Preparation of gold nanoparticles from Mirabilis jalapa flowers by mmcsx

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									Indian Journal of Biochemistry & Biophysics
Vol. 47, June 2010, pp. 157-160




               Preparation of gold nanoparticles from Mirabilis jalapa flowers
                                                Padma S Vankar* and Dhara Bajpai
             Facility for Ecological and Analytical Testing (FEAT), Indian Institute of Technology, Kanpur 208 016, India

                                           Received 28 October 2009; revised 14 May 2010

         Biosynthesis of gold nanoparticles has emerged as an important area in nanotechnology and biotechnology due to
      growing need to develop environmentally benign technologies. Generally, nanoparticles are prepared by a variety of
      chemical methods which are not environmentally friendly. In the present study, we report a rapid and convenient method to
      reductively prepare gold nanoparticles from auric chloride using aqueous extract of Mirabilis jalapa flowers. The flower
      extract acts as a reducing agent and encapsulating cage for the gold nanoparticles. The production of gold nanoparticles has
      been done by the controlled reduction of the Au3+ ion to Au0. The formation of gold nanoparticles has been established by
      FT-IR and UV-Vis spectroscopy, as well as by TEM, XRD, EDAX and AFM. The study suggests that M. jalapa flowers can
      be a cheap source as a reductant for the production of gold nanoparticles.

      Keywords: Gold nanoparticles, Mirabilis jalapa, FT-IR, UV, X-Ray Diffraction, Energy Dispersive X-ray, Transmission
                electron microscopy, Atomic Force Microscopy

Plant extracts have been found to be cost-effective                   choice for the preparation of gold nanoparticles. Here,
and environment friendly for the large-scale synthesis                we report a rapid and convenient method to
of nanoparticles1. Reports have shown that                            reductively prepare gold nanoparticles from auric
microorganisms, such as bacteria and fungi are                        chloride at room-temperature in just 1-2 h using the
capable of synthesizing metal nanoparticles both intra                aqueous extract of M. jalapa flowers. The formation
and extra-cellularly. The gold particles of nanoscale                 of gold nanoparticles has been established by FT-IR
dimensions may be readily precipitated within                         and UV spectroscopy, as well as by TEM, XRD,
bacterial cells by incubation with Au3+ ions2. The                    EDAX and AFM.
nanocrystals of gold, silver and their alloys have also
been synthesized by reaction of the corresponding                     Materials and Methods
metal ions within the cells of lactic acid bacteria                   Plant material and preparation of extract and gold
present in buttermilk3. The alkalo-thermophilic                       nanoparticles
(extremophilic) actinomycete Thermomonospora spp                         The fresh flowers (20 g) of Mirabilis jalapa
have also been reported to synthesize high                            collected from Horticulture Department of Indian
concentration of gold nanoparticles of 8 nm average                   Institute of Technology, Kanpur were washed, finely
size with good monodispersity extra-cellularly4. Fungi                cut and soaked in 100 ml boiling distilled water for
are also capable of synthesizing gold nanoparticles5,6.               5-10 min and filtered through Whatman filter paper
Gold and silver nanoparticles have been synthesized                   no. 42. For preparation of gold nanoparticles, 5 ml of
within live alfalfa plants by gold/silver ion uptake                  flower extract was added into 45 ml 0.002 M AuCl4-
from solid media7.                                                    (purchased from Spectrochem Pvt Ltd, Kanpur)
   In our earlier work on natural dyeing of wool with                 solution and kept in dark for 1-2 h. The
Mirabilis jalapa flower extract8, we also found the                   morphological identification of gold nanoparticles
presence of pink colorant (anthocyanin) as an obvious                 was carried out by TEM and AFM.
——————                                                                UV-VIS and Fourier Transform-infrared (FT-IR) spectral
*Corresponding author                                                 analysis
Tel: +91-(512)2597844; Fax: +91-(512)2597436                             The bioreduction of Au3+ in aqueous solution was
E-mail: psv@ iitk.ac.in
                                                                      monitored by periodic sampling of aliquots (0.2 ml)
Abbreviations: AFM, atomic force microscopy; EDAX, energy
dispersive X-ray; FT-IR, Fourier Transform-Infrared TEM,              of the suspension, each time the sample was diluted
transmission electron microscopy; XRD, X ray diffraction.             with 2 ml deionized water and UV-VIS spectra was
158                                  INDIAN J. BIOCHEM. BIOPHYS., VOL. 47, JUNE 2010


recorded on Heλious α Thermo Electron Corporation
Spectrophotometer.
   FT-IR spectra of extracted dye and gold
nanoparticles were recorded on Vertex 70 model of
Bruker The residual solution of containing the
naoparticles was centrifuged at 4800 rpm for 10 min
and the resulting suspension was redispersed in 20 ml
sterile distilled water. The centrifuging and
redispersing process was repeated three-times.
Thereafter, the purified suspension was completely             Fig. 1—UV-Vis spectra of Mirabilis gold nanoparticles [A and B
dried at 60°C.                                                 are after and before bioreduction, respectively]

Transmission electron microscopy         (TEM)     and   AFM   bimetallic nanoparticles by reduction of the metal ions
observations of gold nanoparticles                             is possibly facilitated by reducing sugars and/or
   The biomass after reaction spontaneously                    terpenoids present in the neem leaf broth9.
precipitated at the bottom of conical flasks in 2 h.              It is generally recognized that UV-VIS
After precipitation, the suspension above the                  spectroscopy can be used to examine size-and
precipitate was sampled for TEM observations                   shape-controlled      nanoparticles     in     aqueous
performed on FEI TECNAI Machine having software                suspensions. Figure 1 shows the UV-Vis absorption
TECNAI G2 and EDAX Genesis Rev. 3.0 operated at                spectra recorded from the gold nanoparticles solution
an accelerating voltage of 120 kV. The TEM samples             after 2.0 h of bioreduction reaction (curve A) and the
were prepared by placing a drop of the aliquots on             flower extract (curve B). In the UV-Vis spectra
carbon-coated copper grids of aqueous suspension of            recorded at different intervals for monitoring the
gold nanoparticles and the water was allowed to                reaction, the appearance of a surface plasmon
evaporate. Size distribution of the resulting                  resonance (SPR) band at about 570 nm increased in
nanoparticles was estimated using high resolution The          intensity with time10. It also revealed the production
TEM images were obtained and energy dispersive                 of gold nanoparticles within 1 h. After addition of the
X-ray (EDAX) analyses were performed on a Tecnai               extract to the AuCl3 solution, the solution changed
F30 microscope. The colloidal suspension of gold               from dark pink to steel grey in about 1 h.
nanoparticles was cast on to a graphite substrate and             It is thought that phenolic acid-type biomolecules
they were measured by AFM in the contact mode on a             present in mirabilis flower extract might be
multimode scanning probe microscope (PicoScan)                 responsible for the reduction of chloroaurate ions10,
with a Nanoscope IIIa controller.                              and also for the stabilization of nanoparticles
   AFM data were obtained on Molecular Imaging                 throughout by electrostatic attraction. The initial
Agilent Machine and pictures were collected on                 metal ion concentrations and reaction time also play a
PicoScan software.Cantilevers µ Masch (Cu-Au) with             crucial role in the size obtained for these
Tip curvature less than 10 nm were used in Molecular           nanostructures. Biomolecular encapsulation of
Imaging probe.                                                 individually separated nanoparticles is advantageous
                                                               for bioconjugation and applications to (nano)
Results and Discussion                                         biotechnology, as these coatings are non-toxic and
Biosynthesis of gold nanoparticles by flower extract           easy to functionalize, and protect core nanoparticles
   Au3+, which is a soft metal, binds to the biomass           from deleterious reactions, such as oxidation.
mainly through amino and sulfydryl groups that are             Especially, in the case of gold nanoparticles,
considered soft ligands and carry more positive                biomolecular encapsulation would be one of the
charge at low pH values, making them available for             methods for stabilizing these nanoparticles.
the binding and reduction of Au3+ to Au0. Also,                   FT-IR absorption spectra can provide the
-COOH groups, which are abundant in the biomass                information about the chemical change of the
are protonated at low pHs and could also contribute to         functional groups involved in bioreduction. Figure 2
the binding of Au3+ ions, even though they are                 shows FT-IR absorption spectra of mirabilis flowers
considered as a hard ligand7. It has been reported9 that       extract before and after bioreduction. To a large
formation of pure metallic nanoparticles and                   extent, the band at 1101 cm−1 might be contributed by
                         VANKAR & BAJPAI : GOLD NANOPARTICLES FROM M. JALAPA FLOWERS                                        159




                                                                  Fig. 3—TEM pictures of gold nanoparticles formed by Mirabilis
                                                                  with capsulation cage

Fig. 2—FT-IR of Mirabilis flower extract and gold nanoparticles
generated from the Mirabilis




                                                                       Fig. 5—XRD of gold chloride and gold nanoparticles

                                                                  provided evidence for the extra-cellular formation
                                                                  of gold nanoparticles. The diffraction peaks at
Fig. 4—EDAX of gold nanoparticle prepared from Mirabilis
                                                                  2θ = 38.2º, 44.4º and 64.6º were identical with those
extract
                                                                  reported for standard gold metal (Au○). The presence
the –C–O groups of the polyols, such as flavones,                 of intense peaks corresponding to the nanoparticles
terpenoids and polysaccharides in the biomass11,12.               was in accordance with the Bragg reflections of gold
The disappearance of band at 1101 cm−1 after                      identified in the diffraction pattern13. A strong
bioreduction suggested that the polyols might be                  diffraction peak located at 38.2° was ascribed to the
partly responsible for the reduction of chloroaurate              {1 1 1} facets of face-centered cubic metal gold
ions. FT-IR analysis of bioextract before and after the           structures, while diffraction peaks of other two facets
addition of gold solution also revealed the strong                were much weak as shown in Fig. 5. These
bands at 1021, 1443, 1634 and 3428 cm−1. The band                 observations indicated that gold nanoparticles formed
at 1021 cm−1 corresponds to C–N stretching vibrations             by the reduction of Au3+ by flower extract were
of amine and at 1443 cm−1 corresponds to C–H and                  dominated by the {111} facets.
OH bending and 3428 cm−1 is characteristic of –NH                    AFM showed some typical topography of our
stretching of amide (II) band. The weaker band at                 samples. As can be seen it clearly resolves aggregates
1634 cm−1 corresponds to amide I, arisen due to                   of the order of 2000-4000 Å, it showed that gold
carbonyl stretch in proteins.                                     nanoparticles were resolved and that these aggregates
   The TEM images (Fig. 3) showed well-separated                  were constituted by smaller nanoparticles (gold
gold nanoparticles with occasional aggregation,                   nanoparticles). Figure 6a shows the AFM topographic
mainly spherical in the size and having three different           image of the gold nanoparticles ranging from 35.8 to
sized particles (159.2, 100 and 114.8 nm). These                  62.6 nms. The depth (Z-axis) was between 33.86 to
images clearly showed the presence of capping on the              140.84 Å at resolution of 3200 Å. AFM showed
gold nanoparticles and it was fascinating to note that            well-dispersed, heterogeneously-shaped nanoparticles
almost all the particles were separated from each                 of different size ranges i.e. 62.6 nm-41.56 Å;
other by not so uniform inter-particle distance.                  35.8 nm-33.86 Å;35.9 nm-140.84 Å ;53.7 nm-98.51 Å
   The EDAX analysis of the particles showed                      and 53.6 nm-46.95 Å.
presence of Au as shown in Fig. 4 that confirmed as                  The topographic image of one of the heterogeneous
presence of elemental Au0. The XRD analysis further               nanoparticles showed size ranging from 57.3 to
160                               INDIAN J. BIOCHEM. BIOPHYS., VOL. 47, JUNE 2010




                                                                  Fig. 7—Distribution of different sizes of gold nanoparticles

                                                             such as M. jalapa flower could produce metal
                                                             nanostructures in aqueous solution at ambient
                                                             temperature, avoiding the presence of hazardous and
                                                             toxic solvents.

                                                             Acknowledgement
                                                               The author (DB) expresses her sincere thanks to the
                                                             Council of Scientific and Industrial Research, New
                                                             Delhi for financial support for Senior Research
                                                             Fellowship award.

                                                             References
Fig. 6—AFM of gold nanoparticle by Mirabilis at resolution
                                                             1     Sastry M, Ahmad A, Khan M I & Kumar R (2003) Curr Sci
3200 Å (A) and 4000 Å (B)
                                                                   85, 162-170
                                                             2     Southam G & Beveridge T J (1996) Geochim Cosmochim
123 nm on surface depth of 91.8 to 339.4 Å at                      Acta 60, 4369-4376
resolution of 4000 Å. Figure 6b shows nanoparticles          3     Nair B & Pradeep T (2002) Cryst Growth Des 2, 293-298
ranging from 57.3 to 79.5 nm in the topographic              4     Ahmad A, Senapati S, Khan M I, Kumar R & Sastry M
image. The depth (Z-axis) was between 91.82 to                     (2003) Langmuir 19, 3550-3553
339.4 Å. Some of the particles had the following             5     Mukherjee P, Ahmad A, Mandal D, Senapati S, Sainkar, S R,
                                                                   Khan M I, Kumar R & Sastry M (2001) Angew Chem lnt Ed
dimensions: 79.5 nm-213.11 Å; 78.7 nm-167.25 Å;                    40, 3585-3588
57.3 nm-91.82 Å and 68.4 nm-339.4 Å. Figure 7                6     Mukherjee P, Senapati S, Ahmad A, Khan M I & Sastry M
shows the maximum size of gold nanoparticles                       (2002) Chem Biochem 3, 461-463
obtained was between 60-70 nm.                               7     Gardea-Torresdey J L, Parsons J G, Gomez E, Peralta Videa
                                                                   J, Troiani H E & Santiago P (2002) Nano Lett 2, 397-401
                                                             8     Vankar P S & Shanker R (2005) Colourage 2, 57-60
Conclusion                                                   9     Shivshankar S, Rai A, Ahmad A & Sastry M (2004)
   The reduction of Au3+ ions by M. jalapa flower                  J Colloid Interface Sci 275, 496-502
extract resulted in the formation of stable                  10    Vilchis-Nestor A R, Sánchez-Mendieta V, Camacho-López
                                                                   M A, Gómez-Espinosa R M, Camacho-López M A and
nanoparticles with multi-shaped morphologies with                  Arenas-Alatorre J A (2008) Mater Lett 62, 3103-3105
some of the particles having were size smaller than          11    Kang S M, Lee B S, Sang-gi Lee S & Choi I S (2008)
100 nm. The rate of reaction for the synthesis of                  Colloids Surfaces A: Physicochem Eng Aspects 313,
nanoparticles by this method (1.0 h) was rapid than                150-153
                                                             12    Shankar S S, Ahmad A, Pasricha R & Sastry M (2003)
Coriander leaf-mediated synthesis (12 h)14 and the                 J Mater Chem 13 1822-1826
microbes-mediated synthesis (24-120 h)15. Gold               13    Shankar S S, Ahmad A & Sastry M (2003) Biotechnol Prog
nanoparticles synthesized by the green chemistry                   19, 1627-1631
approach reported in this study may find potent use in       14    Narayanan B K & Sakthivel N (2008) Mater Lett 62,
biomedical     and    pharmaceutical     applications.             4588-4590
                                                             15    Sharma N C, Sahi S V, Nath S, Parsons J G, Gardea-
Furthermore, we demonstrated that use of a natural,                Torresdey J L & Pal T (2007) Environ Sci Technol 41,
renewable and low cost biological reducing agent,
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