nature inspired synthesis of gold nanoparticles - ijrise

International Journal of Research In Science & Engineering CHEMCON Special Issue : March 2018

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e-ISSN: 2394-8299 p-ISSN: 2394-8280

NATURE INSPIRED SYNTHESIS OF GOLD NANOPARTICLES Anupam Mukherjee1, Ishita Sinha2, Achinta Tripathy3, Rabindranath Jana4* 1

Graduate Student, Department of Chemical Engineering, Haldia Institute of Technology, W.B., India, E-mail: [email protected] 2 Graduate Student, Department of Chemical Engineering, Haldia Institute of Technology, W.B., India, E-mail: [email protected] 3 Graduate Student, Department of Chemical Engineering, Haldia Institute of Technology, W.B., India, E-mail: [email protected] 4 Associate Professor, Department of Chemical Engineering, Haldia Institute of Technology, W.B., India, * Corresponding Author, E-mail: [email protected] ABSTRACT Because of their small size, nanoparticles (NPs) can undergo unlikely and amazing interactions with a number of biomolecules within and on the surfaces of the human cells. These physical and chemical properties of NPs, including their biological, catalytic, electronic, magnetic, mechanical and optical properties, could be beneficial in various medical applications such as drug targeting, drug delivery, and drug formulations. The shape, size and the surface morphology of these particles have been found to be vital in tuning the properties of nano sized metal particles and their potential applications in different fields. Several methodologies including physical, electrochemical, sonochemical, photochemical and biochemical processes have been investigated for development of a suitable method of metallic NPs synthesis; however, most of these methods have utilized toxic and hazardous chemicals, had a high cost of production, or were subject to difficulty in purification of the end product. Here we report the synthesis of NPs using plants extracts, especially those with medicinal potential, and found to have a more rapid synthesis process, to display more stability, and better controlled shape and size, and to contain higher levels of important reducing agents in comparison to those produced from other organisms. The synthesized nanoparticle may be suitable as the carrier for drug delivery system in cancer treatment.

Keywords: Gold Nanoparticle, SEM, EDX, XRD, Cancer ----------------------------------------------------------------------------------------------------------------------------1. INTRODUCTION An extensive volume of literatures for the successful NPs synthesis using bioorganic compounds were available [15]. As a reducing agent and capping agent in biogenesis, a large member of organisms have been used in the biosynthesis of nanoparticles, including prokaryotes (bacteria and actinomycetes), eukaryotes (yeasts, fungi and plant), animal cells or cell lines and their biomolecules have been explored as a potential bio factory for synthesis of nanoparticles [6,7]. There is a report to synthesize Ag NPs (10 to 25 nm size) from Emblica Officinalis (amla, Indian Gooseberry) (Euphorbiaceae) fruit extract used as the reducing agent [8]. Amla fruit extract is used for helminthes management previously. Piper nigrum (Piperaceae) fruit extract showed spherical shaped Ag NPs (40-60nm) syntheses, cells [9]. The anticancer activity of eco-friendly gold nanoparticles against lung and liver cancer that gold nanoparticles has many applications in biomedical field [10]. Improving delivery of anticancer agents to tumors using nanoparticles is one of the most promising research arenas in the field of nanotechnology. XRD analysis showed that the strong four intense peaks indicate crystalline nature of nanoparticles. Morphology of nanoparticles was analyzed by TEM showed that they were mostly spherical in shape with size ranging from 6 to 13 nm. Abou Talib et al [11] found an innovative method for stabilization of gold nanoparticles (GNPs) in the aqueous solution using natural plant extract from Aloevera. GNPs were synthesized using conventional Citrate reduction method. pH of the GNPs was adjusted to 5.3 and 7.4 using 1 M NaOH and acetic acid. Morphological feature as well as surface protection of GNP surfaces was confirmed by Field Emission Scanning Electron Microscopic (FESEM) analysis and Fourier Transform Infra-Red (FTIR) Spectroscopy respectively. It was found that higher ratios of GNPs and Gel lead to more stabilization of nanoparticles). They suggested that Gel stabilized GNPs can be an exceptionally eco-friendly approach for numerous applications.

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Green biosynthesis of gold nanoparticles by onion peel extract and its Synthesis, characterization and biological activities was studied by J. K. Patra et. al [12]. In this way they developed a suitable, eco-friendly and nontoxic, one step synthesis procedure for the production of gold nanoparticles using the dried outer peel of onion. The formulated AuNPs were surface capped with a number of phenolic bioactive compounds, including cysteine derivatives, and had an average size of 45.42 nm based on various characterization techniques. This study demonstrated the potential for utilization of biological waste materials in the green synthesis of gold nanoparticles and their possible wide spectrum of applications in biomedical, cosmetic, food sector and pharmaceutical industries. The green synthesis of the AuNPs, was reported by S. J. Hwang et. al [13]. The intense diffraction peaks from the AuNPs represented the face-centered cubic structure of an atomic gold crystal, confirming the crystalline nature of the AuNPs. Angel Leiva et al [14] used chitosan polysaccharide and its graft copolymers with -caprolactone and Nvinyl-2-pyrrolidone chains to synthesis and stabilize gold nanoparticles. The nanoparticle synthesis was performed directly by reaction of polymers with potassium tetrachloroaurate in an aqueous medium and it was demonstrated that the polymers can act as reducing and stabilizing agents. They showed that the modification of chitosan considerably affected the copolymer performance during the gold nanoparticle synthesis. Metal nanoparticles have several applications such as optics, biomedical sciences, drug delivery, catalysis and electronics. D. Mukundan et. al [15] studied with the green synthesis of gold nanoparticles (AuNP) using leaves extract of Bauhinia tomentosa Linn and its in-vitro anticancer activity. Qualitative phytochemical analysis of the leaves extract showed the presence of tannins, saponins, flavonoids, alkaloids, proteins, steroids and quinones. Aqueous extract (pH 7.4 inherent pH of the extract) was reacted with 1 ml Chloroauric acid (HAuCl 4.3H2O) and kept at room temperature. The immediate change in color from pale yellow to ruby red indicated the reduction of Au3+ ions to Au0. The synthesized AuNP’s were monitored using UV-Visible spectrophotometer. Gold Surface Plasmon Resonance (SPR) occurred at 563 nm and steadily increased in intensity with longer duration of incubation time without shift in wavelength. FTIR spectra revealed the presence of reducing groups in the extract responsible for AuNP synthesis. FESEM analysis showed the presence of polydispersed spherical AuNP’s. EDAX confirmed the presence of elemental gold. HR-TEM showed that the gold nanoparticles were near spherical with average diameter 31.32 nm. The XRD peaks at 38.04, 44.12, 64.52, 77.49 and 81.53 showed that the AuNP’s were nanocrystalline with fcc crystal structure. The in-vitro anticancer activity confirmed by MTT assay on the cell lines of laryngeal HEp-2 carcinoma cells showed IC50 values of extract at 53.125 μg/mL and AuNP’s at 34.375 μg/mL. Use of various plants extracts for the synthesis of NPs was highlighted [16]. Most of the plant extracts contain proteins, or tannins or phenolic compounds which act as both reducing and capping agents, forming stable and shape - controlled Ag NPs. They noted that the pH of the plant extract also governs the time of synthesis of Ag NPs. The mechanism of the Ag NPs against micro and macro organism is discussed in terms of microbicidal and insecticidal value. Nazarul Islam et. al [17] report a facile and reproducible green extracellular synthetic route of highly stable gold nanoparticles. The aqueous gold ions when exposed to Salix alba L. leaves extract were bioreduced and resulted in the biosynthesis of Gold Nanoparticle (Au-WAs). The nanoparticles were characterized by UV-Visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Their stability was evaluated against varying volumes of pH and sodium chloride as well as at elevated temperature along with enzymes inhibition, antibacterial, antifungal, muscle and sedative activities. Tasnsneem Abbasi et all [18] presented a new method for the biomimetic synthesis of Gold Nanoparticles (GNPs), in which a highly invasive and harmful weed Ipomoea carnea has been employed for the first time as the main bioagent. Extracts of all the three basic components of the plant leaves, stem and root – were explored and were found to be suitable in effecting the GNP synthesis. The electron micrographs of the synthesized GNPs revealed the presence of particles of monodispersed spherical and polydispersed triangular, hexagonal, polygonal, rod and truncated triangular shapes in sizes ranging 3-40 and 10-100 nm, respectively. The presence of gold atoms was confirmed from the EDAX and X-Ray diffraction studies. The FT-IR spectral study indicated that the polysaccharides and proteins in the plants extract could have been responsible for the reduction of gold ions to GNPs and the latter’s stabilization. Sustainable and greener synthesis of intracellular gold nanoparticles using mushroom Flammulinavelutiples is reported by Kannan Badri Narayanan [19]. Incubation of a mushroom in chloroaurate solution resulted in the synthesis and immobilization of stable gold nanoparticles inside the mushroom mycelia. Transmission electron


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microscopic (TEM) analysis revealed the presence of gold nanoparticles (≤ 20 nm) inside the mycelia, primarily on the inner surface of the cell membrane. The reduction of Au3+ ions to Au0 and stabilization of gold nanoparticles occurred within 1h, and the formation of FCC crystalline gold nanoparticles was confirmed by X-Ray diffraction (XRD) analysis. In the present scenario of the nanotechnology, plants are better synthesizers as compared to the other biological methods due to the abundance of the availability of the plant resources when compared to the other forms of biological resources. Also, plants provide a better platform for nanoparticles synthesis as they are nontoxic chemicals and provide natural capping agents. Additionally, use of plant extracts also reduces the cost of microorganism isolation and culture media enhancing the cost competitive feasibility over nanoparticles synthesis by microorganisms. The advantage of using plant for the synthesis of nanoparticle is that they are easily available and safe to handle and possess a broad variability of secondary metabolites. 2. EXPERIMENTAL 2.1 Materials: Tetra chloroauric acid solution was prepared from a gold metal strip. About 100 ml aqua regia solution was prepared by adding 25 ml nitric acid (HNO3) and 75 ml hydrochloric acid (HCl) acid. The solid gold strip (43 mg) was added to the solution and heated at 60oC with constant stirring for 30 min to get deep brown coloured solution. Afterwards another 100 ml HCl was added to it and boiled for 2 hours to remove nitrogen dioxide completely, finally to get light yellow coloured tetrachloroauric acid solution. 2.2 Methods of synthesis of Gold Nanoparticles: (i) Using Guava Leaves 10 gms of Guava leaves were collected and washed properly. Then the leaves were grounded and squeezed which was then filtered. Next 50 ml of filtrate was added to 10 ml of chloroauric acid solution. That solution mixture was heated at 80oC for 1 hour. The colour changed from light yellow to light brown which confirmed the presence of gold nanoparticles. (ii) Using Lemon extract: Two lemons (250 gms) were collected and washed properly. It was crushed and squeezed to produce lemon juice, which was then filtered. Then 5 ml of the filtrate was added to 20 ml of chloroauric acid solution. This solution mixture was heated at 80oC for 1 hour and finally the colour changed to light orange. (iii) Using Tamarind: About 50 gm of tamarind was bought from market and washed properly. Then it was grounded and squeezed to produce tamarind solution, which was then filtered. Then 5 ml of this filtrate was added to 10 ml of chloroauric acid solution. The mixture was heated at 80oC for 1 hour and colour changed to light brown which showed the presence of GNPs. 2.3 Characterization: The SEM was also carried out by using a Scanning Electron Microscope (made ZEISS, Japan, at CRF Lab, I.I.T., Kharagpur). The XRD spectra were obtained using a Rigaku D/MAX-2000 diffractometer operated at 45 kV and 40 mA, with a Cu anode. The scanning range was 1– 90° at 0.5 deg./min. 3. RESULTS & DISCUSSION The prepared gold nanoparticles were characterized using high resolution SEM analysis. The samples were prepared by simple drop coating of the suspension of silver and gold solutions onto an electric clean glass and allowing the solvent (water) to evaporate. The samples were left to dry completely at room temperature.


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(a) (b) Fig. 1 SEM phase morphology of GNPs synthesized with Guava extract at different magnification, (a) at 2500x and (b) 5000x Figure 1(a) & (b) show representative SEM images recorded at different magnifications (2500 x and 5000 x) from drop-coated films of the gold nanoparticles synthesized by treating chloroauric acid solution with guava extract. The resulting gold nanoparticles were predominantly of uniform size. Higher magnification showed the average diameter of these nanoparticles to be about 10 to 50 nm.

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Fig. 2 SEM of Lemon Extract Solution at different magnifications (a) 50000x, (b) 100000x Figure 2(a) & (b), show representative SEM images recorded at different magnifications from drop-coated films of the gold nanoparticles synthesized by treating chloroauric acid solution with lemon extract. The resulting gold nanoparticles were predominantly of uniform size. It shows the average diameter of the nanoparticles to be about 20 to 35 nm.


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(c) (d) Fig. 3 SEM of Tamarind Extract Solution (a) 2500x, (b) 5000x (c) 25000x, (d) 50000x. Figure 3 (a), (b), (c) & (d) show representative SEM images recorded at different magnifications from drop-coated films of the gold nanoparticles synthesized by treating chloroauric acid solution with tamarind solution. The resulting gold nanoparticles were of uniform size of about 55 to 80 nm diameter.

Fig. 4 Electron Image of Lemon Extract Solution The Fig. 4 shows the energy dispersive X-ray analysis (EDX) of natural lemon derived gold nanoparticles reveal the strong signal in the gold region and confirms the formation of Au nanoparticles. Metallic gold nanocrystals generally show typical strong optical absorption peak was observed due to surface plasmon resonance. The electron image shows the uniform size and homogenous distribution of the nanoparticles formed. The percentage of different elements present with O having the highest weight percentage of 50.48, Si having 24.68%, Zn having 8%, Al having 2.7 %, Au having 6% and Pd having 7.42 %.


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Fig. 5 Electron Image of Tamarind Extract Solution The Fig. 5 shows the energy dispersive X-ray analysis (EDX) of natural tamarind derived gold NPs reveal strong signal in the gold region and confirms the formation of Au nanoparticles. Metallic gold nanocrystals generally show typical strong optical absorption peak was observed due to surfaceplasmon resonance. The electron image shows the uniform size and homogenous distribution of the nanoparticles formed. The percentage of different elements present with O having the highest weight percentage of 44.98, Si having 17.92 %, Al having 2.5 %, Au having 4.01%, Na having 6.09% and C having 25.2 %.

Fig 6 : Electron Image of Guava Extract Solution The Fig. 6 shows the energy dispersive X-ray analysis (EDX) of natural guava derived gold nanoparticles. It reveals the strong signal in the gold region and confirms the formation of Au nanoparticles. The electron image shows the uniform size and homogenous distribution of the nanoparticles formed. The percentage of different elements present with O having the highest weight percentage of 50.10, Au having 3.09 %, Mg having 2.57%, Na having 3.77 %, Pd having 1.66% and C having 38.81 %. Gold nanoparticles are versatile materials with a broad range of applications in a variety of fields. Researchers have coated gold particles with DNA and injected them into plant embryos or plant cells. This will ensure that some genetic material will enter the cells and transform them. This method enhances plant plastids.The July 2007 issue of Analytical Chemistry reported that scientists from Purdue University were able to use gold nanoparticles to detect breast cancer. Later it was also discovered that the nanoparticles could detect toxins and pathogens. The opticalelectronics properties of gold nanoparticles are being explored widely for use in high technology applications such as sensory probes, electronic conductors, therapeutic agents, organic photo voltaics, drug delivery in biological and medical applications, and catalysis. Other applications of gold nanoparticles include as an anti-biotic, anti-fungal, and anti-microbial agent when added in plastics, coatings, nanofibres and textiles, nanowires and catalyst applications, variety of sensors e.g., colorimetric sensor, therapeutic agent delivery, photodynamic therapy,


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biological imaging applications, probes for transmission electron microscopy, biomarkers in the diagnosis of cancers, heart diseases, and infectious agents. 4. CONCLUSIONS We successfully synthesized gold nanoparticles from tetra chloro auric acid. Depending on size, the color of the colloidal solution may be different, that means observing the color of colloidal solution we may have an idea about the size of the gold nanoparticles. The SEM results were obtained in the range of 10-50 nm in case of guava solution , 20-35 for lemon solution and 55-80 nm in case of tamarind solution which agrees with the theoretical range for cancer treatment which is below 100 nm. For further analysis the sample has been given for test. Bio-synthesized gold nanoparticles can be used in different medical purposes as it does not involve any toxic chemicals. Selection of proper bio process also may lead to the cost effective synthesis of gold nanoparticles (E.g, Using tamarind or lemonor guava). So we can conclude that the green synthesized gold nanoparticle has given us a better quality of life.

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