Green synthesis of novel Ag–Cu and Ag–Znbimetallic nanoparticles and their in vitro biological, eco-toxicity and catalytic studies
Graphical abstract
Introduction
In recent years, effluents from pharmaceutical and textile industries have been recognized as a new threat due to their unwarranted drugs and dyes, which are lethal/toxic to humans and environment [1]. Dyes are organic molecules which are impossible for biological degradation. Therefore, the degradation of these toxic dyes/contaminants requires significant research and scientific attention. It is imperative to reduce/remove these dyes from wastewater as it is undeniably affecting the life quality [2], [3]. Among them, azo dyes like rhodamine-B (rh-B) and methyl orange (MO) being cost effective, durable and versatile are extremely applied in textile industries [4]. Various existing conventional techniques such as filtration, membrane systems, chemical precipitation, adsorption and ion-exchange are employed in water remediation, which are non-destructive and time consuming. Hence, it is highly essential to eliminate these toxic dyes and other organic contaminants with effective catalyst constituents [5], [6]. Environmental nanotechnology plays a vital part in developing innovative, economical and eco-friendly techniques to detect, degrade and eliminate these toxic dyes/contaminants [7], [8]. Degradation/reduction of azo dyes by NPs as a remarkable catalyst in the presence of NaBH4 is a novel technique and rapidly gaining attention for the degradation of toxic contaminants in the wastewater [9], [10], [11], [12], [13].
BNPs are favoured over their counter parts monometallic NPs (MNPs) because of their significantly enhanced optical, catalytic and biological attributes [14]. BNPs have two distinctive metal atoms bound together into one single NP. Apart from the amalgamation of attributes associated by the existence of two distinct metals, it is also projected that BNPs might exhibit novel attributes because of the synergistic effects of the metals combined [15]. BNPs potential properties are defined by the arrangement of the metal atoms [16]. BNPs orientation could be core–shell, hetero structure, multi shell, cluster-in-cluster and random alloy which is significantly influenced by the redox potentials of the metal ions along with the nature of reducing agent(s) used [15], [17]. Application of various reducing agent(s) and metal ion(s) will affect the morphological features of BNPs eventually modifying their characteristics [18]. The colour exhibited by the colloidal dispersions of BNPs can also be affected by their composition, shape, size and more significantly by distribution of their metal ions. Colour of solution for alloy structures is largely because of the presence of excess metal ions while for core–shell structures it is mainly due to the metal present over the NPs surface.
BNPs are prominent in diverse fields like medicine, catalysis and pharmaceuticals, it is mainly due to their structure, morphology and composition [15]. The fabrication process also matters as it directs the crystal structure and metal ions distribution of the BNPs. BNPs are conventionally synthesized either through sequential/successive reduction or co-reduction/simultaneous reduction [19]. Among the various chemical and physical techniques used for the BNPs synthesis, the most regularly employed technique is the reduction of chemicals in water based solutions, which obtains the BNPs of various features [15]. But, these synthesis processes are high labour demanding, not economical and normally requires hazardous/toxic chemicals [20], [21]. In this regard, a safer, greener and eco-friendlier process is extremely required.
Biological classifications such as bacteria, fungi, yeast and plants have shown great potential as bioreactors in the fabrication of NPs [20], [22], [23], [24]. Among them, plants have demonstrated their potential to be significant and extremely advantageous over the others because of their huge availability, economical and mainly they are safer to living organisms and environment [19]. Secondary metabolites (phytochemicals/bio-active compounds) are present in plant extracts which can reduce the metal ions and promote the NPs formation [25]. More importantly, employing plant extracts for NPs fabrication can be scaled up effortlessly for large-scale fabrication. Bio-fabricated BNPs are now widely applied in the fields of drug delivery, labelling, luminescence tagging, imaging and biomedical field because of their compatible nature in in vivo screening [26]. Therefore, an easy, economical and environment friendly process for the bio-fabrication of Ag–Cu and Ag–Zn BNPs was developed and validated in this work.
In view of this, there is an immediate requirement in the development of eco-friendly approach to fabricate BNPs with superior biomedical potential without involving hazardous chemicals. Traditional medicinal plants are always favoured due to their biocompatibility, proficient and swift fabrication process [27], [28], [29]. A. muricata has enormous therapeutic importance in traditional medicine as per literature for anti-bacterial, anti-fungal, larvicidal, anti-oxidative, wound healing, anti-inflammatory, anti-diabetic and anti-cancer properties [10], [30]. So far, bio-fabrication of Ag–Cu and Ag–Zn BNPs using A. muricata was not yet reported. The objectives of the work were: (i) synthesis of Ag–Cu and Ag–Zn BNPs using aqueous A. muricata leaf extract (AMLE) and their characterization, (ii) evaluating their biological potential using several in vitro assays, (iii) role of BNPs as catalyst in the degradation of textile dyes and (iv) to determine the eco-toxicity of BNPs using brine shrimp model.
Section snippets
Materials
A. muricata leaves were collected from School of Life Sciences, University of Hyderabad (Telangana, India). Silver Nitrate (AgNO3), copper (II) sulphate pentahydrate (CuSO4.5H2O), zinc chloride dihydraye (ZnCl2.2H2O), 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH), dimethyl sulfoxide (DMSO), rhodamine-B,methyl orange and sodium borohydride were purchased from Hi-media Laboratories. -glucosidase and 4-nitrophenyl--D-glucopyranoside (4-NGP) were purchased from Sisco Research Laboratories (P)
Characterization studies
FTIR spectrum specified the occurrence of phytochemicals which might be accountable for the fabrication of BNPs by showing strong absorption peaks at 3478, 2940, 1668, 1450, 1080 and 659 cm −1 (Fig. 1a). BNPs morphology was confirmed by using SEM analysis (Fig. 1c). BNPs showed spherical structures and seem to be agglomerated. EDX spectrum confirms the presence of Ag (49.32%) and Cu (19.21%) in Ag–Cu BNPs. Whereas presence of Ag (52.85%) and Zn (29.08%) in Ag–Zn BNPs. Therefore, EDX spectrum
Conclusion
This is the first report on the rapid and efficient synthesis of Ag–Cu and Ag–Zn BNPs fabricated using AMLE. Both the BNPs showed spherical structures. The bio-fabricated BNPs showed anti-bacterial, protein denaturation inhibition, anti-diabetic, anti-oxidative and anti-cancer potentials. Ag–Cu BNPs displayed good catalytic potential compared to Ag–Zn BNPs. Based on the results, Ag–Cu BNPs showed better potential compared to Ag–Zn BNPs in all the investigated studies. However, brine shrimp
CRediT authorship contribution statement
Aditya Velidandi: Conceptualization, Methodology, Data curation, Writing - original draft. Ninian Prem Prashanth Pabbathi: Writing - review & editing. Swati Dahariya: Schematic representation. Rama Raju Baadhe: Supervision.
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
Authors thank the Director, National Institute of Technology, Warangal, Telangana, India for providing the lab facilities required for the work. Also thank the M.H.R.D. for providing the fellowship. All authors approved the version of the manuscript to be published.
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