UV–Vis Spectrophotometer: Fig. 1, comprises the room-temperature optical absorption of Sn-ZrO2 nanocomposites in the range of 200–800 nm. The sharp absorption peak seen at around 260 nm can be attributed to ZrO2. (Chelliah et al. 2023). The synthesized nanocomposites demonstrated absorbance band from 280-550 nm shows deposition of Sn nanoparticles on the surface of nanocomposites successfully (Sohail et al. 2020).
FTIR analysis: Fig. 2 reveals the FTIR spectrum of green synthesis Sn-ZrO2 nanocomposites. The characteristic broad peaks of OH groups are found at 3428.71 and 1628.34 cm-1 corresponds to the water molecules that have been absorbed on the surface of the nanoparticles. The stretching and bending vibrational modes of the water molecule are responsible for these broad peaks (Sagadevan et al. 2016). The weak bands at 2922.36, 2852.34, and 1384.31 cm−1were associated with the vibrations of organic residuals (Alharthi et al. 2020). The absorption band that was most prominent and sharpest emerged at 1121.69 and 617.74, cm−1 potentially indicating a correlation with the Zr–O bonds. The bending vibration of hydroxyl groups attached to ZrO2 is responsible for the peaks at 1121.69 cm−1 and 617.74 cm−1. The Zr–O vibration is represented by the band at 617.74 cm−1, and the breadth of the band indicates that the ZrO2 powders are nano crystals (Yakout et al. 2014).
XRD: X-ray diffraction measurements were used to investigate the crystallinity and phase form of the synthesised nanomaterials. Fig. 3 demonstrate the XRD pattern of Sn-ZrO2 nanocomposites and bare ZrO2 nanoparticles. The diffraction peaks in a wide range angle of 2θ are at 30.64°, 35.22°, 50.26°, and 60.17° corresponds to the crystal planes of (101), (110), (112), and (211), respectively, attributed to the preparation of monoclinic phase of ZrO2 nanoparticles (Horti et al. 2020) (JCPDS card no. 01‐075‐2550). Comparison of XRD pattern reveals the appearance of strong intense peaks at 2θ = 30.10° and 35.05° to be (101) and (110) crystal planes of Sn doping on ZrO2 as shown in Fig. 3 (Długosz et al. 2021). The XRD patterns do not exhibit distinctive peaks associated with Sn, indicating that all Sn atoms have successfully integrated into the ZrO2 lattice. Additionally, the absence of any other diffraction peaks confirms the synthesized nanocomposites high purity.
SEM and EDS analyses
The detailed morphology, particle size, and shape of the biomorphic Sn-ZrO₂ nanocomposites were examined using SEM analysis. The results revealed a non-uniform distribution of spherical tin particles on the surface of zirconia nanoparicles. The average size of Sn-ZrO2 nanocomposites is 25nm-50nm (Fig. 4a, b). The elemental composition of the Sn-ZrO₂ nanocomposites was determined by EDS analysis, confirming the presence of zirconium (Zr), tin (Sn), and oxygen (O) as shown in Fig. 5. Additional presence of elements (calcium) is also observed due to the presence of some phytochemicals from extract.
Adsorption performance of Sn-ZrO2 nanocomposites: This experimental work was conducted using a 10 ppm MG dye solution. 30 mg of Sn-ZrO2 nanocomposites were put to a beaker containing 20ml of MG dye solution. The mixture is shaken constantly for 25 minutes or until equilibrium is reached. The Sn-ZrO2 nanocomposites was used to study the adsorption of MG dye from an aqueous solution at different dye concentrations, contact times, dosages of the adsorbent, pH levels, and temperatures. The absorbent was changed from 5 to 40 mg/L while all other parameters remained same. The pH was adjusted to a range between 3 and 10 ppm using 0.1 M HCl and 0.1 M NaOH solutions. The shake took longer than five minutes to complete. The adsorbate solution was taken out and filtered once the allotted time had elapsed in order to isolate the adsorbent. Following filtering, a UV-Vis spectrophotometer that had previously been calibrated was used to measure the solution's concentration at 615 nm.
Alterations in adsorbent dose: Doses are crucial during the adsorption process. To investigate the effect of the Sn-ZrO2 nanocomposites dosage on the adsorption of MG dye (10 mg/L), adsorbent dosages ranging from 5 mg to 40 mg were used. The removal effectiveness was increased from 5 to 40 mg of Sn-ZrO2 nanocomposites, as shown in Fig. 6(a). This is because larger surface areas and more active sites are present in adsorbent. It was shown that the Sn-ZrO2 nanocomposites had an optimal dose of 30 mg. Once the optimal adsorbent dose has been reached, the removal efficiency falls.
Variation with pH: Since pH influences the surface charge of the adsorbate (MG dye) and Sn-ZrO2 nanocomposites adsorbent, it plays a significant part in adsorption processes. The influence of pH on the effectiveness of nanocomposites' removal of MG dye is shown in Fig. 6b. To adjust the required pH, 0.1 M sodium hydroxide or 0.1 M hydrochloric acid was used. As the pH rose from 8 to 10, the removal efficiency significantly declined after increasing from 3 to 8.
Effect of temperature: Temperature is thought to be a significant element that affects how well the MG is adsorbed and removed. At various temperatures between 303 and 353 K, the adsorbent dosage (30 mg/L), pH (8), contact period is 25 min, and constant agitation speed (450 rpm) were maintained in order to assess the impact of temperature on MG dye adsortion. As the temperature was elevated from 303 to 353 K, the rate of MG adsorption on Sn-ZrO2 nanocomposites decreased, as shown in Fig. 7(a). This suggests that the adsorption process was somewhat endothermic.
Influence of contact time: Analyzing the effect of the time of contact is important because the results of this type of study provide basic information about the rate at which the adsorption process reaches equilibrium. The effect of altering the contact time within the range of 15 to 20 minutes on the adsorption capacity was examined, keeping all other parameters fixed. The experiment started with fast dye adsorption, which gradually slowed down when the equilibrium condition was approached after around 15-20 minutes, based on the results displayed in Fig 7(b).
Fig. 8 outlines a proposed mechanism for the formation of Sn-ZrO2 nanocomposites. Amorphous hydrous oxide precipitates are formed when zirconium nitrate is hydrolyzed in aqueous circumstances, resulting in Zr(OH)4, which is naturally unstable and prone to condensation processes (Muthulakshmi et al. 2023; Chelliah et al. 2023). These condensation reactions are catalyzed by the hydroxyl groups present in banana peel extract, which are renowned for their antioxidant properties.
Meanwhile, in the aqueous solution, tin chloride quickly separates into tin and chloride ions. As seen in the Fig. 8, the reducing phytochemicals in the extract bind and cap the tin ions to produce stable nanoparticles. The primary organic substances accountable for this process include the carotenoids and other phytonutrients found in banana peel extract, as well as anthocyanins, delphinidin, cyaniding, and catecholamines (Hikal et al 2022). The resultant Sn-ZrO2 nanocomposites are then subjected to a 500°C calcination process in order to remove remaining phytochemical residue and water molecules.
Antimicrobial activities of synthesised Sn-ZrO2 nanocomposites
Green synthesized Sn-ZrO2 nanocomposites and ZrO2 nanoparticles were tested against Gram positive and Gram negative bacteria, including B. subtilis, S. aureus, K. pneumonia and P. aeruginosa. Fig. 9 illustrates the zone of inhibition observed in bacteria due to the synthesized Sn-ZrO₂ nanocomposites at four different concentrations, compared to ZrO₂ nanoparticles. At an 80 µg/mL concentration of Sn-ZrO₂ nanocomposites, the largest zone of inhibition was recorded for K. pneumoniae (21 mm), followed by B. subtilis (20 mm). The smallest inhibitory zone was observed for S. aureus (5 mm) at a 20 µg/mL concentration of Sn-ZrO₂ nanocomposites. Through conducting studies with varying concentrations of nanocomposites, we discovered that the zone of inhibition rises as the concentration of Sn-ZrO2 nanocomposites increases (Table 1). Bacterial membrane integrity is further compromised by lipid peroxidation, which is influenced by elevated levels of ROS. As the concentration of nanoparticles rises, the breakdown of the bacterial cell wall causes the bacteria to die (Ozdal et al. 2022). The likelihood that the nanoparticles will penetrate and harm the bacterial membrane increases with their size (Ozdal et al. 2022). The passage of nanoparticles across the plasma membrane has been facilitated by the presence of ion channels and transporter protein (Chen et al. 2020). The increase level of ROS affects lipid peroxidation in bacteria which further influence the integrity of bacterial membrane. The destruction of the bacterial cell wall results bacterial death with increase in concentration of nanoparticles (Juan et al. 2021).
In comparison to ZrO2 nanoparticles, the Sn-ZrO2 nanocomposites exhibits a larger zone of inhibition. When tin ions are released from a Sn-ZrO2 nanocomposites, it strengthens its ability to connect with bacterial enzymes that inactivate bio cells by breaking through their cell walls and damaging the bacteria. (Nikolova et al. 2020).
Table 1: Zone of inhibition (mm) at various concentrations of green-synthesised Sn-ZrO2 nanocomposites and ZrO2 nanoparticles.
|
Zone of Inhibition in mm
|
Gram negative bacteria
|
Gram positive bacteria
|
Concentration
|
K. pneumoniae
|
P. aeruginosa
|
B. subtilis
|
S. aureus
|
ZrO2
|
Sn-ZrO2
|
ZrO2
|
Sn-ZrO2
|
ZrO2
|
Sn-ZrO2
|
ZrO2
|
Sn-ZrO2
|
20µg/ml
|
8
|
12
|
5
|
8
|
7
|
9
|
4
|
5
|
40 µg/ml
|
10
|
13
|
7
|
10
|
12
|
14
|
6
|
8
|
60 µg/ml
|
14
|
17
|
10
|
15
|
16
|
18
|
9
|
12
|
80 µg/ml
|
16
|
21
|
11
|
18
|
18
|
20
|
10
|
13
|
Similarly, ZrO2 nanoparticles and green-synthesised Sn-ZrO2 nanocomposites were tested for their antifungal properties against two different fungi, C. albicans and C. tropicalis, as shown in Fig. 10. The synthesized Sn-ZrO2 nanocomposites had strong antifungal activity against C. albicans, but only weak activity against C. tropicalis. As shown in Table 2, a relatively small amount of green Sn-ZrO₂ nanocomposites (20 µg/mL) was sufficient to disrupt the fungal cell membrane and ultimately kill the fungi. Comparing the antifungal activity of the synthesized Sn-ZrO2 nanocomposites to ZrO2 nanoparticles, it demonstrates a greater zone of inhibition of Sn-ZrO2 nanocomposites much like the antibacterial assay. The higher antifungal activity of synthesised Sn-ZrO2 nanocomposites was partly attributed to the smaller particle size attained through sonication. This is because smaller particles have a larger surface to volume ratio, which permits more drug molecules to be adsorbed on the surface. These molecules are anticipated to act as a powerful agent in breaking down cell walls (Bruna et al. 2021). The findings show that, in comparison to ZrO2 nanoparticles, synthesized Sn-ZrO2 nanocomposites is a more effective antimicrobial agent with a greater potential to kill germs.
Table 2: Zone of inhibition (mm) at different concentrations of green synthesised Sn-ZrO2 nanocomposites and ZrO2 nanoparticles against C. albicans and C. tropicalis
Concentration
|
Zone of Inhibition in mm
|
C. albicans
|
C. tropicalis
|
ZrO2
|
Sn-ZrO2
|
ZrO2
|
Sn-ZrO2
|
20µg/ml
|
4
|
8
|
2
|
4
|
40 µg/ml
|
6
|
9
|
4.2
|
6.5
|
60 µg/ml
|
9.2
|
11
|
6
|
8.3
|
80 µg/ml
|
11.5
|
13
|
9
|
10.4
|
Nonetheless, Musa paradisiaca has long been a well-known traditional herb used in medicinal field. Its exceptional biological potentials are an added benefit, and combined with the potent biological properties of tin and ZrO2, these properties would greatly encourage the green synthesis of Sn-ZrO2 nanocomposites utilizing this well-known herb. Previous research has also shown that biosynthesised nanoparticles have potent antimicrobial efficacy than pure chemically synthesized nanoparticles. (Khan et al. 2020).
Antioxidant activity of Sn-ZrO2 nanocomposites
Free radicals are neutralized by an antioxidant substance, which halts the oxidation process. Green synthesised Sn-ZrO2 nanocomposites and ZrO2 nanoparticles were tested against DPPH at various doses in an antioxidant assay (Fig. 11a). Significantly, Sn-ZrO2 nanocomposites showed higher radical scavenging activity than ZrO2 nanoparticles, indicating that the inclusion of tin particles improves the antioxidant nature of nanocomposites by effectively separating electron-hole pairs (Tran et al. 2022). The findings demonstrated that the Sn-ZrO2 nanocomposites inhibits DPPH activity in a dose-dependent manner, means that radical scavenging assay enhances with the increase in concentration of the nanocomposites.
The antioxidant experiment was conducted against ABTS using varying quantities of ZrO2 nanoparticles and green synthesised Sn-ZrO2 nanocomposites (Fig. 11b). Peels of Musa paradisiaca are rich in bioactive substances (polyphenols and oils containing essential fatty acids) that may be able to be scavenged because of their hydroxyl groups (Widoyanti et al. 2023). Similar to DPPH scavenging, dose-dependent action for ABTS was also observed. At greater concentrations, the green-synthesised Sn-ZrO2 nanocomposites demonstrated stronger activity in blocking the ABTS radical than ZrO2 nanoparticles.
Musa paradisiaca peel extract contains phytochemicals, which are well-known for their antioxidant qualities. Tin and ZrO2's inherent antioxidant properties also contributes to the extract's increased scavenging activity, making it more powerful and active. Based on the aforementioned findings, it can be concluded that the environmentally friendly green Sn-ZrO₂ nanocomposites, synthesized using Musa paradisiaca peel extract under ultrasound irradiation, is a more viable option for antioxidant drugs compared to ZrO₂ nanoparticles and serves as a superior alternative to chemically synthesized options.
Plausible mechanism responsible for the different applied dimensions of Sn-ZrO2 nanocomposites
Fig. 12 illustrates a plausible mechanism for the application of Sn-ZrO₂ nanocomposites in the adsorption potential, antimicrobial activity and antioxidant activity. Through metabolic processes, biogenic Sn-ZrO2 nanocomposites most likely interacts with the membranes and cell walls of bacteria. They are more likely to produce ROS, which can lead to a variety of problems, including the deactivation of vital enzyme and protein functions. Consequences include rupture of the cell membrane, cytoplasmic leakage, damage to proteins, DNA, and mitochondria, and finally, cell death (Kumar et al. 2020). The Sn-ZrO2 nanocomposites, which was created from banana peel extract, demonstrated superior efficacy in scavenging a range of ROS when tested for antioxidant activity using the ABTS and DPPH free radical assay (Kumar et al. 2020). The adsorption mechanism of MG dye on nanocomposites surfaces is influenced by various interactions, which are affected by specific phytochemicals. These include π–π stacking interactions between the surface of Sn-ZrO2 nanocomposites and aromatic rings of MB, hydrogen bonding interactions between the functional groups on the nanocomposites surface and the nitrogen atoms of MG dye, and electrostatic interactions between the positively charged nitrogen atoms present on the dye and the negatively charged functional groups on the nanocomposites surface (Trieu et al. 2023).