Materials Letters 116 (2014) 275–277

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

Green biosynthesis and characterization of zinc oxide nanoparticles

using brown marine macroalga Sargassum muticum aqueous extract
Susan Azizi a,n, Mansor B. Ahmad a, Farideh Namvar b,d, Rosfarizan Mohamad b,c
a
Department of Chemistry, Faculty of Science, Universiti Putra, Malaysia
b
Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra, Malaysia
c
Department of Bioprocess Technology, Faculty of Biotechnology and Biomolecular Sciences,Universiti Putra, Malaysia
d
Department of Medicine & Applied Biology Research Centre, Mashhad Branch, Islamic Azad University, Mashhad 917568, Iran

art ic l e i nf o a b s t r a c t

Article history: Biosynthesis of nanoparticles is an important area in the field of nanotechnology which has economic
Received 6 June 2013 and eco-friendly benefits over chemical and physical methods of synthesis. The present contribution
Accepted 7 November 2013 deals with one pot method for synthesis of zinc oxide nanoparticles (ZnO NPs) through green process
Available online 16 November 2013
using the brown marine macroalgae Sargassum muticum (S.muticum) aqueous extract. FTIR spectra
Keywords: revealed the involvement of sulfate and hydroxyl moieties of polysaccharide in the formation of ZnO NPs.
Sargassum muticum Pure ZnO NPs were obtained after calcination of S.muticum formed ZnO at 450 1C. FESEM analysis shows
Marine macroalgae that the pure ZnO NPs synthesized have hexagonal wurtzite structures and the average size ranged from
Sulfated polysaccharide 30 to 57 nm. The UV–vis absorption spectra of the pure ZnO NPs exhibited absorption peaks in the UV
Zinc oxide nanoparticles
region which were attributed to the band gap of the ZnO NPs.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction offers numerous advantages of eco friendliness and compatibility for

Recently, there is a growing necessity to develop environmen-
tally friendly nanoparticle synthesis methods which does not use
toxic materials in the synthesis procedures. Biological processes
for nanoparticle synthesis using microorganisms, enzymes, plants,
and alga have been proposed as feasible ecofriendly alternatives to
chemical and physical methods, because they are hazardous and
costly [1].
Marine macroalgae are planted like organisms categorized
according to their pigmentation into green (chlorophytes), brown
(phaeophytes) and red (rhodophytes) which live either in marine
or brackish water environment. Recently, some of studies showed
that marine algae can be used as a bio-factory for synthesis of
silver and gold nanoparticles [2–6]. However, review of literature
revealed that the synthesis of metal oxides and semiconductors
nanoparticles using algae has been explored in number of few
literature [7], which aroused our interest in the present study.
Zinc oxide (ZnO), an important semiconductor nanoparticle has
been interesting attention for its wide range of applications, such as
electronics, optics, optoelectronics and biomedical [8]. More
recently, some of researchers have described that the use of
ecofriendly benign materials like leaf extract (aloe barbadensis) [9],
bacteria [10], and fungus [11] for the synthesis of ZnO nanoparticles
n
Corresponding author. Tel.: þ 60 622 802 9.
E-mail addresses: susanazizi@yahoo.com, azisusan@gmail.com (S. Azizi).
pharmaceutical and other biomedical applications, where toxic
materials are not used for the synthesis producers.
The present study describes a single step, green, and rapid
synthesis and characterization of ZnO nanoparticles prepared by
biological (green) techniques using S.muticum. S.muticum is a brown
marine macroalga, is generally used in the food, drug, and manu-
facturing industries with potential medicinal applications [12].
Biochemical profile of this seaweed constituent's viz. polysacchar-
ides, protein, lipids, polyphenols, fiber, vitamins, and minerals.
2. Experimental details
Synthesis and characterization of ZnO nanoparticles: Dried algae
powder (2 g) was mixed with 100 ml distilled water and heated to
100 1C and then filtered through Whatman 41 filter paper. Zinc
acetate dehydrate (Zn(Ac)2
2H2O) (2 mM) solution was made to
react with 50 ml of the aqueous extract for 3–4 h in an aqueous
bath system under continuous stirring at 70 1C. The pale white
solid product was collected through centrifugation at 4000 rpm
for 10 min and careful washing with distilled water and then dried
at 100 1C overnight. The pure ZnO NPs were obtained by heating
the ZnO–S.muticum at 450 1C for 4 h.
Phase purity and particle size were determined by X-ray
diffraction (XRD) analysis recorded by diffractometer (XPERT-
PRO). The chemical structure was examined by using FTIR spectro-
meter (Perkin-Elmer 1725X). The shape and size of the sample

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.11.038
276 S. Azizi et al. / Materials Letters 116 (2014) 275–277

were characterized by using field emission scanning electron

microscope (FESEM) (JSM-6360LA). Size distribution and the
average size of the nanoparticles were estimated on the basis of
FESEM image with the assistance of Sigma-Scan Pro software
(SPSS IBM, Statistics 20). The pure sample was analyzed for UV–vis
absorption and optical band gap (Eg) using UV–Vis spectrophot-
ometer (a Lambda 25-Perkin Elmer).

3. Results and discussion

The formation of ZnO NPs was confirmed through visual

assessment. The color of mixture reaction was changed from dark
brown to a pale white color during the reaction, indicating the
synthesis of ZnO NPs. Functional groups exist in bioactive com-
pounds of marine alga are: amino, sulfate, carboxyl and hydroxyl
groups. These groups can play important roles in the formation
and stabilization of ZnO NPs.
FTIR spectrum (Fig. 1a) confirmed the structure of S.muticum with
bands at 3340, 1610, 1420, 1235 and 1037 cm  1 [13]. Fig. 1b displays
the FTIR spectrum of S.muticum formed ZnO NPs, in which signal at
1235 cm  1 of asymmetric stretching vibration of a sulfate group
disappeared and the bands intensity around 1037–3340 cm  1 corre-
sponded to the symmetric C–O vibration associated with a C–O–SO3
[14] and hydroxyl groups, respectively decreased after synthesis of
ZnO NPs indicated the involvement of sulfate and hydroxyl groups in
the formation of nanoparticles. The above bonds commonly occur in
polysaccharides indicating the participation of sulfated polysacchar-
ides in the synthesis of ZnO NPs. Another band observed at 1610 cm  1
is attributed to the stretching vibration of (NH) C¼O group that are
characteristic of proteins slightly shifted from 1630 cm  1 and became
broader, indicating a member of (NH) C¼O group within the cage of
cyclic peptides is involved in stabilizing the nanoparticles. The signal
at 441 cm  1 corresponded to the stretch band of zinc and oxygen.
The FTIR spectrum for bare ZnO NPs (Fig. 1c) only shows an intense
band at 430 cm  1, indicating the surfaces of ZnO NPs are free of
the functional groups associated with bioorganic compounds of
S.muticum after calcination.
The FESEM image Fig. 2 (A ) and particle size distribution graph
Fig. 2 (B) show the pure ZnO NPs formed were agglomerated with
a hexagonal structures and particle size ranging from 30 nm to
57 nm with some deviations. This agglomeration is due to polarity
and electrostatic attraction of ZnO nanoparticles [15].
Fig. 2 (C) shows the XRD pattern of the biosynthesized ZnO
NPs. Positions and intensities of all relative peaks of the ZnO NPs
matched the Joint Committee on Powder Diffraction Standard
(JCPDS) card number 36-1451. All the recorded peak intensity
profiles were characteristic of the nanoparticles' hexagonal

Fig. 2. (A) FESEM image of ZnO NPs, (B) particle size distribution graph and
(C) XRD pattern of ZnO NPs.

wurtzite structure. In addition, no diffraction peaks from other

types could be detected, which illustrates that all the precursors
have been completely decomposed and no other crystal materials
have been maintained. The distinct diffraction peaks give evidence
of well-crystallized structure of bio-synthesized ZnO NPs. The
mean particle sizes of the nanoparticles were estimated from
FWHM using the Scherrer's equation [16],
d ¼ 0:89λ=β cos θ ð1Þ

Where d, λ, θ, and β indicate the mean particle size, the X-ray

wavelength (1.5406 A1), Bragg diffraction angle corresponding to
Fig. 1. FTIR spectra of (a) S.muticum,(b) S.muticum formed ZnO NPs and (c) pure the (101) plane, and full width at half maximum (FWHM) of the
ZnO NPs. (101) plane, respectively. The mean particle size of the pure ZnO
 S. Azizi et al. / Materials Letters 116 (2014) 275–277
Fig. 3. (A) UV Spectroscopy and (B) plots of (αhʋ)2 versus hʋ of pure ZnO NPs.
NPs was around 42 nm, which is well matched with the measured
crystal diameter obtained from FESEM images.
The UV–vis absorption spectrum of the pure ZnO nanoparticles
is shown in Fig. 3A. A sharp absorption in the wavelength of
334 nm clarified the basic band gap absorption of ZnO crystals
because the electron transitions from the valence band to the
conduction band (O2p-Zn3d). Additionally, the direct band gap
of ZnO nanoparticles estimated from a plot of (αhʋ)2 versus the
photo energy (hʋ) consistent with the Kubelka–Munk model [17],
shown in Fig.3B, was 3.30 eV.
4. Conclusion
In this study, a simple, ecofriendly and economic biological
process has been developed to synthesize zinc oxide NPs. Accord-
ing to the FTIR analysis, the polysaccharides present in the
aqueous extract of S.muticum involved in the formation of zinc
oxide NPs. The zinc oxide nanoparticles have hexagonal structures
and the particle size ranges from 3 nm to 57 nm with a mean size
of 42 nm. The biosynthesized zinc oxide nanoparticles prepared
from S.muticum is expected to have notable applications in
pharmaceutical and biomedical fields and in cosmetic industries.
Acknowledgments
The authors are grateful to staff of the Department of Chemistry
UPM for their technical assistance, and Universiti Putra Malaysia
for the research grant RUGS 9199840.
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