Materials Letters 74 (2012) 8–11

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis and characterization of CdS nanoparticles using C-phycoerythrin from the

marine cyanobacteria
D. MubarakAli a, V. Gopinath b, N. Rameshbabu c, N. Thajuddin a,⁎
a
Department of Microbiology, School of Life Sciences, Bharathidasan University, Tiruchirappalli-620 024, Tamil Nadu, India
b
Department of Biotechnology, School of Bioengineering, SRM University, Chennai, Tamil Nadu, India
c
Department of Metallurgical and Materials Engineering, National Institute of Technology, Tiruchirappalli, Tamil Nadu, India

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

Article history: In the background that the marine cyanobacteria offer great potentials as source of fine chemicals, pharma-
Received 16 September 2011 ceuticals, biofuels, etc., in the present study the pigment, C-phycoerythrin (C-PE) extracted from the marine
Accepted 6 January 2012 cyanobacterium, Phormidium tenue NTDM05 was used to synthesize CdS nanoparticles. The CdS nanoparticles
Available online 18 January 2012
thus synthesized were characterized adopting UV–Visible spectrum, Fourier transform infra-red spectrum,
EDAX and transmission electron microscopy. The size of the CdS nanoparticles was found to be about 5 nm.
Keywords:
Biosynthesis
Essentially, it was found that the pigment stabilized the CdS nanoparticles. The pigments labeled CdS nanopar-
CdS nanoparticles ticles could be applied as a biolabel.
C-phycoerythrin © 2012 Elsevier B.V. All rights reserved.
Biolabeling

1. Introduction

Recently, there is great emphasis on nanomaterials. The nanoma-

terials are synthesized adopting physical and chemical and biological
approaches. The products of synthesis adopting the physical and
chemical methods contribute to contaminations to the environment,
and it is believed that the nanoparticle synthesis adopting biological
methods is simple, safe and environmentally friendly. Cadmium
sulfide nanoparticles (CdS NP's) are among the widely studied in
semiconductor nanoparticles that possess unique, photochemical and
photophysical properties. The semiconductor nanoparticles are often
referred to as Quantum Dots (QDs). These particles, when embedded
within an appropriate matrix, act as potential wells that confine and
stabilize electrons in discrete energy levels. The technologically useful
properties of CdS QDs are due in part to the fact that the band-gap is
tunable over a range of 1.5 to 3.5 eV [1].
CdS NPs have been successfully synthesized using a wide range of
organisms, like algae [2, 3], fungi [4], yeast [5, 6] and bacteria [6, 7].
Apart from the synthesis of such CdS NPs, the stabilization of synthe-
sized particles is also important. Several stabilizing agents such as en-
zymes [4], starch [8-10], chitosan [11], 3-mercaptopropionic acid
(MPA), mercaptosuccinic acid (MSA), and glutathione (GSH) have
also been used to synthesize CdS NPs. These stabilizing agents provide
the thiol group that would bind Cd through the S\H group [12].
R-phycoerythrin also has this property [13]. Phormidium tenue, a marine
cyanobacterium is a rich source of phycoerythrin, the C-phycoerythrin.

⁎ Corresponding author.
E-mail address: thajuddin@gmail.com (N. Thajuddin). Fig. 1. Biosynthesis of CdS nanoparticles.

0167-577X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.01.026
 D. MubarakAli et al. / Materials Letters 74 (2012) 8–11 9

The major advantages of C-phycoerythrin are that its content in the

cyanobacterium is about 70% of the total protein, and it can be easily
extracted from the cell.

2. Materials and method

The C-phycoerythrin pigment used in this study was extracted

from the marine cyanobacterium, Phormidium tenue NTDM05 adopt-
ing a procedure recently modified from the one already in practice
[14]. CdS nanoparticles were synthesized by reacting Cd 2 + with the
extracted C-phycoerythrin. Simply, the extract was mixed with aque-
ous CdCl2 and Na2S in the concentration 0.25 mM and 1 mM, respec-
tively. The reaction mixture was closely monitored for color change;
the temperature and pH of the solution were also measured periodi-
cally over a period of 5 days.
The appearance of nanoparticles was gauzed in a UV–vis spectro-
photometer, in the wavelength range 200 to 900 nm, periodically.
Once the nanoparticles were formed, the preparation was lyophilized
and analyzed adopting FTIR and EDAX, with Li drift Si detector (Ther-
mo elution corporation, USA). A drop of the sample was placed onto a
carbon coated copper grid, and air-dried and then analyzed in a trans-
mission electron microscope (TEM).

3. Results and discussion

In the earlier study, cytotoxicity of C-PE was evaluated in human

cell lines by assessment of cell proliferation and neutral red uptake;
it was found that the C-PE is not cytotoxic [15]. Among various con-
centrations of CdCl2 and Na2S, CaCl2 at 0.25 mM and Na2S at 1 mM
proved to be most optimum concentration for the synthesis of CdS
nanoparticles. The first step in this reaction sequence in the nanopar-
ticles synthesis was formation of C-PE–Cd 2 + complex, then this
complex reacted with Na2S to produce CdS nanoparticles, when the
color reaction mixture changed to yellow to orange (Fig. 1). CdS
nanoparticles thus synthesized measured about 5 nm and, this size
remains unchanged well over 8 months of storage. In an earlier
investigation using R-PE, the solution contains only coarse CdS
nanoparticles.
It also found that R-PE prevents the growth and aggregation of
nanoparticles [13]. A similar experiment in higher pH the charged
Fig. 3. FTIR spectrum recorded for CdS nanoparticles stabilized by C-PE. (A) Spectrum
capping agent was found to be very high, which might be the basis
of C-PE (B) the bands seen at 1364 and 1034 cm− 1 were assigned to the C\N
of the colloidal stability of QDs. Also, the size of the Cd–R-PE complex stretching vibrations of the aromatic amino amines.
was primarily depending on the concentration of salts, pH of the reac-
tion mix and the concentration of the pigments. [12].
Soluble starch has also been used as a capping agent in the synthe- for the stabilization of the CdS nanoparticles in aqueous solution
sis of CdS and CdSe nanoparticles, ranging from 8 to 15 nm [8, 16]. [10]. The synthesis of CdS nanoparticles occurs due to pH sensitive
The hydroxyl group of the starch polymer acts as passivation contacts membrane-bound oxido-reductase and carbon source-dependent rH2

Fig. 2. UV–vis spectrum of CdS nanoparticles, the peak corresponds to the formation of CdS nanoparticles capped with C-PE at 470 nm (a) and absorption peak of C-PE at 550 nm (b).
10 D. MubarakAli et al. / Materials Letters 74 (2012) 8–11
in the culture solution [6]. This work also emphasizes that the fluores-
cent protein in the pigment is mainly due to tyrosine, phenylalanine
and tryptophan moieties, which would be the basis of the very efficient
formation of CdS nanoparticles and stabilizing it to prevent
agglomeration.
The presence of CdS nanoparticles was confirmed by the absorp-
tion peak at 470 nm. The maximum absorption peak position of hol-
low nanoparticle chains is at 487 nm with the band gap at 2.56 eV
[17]. Compared with that of bulk material (515 nm, 2.42 eV), the ab-
sorption peak was a blue shift at 28 nm and its band gap enlarged
about 0.14 eV. This is an indication of quantum size effect [18]. It
was reported that the band gap value 2.57 eV is shifted compared
with the bulk value and this could be a consequence of a size quanti-
zation effect in the sample [19] and the absorption peak of C-PE was
550 nm (Fig. 2).
The FTIR spectrum of the C-phycoerythrin is shown in Fig. 3a. The
characteristic bands due to S\H stretching, appearing at 3398, 2074,
1637, 1365 cm − 1 for pure C-PE were not seen in capped CdS, which is
due to the interaction of thiol group of the capping agent with CdS.
The characteristic band such as S\H stretching was found in the
entire capping agent that was not found in all capped CdS. It could be
formed due to bonding with CdS NPs [12]. In the interaction between
Fig. 4. CdS nanoparticle. (a) TEM image, spherical shaped CdS nanoparticles in the range of 5 nm in size and (b) EDAX of the CdS nanoparticles confirming the presence of CdS
signals in higher percentage.
carboxymethyl chitosan (CMCH) and CdS NPs, there were two kinds
of bonding; carboxymethyl group was strongly bonded by coordination
with Cd ions on to the particle surface and the unsubstituted other
groups were linked to the particle surface via hydrogen bonding [20].
From this observation, it was suggested that the biological molecules
can possibly perform the function for formation as well as stabilization
of the CdS nanoparticles in aqueous medium [7].
The peak at 1543, 1364, 1223 cm − 1 appeared only in CdS–CPE
complex (Fig. 3b). This new band was not observed in unbound
CdS, which indicates a new vibration from the CPE due to C\S band
at another possible scheme of bonding between CPE and CdS and
the bands seen at 1364 and 1034 cm –1 were assigned to the C–N
stretching vibrations of the aromatic amino amines. The interaction
mechanism is mainly due to hydrogen bonding. Generally CdS QDs
grow well in a solution that may has a large amount of hydroxyl
groups and in water-bound surface, which are active sites for the for-
mation of hydrogen bonding with the surrounding molecules [21].
The morphology and size of the CdS nanoparticles were observed
adopting TEM. It was found that the nanoparticles were of uniform
size, at about 5 nm. The EDAX revealed the presence of both Cd and
S in the nanoparticles synthesized (Fig. 4). The lifetime of capped
CdS QDs was higher than that of uncapped CdS QDs. The results also
 D. MubarakAli et al. / Materials Letters 74 (2012) 8–11
indicated that the lifetime of the particles increased with increase in
size, which may be due to the uniform passivation caused by MSA
on the surface of CdS particles [12].
In the present study the particle size was 5.1 ± 0.2 nm. This size
range may possibly be due to the formation of nanoparticles over a
time period. In support of this inference, an earlier report also found
difference in size of the particles over the incubation time [6]. Since
CdS nanoparticles, synthesized in aqueous phase, could be a novel
fluorescence probe for ultrasensitive detection of DNA as a biolabel
[22], the enhanced syntheses of CdS nanoparticles using C-PE, are
the unique properties of the particles that might prove to be of
great advantage.
4. Conclusion
CdS nanoparticles were synthesized using C-phycoerythrin as the
capping agent. A bright fluorescent protein was extracted from the
genetically characterized marine cyanobacterium, Phormidium tenue
NTDM05 (GU585847). This protein was used for the biosynthesis of
CdS nanoparticles, which was characterized adopting UV–vis and
FTIR. CdS elemental signals were confirmed by EDAX. The TEM result
confirmed the spherical shape of nanoparticles at the size of about
5 nm. The simplicity of the procedure in this study can be useful in
commercial scale production of stable CdS nanoparticles of fairly uni-
form size.
Note: The 16S rDNA nucleotide sequences of the Phormidium
tenue NTDM05 have been submitted to the GenBank (NCBI) with
accession number GU585847.
Acknowledgment
The first and corresponding authors are grateful to Prof. M.A.
Akbersha, Director, Mahatma Gandhi Dorencamp Centre (MGDC)
for his critical evaluation of the manuscript and thankful to the
11
Department of Biotechnology (Government of India), New Delhi
(BT/PR11316/PBD/26/164/2008) for their financial assistance.
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