Biomediated Silver Nanoparticles for the Highly Selective Copper(II)
Ion Sensor Applications
C. Joseph Kirubaharan,
†
D. Kalpana,
‡
Yang Soo Lee,
‡
A. R. Kim,
§
Don Jin Yoo,
§
Kee Suk Nahm,*
,§
and G. Gnana Kumar*
,†
†
Department of Physical Chemistry, Madurai Kamaraj University, Madurai-625 021, Tamilnadu, India
‡
Department of Forest Science and Technology, Institute of Agricultural Science and Technology, Chonbuk National University,
Jeonju 561-756, South Korea
§
Department of Hydrogen and Fuel Cells Engineering, Specialized Graduate School, Chonbuk National University, Jeonju 561-756,
South Korea
* S Supporting Information
ABSTRACT: Nanoparticles synthesis is an evergreen research field of 21st century in which the connotation of the biomediated
experimental process is highly imperative. Biomediated silver nanoparticles were synthesized with the aid of an eco-friendly
biomaterial, namely, aqueous Azadirachta indica extract. The effect of pH and temperature on the formation of silver
nanoparticles was analyzed. Formation of the silver nanoparticles was verified by surface plasmon spectra using a UV-vis
spectrophotometer. Morphology and crystalline structure of the prepared silver nanoparticles were characterized by TEM and
XRD techniques, respectively. Furthermore, the biomediated silver nanoparticles without any surface modification were used for
the heavy metal ion sensors in aqueous media. The prepared silver nanoparticles were successful in detecting even the minimal
amount of heavy metal copper(II) ion and exhibited excellent specific metal ion selectivity.
1. INTRODUCTION
Nanoscience is one of the most vibrant growing fields ever
known and continues to rigorously reach its branches into
various modern technologies such as hydrogen storage,
photocatalysis, green energy devices, sensors, biomedical
implants, and photovoltaics.
1-4
Though chemical synthesis
has been widely adopted for the preparation of a variety of
nanostructures, their cost effectiveness, need of sophisticated
equipments, environments, stabilizing and capping agents, and
environmental hitches fade not only the applications of
nanoparticles but also the dream of a green world.
5
For the
emphasis of biological protocol applications of nanoparticles,
there is also an immense need for synthesizing nanoparticles
with a greater biocompatibility.
6
Hence, there is an alarming
demand for finding cheaper and environmentally friendly
nanoparticles synthesis. In recent years, biomediated synthesis
has been considered as an enthralling method for the synthesis
of nanoparticles by bridging the two major criteria, satisfying
the green chemistry principles and stabilizing the formed
nanoparticles with not much more than the bioextract itself.
5
The state of the art biomediated nanoparticles synthesis
satisfies all of the necessary requirements, especially the
mentionable dual nature of the biomass as a reducing as well
as a stabilizing agent.
7
The detection and quantification of heavy metal ions is a
rapid subject of enrollment in recent days which influences
their significant applications in environmental monitoring,
waste management, and clinical toxicology fields.
8
Specifically,
the detection of heavy metal copper is vital due to the existence
of copper(II) ions in wastewater originated from the electro-
plating plants and other metal manufacturing industries and
corrosion of copper pipes.
9
An increase in the Cu
2+
level in the
biological cells leads to kidney related and neurodegenerative
diseases,
10
and the free Cu
2+
elicits toxicity to cells as they
generate hydroxyl radicals, causing apoptosis.
10
Cu
2+
binds with
the histidine-rich regions of the Prion Protein, which results in
misfolding and protein fibrilization.
11
Therefore, on-site and
real-time detection of Cu
2+
ions is important to avoid its toxic
effects. For the successive detection of heavy metal copper ions,
copper(II) sensitive optical sensors have been reported using
immobilized Lucifer Yellow fluorophore,
12
copper chelators
such as Zincon,
13
fast sulphon black F (FSBF),
14
urease
enzyme,
15
and PAN and PAR indicators.
16
However, the
mentioned reports exhibited major limitations such as complex
preparation, expensive, high time consumption, and sample
pretreatment and analyte preconcentration steps which limit
the sensor applications at a large scale. It urges the
identification and development of a copper sensor to satisfy
the simple, rapid, inexpensive, selective, and sensitive character-
istics.
Nanoparticles find extensive application in bio- and eco-
sensors, especially for the detection of heavy metal ions.
Though few nanoparticles have been reported for heavy metal
ion sensors, all of the nanoparticles have been synthesized via
chemical routes and are to be stabilized with the aid of external
chemical stabilizers in which most of them were toxic.
17
An
objective of the sensors is to detect pollutants in the effluents,
Received: February 6, 2012
Revised: May 7, 2012
Accepted: May 8, 2012
Published: May 17, 2012
Article
pubs.acs.org/IECR
© 2012 American Chemical Society 7441 dx.doi.org/10.1021/ie3003232 | Ind. Eng. Chem. Res. 2012, 51, 7441-7446