Gnidia glauca flower extract mediated synthesis of gold nanoparticles and evaluation of its chemocatalytic potential
© Ghosh et al; licensee BioMed Central Ltd. 2012
Received: 2 January 2012
Accepted: 1 May 2012
Published: 1 May 2012
Novel approaches for synthesis of gold nanoparticles (AuNPs) are of utmost importance owing to its immense applications in diverse fields including catalysis, optics, medical diagnostics and therapeutics. We report on synthesis of AuNPs using Gnidia glauca flower extract (GGFE), its detailed characterization and evaluation of its chemocatalytic potential.
Synthesis of AuNPs using GGFE was monitored by UV-Vis spectroscopy and was found to be rapid that completed within 20 min. The concentration of chloroauric acid and temperature was optimized to be 0.7 mM and 50°C respectively. Bioreduced nanoparticles varied in morphology from nanotriangles to nanohexagons majority being spherical. AuNPs were characterized employing transmission electron microscopy, high resolution transmission electron microscopy. Confirmation of elemental gold was carried out by elemental mapping in scanning transmission electron microscopic mode, energy dispersive spectroscopy and X-ray diffraction studies. Spherical particles of size ~10 nm were found in majority. However, particles of larger dimensions were in range between 50-150 nm. The bioreduced AuNPs exhibited remarkable catalytic properties in a reduction reaction of 4-nitrophenol to 4-aminophenol by NaBH4 in aqueous phase.
The elaborate experimental evidences support that GGFE can provide an environmentally benign rapid route for synthesis of AuNPs that can be applied for various purposes. Biogenic AuNPs synthesized using GGFE exhibited excellent chemocatalytic potential.
KeywordsGnidia glauca Gold nanoparticles UV-Visible spectroscopy Transmission electron microscopy High resolution transmission electron microscopy Elemental mapping Energy dispersive spectroscopy Dynamic light scattering X-ray diffraction Chemocatalysis
Nanomaterials of various shapes and sizes have been the subject of utmost interest due to their potential applications in industries, biomedical diagnostics and electronics, over the past decade [1–10]. Most of the available chemical processes for synthesis of gold nanoparticles (AuNPs) involve toxic chemicals that get adsorbed on the surface, leading to adverse effects in medical applications. Presently there is a growing need to develop environmentally benign process for rapid synthesis of nanoparticles .
At present, biological methods have an increasing interest because of the necessity to develop new clean, cost-effective and efficient synthesis techniques. Lately, many biological systems such as bacteria, yeast, fungi and several plant extracts have been investigated due to their ability to reduce metal ions and form nanoparticles [12–22]. Synthesis of nanoparticles employing plants can potentially render more biocompatibility to the nanoparticles [23–25].
In this work, we have investigated the biosynthesis of AuNPs using Gnidia glauca flower extract (GGFE) as a clean technology. G. glauca is an endemic flora of Western Ghats of India. It has an array of medicinal applications in sore throat, abdominal pain, wounds, burns, and snake bites, contusions, swellings, back ache, and joint ache [29, 30]. Recently, we have reported its antidiabetic property . However, there are no reports till date that documents its potential in nanobiotechnology to synthesize nanoparticles and thereby evaluating its chemocatalytic applications.
Herein, we report the biogenic synthesis of AuNPs using aqueous extract of G. glauca flower for reduction of Au3+ ions. We also investigated the effects of reaction conditions such as time course, reaction temperature and concentration of chloroauric acid on the rate of synthesis of the AuNPs. Further, we demonstrated its chemocatalytic potential in reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).
Results and discussion
Biosynthesis of AuNPs by GGFE
TEM, HRTEM and DLS
Fourier Transform Infrared Spectroscopy (FTIR) analysis
Chemoctalytic property of AuNPs
In conclusion GGFE mediated synthesis of AuNPs has been demonstrated to be a rapid and environmentally benign route. Variation of reaction conditions had pronounced effect on the reaction kinetics. Optimum conditions for maximum synthesis were found to be 0.7 mM of chloroauric acid at 50°C. AuNPs with exotic shapes like nanoprisms, nanotriangles, hexagons trapezoids were synthesized. Spherical nanoparticles were in abundance which were found to be face centered cubic (FCC) structured gold (111). Bioreduced AuNPs showed excellent catalytic properties in a reduction reaction of 4-nitrophenol to 4-aminophenol by NaBH4 in aqueous phase. Thus this rapid, eco-friendly and economical route can be used to synthesize AuNPs with wide biotechnological and chemical applications.
Materials and methods
Plant material and preparation of extract
G. glauca flowers were collected from Western Ghats of Maharashtra, India. The flowers were thoroughly washed in running tap water for 15 min and then shade dried for 2 days at room temperature. Dry flowers were ground into fine powder in an electric blender. 5 g of this powder was suspended in 100 mL of distilled water in a 300 mL Erlenmeyer flask followed by boiling for 5 min before finally decanting it. The extract obtained was filtered through Whatman filter paper No.1. The filtrate was collected and stored at 4°C which was used throughout all the experiments.
Synthesis of gold nanoparticles
Reduction of Au3+ ions was initiated by addition of 5 mL of GGFE to 95 mL of 10-3 M aqueous chloroauric acid solution in a 500 mL Erlenmeyer flask. The pH of the extract was found to be neutral. Thereafter, the flasks were shaken at a rotation rate of 150 rpm in the dark at 40°C. Reduction of the Au3+ ions was monitored by measuring the UV-vis spectra of the solution at regular intervals on a UV-1650CP Schimadzu spectrophotometer operated at resolution of 1 nm. Effects of temperature and concentration of chloroauric acid on the rate of AuNPs were studied by carrying out the reaction in water bath at 4-50°C with reflux and by varying the concentration of chloroauric acid from 0.1-5 mM.
Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and Dynamic Light Scattering (DLS) measurements
Morphology of the bioreduced AuNPs was studied by transmission electron microscopy (Tecnai 12 cryo TEM, FEI, Netherland). Further the size and shape of the AuNPs were characterized by JEOL-JEM-2100 higher resolution transmission electron microscope (HRTEM) coupled with elemental composition mapping under scanning transmission electron microscopic mode (STEM). Energy dispersive spectra of AuNPs was taken in the energy dispersive spectrometer (EDS) equipped in JEOL JSM 6360A analytical scanning electron microscope at an energy range 0-20 keV confirmed the synthesis of AuNPs using GGFE. The size of particles was analyzed by using the dynamic light scattering equipment (Zetasizer Nano-2590, Malvern Instruments Ltd, Worcestershire, UK) in 3 mL of reaction mixture in a polysterene cuvette.
X ray diffraction (XRD) measurements
The phase formation of bio-reduced AuNPs was studied with the help of XRD. The diffraction data of thoroughly dried thin films of nanoparticles on glass slides was recorded on D 8 Advanced Brucker X ray diffractometer with Cu Kα (1.54 Å) source.
Fourier Transform Infrared (FTIR) spectroscopy
AuNPs synthesized after 20 min of reaction between 1 mM chloroauric acid solution and GGFE were centrifuged at 10,000 rpm for 15 min at room temperature, following which the pellet was redispersed in sterile distilled water to remove any uncoordinated biological molecules. In order to ensure better separation of free entities from the nanoparticles, the process of centrifugation and redispersion in sterile distilled water was repeated thrice. The purified pellet was then dried and subjected to FTIR (Shimadzu IR Affinity) spectroscopy measurement using the potassium bromide (KBr) pellet technique in the diffused reflection mode at a resolution of 4 cm-1. Au nanoparticle powder was mixed with KBr and subjected to IR source 500-4000 cm-1. Similar process was used for the FTIR study of GGFE before and after bioreduction.
Catalytic reduction of 4-nitrophenol
The catalytic reduction of 4-NP was studied in a standard quartz cuvette by adding 0.8 mL of aqueous NaBH4 solution (1.0 mM) to 1.0 mL of 4-NP aqueous solution (0.1 mM). Then 200 μL of aqueous suspension of AuNPs (0.1 mM) was introduced into the solution and time dependent absorption spectra were recorded after every 5 min in the range of 200-800 nm at 25°C. The progress of reaction was monitored by UV- visible spectrophotometer as both the starting material, 4-NP and the product 4-AP shows a different absorption in the UV-visible region.
S. Ghosh thanks Council of Scientific and Industrial Research (CSIR, Government of India) for Senior Research Fellowship (09/137(0516)/2012-EMR-I). Authors acknowledge Institute of Bioinformatics and Biotechnology, University of Pune, Pune-411007, India for financial support for the work. The authors acknowledge use of TEM facilities in Chemical Engineering and CRNTS funded by the DST through Nanomission and IRPHA schemes. The authors thank Dr. M. Jayakannan, Indian Institute of Science Education and Research (IISER), Pune for DLS facility.
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