International Journal of Nanoscience

Vol. 15, No. 5 (2016) 1650019 (11 pages)

#.c World Scienti¯c Publishing Company
DOI: 10.1142/S0219581X16500198

Green Route for Silver Nanoparticles Synthesis

by Raphanus Sativus Extract in a Continuous
Flow Tubular Microreactor

P. D. Jolhe*, B. A. Bhanvase†, V. S. Patil* and S. H. Sonawane‡,§

*University Institute of Chemical Technology
North Maharashtra University, Jalgaon, MS, India
†Department of Chemical Engineering

Laxminarayan Institute of Technology

Rashtrasant Tukadoji Maharaj Nagpur University
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Nagpur-440033, MS, India

‡Department of Chemical Engineering

National Institute of Technology

Warangal-506004, Telangana State, India
§
shirishsonawane@rediffmail.com

Received 6 November 2014

Accepted 9 May 2016
Published 29 July 2016

The present work deals with the investigation of the greener route for the production of silver
nanoparticles using Raphanus sativus (R. sativus) bioextract in a continuous °ow tubular
microreactor. The parameters a®ecting the particle size and distribution were investigated.
From the results obtained it can be inferred that the ascorbic acid (reducing agent) present in
the R. sativus bioextract is responsible for the reduction of silver ions. At optimum condition,
the particle size distribution of nanoparticles is found between 18 nm and 39 nm. The absor-
bance value was found to be decreased with an increase in the diameter of the microreactor. It
indicates that a number of nuclei are formed in the micrometer sized (diameter) reactor because
of the better solute transfer rate leading to the formation of large number of silver nanoparticles.
The study of antibacterial activity of green synthesized silver nanoparticles shows e®ective
inhibitory activity against waterborne pathogens, Shegella and Listeria bacteria.

Keywords: Microreactor; Raphanus Sativus bioextract; silver nanoparticles; green synthesis;

particle size distribution.

1. Introduction show drastic improvements in the properties than

Metal nanoparticles have found remarkable appli-
cations in diverse ¯elds like catalysis, electronics,
surface coating, drug delivery, biomedical science,
biotechnology, nano°uids, environmental remedia-
tion, energy storage devices, etc.1–7 Nanoparticles
their bulk counterparts and further, the applica-
tions are mainly dependent on their shape, size and
functionalization.8–10 Therefore, it is important to
achieve the required shape and size of nanomaterials
without any other considerable variation11,12 and it

1650019-1
 P. D. Jolhe et al.
is basically dependent on the synthesis method and
precursors used. The main disadvantage of synthe-
sizing nanoparticles in a batch reactor is the re-
quirement of batch to batch optimization with scale
up of batch reactor due to nonuniform mixing.
These nonidealities result in a wider particle size
distribution.13 Thus, any production method that
gives an improved control over the size and shape
of the particles has a great signi¯cance in the area
of chemical engineering.
The process of intensi¯cation based on micro
°uidic devices is an innovative thought in chemical
engineering, which targets the reduction of capital
and energy costs along with the environmental im-
pact of reducing the size of the chemical plant.14
Several workers have used continuous °ow micro-
reactor system for the synthesis of nanomaterials
such as silver, gold, palladium, copper nano-
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particles, etc., and other products in the last couple
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of years.15–22 Patil et al.22 have reported the pro-
duction of silver nanoparticles using the micro-
reactor system. They have studied the e®ect of
surfactants such as sodium dodecyl sulfate (SDS)
and N-cetyl N,N,N,trimethyl ammonium bromide
on the silver nanoparticle size. The mechanism of
nucleation and growth of these particles was also
reported. The decrease in the particle size of silver
has been reported with an increase in the SDS
surfactant concentration.22 Yang et al.23 have used
the continuous microreactor system for the syn-
thesis of gold nanoparticles under UV irradiation in
the presence of citric acid and poly(vinylpyrroli-
done) (PVP) at room temperature. It has been
reported that the synthesis of spherical gold nano-
particles was possible at a higher precursor solution
°ow rate. Further, Ravi Kumar et al.24 have also
used continuous °ow microreactor system for the
preparation of silver nanoparticles using biosurfac-
tants, namely, oleic acid sophorolipid and stearic
acid sophorolipid which can act as reducing and
capping agents. Further, it showed that the in-
creased °ow rate leads to the formation of bigger
and polydisperse particles because of incomplete
reactions.24 Therefore, it has been reported that
larger residence time is essential for the completion
of the reaction which results in spherical, and
monodisperse particles. At a higher °ow rate i.e.,
lesser residence time, the reaction does not get
completed and nucleation may occur at limited
places and then growth of the particles takes place.
Therefore, if su±cient time is provided for the
completion of reaction, complete growth of particle
1650019-2
takes place and spherical and monodispersed
particles are resulted.
It has been reported that diverse types of nano-
materials like copper,25 titanium,1 gold23 and silver
have been used as a antioxidants, however, silver
nanoparticles have been established in practical
application as it has excellent antibacterial proper-
ties.26 During the synthesis of nanoparticles, the use
of bio-based reducing agent makes the process
green. Green synthesis of metal nanoparticles using
bio-based reducing agents such as Punica grana-
tum,27 ocimum leaf extract,28 banana peel,29 Elle-
taria cardamomom,30 Sitophilus oryzae,31 Ananas
comusus,32 citrus sinesis peel extract,26 Papaya fruit
extract,33 Coriander,34 Desmodium tri°orum35 and
Camellia sinensis36 has already been reported.
Amongst the di®erent green synthesis methods, the
use of plant extract is acquiring a great signi¯cance
as it o®ers cheap reducing and coupling agent dur-
ing the preparation of silver nanoparticles. Gar-
deaTorresdey et al.37,38 have reported the formation
of gold and silver nanoparticles by plant extract for
the ¯rst time. Ahmad et al.27 have presented a
simple and eco-friendly biosynthesis of silver nano-
particles using pomegranate peel extract as the re-
ducing agent. The reported reaction was very
simple for the preparation of highly stable silver and
gold nanoparticles at room temperature by using
the biowaste of the fruit. The reported average
particle size of silver nanoparticles was 5
1.5 nm
whereas the gold nanoparticles were reported to be
10
1.5 nm. Huang et al.19 have studied the bio-
logical production of silver nanoparticles by lix-
ivium of sun dried Cinnamomum camphora leaf in
continuous-°ow tubular microreactors. Kasture
et al.20 have also reported in situ synthesis of silver
nanoparticles using biosurfactants called sophor-
olipids as reducing and capping agents.
The continuous °ow microreactor system can be
investigated for an e±cient preparation of metal
nanoparticles to overcome the disadvantages pres-
ent in the conventional method of the synthesis as
mentioned before. A very few studies report the
synthesis of metal nanoparticles in microreactor
with the use of plant bioextract as a reducing agent.
Further, very few studies were found in the litera-
ture which report the preparation of silver nano-
particles using Raphanus sativus bioextract in a
microreactor.39 Also, the e®ect of di®erent size
reactors was not studied. Therefore, in the present
work, green synthesis of monodisperse silver nano-
particles by R. sativus bioextract in a di®erent size
 Green Route for Silver Nanoparticles Synthesis by R. Sativus Extract
continuous °ow tubular microreactor was carried
out. The e®ects of the process parameters a®ecting
colloidal silver nanoparticle synthesis using contin-
uous °ow microreactor system are reported.
2. Experimental Methodology
2.1. Materials
Analytical grade silver nitrate (AgNO3, 99%) and
SDS (NaC12 H25 SO4, 99%) were procured from
Merck Specialties Pvt. Ltd., Mumbai, and Thomas
Baker (Chemical) Ltd, respectively, and used as
were received. Millipore deionized water (resistivity
> 1 M
cm) was used during the entire experimen-
tation. R. sativus bioextract was used as a reducing
agent during the preparation of Ag colloidal nano-
particles.
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2.2. Preparation of R. Sativus
bioextract
Fresh R. sativus was purchased from the local
market and it was thoroughly washed with distilled
water. Further, R. sativus was peeled to remove the
outermost dry layer. The peeled R. sativus was
¯nely cut into small pieces and ground using the
laboratory grinder to produce a homogenous paste.
The paste was further ¯ltered through cheese cloth
and the ¯ltrate i.e., R. sativus bioextract was col-
lected in a 250 mL Erlenmeyer °ask. The obtained
bioextract was cold centrifuged at 8000 rpm and
0  C for 15 min in order to avoid the degradation of
(a)
Fig. 1. (a) Experimental setup for the synthesis of Ag nanoparticles in a microreactor system, (b) Mechanism for formation of Ag
nanoparticles in a microreactor and (c) XRD spectrum for powdered Ag nanoparticle sample in a microreactor.
1650019-3
active reducing compounds and to remove the
remaining R. sativus biomass. The supernatant
obtained was stored at 4  C and then it was used for
the synthesis of silver nanoparticles in the micro-
reactor in varying amounts from 9 mL to 20 mL of
bioextract.
2.3. Green synthesis of colloidal
silver nanoparticles in tubular
microreactor
Continuous °ow microreactor experimental setup
(Length ¼ 2 m, Inner Diameter ¼ 1 and 1.5 mm)
was made up of Polytetra°uoroethylene (PTFE).
Two syringe pumps were used for the injection of
the precursors with a consistent °ow rate [Fig. 1(a)].
The reactants (AgNO3 solution and R. sativus
bioextract) were introduced in the reactor with the
help of two syringes connected in Y shape geometry
mixer made up of glass at the inlet of PTFE
microreactor. The molar concentration of AgNO3
solution was varied from 0.01 M to 0.02 M in order
to study the e®ect of AgNO3 concentration. The
precursor concentrations were varied on the basis
of ice cooled (6
2  C) R. sativus extract solution
(from 9 mL to 20 mL bioextract to make a 100 mL
solution with deionized water) which was used as
a reducing agent during the synthesis of colloidal
silver nanoparticles. SDS was added in AgNO3 so-
lution in varying quantities (0.0075 g to 0.015 g) in
order to investigate the e®ect of SDS during green
synthesis of colloidal silver nanoparticles. Both the
 P. D. Jolhe et al.

O OH
Ag(NO)3 HO OH O
O Na+ HO O OH
-
O S O
HO OH
(H3C)11 O
HO

2+ 0
Ag Ag
(SDS capped)

(b)
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1800
(1 1 1)

1600

1400

1200

1000
Intensity (CPS)

800

600
(2 0 0)

400

200

0
20 30 40 50 60 70
2θ (Degree)

(c)

Fig. 1. (Continued )

solutions (AgNO3 and R. sativus bioextract) were of the reaction, the obtained colloidal silver nano-
¯lled in two separate syringes (50 mL each, UNIEM particle suspension was used for further analysis.
Mumbai, India) and were mounted on syringe
pump. The °ow rate of AgNO3 and R. sativus ex-
tract solutions was set at 0.5, 1 and 1.5 mL/min to 2.4. Characterization
study the e®ect of °ow rate. Di®erent size micro- An initial colorless solution of silver metal ions was
reactors were used in order to investigate the e®ect turned to yellow and ¯nally to brown indicating the
of the size of reactor i.e., residence time. Both pre- formation of colloidal silver nanoparticles. The
cursors were passed through the tubular continuous bioreduced Ag þ ions in the solution were observed
microreactor system and the product was collected on UV-Vis Spectrophotometer (SHIMADZU 160A
in a glass vial. Initially, a colorless solution appeared model) in the 400–700 nm range. During UV-Vis
which turned to brown indicating the formation of spectroscopic analysis, the silver nanoparticle sam-
colloidal silver nanoparticles. After the completion ples were diluted until the absorbance value comes

1650019-4
 Green Route for Silver Nanoparticles Synthesis by R. Sativus Extract

below 1.2 a.u. in order to get the correct value. In all 3.2. XRD analysis of silver
experimentations the same amount of the sample nanoparticles
was taken out and ¯lled in the Quartz cuvettes
Figure 1(c) depicts the XRD pattern of colloidal
completely. Further the dilution of the samples was
silver nanoparticles prepared in the continuous
carried out by adding the 1 mL sample in 4 mL
microreactor system. XRD analysis shows the
deionized water. X-ray di®raction (XRD) patterns
characteristic peaks at 37.5  and 43.8  which are
of colloidal silver nanoparticles prepared in the
corresponding to the (1 1 1) and (2 0 0) crystalline
continuous microreactor system were recorded
planes of Ag (JCPDS cards 4-0783).38 The broader
using a Bruker di®ractometer (D8, Advance, Bruker
nature of the XRD peaks is attributed to the
AXS model) with CuK
radiation ( ¼ 1:5406 nm)
nanosize of the particles. The unassigned peaks
operating at 40 kV and 40 mA. The particle size
might be due to the presence of bioorganic phase on
analysis of the silver nanoparticles was performed
the surface of the Ag nanoparticles. The crystallite
using a Sympatec GmbH System Partikel Technik
size of the colloidal silver nanoparticles prepared by
(Nanophox NX0088), Germany. The morphology of
the green synthesis process in the continuous
colloidal silver nanoparticles prepared in continuous
microreactor system was found to be 5.35 nm which
microreactor was investigated by using scanning
was determined using Debye Scherrer's equation
electron microscopy (SEM) (JEOL JSM, 680LA
given by43,44:
15 kV, magni¯cation 10 000X). A single drop with a
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volume of 8 L of the various silver nanoparticle

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k
suspensions were dried onto 200 mesh grids with a Xd ¼ ; ð4Þ
 cos 
carbon support ¯lm. The dried preparations were
then rinsed with ethanol and dried before being where k ¼ 0:9,  ¼ full-width at half-maximum
mounted on the appropriate SEM holder and placed (FWHM) height and  is a glancing angle of X-rays
in the SEM. with the sample holder. CuK
angel  ¼ 1:5406 nm
radiation was used.
3. Result and Discussion
3.1. Formation mechanism of 3.3. Morphological analysis of silver
silver nanoparticles nanoparticles
Figure 1(b) represents the formation mechanism of
The morphological study of silver nanoparticles
Ag nanoparticles using R. sativus (radish) bioex-
prepared in the microreactor with di®erent sizes for
tract. Radishes are rich in ascorbic acid, folic acid
°ow rate 1 mL/min (for each reactant) is depicted
and potassium.40,41 As reported in Fig. 1(b) R. sati-
in Fig. 2. The distorted spherical morphology of
vus (radish) bioextract was taken as a reducing
silver nanoparticles is observed in the case of
agent during silver nanoparticle synthesis. The
microreactor of the size 1.5 mm [Fig. 2(a)]. How-
component like ascorbic acid is acting as a reducing
ever, Fig. 2(b) shows uniform silver nanoparticle
agent and reduction of Ag þ ions to silver may be due
formation in the case of 1 mm diameter micro-
to the presence of water-soluble antioxidative sub-
reactor system with the lesser particle size of silver
stances like ascorbate. Ascorbic acid is a reducing
nanoparticles. The spherical silver nanoparticle
agent and can reduce, thereby neutralize, reactive
formation is attributed to the size of the micro-
oxygen species leading to the formation of ascorbate
reactor. The reduction in the silver nanoparticle
radical and an electron.42 This free electron reduces
size with a decrease in the size of microreactor is
the Ag þ ion to Ag0. The reaction scheme is given
attributed to the decrease in the residence time of
below. Further, the presence of SDS in the reaction
reaction mixture which does not allow appreciable
mixture can stabilize the formed Ag nanoparticles
crystal growth of silver nanoparticles. Further,
e®ectively and avoid the agglomeration.
narrow distribution of silver nanoparticle size for
H þ 1.0 mm microreactor is due to the formation of
Ascorbic Acid ! Ascorbate Radical þ e  ð1Þ
more nuclei because of the better solute transfer
AgNO3 ! Ag þ þ
NO 
3 ð2Þ rate leading to an increase in the number of silver
þ 
Ag þ e ! Ag 0
ð3Þ nanoparticles.

1650019-5
 P. D. Jolhe et al.

(a) (b)

Fig. 2. SEM images of Ag nanoparticle samples in (a) 1.5 mm microreactor, and (b) 1 mm microreactor.

3.4. E®ect of amount of R. Sativus absorbance of the samples from 1.11 a.u. to 0.81 a.u.
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bioextract It is attributed to the reduction in the number of

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silver nanoparticles for the ¯xed quantity of silver

Figure 3(a) shows UV-Vis spectra of the colloidal
silver nanoparticles obtained for the di®erent
amount of R. sativus bioextract. The amount of
R. sativus bioextract was varied from 9 mL to 20 mL
and total volume was made to 100 mL by adding
deionized water in it in order to investigate the ef-
fect of R. sativus bioextract amount on silver
nanoparticle formation. It is found that the peaks
were shifted toward higher wavelength with an in-
crease in the amount of R. sativus bioextract from
9 mL to 20 mL (with a signi¯cant increase in the
absorbance from 0.76 to 1.11 a.u.). Further, an in-
crease in the amount of R. sativus bioextract
from 14 mL to 20 mL results into a decrease in the
nitrate in a larger volume of bio-extract.
Figure 3(b) shows the e®ect of amount of
R. Sativus bioextract on particle size distribution in
the continuous microreactor system. It is observed
that the particle size range for 20 mL amount of
R. sativus bioextract is from 67 nm to 149 nm. The
particle size range is found to be increased from 67–
149 nm to 104–181 nm with the decrease in the
amount of R. sativus bioextract from 11 mL to
9 mL. It is attributed to the nucleation at limited
places at a lower amount of R. sativus bioextract
which leads to the signi¯cant growth of particles.
However, in the case of the higher amount of

20 mL Raphanus sativus bioextract

30
11 mL Raphanus sativus bioextract
9 mL Raphanus sativus bioextract
1.2 9 mL Raphanus sativus bioextract 25
14 mL Raphanus sativus bioextract
1 11 mL Raphanus sativus bioextract
Absorbance (a.u.)

20
20 mL Raphanus sativus bioextract
% Frequency

0.8
15
0.6
10
0.4

0.2 5

0 0
400 450 500 550 600 650 700 60 80 100 120 140 160 180
Wavelength (nm) Particle Size (nm)

(a) (b)

Fig. 3. E®ect of amount of R. sativus Bioextract on (a) silver nanoparticle formation and (b) particle size distribution in a
continuous microreactor.

1650019-6

R. sativus bioextract, more nucleation events take
place in the reaction medium leading to a limited
growth of silver nanoparticles and also the particle
size is found to be decreased.
3.5. E®ect of AgNO3 concentration
The e®ect of AgNO3 concentration on silver nano-
particle formation was studied by varying the con-
centration of AgNO3 in the microreactor and
depicted in Fig. 4. As discussed in the earlier
section, the absorbance of product sample was ob-
served to be higher for 14 mL of R. sativus bioex-
tract [Fig. 4(a)]. The total °ow rate of addition
of the precursor was maintained at 2 mL/min
(AgNO3 was 1 mL/min and R. sativus bioextract
was 1 mL/min) with 14 mL R. sativus bioextract
in 84 mL deionized water (total 100 mL solution).
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The AgNO3 concentration was varied from 0.01 M
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to 0.02 M. All the experiments to study the e®ect
of AgNO3 concentration were carried out with
an addition of SDS at 0.001 g/mL concentration. It
is found that with an increase in the AgNO3 con-
centration, the absorbance is found to be increased
from 0.36 a.u. to 0.63 a.u. The decrease in the
absorbance with a decrease in the AgNO3 concen-
tration is attributed to the electron surface scat-
tering. The electron reaches the surface faster and
scatters quickly from these nanosize particles, which
results in the broadening of absorption peak width.
The peak width at half maximum (PWHM) values
are also found to be increased with a decrease in the
concentration of AgNO3 from 0.02 M to 0.0125 M.
0.7
0.6
0.5
Absorbance (a.u.)
0.4
0.3
0.2
0.1
0 0
400 450 500 550
Wavelength (nm)
(a)
Fig. 4. E®ect of AgNO3 concentration on (a) silver nanoparticle formation and (b) particle size distribution in a continuous
microreactor.
Green Route for Silver Nanoparticles Synthesis by R. Sativus Extract
Further with an increase in the concentration of
AgNO3 ; the particle size is found to be increased
[Fig. 4(b)]. At 0.01 M AgNO3 concentration, the
silver nanoparticle size range is in between 18 nm
to 39 nm. However, with an increase in the con-
centration of AgNO3 ; the particle size is found to
be in the range from 70 nm to 160 nm. The possible
reason for the increased particle size is attributed
to the increase in the number of silver ions with
an increase in the AgNO3 concentration. The
particle size of silver nanoparticle is found to be
reduced with an increase in the concentration
of AgNO3 from 0.0150 M to 0.0175 M. It is attributed
to formation of more number of nuclei with an
increase in the concentration of AgNO3. As there
is more nucleation events in the reaction mixture,
the Ag ions will get consumed quickly and there is no
signi¯cant growth of silver nanoparticle.
3.6. E®ect of surfactant (SDS) loading
Surfactant namely SDS was considered in the
present experimental investigation (Fig. 5). During
preparation of silver nanoparticles, there is a pos-
sibility of agglomeration of silver nanoparticles in
the absence of a surfactant. SDS is an anionic
surfactant with a negative charge on it. The re-
pulsive forces due to the presence of this negative
charge on the particle avoid the formation of
clusters of silver particles resulting in nanoparticle
size. SDS provides a capping e®ect that can control
nucleation and growth of nanoparticles.22 In order
to study the e®ect of SDS loading on absorbance
0.0100 M Silver Nitrate
30 0.0125 M Silver Nitrate
0.0150 M Silver Nitrate
25 0.0175 M Silver Nitrate
0.0125 M
0.0150 M
20
% Frequency
0.0200 M
15
10
5
600 650 700 10 40 70 100 130 160 190
Particle Size (nm)
(b)
1650019-7
 P. D. Jolhe et al.
(a)
Fig. 5. E®ect of SDS concentration on (a) silver nanoparticle formation and (b) particle size distribution in a continuous
microreactor.
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and particle size, the total °ow rate of addition of
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precursors was maintained at 2 mL/min (0.01 M
AgNO3 ¼ 1 mL/min and R. sativus bioextract ¼
1 mL/min). The absorbance was found to be in-
creased with an increase in the SDS quantity from
0 g to 0.0125 g and further it is found to be de-
creased for 0.0150 g SDS loading [Fig. 5(a)]. It is
observed that the absorbance value is increased
from 0.49 a.u. to 0.77 a.u. with an increase in the
SDS loading from 0 g to 0.0125 g, whereas, it is
found to be decreased to 0.069 a.u. for 0.0150 g
SDS loading. This evidently indicates that with
an increase in the SDS loading, there is an increase
in the number of nuclei formation which consecu-
tively leads to a decrease in the particle size of the
formed Ag nanoparticles. Further, the presence of
negative charge because of the anionic surfactant
i.e., SDS, also leads to the repulsion of forming
particles with negative charges, which signi¯cantly
reduces an agglomeration process of silver nano-
particles resulting into less average sized silver
nanoparticles.
The particle size of silver nanoparticles was
found to be decreased with an increase in the SDS
loading [Fig. 5(b)]. The particle size for 0.01 g and
0.0125 g SDS loading is found to be in the range of
83–185 nm. However, it is observed to be decreased
for 0.0150 g SDS loading and found in the range of
77–170 nm. It is attributed to the more stabilization
of forming nuclei and silver nanoparticles with sig-
ni¯cantly reduced aggregation due to an increase in
the SDS loading resulting in decreased particle size
of silver nanoparticles.22
1650019-8
(b)
3.7. E®ect of di®erent sized
microreactors and °ow rate
in microreactor
The e®ect of the size of microreactor on silver nano-
particle formation is depicted in Fig. 6(a). The ab-
sorbance value was found to be 0.82 a.u. and 0.30 a.u.
for 1.0 mm and 1.5 mm diameter microreactor, re-
spectively. The increase in the absorbance for 1.0 mm
sized microreactor is attributed to the formation of
more number of silver nanoparticles in the solution.45
However, for the case of 1.5 mm sized microreactor,
the absorbance value is found to be lesser which is
attributed to the formation of a lesser number of
silver nanoparticles with larger particle size. Further
an increased absorbance for 1.0 mm microreactor is
attributed to the formation of more nuclei because of
the better solute transfer rate leading to an increase
in the number of silver nanoparticles.45 Whereas, in
the case of the 1.5 mm microreactor system, the
channelling of the precursors may take place, which
leads to the formation of nuclei at limited locations,
resulting in the formation of a lesser number of
silver nanoparticles with large particle size. Further,
Fig. 6(b) depicts the e®ect of size of microreactor on
the particle size. The particle size range for 1.0 mm
and 1.5 mm microreactor is found to be 11–61 nm
and 28–190 nm, respectively. It is attributed to the
better solute transfer rate and the formation of
more nuclei resulting in particle, which is consistent
with the absorbance result reported above.
The e®ect of °ow rate on silver nanoparticle
formation and its particle size is depicted in Fig. 7.
 Green Route for Silver Nanoparticles Synthesis by R. Sativus Extract

1
30
1.0 mm
0.8 25
Absorbance (a.u.)

1.0 mm 1.5 mm

Frequency (%)
0.6 20
1.5 mm
15
0.4
10
0.2
5
0 0
400 450 500 550 600 650 700 0 25 50 75 100 125 150
Wavelength(nm) Particles Size (nm)

(a) (b)

Fig. 6. E®ect of size of microreactor (a) silver nanoparticle formation and (b) particle size distribution in a continuous
microreactor.

In order to study the e®ect of °ow rate, the values of on the particle size. The particle size range for
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feed °ow rates were selected in the range of 0.5 mL/ 0.5 mL/min is 149–257 nm, however, for 1 mL/min,
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min to 1.5 mL/min and the resulting absorbance it is 72 nm and 149 nm. The silver particle size range
values were measured. In order to study the e®ect is found to be in between 90 nm and 172 nm. The
of °ow rate on absorbance and the particle size of decrease in the particle size of silver nanoparticles is
silver nanoparticles, the concentration of AgNO3 attributed to higher °ow rate of precursors. With an
and the amount of R. sativus bioextract was increase in the °ow rate of precursor, the residence
maintained to be 0.01 M and 14 mL, respectively. time is decreased and also at higher °ow rate, the
All the experiments were carried out with an addi- turbulence will be higher resulting in e®ective mix-
tion of 0.01 g SDS. As depicted in Fig. 7(a), with the ing leading to the formation of lesser sized particles
decrease in the °ow rates, UV absorbance shows the with narrow size distribution. Patil et al.22 have
broadening of the peak. It is also found that with an reported that the higher °ow rate leads to the for-
increase in the °ow rate, the absorbance value is mation of silver nanoparticles with narrow particle
decreased from 1.22 a.u. to 0.44 a.u. It is attributed size distribution. Due to the higher °ow rate of
to the lesser residence time at higher °ow rate of precursors into the microreactor, there is a less
precursors, which leads to the formation of nuclei at residence time for nucleation and growth of silver
limited places resulting in lesser number of particles. nanoparticles. Hence at a higher °ow rate of pre-
Further, Fig. 7(b) shows the e®ect of the °ow rate cursors, the particle size is found to be lesser.

1.4 30 0.5 mL/min

1.0 mL/min
1.2
0.5 mL/min 25 1.5 mL/min
Absorbance(a.u.)

1 1.0 mL/min
% Frequency

1.5 mL/min 20
0.8
15
0.6
0.4 10

0.2 5
0
0
400 450 500 550 600 650 700
50 100 150 200 250
Wavelength(nm) Particle Size (nm)
(a) (b)

Fig. 7. E®ect of °ow rate on (a) absorbance and (b) particle size distribution of Ag nanoparticles in a microreactor.

1650019-9
 P. D. Jolhe et al.
10-2
Blank
10-1
Fig. 8. Agar plate method for antimicrobial study (E. Coli
Bacteria) of Ag nanoparticles prepared in a microreactor.
3.8. Antimicrobial study
by UNIVERSITY OF IOWA on 08/24/16. For personal use only.
Int. J. Nanosci. Downloaded from www.worldscientific.com
The antimicrobial activity of silver nanoparticles
was tested by using the standard zone of inhibition
(ZOI) microbiology assay as reported in Fig. 8.
Test bacterium Escherichia coli was included in
this study to assess the susceptibility pattern of
the compounds. Samples of 10 L of blank and two
dilutions of silver nanoparticles samples (10 1 and
10 2 g/L) were added into the wells and the plates
were incubated at 37  C for 24 h for observing the
inhibition rate. The highest bactericidal activity is
due to the silver cations released from silver nano-
particles that a®ect the membrane structure of
bacteria due to their interaction with silver cations
leading to the increased membrane permeability of
bacteria. The Ag nanoparticles showed inhibition
zone against the studied bacteria.
4. Conclusion
Synthesis of silver nanoparticles with the use of
AgNO3 and R. sativus bioextract was successfully
carried out in 1.0 mm and 1.5 mm sized microreactor
system. The use of natural, renewable and low cost
bioreducing agent has been employed in this re-
search work. The observations from di®erent char-
acterization techniques showed that if a su±cient
residence time is given to complete the reaction,
then the spiral geometry of the reactor helps to yield
monodisperse nanoparticles. The lower particle size
of the silver particles is found to be in between
18 nm and 39 nm for 0.01 g/mL SDS loading with
1 mL/min (0.01 M) AgNO3 and 1 mL/min R. sati-
vus bioextract °ow rate. Further, the observations
1650019-10
are consistent with the expected e®ects of °ow rate,
the amount of R. sativus bioextract, surfactant
concentration, AgNO3 concentration in the micro-
reactor system. Also the process of this research
work is the characteristic of continuous-°ow, the
raw materials i.e., aqueous silver nitrate and the
R. sativus bioextract, could be easily scaled up, re-
gardless of the microreactors. This method should
therefore be encouraged in the exploitation of the
mass production of silver nanoparticles by plant
extract.
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