Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Phoenix dactylifera L. leaf extract phytosynthesized gold nanoparticles;

controlled synthesis and catalytic activity
Mervat F. Zayed a,⇑, Wael H. Eisa b
a
Chemistry Department, Faculty of Science, Menoufia University, Egypt
b
Spectroscopy Department, Physics Division, National Research Center (NRC), Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A Phoenix dactylifera is an excellent

sink for biosynthesis of the gold
nanoparticles.
 Carbohydrates, flavonoids, tannins
and phenolic acids present in P.
dactylifera acts as reducing and
capping agents.
 The as-synthesized Au colloids
exhibited good catalytic activity for
the degradation of 4-nitrophenol.

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

Article history: A green synthesis route was reported to explore the reducing and capping potential of Phoenix dactylifera
Received 25 August 2013 extract for the synthesis of gold nanoparticles. The processes of nucleation and growth of gold nanopar-
Received in revised form 8 October 2013 ticles were followed by monitoring the absorption spectra during the reaction. The size and morphology
Accepted 19 October 2013
of these nanoparticles was typically imaged using transmission electron microscopy (TEM). The particle
Available online 1 November 2013
size ranged between 32 and 45 nm and are spherical in shape. Fourier transform infrared (FTIR) analysis
suggests that the synthesized gold nanoparticles might be stabilized through the interactions of hydroxyl
Keywords:
and carbonyl groups in the carbohydrates, flavonoids, tannins and phenolic acids present in P. dactylifera.
Green synthesis
Gold nanoparticles
The as-synthesized Au colloids exhibited good catalytic activity for the degradation of 4-nitrophenol.
Phoenix dactylifera Ó 2013 Elsevier B.V. All rights reserved.
4-Nitrophenol

Introduction use expensive and toxic reagents as reducing and stabilizing

Gold nanoparticles have been considered as important area of
research due to their diverse applications in various fields includ-
ing drug delivery, tissue/tumor imaging, photothermal therapy,
catalysis, water purification, surface-enhanced Raman Scattering
detection and optoelectronics [1–7]. Researchers make a great ef-
fort in synthesis of gold nanoparticles by a variety of chemical
and physical methods [8–16]. However, these methods not only
⇑ Corresponding author. Tel.: +20 48 2210369.
E-mail address: waeleisa@yahoo.com (M.F. Zayed).
agents, but it is very likely that residual unreacted toxic chemicals
and by-products make gold nanoparticles so produced unsuitable
for use in biomedical applications. As a result, the search for envi-
ronment friendly molecules for the synthesis of nanoparticles has
gained a great deal of effort.
Synthesis of nanoparticles using biological systems, such as
microorganisms and plants, has gained a great importance in re-
cent years due to using of less harmful, biodegradable and cost-
effective reagents. Moreover, nanoparticles synthesized with bio-
logical base are interesting, predominantly because they exhibit
the best compatibility with biomolecules [17]. Although gold

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.10.092
 M.F. Zayed, W.H. Eisa / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244 239

nanoparticles synthesis using plant extracts has already been re- distribution of the gold nanoparticles. Furthermore, we demon-
ported with various plants [18–25], there is still a lot of attention strated its chemocatalytic potential in reduction of 4-NP to 4-ami-
paid to this field because of the high potential of plants in produc- nophenol and the size-dependence of the catalytic activity of gold
ing nanoparticles with different sizes and shapes, as well as the nanoparticles.
broad diversity of plant metabolites that may aid in the reduction.
Phoenix dactylifera L. (Palmae) commonly known as the date
Experimental
palm has been cultivated in the Arab world for centuries [26]
and its cultivation has now spread to Middle East, parts of Central
Chemicals
and South America, and Southern Europe [27,28]. It is considered
as one of the most important commercial crops; the fruits of date
All the reagents purchased were of analytical grade and used as
palm constitute a substantial part of the diet in the Arabian world.
received. Chloroauric acid (HAuCl43H2O) was obtained from Sig-
In addition to its dietary use, the leaves are used in traditional
ma–Aldrich Co. 4-Nitrophenol was purchased from LOBA CHEMIE,
medicine to treat intestinal hemorrhage, diarrhoea, jaundice and
India. Sodium borohydride (NaBH4) was provided by Merck Co. All
diabetes [29–31]. It is reported to possess antioxidant, antimicro-
aqueous solutions were prepared using deionized double distilled
bial, antidiabetic and antilipaemic activities [32–34]. However,
water.
there are no reports till date that documents its potential in nano-
biotechnology to synthesize nanoparticles and thereby evaluating
Preparation of plant extract
its chemocatalytic applications.
Nitrophenols are among the most common organic waste water
Fresh leaves of P. dactylifera were collected from Shebin El-kom
pollutants widely used in the chemical industry. 4-Nitrophenol (4-
city, Egypt and had been washed thoroughly with de-ionized
NP) is an important chemical that is being used as a precursor or
water. The leaves (20 g) were extracted by maceration with 70%
intermediate for the preparation of pesticides, insecticides, herbi-
ethanol/water (100 mL). The extraction process was done at room
cides, explosives, synthetic dyes and pharmaceuticals. 4-NP is
temperature for 7 days, and then the solution was filtered and
highly soluble and stable in water so it stays a very long time in
stored at 4 °C for further experiments.
the soil and ground water without degradation [35]. This accumu-
lation rises the environmental risk due to the carcinogenic activi-
ties of 4-NP [36,37]. Many processes have been employed for the Synthesis of gold nanoparticles
removal of nitrophenols [38–40] but these methods are energy
consuming and use organic solvents. However, GNPs are used as Gold nanoparticles were prepared by adding varying volumes of
a catalyst to degrade 4-NP to 4-aminopenol as an easy, rapid and the plant extract (100, 200 and 400 lL) to 10 mL of aqueous chlo-
energy saving operation [41–44]. On the other hand, 4-aminophe- roauric acid solution (0.4 mM) at room temperature. A control
nol is considered as an environmentally safe end product because experiment was done without addition of chloroaurate ions. The
it is an important intermediate for the manufacture of analgesic biotransformation of chloroaurate ions to gold nanoparticles was
and antipyretic drugs. periodically monitored using UV–vis spectrophotometer.
In this paper we describe a rapid, simple, economic and envi-
ronmentally benign method for synthesis of gold nanoparticles Characterization of gold nanoparticles
using leaves extract of P. dactylifera as reducing and capping agent
without adding chemicals (see Scheme 1). We also investigated the The UV–vis spectra measurements were recorded on a PG
effects of reaction conditions such as the extract quantity and Instruments T80+ UV–vis double beam spectrophotometer (PG
contact time on the rate of synthesis, size, shape and size Instruments, United Kingdom). The morphologies and sizes of the

Scheme 1. P. dactylifera extract assisted phytosynthesis of Au nanoparticles.

240 M.F. Zayed, W.H. Eisa / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244
as-prepared samples were performed using transmission electron
microscope (TEM) of the type JEOL-JEM-1011. A Jasco FT/IR 6100
spectrometer was employed to demonstrate the chemical nature
of the synthesized composites in the range of 4000–400 cm1.
The gold concentration measurement was carried out using atomic
absorption spectrometer Varian SpectrAA (220) with graphite fur-
nace accessory and equipped with deuterium arc background
corrector.
Catalytic activity of P. dactylifera stabilized Au nanoparticles in
degradation of 4-nitrophenol
For studying the catalytic activity of as-prepared gold nanopar-
ticles, the reduction of 4-NP to 4-aminophenol by NaBH4 is per-
formed as a probe reaction. The effect of nanoparticle size on the
speed of catalytic reduction is studied using the gold colloids pre-
pared with three different quantities of P. dactylifera extract (100,
200 and 400 lL). The method reported by Narayanan and Sakthivel
[43] was applied here but with using smaller volumes of gold
nanoparticles. In standard quartz cell with a 1-cm path length,
2.77 mL of water was mixed with 25 lL (102 M) of 4-NP solution
and 200 lL of freshly prepared NaBH4 solution (101 M). Thereaf-
ter, 50 lL of gold solution was added to the above mixture. The
same atomic concentrations of Au nanoparticles (40 ppm) were ap-
plied in all experiments of the catalytic reduction. After the addi-
tion of gold colloid, reduction is ascertained by recording the
UV–vis spectra.
Results and discussions
Time-dependent UV–vis spectra and kinetics of nanoparticles
formation
When light strikes the gold nanoparticles, they get excited and
show a strong absorption band in the visible region. This takes
place when the frequency of the electromagnetic field is resonant
with the coherent electron motion what is known as ‘‘surface plas-
mon resonance (SPR) absorption’’ [45]. This feature makes the UV–
vis spectroscopy is the most frequently used technique to judge the
success of Au nanoparticles production.
The UV–vis spectrum shown in Fig. 1, explains the impact of dif-
ferent volumes (100, 200 and 400 lL) of P. dactylifera extract on
biosynthesis of gold nanoparticles. The SPR band can be easily ob-
served on the visible range for all the spectra. This SPR band was
recorded at 552 nm for the sample prepared with the aid of
Fig. 1. The UV–vis spectra of the Au nanoparticles as a function of P. dactylifera
extract volumes.
100 lL of extract. Increasing the volume of the P. dactylifera extract
to 200 and 400 lL shifted the SPR band to 544 and 538 nm, respec-
tively. The blue shift of the SPR band is due to a size dependent
phenomenon called quantum confinement i.e. smaller Au nanopar-
ticles were formed. In addition, the SPR band got narrower and
sharper under the action of increasing extract volumes. The in-
crease in intensity could be due to increasing number of nanopar-
ticles formed as a result of reduction of Au3+ ions presented in the
aqueous solution.
Time-dependent UV–vis spectra were recorded to shed light on
the processes of nucleation and growth of gold nanoparticles re-
duced under the action of different P. dactylifera extract volumes.
For comparison sake, the time-dependent UV–vis spectra were ta-
ken at regular time intervals as well as keeping the concentrations
of metal ions the same in each system.
The nucleation and growth processes of Au nanoparticles can be
monitored by following the behavior of the surface plasmon reso-
nance (SPR) as a function of the time elapsed after the addition of P.
dactylifera extract (see Fig. 2). The UV–vis spectra showed in-
creased absorption with increasing time in the spectral region
(500–600 nm). The increase in intensity could be due to increasing
number of nanoparticles formed as a result of reduction of Au3+
ions presented in the aqueous solution.
Three more remarkable results could be addressed here. First,
the reaction rate increases with increasing the P. dactylifera extract
volumes, i.e. shorter incubation times were required at higher ex-
tract volumes; for 100 lL of extract the incubation time was
40 min; for 200 lL the incubation time was 15 min whereas for
400 lL of extract the incubation time was only 3 min. Secondly,
as the reaction process continued, the SPR band kept increasing
in intensity, narrowing in the FWHM and its position in the spec-
trum shifted to longer wavelengths. The color of the growth solu-
tion gradually evolved into blue-purple. Thirdly, the UV–vis
spectrum of the sample prepared with 100 lL of extract was dom-
inated with an absorption tail extended to the near IR regions. This
tail was obviously limited by increasing the volume of the extract
in the reduction reaction. The Appearance of the absorption tail in
the spectrum may be either because of the size distribution of the
particles and/or formation of non-spherical gold nanoparticles
with increasing aspect ratio. The combination of both the above
phenomenon is also possible [46].
In the light of the spectral results, the reaction pathway for pro-
ducing Au nanoparticles passes through the following successive
stages: reduction of the soluble tetrachloroauric acid by P. dactylif-
era extract, nucleation of metallic gold, and growth of individual
nuclei.
Upon addition of the P. dactylifera extract to aqueous solution of
tetrachloroauric acid the Au3+ species are reduced to metallic gold.
The concentrations of metallic gold in solution increase, reaching
the super saturation conditions and finally the critical concentra-
tion to nucleate. Thereafter, spontaneous nucleation takes place
and many nuclei are formed with time. These nuclei in the growth
solution are quasispherical in shape, with polydisperse distribu-
tion, which is collected from the low intensity and wide FWHM
of the SPR band of the initial growth solution. As the reaction go
on, the nuclei grow by the deposition of metallic gold to give birth
to spherical nanoparticles of uniform size. This is confirmed by the
spectral evolution of the growth solution as the intensity of the SPR
band increases considerably while its FWHM narrows and its posi-
tion is red shifted.
The particle size of the gold nanoparticles depended strongly on
the amount of P. dactylifera extract. It is well stated that, in order to
obtain monodispersed metal nanoparticles, rapid nucleation in a
short period of time is important; that is, almost all ionic species
have to be reduced rapidly to metallic species simultaneously,
followed by conversion to stable nuclei so as to be grown [47].
 M.F. Zayed, W.H. Eisa / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244
Fig. 2. The UV–vis spectral evolution of the growth solution of gold nanoparticles
under the action of (a) 100, (b) 200 and (c) 400 lL of P. dactylifera extract.
Hence, at the smallest extract volume (100 lL) larger particles
were generated, most likely due to a slower nucleation rate, while
at a highest extract volume (400 lL) faster nucleation produced
monodispersed and smaller-sized particles.
FT-IR analysis
To better understand the reaction mechanism between
P. dactylifera extract and gold salt, FTIR spectra were recorded for
241
Fig. 3. FTIR spectra of P. dactylifera and P. dactylifera-stabilized gold nanoparticles.
P. dactylifera extract and the Au nanoparticles capped with P. dacty-
lifera extract and displayed in Fig. 3.
It has been reported that the whole date plant of P. dactylifera
(including pits and leaves) contains carbohydrates, alkaloids, ste-
roids, flavonoids, saponins and tannins [34]. The phenolic profile
of the plant revealed presence of mainly cinnamic acids, flavonoid
glycosides, flavanols, four free phenolic acids and nine bound phe-
nolic acids [48–51]. The vibrational stretching of OH group of P.
dactylifera was appeared as an intensive band at 3415 cm1. This
band undergoes a shift to 3398 cm1 and become broader upon
interaction with gold salt. P. dactylifera spectrum shows a sharp
peak at 1632 cm1 due to the stretching vibrations of the AC@O
group [52]. The reduction of gold salt into gold nanoparticles
caused the 1632 cm1 IR absorption band of P. dactylifera to be
splitted into two peaks at 1651 and 1613 cm1. These evidences
indicate that during the formation of Au nanoparticles, there is
coordination between Au3+ ions and the oxygen atoms of AOH
groups and/or AC@O groups.
On the light of FTIR analysis, it can be stated that the hydroxyl
and carbonyl groups present in carbohydrates, flavonoids, tanins
and phenolic acids of P. dactylifera may be accountable for the
reduction of the Au ions and stabilization of Au nanoparticles.
TEM analysis
TEM micrographs were taken to assess the size, size distribution
and shape of the green synthesized gold nanoparticles with the aid
of P. dactylifera extract. The micrographs reveal that the Au nano-
particles are surrounded by a thin layer of biomaterial which ap-
pears to be characteristic of Au nanoparticles prepared in plant
extracts. Using low volume of the plant extract will result in irreg-
ular shapes (mixture of triangles, tetragonals and nanorods) as well
as wide size distribution of the reduced gold nanoparticles (see
Fig. 4a). In presence of excess extract to reduce the chloroaurate
ions, the biomolecules strongly shaped the nanoparticles on the
spherical shape (see Fig. 4b and c). These observations may reflect
the fact that the P. dactylifera extract is considered as reducing and
stabilizing agent in synthesis of gold nanoparticles.
The quantitative measurements of the TEM micrographs were
executed through performance of particle size histograms together
with their Gaussian fits as displayed in Fig. 4a0 –c0 . Average particle
size was determined from the peak of the Gaussian curve. Three
different sizes of Au nanoparticles were synthesized by tuning
the volume of P. dactylifera extract from 100 to 400 lL. The largest
particle size is 45 nm for the lowest volume of the extract (100 lL)
242 M.F. Zayed, W.H. Eisa / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244
Fig. 4. TEM micrographs of gold nanoparticles prepared with (a) 100, (b) 200 and (c) 400 lL of P. dactylifera extract. The corresponding histograms were represented by (a0 ),
(b0 ) and (c0 ).
while the smallest one is 32 nm for the highest volume of the ex-
tract (400 lL). The FWHM of the Gaussian fit was narrowed with
increasing extract volume. Thus, a significant improvement in the
monodispersity has been achieved using excess of P. dactylifera
extract.
Au nanoparticles catalyzed the reduction of 4-nitrophenol to 4-
aminophenol
The reduction of 4-NP by NaBH4 has been chosen as a bench-
work reaction for monitoring the catalytic activity of Au
nanoparticles.
The aqueous solution of 4-NP shows two distinct absorption
peaks at 320 and 396 nm (see Fig. 5). The electronic band at 320
is the characteristic band of 4-NP whereas the one at 400 nm
Fig. 5. UV–vis spectra of 4-NP before and after adding NaBH4 solution.
was attributed to the presence of 4-nitrophenolate ions in the sys-
tem. After immediate addition of freshly prepared aqueous solu-
tion of NaBH4, the absorption band at 320 disappeared totally
whereas the absorption band at 400 nm grew markedly to up to
twice of its original value as displayed in Fig. 5. These spectral
changes may be attributed to the conversion of 4-nitrophenol to
4-nitrophenolate ions in basic medium. It is well known that nitro
compounds are inert to NaBH4 if it is used alone [43]. This is ex-
actly consistent with our practical visual inspections. In the ab-
sence of proper catalyst, the intense yellow color of the 4-
nitrophenolate solution remained unaltered for several days.
Fig. 6 shows the behavior of catalytic conversion of 4-nitrophe-
nol to 4-aminophenol after addition of 50 lL Au nanoparticles
using UV–vis spectrophotometer. The process was quantitatively
monitored as a successive decrease in the peak height at 400 nm
together with the gradual development of the new peak at
300 nm which indicates the formation of 4-aminophenol [44].
These spectroscopic data were corresponded to a change in solu-
tion color from yellow to colorless within few minutes. The effect
of Au nanoparticle size on catalytic efficiency was studied as well.
As expected, the smaller the size of the catalyst the shorter is the
time of the reduction process (see Fig. 6).
This catalytic reaction was carried out in large excess of NaBH4
concentration as compared with that of 4-NP. Hence, it is conve-
nient to consider the concentration of borohydride ion is constant
throughout the experiment. Hence, the reaction rate (Ka) of the
reduction is assumed to be only dependent of 4-NP concentration.
Therefore, the rate is assumed to follow first order kinetics [53].
The kinetic equation for the reduction can be written as
K a t ¼ ln ðC t =C 0 Þ ¼ ln ðAt =A0 Þ
where Ct and At are the concentration and absorption of 4-NP at
time t while C0 and A0 are the concentration and absorption of
4-NP at the starting of the reaction. The rate constant (Ka) can be
 M.F. Zayed, W.H. Eisa / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 121 (2014) 238–244
Fig. 6. Successive UV–vis absorption spectra of the reduction of 4-NP by the P. dactylifera-stabilized gold nanoparticles.
calculated from the linear fitting of the graphical representation of
ln (At/A0) against the reaction time (t) which is displayed in Fig. 6.
The rate constant of 32 nm gold nanoparticles is 3.1  103 s1,
which is higher than those of gold nanoparticles with larger sizes,
(1.5  103 s1 and 1.12  103 s1 for 36 and 45 nm gold nano-
particles, respectively). It is well known that the surface area of
the metals is the most important criteria that determine the effi-
ciency of the metals as catalytic agents [54]. Therefore, particles
with smaller sizes have a higher surface-to-volume ratio so they
can facilitate the electron relay from the donor to the acceptor.
In addition, it needs to be noted that the total number of Au nano-
particles of the 32 nm sample would be larger than those of 36 and
45 nm samples because the size of 32 nm sample is smaller com-
pared with other samples. The calculated rate constant is compara-
ble with previously reported values of glucan and casein-stabilized
gold nanoparticles [55,56].
4. Conclusion
P. dactylifera extract is confirmed to be an efficient candidate for
bio-fabrication of gold nanoparticles due to its controlled reducing
243
power as well as presence of capping molecules. The size of colloi-
dal Au nanoparticles could be easily tuned in the nanometer range
by adjusting the used volume of P. dactylifera extract solution.
Increasing the added extract volume increases the rate of reduction
and reduces the particle size as well as their agglomeration. The
stabilized gold nanoparticles exhibit size dependent catalytic
activity toward degradation of 4-NP. The rate constant of the cata-
lytic reaction was increased with decreasing particle sizes.
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