Synthesis of silver and copper oxide nanoparticles using Myristica fragrans fruit extract: Antimicrobial and catalytic applications
Graphical abstract
Introduction
For the last two decades, nanomaterials have gained much attention due to their interesting properties that can be attributed to the change in geometry, size, shape, and morphology when compared with bulk materials (Thangavel and Ramaraj, 2008; Nadagouda and Varma, 2006). Moreover, nanotechnology and natural science offer diverse and easy biosynthetic pathways that can extend the application of nanoparticles in catalysis, pollution control, agriculture, waste management, and in the biomedical field as antimicrobial, anticancer agents (Lewinski et al., 2008). Among the metal nanoparticles, copper and silver nanoparticles are comparatively more important due to their wide range of applications in biology (Nasrollahzadeh et al., 2019a, Nasrollahzadeh et al., 2019b). They are known to have a broad range of antimicrobial properties and most of them are not detrimental to human health (Koduru et al., 2018). Biosynthesis of nanoparticles is generally a bottom-up approach involving reduction and oxidation reactions which utilise plant extracts, bacteria, fungi as raw materials (Hebbalalu et al., 2013). Although the exact synthetic mechanism is still unknown, synthesis of nanoparticles requires the presence of reducing and stabilizing agents where the organic molecules are able to handle both the roles. Metal oxide nanoparticle possesses exclusive chemical and physical properties because of their high density and surface area. Developing environmentally benign methods for the synthesis of metal nanoparticles relies on the utilization of non toxic chemicals (Anastas and Kirchhoff, 2002). Use of microwave has emerged as an effective tool in synthesis of nanoparticles in aqueous media (Baruwati et al., 2009; Kou and Varma, 2012). Such green chemistry protocols protect the environment by reducing waste by utilizing renewable sources and energy efficiency (Baruwati and Varma, 2009).
Plant extract mediated synthesis of nanoparticles has been copiously reported in the recently. (Saratale et al., 2018). Nanoparticles have been synthesized from bio-resources utilizing the rich reservoir of alkaloids and flavonoids present in it (Nadagouda and Varma, 2008; Nadagouda et al., 2014). Such green nanoparticle synthesis is simple and possesses innumerable applications (Varma, 2012; Abdelghany et al., 2018). Biological applications of such nanoparticles include their potential cytotoxicity towards different cancerous cells (Jadhav et al., 2018a, Jadhav et al., 2018b), antimicrobial power (Zheng et al., 2018), antioxidant, DNA cleavage properties (Jadhav et al., 2018a, Jadhav et al., 2018b) and anticoagulant capacity (Tian et al., 2014). Metal oxide nanoparticle found out its application in optoelectronics (Yu et al., 2016), sensors (Cho et al., 2017) and in fuel cells (Sun et al., 2019). They have been also used in biomedical and environmental sensors (Belushkin et al., 2018). In addition to the above applications, silver nanoparticles are widely used in degradation of dyes (Polepalli and Rao, 2018) and in mosquito control (Sooresh et al., 2011). However, there are only a few reports on the catalytic activity of nanoparticles synthesized using plant materials (Xia et al., 2013; Nasrollahzadeh et al., 2019a, Nasrollahzadeh et al., 2019b).
Conventionally, Husigen's 1,3-dipolar cycloaddition reaction between azide and alkyne was utilized for the construction of triazole ring. This uncatalyzed reaction required high temperature but was slow in nature affording both 1,4- and 1,5-disubstituted triazoles in equal amounts (Huisgen, 1963). Introduction of copper (I) species as a catalyst for the regioselective synthesis of the 1,4-isomer has received wide attention after the work of Sharpless (Kolb et al., 2001), who coined the term Click Chemistry. It has a wide range of applications in organic chemistry (Bock et al., 2006; Meldal et al., 2017), medicinal chemistry (Anseth and Klok, 2016), polymers, material sciences (Lutz, 2007) and bioconjugation (Lutz and Zarafshani, 2008). Development of new synthetic protocols using principles of green chemistry are much sought after. In this context, green synthesis of metal nanoparticles using biosources has been suggested.
Myristica fragrans belongs to the family Myristicaceae, the source of the spices nutmeg and mace. Outer pericarp of the fruit possesses little commercial value and is usually thrown away after extracting the seed and aril. Myristica fragrans fruit is used for the treatment of digestive disorders in traditional medicines (Acuña et al., 2016). Its extract possesses antioxidant and anti-inflammatory properties and has been widely used in food industry (e.g., jam, pickle, cake, and jelly) and in beverage preparations (Sulaiman and Ooi, 2012). The pharmacological evaluation reveals that aqueous extract of the pericarp contains terpenoids, flavones, phenols, tannins, sugars etc. (Zhao et al., 2019; Pandey et al., 2016). In the present study, extract of the pericarp was used for preparing copper oxide and silver nanoparticles. The synthesized nanoparticles were well characterized. Further, the efficiency of copper oxide nanoparticle towards catalyzing the click reaction for the regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles and antimicrobial activity of the silver nanoparticle by disc diffusion method was investigated.
Section snippets
Plant material collection and processing
Myristica fragrans fruit (Fig. 1a) was collected from Thrissur, Kerala. The fruit was washed with distilled water and its pericarp (500 g) was separated from the seed. The pericarp was dried well under sun shade for four days to remove the moisture content and crushed into small pieces. It was boiled with water and the extract thus obtained was used for the synthesis of CuO and silver nanoparticles.
Characterization
All the reagents used were purchased from Merck chemicals, Bangalore, India, unless otherwise
Synthesis of CuO and Ag NPs nanoparticles
For the phytosynthesis of copper and silver nanoparticles, aqueous fruit extract of Myristica fragrans was used (Fig. 1b). The fruit extract was added to copper acetate solution and the resulting solution was irradiated under microwave for 5 min. Colour of the solution changed from blue to bluish green and then to greenish brown suspension within this period of time which was a clear indication of the formation of copper oxide nanoparticles (Fig. 1c). Copper oxide nanoparticles thus obtained
Conclusion
In conclusion, we have demonstrated a green, cost-effective, rapid synthesis of CuO and silver nanoparticle using Myristica fragrans fruit extract. The nanoparticles synthesized were characterized using analytical techniques like FT–IR, UV–Vis, FESEM, EDS, TEM etc. The CuO nanoparticle was found to be an excellent heterogeneous catalyst for CuAAC reaction in water. The catalyst can be recycled and reused five successive cycles with little compromise in the triazole yield. It was observed that
CRediT authorship contribution statement
Drishya Sasidharan: Writing - original draft, Data curation. T.R. Namitha: Methodology. Smera P. Johnson: Investigation, Resources. Vimala Jose: Conceptualization, Formal analysis. Paulson Mathew: Supervision, Funding acquisition, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
PM thanks the University Grants Commission (UGC), New Delhi for the generous support for a GCMS system under Innovative Programme (No.F.14-18/2013 Inno/ASIT). We thank SAIF, Cochin University of Science and Technology (CUSAT), Kerala, INDIA for providing NMR and other analytical data.
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