal ions sensor
Cd2+ sensor
Pb2+ sensor

1. Introduction nanomaterials [8] including the development of ultrasensitive detection and

High sensitive and selective determination of heavy metal ions such as
2+ 2+ 2+
Cd , Pb , and Hg have received significant attention in the recent years
due to their potential hazardness to health and environment [1]. The
2+
increasing exposure of Cd could causes seri-ous injury to the human
kidney, lung, bone and nervous system, that results in renal dysfunction,
calcium metabolism disorders, and an increased incidence of certain forms of
2+
cancers [2]. Hg , which is one of the most prevalent toxic elements in the
2+
envi-ronment, is considered to be serious health threat. High affinity of Hg
for thiol groups in proteins and enzymes, leads to the dys-function of cells in
2+
the brain, kidney, and central nervous system [3]. Similarly, lead (Pb ) is
the second most abundant element in the environment (from the list of toxic
substances in the environ-ment) due to its wide distribution and use in
batteries, gasoline and pigments [1,4]. Even low level exposure to lead can
cause neurolog-ical, reproductive, cardiovascular and developmental
disorders [5]. Children with mutant form of genes involved in iron
metabolism may be more susceptible to lead absorption and accumulation [6].
The World Health Organization established a guideline for drink-ing water in
1996, which stipulated that the maximum permissible quantity of lead in
drinking water should be within 10 mg l− [7].
1 pentadecylphenol Langmuir monolayers [17]. Organic phenolic ligands based
The recent advancements in the field of nanoscience and nano-technology
have opened up new arenas for the applications of
∗ report the synthesis of AgNPs
Corresponding author. Tel.: +91 4362264101; fax: +91 4362264120. E-mail address:
philip@biotech.sastra.edu (S.P. Anthony).
imaging methods in the analytical sciences [9]. Particularly, colorimetric
sensor based on silver (Ag) and gold nanoparticles (AuNPs) is now gaining
increasing attention because of their strong localized surface plasmon
resonance absorption and interparticles distance dependent optical properties
[10]. Colori-metric sensing methods are having many advantageous such as
simplicity and rapidity, high sensitivity, cost-effectiveness and ease of
measurement [11,12]. The surface functionalization of NPs plays a critical
role in the development of noble NPs based colorimetric sensor for metal ions
[13]. For example, AgNPs functionalized with judicious choice of small
organic and bio-macromolecules exhib-ited selective colorimetric sensing of
different heavy metal ions [3,14]. Recently, plant extract based chemical
functionalities were successfully utilized in the eco-friendly green synthesis of
2+ 2+ 2+
AgNPs for selective colorimetric sensing of Hg , Zn and Pb in aqueous
solution at wide pH range [15].
The easy ionization properties of phenolic groups have been exploited in
the synthesis of AgNPs in the past [16]. For example, 2-d assemblies of
AgNPs were prepared by the spontaneous reduc-tions of silver ions by
on amino acids exhibited versatile coordination behaviour with different metal
ions that resulted in the formation of intriguing structures including helical
supramolecular structures in the solid state [18]. It was hypoth-esized that
utilization of amino acid attached phenolic ligands in the AgNPs synthesis
would provide metal ions interacting surface functionality for developing
selective colorimetric sensor for toxic metal ions. In this manuscript, we

0925-4005/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.09.089
32 V. Vinod Kumar, S.P. Anthony / Sensors and Actuators B 191 (2014) 31–36

using valine and isoleucine attached phenolic ligands (VP-AgNPs and ILP-
AgNPs) at room temperature and demonstrated the selec-tive colorimetric
2+ 2+ 2+
sensing of multiple toxic metal ions such as Cd , Pb and Hg in
aqueous solutions at ppm level. The sensing abil-ity and detection limits were
modulated by incorporating different co-stabilizing agents (tri-sodium citrate
(TSC), ethylenediamine tetraacetate (EDTA) and poly(vinylalcohol) (PVA))
in the VP-AgNPs and ILP-AgNPs solution. Importantly, the synthesized
2+
AgNPs were successfully employed for selective sensing of Cd ions in the
pol-luted ground water samples.

2. Experimental

2.1. Materials

Valine, isoleucine, ethanol, tri-sodium citrate, ethylene diamine

tetraacetate (EDTA) and NaOH were obtained from Ranbaxy fine chemicals
and were used as received. Salicylaldehyde, NaBH4 , AgNO3 , poly(vinyl
alcohol) (PVA), sodium salt of poly(styerene sulfonate) (PSS) and poly(vinyl
pyrrolidone) (PVP) were obtained from Sigma–Aldrich and used as-received.
Valine and isoleucine attached phenolic ligands (VP, ILP) were synthesized
according to the procedure reported earlier [19]. All the heavy metal salt
solutions used for the experiments were prepared by mixing the requisite
amount of salt in Mill-Q water. Ground water samples were collected from
Vellore and Sriperumpudhur, Tamil Nadu, India. These two places were
chosen since many industries were located in this area.

2.2. Preparation of VP-AgNPs and ILP-AgNPs

Silver nitrate (5 ml of 10− M) was added into VP and ILP (5 ml, 10 −

3 3

M) solution under stirring at room temperature. The imme-diate appearance

of yellow colour indicated the reduction of silver ion into AgNPs [15,16]. The
solution was allowed to stir at room temperature for another 10 min. The
reactions were repeated at least three times to confirm the reproducibility of
NPs formation. The characterisation of the synthesised AgNPs was carried
out after allowing the solution to stand at room temperature for more than one Fig. 1. Absorption spectra of (a) VP- and (b) ILP-AgNPs and also with surfactants.
week.
into AgNPs. The synthesized AgNPs using VP and ILP ligands was yellow
and transparent, indicating the good dispersity in water. The absorption
2.3. Characterization spectrum of VP- and ILP-AgNPs showed a typical and intense absorption
peak at 412 nm and 414 nm, respectively, due to surface plasmon resonance
The UV–vis measurement of the green synthesized AgNPs were analysed vibration (Fig. 1) [20]. The synthesized AgNPs size and morphology were
in a Perkin Elmer model UV–Vis double beam spectropho-tometer from 250 characterized by using HR-TEM and FE-SEM that confirmed the poly-
2+ 2+
to 800 nm, at the resolution of 1 nm. The Cd and Pb presence in ground dispersed spherical crystalline AgNPs formation in both the samples (Fig. S1).
water sample was analysed using Varian AA240 model. The purified powders VP and ILP ligand was expected to confer metal ions interacting surface
of HL- and HS-AgNPs were sub-jected to FT-IR spectroscopy measurement. functionality to the AgNPs. Prominent IR bands were observed at 3434, 2931,
2853, 1696, 1615, 1430 and 1385 cm− for both VP- and ILP-AgNPs, which
These measurements were carried out on a Perkin–Elmer Spectrum-One 1
instrument in the diffuse reflectance mode at a resolution of 4 cm− in KBr
1
confirmed the surface functionalization of AgNPs by VP and ILP molecules
pellets. (Fig. S2).
The size and morphology of AgNPs were investigated using field
emission scanning electron microscope (FE-SEM) (JSM-6701F, JEOL Japan The selective colorimetric sensing properties of VP-AgNPs for a series of
INC) and High Resolution Transmission Electron Microscopy (HR-TEM). 3+ 3+ 2+ 2+ 2+ 2+ 2+
heavy metal ions such as Cr , Mn , Cd , Ca , Cu , Hg , Zn ,
Samples for TEM measurements were prepared by pla-cing a drop of NPs 2+ 2+ 2+ 3+ 3+
Mg , Ni , Pb , Fe and Co were explored in aqueous solution. VP-
solution on the graphite grid and drying it in vacuum. Transmission electron 2+
micrographs were taken using JEOL JEM-2100F operated at an accelerated AgNPs showed selective colorimetric changes upon addition of Cd (yellow
2+
voltage of 200 kV and an ultra high-resolution pole piece. to strong orange) and Pb (yellow to light orange, Fig. 2). Addition of other
metal ions did not exhibit signif-icant colour change. The absorption spectra
also showed selective red shifting of absorption from 412 to 520 nm for both
2+ 2+ 2+
3. Results and discussion Cd and Pb metal ions. The minimum detectable concentration of Cd
ions were determined by adding different volume of 10 − M metal
2+ 6
and Pb
Addition of silver nitrate solution (5 ml of 10 − M) with VP and ILP (5
3 ions into VP-AgNPs (Fig. 3a and b). Absorption intensity of VP-AgNPs was
2+
ml, 10− M) under stirring at room temperature produced immediate yellow
3 reduced at initial Cd additions, however, new peak at longer wavelength
colour that confirmed the reduction of silver ions was observed after 300 l additions. Similarly,
 V. Vinod Kumar, S.P. Anthony / Sensors and Actuators B 191 (2014) 31–36
Fig. 2. (a) Digital images and (b) absorption of spectra of VP-AgNPs with different metal ions.
Fig. 3. Change of VP-AgNPs absorption Vs Cd2+ (a) and Pb2+ (b) concentration.
33
Fig. 4. (a) Digital images and (b) absorption of spectra of ILP-AgNPs with different metal ions.
2+
Pb also showed reduction in the AgNPs absorption intensity at
initial additions and a new peak at longer wavelength appeared
after 220 l additions.
The selective colorimetric studies of ILP-AgNPs with various
2+
metal ions also showed selective colorimetric changes for Cd
2+
and Pb (Fig. 4). The other metal ions did not show any sig-
nificant colour changes. Absorption studies showed selective red
2+ 2+
shift of ILP-AgNPs absorption for both Cd and Pb . Addition of
2+
Cd produced new absorption peak at longer wavelength (500 nm)
together with initial absorption (404 nm, slightly blue shifted from
2+
414 nm). Whereas, Pb addition exhibited red shifted absorption
(414 nm to 440 nm) as well as cut-off . The minimum detectable con-
2+ 2+
centration studies of Cd and Pb with ILP-AgNPs showed slightly
higher amount of metal ion requirement to complete the red shif-
ting than VP-AgNPs (Fig. 5). Similar to VP-AgNPs, the initial addition
2+ 2+
of both Cd and Pb reduced the absorption intensity. The new
peak at longer wavelength was observed after 600 and 360 l addi-
2+ 2+
tion of Cd and Pb , respectively. Both VP- and ILP-AgNPs showed
2+ 2+
comparatively higher sensitivity towards Pb than Cd ions. The
presence of different metal ions in VP- and ILP-AgNPs had very little
2+ 2+
influence on the selective sensing of Cd and Pb ions (Fig. S3, S4).
2+ 2+
Similarly anions of Cd and Pb metal ions also did not show any
significant change in the selective colorimetric changes (Fig. S5).
With the intent of modulating colorimetric sensing properties
of VP- and ILP-AgNPs without doing iterative synthesis, different
stabilizing agents, small organic metal coordinating ligand to poly-
mers (TSC, EDTA and PVA), were added into AgNPs solution. The
presence of different stabilizing agents was expected to influence
the metal ion interaction. The absorption studies of VP- and ILP-
AgNPs with TSC, EDTA and PVA did not show any significant change
except for a small blue or red shift (Fig. 1). The colorimetric sensing
2+
studies of VP-AgNPs-TSC showed selective sensing of Cd and
2+
Pb metal ions in aqueous solution similar to VP-AgNPs (Fig. 6a).
It was observed that inclusion of TSC with VP-AgNPs produced
additional absorption peak at 500 nm (Fig. 1a). TSC has been exten-
sively utilized as organic capping, structure directing and reducing
agent in the synthesis AgNPs [21]. But the role of citrate ions on
various aspects of AgNPs formation is still subject to active investi-
2+
gation [22]. The concentration dependent studies of both Cd and
2+
Pb showed reductions in the absorption intensity at initial addi-
tions. But the 500 nm absorption peak was red shifted to longer
34 V. Vinod Kumar, S.P. Anthony / Sensors and Actuators B 191 (2014) 31–36

2+ 2+
wavelength beyond 500 and 180 l addition of Cd and Pb ions,
respectively (Fig. S6). Interestingly, addition of TSC with VP-AgNPs slightly
2+ 2+
enhanced the sensitivity for Pb and reduced the sen-sitivity for Cd . TSC-
AgNPs without amino acid-phenolic ligand were synthesized to explore the
role of TSC on the AgNPs selec-tive metal ion colorimetric sensor properties.
2+ 2+
TSC-AgNPs showed selective colorimetric sensing of only Hg and Pb
metal ions in aqueous solution (Fig. S7). The former showed complete
decolouri-sation of yellow colour and latter exhibited brownish red colour.
2+
Although Cd addition showed slightly different colour from rest of the
metal ion addition, the colour change was not clearly distin-guishable.

2+ 2+
VP-AgNPs-EDTA also exhibited selective detection of Cd and Pb
ions with clearly discernible colour differences (Fig. 6b). Initial addition of
2+
Cd reduced the absorption intensity and sub-sequent additions (280 l)
produced another absorption peak at longer wavelength (540 nm) (Fig. S8a).
2+
VP-AgNPs-EDTA with Pb showed complete red shifting of absorption
from the initial addi-tion onwards (Fig. S8b). The absorption peak was
2+
completely red shifted to 450 nm with the addition of 220 l of Pb . The
control experiment with EDTA-AgNPs alone could not be performed since
attempts to prepare stable AgNPs with EDTA were not successful. VP-AgNPs
2+
with PVA showed selective yellow colour disappearance for Hg and light
2+
orange colour formation for Pb (Fig. S9a). The concentration dependent
studies revealed that AgNPs absorption peak completely disappeared with the
2+
addition of 340 l of Hg
2+
whereas addition of 480 l of Pb showed red shift of cut-off (Fig. S9b,c).
Metal ion sensor studies of PVA-AgNPs showed selective
2+
decolourisation only for Hg (Fig. S9d).
2+
ILP-AgNPs-TSC also showed similar colorimetric changes for Cd and
2+
Pb metal ions but at different concentrations (Fig. 6c, S10). ILP-AgNPs
2+
with PVA showed only slight decrease in colour intensity with Hg (Fig.
S11). In contrast, ILP-AgNPs-EDTA dis-played selective colorimetric sensing
2+ 2+ 2+
of Cd , Hg and Pb with distinct colour changes for each metal ion (Fig.
2+
6d). ILP-AgNPs-EDTA with Hg exhibited complete decolourisation
2+
whereas Pb
Fig. 5. Change of ILP-AgNPs absorption Vs Cd2+ (a) and Pb2+ (b) concentration.

Fig. 6. Digital images of (a) VP-AgNPs-TSC, (b) VP-AgNPs-EDTA, (c) ILP-AgNPs-TSC and (d) ILP-AgNPs-EDTA with different metal ions.
 V. Vinod Kumar, S.P. Anthony / Sensors and Actuators B 191 (2014) 31–36 35

Fig. 7. TEM images of (a) Cd2+ and (b) Pb2+ with ILP-AgNPs-EDTA.

2+ 2+ 2+
showed strong orange colour. Interestingly, addition of Cd into ILP- might be due to the stronger interactions of Cd and Pb metal ions. The
AgNPs-EDTA produced blue colour. Concentration dependent studies addition TSC with VP- and ILP-AgNPs showed almost sim-ilar selectivity
2+ with slight sensitivity differences. EDTA inclusion with ILP-AgNPs displayed
showed appearance of new peak at longer wavelength for Cd , after 300 l
2+ 2+ 2+
addition and complete disappearance of absorption peak upon addition of 420 distinct colour changes for Hg , Cd and Pb . However, inclusion of
2+ 2+ PVA exhibited completely different selectivity. This might be due to the
l of Hg . The initial addition of Pb only reduced the absorption intensity
and subse-quent addition (240 l) red shifted the absorption. The absorption cooperative effect of differ-ent stabilizing agents with AgNPs. The metal ion
peak was completely red shifted to 470 nm at 280 l addition (Fig. S12). interacting ability and smaller size of TSC and EDTA might be facilitating the
for-mation of AgNPs aggregates. Whereas, PVA might be preventing AgNPs
aggregates formation due to its high molecular weight. The addition of other
2+ polymer (PSS, PVP) into VP-AgNPs also showed similar results and
The mechanism of Hg sensing by PVA-AgNPs, VP-AgNPs-PVA and
confirmed that polymer stabilizing agents might not facilitate smaller AgNPs
ILP-AgNPs-EDTA could be explained based on the electrochem-ical
+ 2+ aggregates formation upon metal ion interactions (Fig. S13). The
differences of Ag and Hg ions [15]. The standard reduction potential for 2+
enhancement of Pb sensitivity might be due to the selective interactions of
Ag is +0.80 V (Ag + e− = Ag) whereas that of Hg is +0.92 V (2Hg (aq)
+ 2+ 2+
2+
Pb with both co-stabilizing agents and VP/ILP. These results suggested that
+ 2e− = Hg2
2+
(aq)) and according to the elec-trochemical series, metals metal ion inter-acting small organic ligands could function as useful
with higher reduction potential acts as better oxidising agents. Amino acid candidates for modulating colorimetric sensing properties of AgNPs without
appended phenolic ligands have been extensively explored in the synthesis of iterative synthesis.
coordination polymers with intriguing solid state structures including chiral
helical assemblies that exhibited single crystal-to-single crystal topochemical
conversion [18]. The coordination versatility of metal ions was exploited to
2+
produce different molecular organization in the solid state. It is expected that Importantly, the applicability of ILP-AgNPs-EDTA in detec-ting Cd
coordination of metal ions with VP and ILP would lead to the formation of ions in polluted ground water samples have also been demonstrated (Fig. 8).
smaller aggregates of AgNPs with closer contacts with each other. HR-TEM Addition of five drops of each samples into ILP-AgNPs-EDTA produced blue
2+ 2+
studies clearly revealed the formation of aggregates of AgNPs in Pb and colour for sample 1 (contain only Cd ) and reddish orange for sample 2
2+ 2+ 2+
Cd complexes (Fig. 7). Theoretical and experimental studies has shown which contains both Cd and Hg . The polluted ground water samples
that the plasmon oscillation of metal nanoparticles couple to each other when were collected from two different places in Tamil Nadu, India. The presence
they are brought in proximity and exhibited different colours [23,24]. 2+ 2+ 2+
of Cd (sam-ple 1) and Cd and Hg (sample 2) in the collected ground
Although amino acid-phenolic ligands were shown to coordinate with various
2+ water samples were confirmed by atomic absorption spectroscopy (Fig. S14,
metal ions, the reason for the selec-tive colorimetric changes with only Cd 2+
2+ S15). It was observed that addition of Cd alone with ILP-AgNPs-EDTA
and Pb is not clear. It 2+ 2+
exhibited blue colour whereas addition of Cd and Hg together at
equimolar concentrations showed reddish orange

Fig. 8. ILP-AgNPs-EDTA colorimetric sensing of Cd2+ in the ground water samples.

36 V. Vinod Kumar, S.P. Anthony / Sensors and Actuators B 191 (2014) 31–36
colour (Fig. S16). Currently, the effect of different amino acids in the
phenolic ligands on the colorimetric sensitivity and selectivity of heavy metal
ions is under progress.
In conclusion, amino acid based phenolic ligands (VP and ILP) has been
successfully employed in the synthesis of stable AgNPs with metal ion
interacting surface functionality that leads to the selective colorimetric
2+ 2+ 2+
sensing of individual and multiple, toxic Cd , Hg and Pb metal ions in
aqueous solution at ppm level. The colorimetric sensitivity and selectivity
were modulated by cooperative effect of different stabilizing agents.
Importantly ILP-AgNPs-EDTA exhibited selective colorimetric detection of
2+
Cd ions in the polluted ground water samples.
Acknowledgements
Financial supports from Department of Science and Technology, New
Delhi, India (DST Fast Track Scheme No. SR/FT/CS-03/2011(G) is
acknowledged with gratitude.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online
version, at http://dx.doi.org/10.1016/j.snb.2013.09.089.
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Biographies
V. Vinod Kumar received his bachelor’s degree in chemistry in 2009 and master degree in
chemistry in 2011 from VIT University, India. In his postgraduate stud-ies, he worked on the
synthesis of inorganic nanostructured materials for drug delivery. He is currently researching on
the developing nanostructured materials for environmental sensing, catalysis and optoelectronic
applications.
Savarimuthu Philip Anthony received his Ph.D. degree in Materials chemistry (optical
materials) from University of Hyderabad, India, in 2005. He got his first postdoctoral training in
Pohang University of Science and Technology (POSTECH) in Korea on the fabrication of
nanostructures using block copolymer template for optoelectronic applications. Then he moved
to School of Chemistry, Trinity College Dublin, Ireland as Marie-Curie research fellow in 2008
and worked on molecular fluorescent materials. He is now working at SASTRA University as a
Senior Assis-tant Professor. His research interest includes synthesis and application of molecular
and nanostructured materials for environmental sensing, bio-sensing and optoelec-tronic
devices.