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Synthesis and characterization of ZnO/β-cyclodextrin/nicotinic acid nanocomposite and its biological and environmental application

  • Mohammed S. Alqahtani , Rabbani Syed EMAIL logo , Mudassar Shahid and Jilani Purusottapatnam Shaik
Published/Copyright: July 25, 2023
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Abstract

In the present work, the disk-shaped zinc oxide (ZnO) nanoparticles were synthesized and functionalized with β-cyclodextrin (β-CD) and nicotinic acid (vitamin B3) using the wet co-precipitation method. The functionalized ZnO/β-CD/nicotinic acid nanocomposite materials were characterized using UV-visible spectroscopy (UV-Vis), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), field emission electron microscopy (FESEM), and band-gap energy analysis. The band gap value (E g) was 4.3 eV. The average XRD crystallite size was determined using the Scherrer formula and was found to be 50 nm. The ZnO/β-CD/nicotinic acid nanocomposite material showed a photocatalytic effect for dye-polluted wastewater. It also showed an antibacterial effect against the Gram-positive bacterial strain Streptococcus aureus (S. aureus) but did not show any antibacterial activity with Gram-negative Escherichia coli (E. coli). The ZnO/β-CD/nicotinic acid nanocomposite also showed antifungal activity with Aspergillus niger (A. niger). It was noticed that ZnO/β-CD/nicotinic acid nanocomposite showed efficient anticancer activity with IC50 = 14.95 µg·mL−1 in MCF-7 cell lines. Because of the formation of singlet oxygen (O2˙) and hydrogen oxide radical (–OH˙), the composite material showed a photodegradation reaction against aq. solution of methylene blue dye. After 190 min, the blue colour of aq. solution methylene blue was decolourized at 6 pH at a constant time interval.

1 Introduction

In the last few years, nanomaterials are used in almost every field including drug delivery [1], sensors and photonic devices [1], electro-catalytic degradation of dyes, removal of metal ions [2,3,4], energy storage, etc. Because of environmental friendliness as well as unique electrical, optoelectronic, photochemical, catalytic, and biomedical [5] properties, zinc oxide (ZnO) nanomaterials were extensively used [6,7,8,9]. ZnO, one of the earliest materials, was used as a gas sensor because of the high mobility of conduction electrons in the material and good chemical and thermal stability [10,11]. ZnO nanomaterials also attract interest because of their wide range of applications [12,13]. They had a wide band energy gap and are used in electronics, semiconductors, and sensor technology [14,15]. Recently, Cu–ZnO nanocomposite materials played an important role under reduced reaction conditions [16].

The ZnO nanomaterials were synthesized by different synthetic methods like sol–gel technique [17,18], microemulsion process [19], mechano-chemical process [20], spray pyrolysis and drying process [21], plasma synthesis [22], hydrothermal process [23], sonochemical or microwave synthesis [24,25], direct precipitation process [26], etc. However, due to the presence of water, the formation of Zn–O–Zn bonds and hard agglomerates in the nanomaterial impede applications of ZnO nanomaterials. Thus, the reduction of water from the nanomaterial is an important process for reducing hard agglomerates. Nowadays, water pollution has increased due to the contamination of non-biodegradable pollutants from many industries [27].

Today, the most common water pollutants are organic dyes, which affect the photosynthesis process and also cause medical conditions like skin irritation, allergy, cancer, etc., in humans [28]. For the treatment of dyes, various physicochemical and biological processes have been developed; each of them has some advantages and disadvantages [29]. The most useful and important method is semiconductor photocatalysis. It is cheap, easy to synthesize, and also has high removal efficiency of dyes [30]. Numerous metal oxides such as Fe2O3, ZnO, TiO2, and Co3O4 are used as photocatalysts for dye degradation [31,32,33]. Zinc oxide nanoparticles (ZnO NPs) are able to remove both cationic and anionic dyes and also have good adsorption capacity, reusability, selectivity, and antibacterial properties [34]. There were two ways to modify the metal oxide nanoparticles: the first is doping with other metals, non-metals, and metal oxides; and the second method is the synthesis of the composite of metal oxides with macromolecules or polymers [35]. β-Cyclodextrin (β-CD) is a common host molecule and possesses photocatalyst, energy transfer, drug carrier, and photoelectric activities [36]. β-CD is a biodegradable oligosaccharide and its modified form is used in photocatalytic degradation [37], cell imaging [38], decolouration of ethyl violet dye [39], oil spill remediation [40], antiseptic to avoid skin diseases [41] as well as the removal of persistent organic pollutants like perfluorooctanoic acid, perfluorooctane sulphonate and Cr(VI) [42]. It is also used as a mediator between the surface of the photocatalyst and guest molecules. β-CD with metal oxide (like ZnO) composites acts as an electron-donating and hole-capturing species and enhances the photocatalytic activity via reduced charge hole recombination. β-CD used solar energy and extended up to visible light, whereas metal oxides usually used only UV rays [43].

On the other hand, nicotinic acid, also known as vitamin B3, received great attention because of its pharmaceutical use. Every year, around 20,000 tons of vitamin B3 are produced worldwide. These days, chromic acid commonly used as an oxidizing agent for the formation of vitamin B3 is characterized as corrosive. The development of an efficient catalytic system is very important to minimize the inorganic wastes and obtain vitamin B3 in high yield [44]. Owing to biological importance [45], vitamin B3 is produced by the catalytic oxidation of 3-pyridinemethanol [45], 3-pyridinecarboxyaldehyde [46], or picoline [47]. Nanostructured catalysts attract the interest of scientists because of their heterogeneous catalytic properties with improved characteristics [48,49]. Today, the use of recyclable nanocatalysts in oxidation reactions get more attention because of their eco-friendly nature [50,51].

Therefore, we described here a recyclable, eco-friendly, and efficient ZnO/β-CD/nicotinic acid nanocatalytic composite material, with a short reaction time. It is morphologically characterized by X-ray diffraction (XRD) and field emission electron microscopy (FESEM). It is also characterized by UV-visible (UV-Vis) spectroscopy, band gap energy analysis, Fourier transform infrared (FTIR) spectroscopy, and weight percentage of elements determined via energy dispersive spectroscopy (EDS). We also explore the biological and photocatalytic applications of the functionalized ZnO/β-CD/nicotinic acid nanocomposite material.

2 Experimental

2.1 Chemical and reagents

Methylene blue (MB) and β-CD were obtained from Merck (99.8%). Zinc acetate dihydrate (Zn(CH3COO)2·2H2O, 99%) and other chemicals used were of analytical grade and received from Merck. Nicotinic acid and tetramethylethylenediamine (TMED) were purchased from Sigma Aldrich. All reagents and solvents were of commercial grade and used without purification. Escherichia coli (E. coli) and Streptococcus aureus (S. aureus) pure culture, agar media (Hi-Media), and PDA were used; deionized distilled water was used as a solvent.

2.2 Instrumentation

In the absorbance mode, UV-Vis spectra were acquired using a UV-1900i Double beam spectrophotometer. Samples were dispersed in ethanol to determine the absorbance. X-ray diffraction of the composite material was analysed using an Advanced D8 Bruker X-ray diffractometer with Ni-filtered Cu-K (1.5405) (2–10–80° and step size of 0.02°). The vibration spectra were recorded using an Avtar 370, Thermo Nicolet, Fourier transform infrared (FT-IR) spectrophotometer equipped with a DTGS detector with 4 cm−1 resolution and samples were prepared with KBr discs for this study. For the FESEM study, a CARL ZEISS UHR FESEM MODEL GEMINI SEM 500 KMAT with 0.8 nm resolution and probe current of 3 pA to 100 nA was used.

2.3 Synthesis

2.3.1 Synthesis of ZnO nanoparticles

ZnO nanoparticles were synthesized by modifying the method of Royer et al. [28]. About 2.195 g of zinc acetate dihydrate was dissolved in 90 mL of ethanol under vigorous stirring for 15 min on a magnetic stirrer at ambient conditions. After that, 1.122 g of KOH was dissolved in 30 mL of distilled water, and it was added to the zinc acetate solution dropwise. A viscous milky white precipitate was obtained which was then heated at 90°C up to 3 h. Then, the suspension was centrifuged and the resultant product was washed 3–5 times with ethanol for removing impurities. Finally, the dried solid product was heated in a furnace at 70°C up to 24 h to obtain the ZnO nanoparticles powder.

2.3.2 Synthesis of the ZnO/β-CD nanocomposite material

For the synthesis of the ZnO/β-CD nanocomposite material, 30 mg of ZnO nanoparticles was dispersed in 10 mL of deionized water and sonicated for 15 min. After that, 30 mg of β-CD was dissolved in 10 mL of deionized water and stirred at 600 rpm for 10 min to obtain a transparent solution. Both solutions were mixed and continuously stirred at 600 rpm. After 6 h, the ZnO/β-CD nanocomposite was separated via centrifugation and washed three times with deionized water. The supernatant was freeze-dried, and the residue was weighed. Finally, the residue was dried in an oven below 80°C.

2.3.3 Synthesis of the ZnO/β-CD/nicotinic acid nanocomposite

For the synthesis of the ZnO/β-CD/nicotinic acid composite, 0.32 g of nicotinic acid was dissolved in 50 cm3 of hot water (80°C) and then cooled at room temperature. Then, 0.23 g of ZnO/β-CD was dissolved in a 1:1 ratio of methanol/water solution. This was added to aq. solution of nicotinic acid. The reaction mixture was stirred for up to 10 min. After that, 0.39 mL of TMED was added dropwise to the reaction mixture. Then, the whole reaction mixture was stirred for up to 30 min. The resultant white crystalline material was obtained and washed with distilled water and methanol. The solid crystalline material obtained was dried under a vacuum.

2.4 Antibacterial activity

To determine the antibacterial activity, we used the well diffusion system on a nutrient agar medium. First, the agar medium was put into two different Petri dishes under sterile conditions and kept for 1 h for solidification. After that, fresh, overnight-cultured E. coli and S. aureus (100 µg·mL−1) bacterial strains were spread onto both solidified agar media. Then, both the dishes were left up to 15–20 min for complete absorption of bacterial cultures. After that, three wells were prepared in each Petri dish by the gel puncture (6 mm) procedure under aseptic conditions. Samples of the ZnO/β-CD/nicotinic acid nanocomposite material were introduced in those wells at different concentrations of 10, 20, and 30 µg·mL−1. After that, for the diffusion of the extract, both treated dishes were kept at room temperature for 30 min. Later, they were incubated at 37°C up to 24 h for maximum growth of microorganisms. After incubation, the ZnO/β-CD/nicotinic acid composite material showed inhibition of bacterial growth via a clear zone of inhibition (ZOI) around the well.

2.5 Antifungal activity

For antifungal activity, we used the well diffusion system on a PDA medium. First, the PDA medium was into a Petri dish under sterile conditions and kept for 1 h for solidification. The antifungal activity of the ZnO/β-CD/nicotinic acid nanocomposite was examined against cultured and tested fungal species Aspergillus niger (A. niger). A 5-day-old A. niger fungus was used for antifungal activity against the ZnO/β-CD/nicotinic acid nanocomposite. In this process, 3–4 mL of sterile normal saline was used for the fungal growth and gently scraped to collect the conidia. About 100 µL of the liquid spore suspension was spread evenly on the PDA dish. A sterile cork-borer was used to puncture two 6 mm-diameter circular wells on the PDA medium. Both wells of the Petri dish were filled with 20 and 40 µL of concentrated ZnO/β-CD/nicotinic acid nanocomposite to check for antifungal activity. Then, the petri dish was incubated at 25°C for 2–3 days and the zone of inhibition was measured [52].

2.6 Dye remediation

The MB adsorption experiment was used for photocatalysis via the ZnO/β-CD/nicotinic acid nanocomposite material. First, the standard stock solution of MB was made. Then, it was diluted with deionized water at various concentrations. The obtained MB solution was kept in a fixed volume flask (10 mL of 5 ppm) to which was added the ZnO/β-CD/nicotinic acid nanocomposite material. At room temperature, the whole solution (pH = 6) was placed in a sonicator for up to 170 min. The upper layer of the solution was analysed at 600 nm wavelength using a UV-Vis spectrometer (UV-Visible 1900i, Shimadzu, Japan). The ZnO/β-CD/nicotinic acid was removed by centrifugation when the experiment was completed. The removal (R%) was calculated by Eq. 1:

(1) R % = C o C e C o × 100

where C o is the initial concentration of MB (mg·L−1) and C e is the equilibrium concentration of MB (mg·L−1).

2.7 Cytotoxicity study

The cytotoxic action of various cell lines toward different oncology products was determined using the high-throughput cell-based 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Cytotoxicity evaluation of the ZnO/β-CD/nicotinic acid nanocomposite was performed using MCF-7 cell lines collected from the cryopreservation cells that were thawed properly. They were initially grown in Dulbecco's modified Eagle’s medium (DMEM) in a 50 mL flask with 5% fetal bovine serum and antibiotics in a 5% CO2 incubator. After incubation, the affluent cells were counted with a Neubauer chamber, and different concentrations of cells were seeded in 96 well plates. The twofold serially diluted ZnO/β-CD/nicotinic acid nanocomposite was added to the 96 well plates and incubated at 37°C for 2 h in a 5% CO2 incubator. After incubation, 96-well plates were washed and 100 µL of the MTT reagent was added to each well. After incubation for 4 h, the plates were washed with PBS buffer, and 100 µL of dimethyl sulphoxide was added to solubilize the unbounded formazan, followed by measuring the absorbance of the plate at 570 nm using a plate reader (Biotek, USA). The complete evaluation was carried out in triplicate, and it was based on the formazan dye’s colour intensity, which was assumed to be directly proportional to the number of live cells.

3 Results and discussion

3.1 Characterization of nanocomposite materials

3.1.1 UV-Vis absorption

The UV-Vis spectra of the functionalized ZnO/β-CD/nicotinic acid nanocomposite material showed an absorption peak at 217 and 353 nm with one hump at 304 nm (Figure 1). The characteristic absorption spectra of the ZnO composite material in the quantum size regime absorption observed blue shift [53].

Figure 1 
                     The UV-Vis absorption spectrum of the ZnO/β-CD/nicotinic acid nanocomposite.
Figure 1

The UV-Vis absorption spectrum of the ZnO/β-CD/nicotinic acid nanocomposite.

The optical bandgap (E g) of the nanomaterial can be determined using the classical Tauc approach [54], which shows a relationship between the incident photoenergy () and the absorption coefficient (α) near the absorption edge, as follows (Eq. 2):

(2) α h ν = A 0 ( h ν E g ) n

It depends on the interband transition (e.g. n = 1/2 for direct transitions and n = 2 for indirect transitions). A 0 is a constant, band tailing parameter and E g is the intercept of the extrapolated line, when (αhν)1/n vs is plotted. Figure 2 shows a Tauc plot of ZnO/β-CD/nicotinic acid nanocomposite and the band gap value was 4.3 eV.

Figure 2 
                     The Tauc plot of the ZnO/β-CD/nicotinic acid composite material, which was derived from UV-Vis absorption, where the band gap value (E
                        g) was 4.3 eV.
Figure 2

The Tauc plot of the ZnO/β-CD/nicotinic acid composite material, which was derived from UV-Vis absorption, where the band gap value (E g) was 4.3 eV.

3.1.2 FTIR spectra

The FTIR spectrum (Figure 3) shows that water molecules and organic moieties are present in the precursor of the nanocomposite material. The FTIR spectrum of the ZnO/β-CD/nicotinic acid nanocomposite material showed a broad peak at 3,153.38 cm−1, which is a characteristic peak of the O–H group. The H–O–H bond of β-CD has a prominent absorption peak at 1,639.09 cm−1. The peak at 1,581.78 cm−1 is attributed to υ as(COO) (asymmetric stretches). The peaks at 1,472.45 and 1,426.19 cm−1 are attributed to υ(C═C) and υ(C═N) of nicotinic acid. The peak at 1,400.53 cm−1 is assigned for υ s(COO) (symmetric stretch) of the carboxyl group (18-009). The peaks at 1,315.09 and 1,189.85 cm−1 correspond to the bending signals of the imidazole ring and C–N stretching vibrations [55,56]. The peak at 1,156.94, 1,099.05, 1,045.08, and 1,016 cm−1 correspond to υ(C–O), C–O–C of β-CD attached to ZnO. The peaks observed at 906.75, 816.86, 762.14, 749.76, 704.93, 995, and 760 cm−1 can be assigned to C–N and C–H bending vibrations, respectively. Most characteristic peaks occur at 500–400 cm−1, which correspond to the Zn–O bond [38,57]. The Zn–O and Zn–N bonding vibration exhibited peaks at 421.31 and 571.87 cm−1 for Zn–O and the Zn–N stretching mode, respectively.

Figure 3 
                     The FTIR spectrum of the ZnO/β-CD/nicotinic acid nanocomposite material.
Figure 3

The FTIR spectrum of the ZnO/β-CD/nicotinic acid nanocomposite material.

3.1.3 XRD

The XRD pattern of hexagonal ZnO/β-CD/nicotinic acid composite nanomaterials is described in Figure 4. It has a similarity with the ZnO wurtzite structure [58]. The XRD peak values relate to diffraction peaks such as 2θ, (h k l), and inter-planar spacing d hkl as described in Table 1. In the XRD pattern, a few peaks different, in comparison with the pure ZnO structure are observed, which indicates that the synthesized nanomaterial was the composite of ZnO/β-CD/nicotinic acid. With the increase in the calcination temperature, the intensity of XRD peaks and the average crystallite size increased [59]. At high temperatures, small grains aggregate to form large particles, and migration of molecules is observed.

Figure 4 
                     The XRD spectrum of the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite material.
Figure 4

The XRD spectrum of the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite material.

Table 1

Recycling of the used nanocatalyst ZnO/β-CD/nicotinic acid composite material

Sl. no. Recycling Time of reaction (min) Yield after wash (%)
1. 1st 190 95.4
2. 2nd 190 94.0
3. 3rd 190 93.1
4. 4th 190 91.7
5. 5th 190 90.0

The XRD of the ZnO/β-CD/nicotinic acid nanocomposites was analysed using the following formula [60]:

(3) 1 d hkl 2 = 4 3 h 2 + hk + k 2 a 2 + l 2 c 2

where d is the inter-planar spacing; h, k, l are Miller indices; a and c are lattice constants with a = 3.2554 Å, c = 4.9569 Å, and c/a = 1.5227 Å.

The presence of finite broadening in the XRD diffraction peaks showed that the ZnO composite material had a nanometre range. The average crystallite size of the synthesized ZnO/β-CD/nicotinic acid nanocomposite material was calculated using the Debye–Scherrer’s formula [61] as follows:

(4) D = 0 . 9 λ β cos θ

where λ is the wavelength of the source Cu Kα (0.15406); β is full width at half-maximum of the XRD peak; and θ is the diffraction angle of the peak.

The crystallinity of the functionalized ZnO/β-CD/nicotinic acid composite material was confirmed by XRD analysis (Figure 4). The XRD pattern of the functionalized ZnO nanocomposite material exhibited peaks at 2θ = 8.95°, 16.02°, 17.53°, 31.74°, 34.38°, 36.11°, 47.46°, 56.57°, 62.82°, 67.85°, and 69.05° corresponding to (141), (180), (042), (002), (101), (102), (110), (103), (220), and (112) planes of the hexagonal ZnO/β-CD/nicotinic acid nanocomposite, respectively (Figure 4 and Table 1). Also, we calculated the average particle sizes using the first three prominent peaks at 2θ = 31.74°, 34.38°, and 36.11°, which are indexed as (100), (002), and (101) peaks of the X-ray diffraction, respectively. The grain sizes were calculated to be 45.87, 51.21, and 55.28 nm, respectively. Thus, the average size of nanoparticles was around 50 nm.

3.1.4 FESEM

The morphological analysis of the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite material was done using FESEM (Figure 5). The FESEM images of the functionalized ZnO/β-CD/nicotinic acid nanocomposite material on a graphite surface are shown in Figure 5. As clearly shown in Figure 5, the ZnO nanocomposite sample was uniformly dispersed on the surface. The incorporation of functionalized ZnO composite promoted the migration of vacancies from the pores of the grain of the nanocomposite, which ultimately creates voids in the electrode. These voids provided a path for the ionic movement.

Figure 5 
                     The FESEM image of the ZnO/β-CD/nicotinic acid nanocomposite material.
Figure 5

The FESEM image of the ZnO/β-CD/nicotinic acid nanocomposite material.

Here, the surface of the ZnO/β-CD/nicotinic acid nanomaterial composite was loosely packed and was hexagonal disk-shaped, which was more active. Thus, its photocatalytic activity is increased due to the aggregation of the composite on surfaces. It provided a superior adsorption environment and more active sites for the photocatalytic reaction.

3.1.5 EDS

The elemental composition and the purity of ZnO/β-CD/nicotinic acid nanocomposite material were determined by EDS analysis (Figure 7). A uniform distribution of C, N, O, and Zn on the matrix was observed in the EDS spectrum and mapping (Figures 6 and 7). No other corresponding peak of impurity was observed. It contained a smooth surface, which was associated with heterogenous mixing of C, N, O, and Zn, resulting in a single-phase surface morphology as observed (Figure 7).

Figure 6 
                     EDS mapping for the ZnO/β-CD/nicotinic acid nanocomposite material.
Figure 6

EDS mapping for the ZnO/β-CD/nicotinic acid nanocomposite material.

Figure 7 
                     The EDS spectrum with a weight percentage table of ZnO-β-CD.
Figure 7

The EDS spectrum with a weight percentage table of ZnO-β-CD.

3.2 Photocatalysis

The photocatalytic experiment of ZnO/β-CD/nicotinic acid nanocomposite samples was analysed via the degradation of MB dye in aqueous solution under UV and visible irradiation. The photodegradation experiment was followed by UV-Vis absorption spectroscopy at different irradiation times (Figure 8) [62].

Figure 8 
                  The photocatalysis experiment via the absorption spectra of MB dye with the ZnO/β-CD/nicotinic acid nanocomposite material under UV-Vis irradiation.
Figure 8

The photocatalysis experiment via the absorption spectra of MB dye with the ZnO/β-CD/nicotinic acid nanocomposite material under UV-Vis irradiation.

In this photocatalysis process, the MB dye was degraded under light irradiation, where UV-Vis light was used as an irradiation source. We described here the photocatalysis reaction of ZnO/β-CD/nicotinic acid nanocomposite with MB. In the presence of light and air, 40.0 mg of the ZnO/β-CD/nicotinic acid nanocomposite material was added to 10.0 mL aq. solution of MB (1.0 × 10−4 M) (pH = 6). After 10 min, the degradation of blue colour starts. At a constant time (10 min) interval, the ZnO/β-CD/nicotinic acid nanocomposite degrades the blue colour of the solution (Figure 8). A scanning range between 200 and 800 nm was used for the MB solution. According to previous studies, the absorption peak of MB was observed at 650 nm. After adding 40.0 mg of the ZnO/β-CD/nicotinic acid nanocomposite, the absorption peak shifted and λ max was obtained at 587 nm because of the formation of tetramer, which is responsible for the blue shift [63].

In the presence of visible light, the ZnO/β-CD/nicotinic acid nanocomposite material formed OH in the presence of water (H2O). The whole reaction was monitored via MB degradation at 587 nm wavelength in an aq. solution by a decrease in the absorbance (Figure 9).

Figure 9 
                  Demonstration of the photodegradation process of MB in the presence of ZnO/β-CD/nicotinic acid nanocomposite at a 587 nm wavelength up to 190 min.
Figure 9

Demonstration of the photodegradation process of MB in the presence of ZnO/β-CD/nicotinic acid nanocomposite at a 587 nm wavelength up to 190 min.

According to Figure 9, in the presence of the ZnO/β-CD/nicotinic acid nanocomposite, the blue colour of aq. MB dye decreased with time, and it was clearly observed at a wavelength of 587 nm. At a constant time interval (10 min), the blue colour decreased and the peak at 587 nm also decreased. After 190 min, the peak converted into a straight line and the blue colour of the aq. solution of MB became transparent and colourless.

According to Figure 10, at 587 nm wavelength, the absorption decreased at a constant time interval (10 min). After 10 min, the absorption was decreased and as time increased, the absorption of blue dye decreased. Resultant force of optical density, get a straight line with constant time interval (10 min). After the completion of the photodegradation process, the absorption was constant and the blue colour of the solution also turned colourless.

Figure 10 
                  The addition of the ZnO/β-CD/nicotinic acid nanocomposite material (40.0 mg), at 587 nm wavelength. The time increased, the absorption decreased up to 190 min at a constant time interval (10 min) and the blue colour of the solution was decolourized.
Figure 10

The addition of the ZnO/β-CD/nicotinic acid nanocomposite material (40.0 mg), at 587 nm wavelength. The time increased, the absorption decreased up to 190 min at a constant time interval (10 min) and the blue colour of the solution was decolourized.

3.3 Cytotoxicity test (MTT assay)

The MTT assay is a high-throughput cell-based assay and is used to evaluate the cytotoxic response of different cell lines to different oncology products. In the present work, the MTT assay was reformed as a chemosensitivity test and its potential was examined. This technique also has numerous benefits regarding speed, quantitation, managing various samples, and cell number. The application of this assay for chemosensitivity testing appears to be valuable and advantageous. MTT examines cell respiration, and the amount of formazan formed is proportional to the number of living cells present in the culture. An increase or reduction in the cell number results in a concomitant change in the quantity of formazan formed, demonstrating the degree of cytotoxicity initiated by the drug. The IC50 (concentration) value of the tested drug determines the ability of the drug to cause the death of 50% of the cells and can predict the degree of its cytotoxic effect. The lower the value, the more cytotoxic the substance will be. Figure 11 shows the comparative graph of the IC50 values of as-synthesized ZnO/β-CD/nicotinic acid nanocomposites against MCF-7 cancer cell lines. The percentage cell viability of cancer cells response to various doses of ZnO/β-CD/nicotinic acid nanocomposite is shown. The ZnO/β-CD/nicotinic acid nanocomposite ability to promote cell proliferation was tested at concentrations between 0.7 and 200 µg·mL−1; the IC50 value was 14.95 µg·mL−1 after 24 h. The cytotoxicity results clearly indicate that the ZnO/β-CD/nicotinic acid nanocomposite has the best ability to be used as an anticancer agent in oncology treatment. ZnO nanoparticles are known to be a potential anticancer agent, which was proven by many previous studies [64].

Figure 11 
                  The MTT assay using the ZnO/β-CD/nicotinic acid nanocomposite in MCF-7 cell lines.
Figure 11

The MTT assay using the ZnO/β-CD/nicotinic acid nanocomposite in MCF-7 cell lines.

3.4 Reuse of the catalyst

For the reuse of the catalyst, the stability of the catalyst is highly important. We use the Fenton reaction to evaluate the stability of the ZnO/β-CD/nicotinic acid nanocomposite material; we used it many times for several consecutive MB removal cycles. At each cycle, the solid nanocomposite catalyst was separated by centrifugation from the solution and washed with ethanol and distilled water. After that, it was dried in a vacuum and was ready to be reused as a catalyst in the next reaction. In the whole process, we also observed a slight weight loss of the catalyst after every cycle (190 min). As shown in Figure 12, it is clear that the weight of ZnO/β-CD/nicotinic acid nanocomposite material decreased in each cycle from 95.4%, 94.0%, 93.1%, and 91.7%, and retained up to 90.0% of its catalytic activity after 5th cycle (Table 1). The small decrease in its catalytic activity after each cycle might be attributed to its incomplete removal during washing. This showed that the ZnO/β-CD/nicotinic acid nanocomposite was highly stable in an aqueous solution during the photocatalysis process.

Figure 12 
                  Recycling experiment of ZnO/β-CD/nicotinic acid nanocomposite materials for the MB degradation process.
Figure 12

Recycling experiment of ZnO/β-CD/nicotinic acid nanocomposite materials for the MB degradation process.

3.5 Antimicrobial activity

The antibacterial properties of the ZnO-β-CD nanocomposite material prevented further growth of two bacterial strains E. coli and S. aureus. Figure 13 shows that the different ZOI (zones of inhibition) for antibacterial activity obtained with different concentrations (10, 50, and 100 µg·mL−1) of the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite. It is clear that the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite produced a good ZOI for the S. aureus bacterial strain (Figure 13a) with a clear area around the sample showing complete inhibition. But with E. coli it did not show the ZOI area (Figure 13b). The probable antimicrobial action of the nanocomposite is due to the inhibition of microbial proteins causing eventual cell damage and the death of microbes [65].

Figure 13 
                  (a) S. aureus- and (b) E. coli-treated with the ZnO/β-CD/nicotinic acid nanocomposite material at different concentrations in methanol (10, 50, and 100 µg·mL−1).
Figure 13

(a) S. aureus- and (b) E. coli-treated with the ZnO/β-CD/nicotinic acid nanocomposite material at different concentrations in methanol (10, 50, and 100 µg·mL−1).

The antifungal activity was studied with different concentrations (20 and 40 µL) of the ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) nanocomposite. It clearly showed that ZnO/β-CD/nicotinic acid (ZnO/β-CD/nicotinic acid) produced a minimum ZOI for A. niger (Figure 14b). The clear area around the sample showed a complete inhibition zone. Figure 14 shows that increased concentrations of the ZnO/β-CD/nicotinic acid nanocomposite result in the decreased growth rate of Aspergillus niger. On comparison of both wells, the well with 40 µL of the ZnO composite sample showed good activity than the well with 20 µL of the sample. When A. niger was treated with the Zn/β-CD/nicotinic acid nanocomposite, it released proteins, carbohydrates, and lipids by damaging the cell membranes. As a result, decreased amounts of proteins, carbohydrates, and lipids were observed in the fungal cells, which leads to the death of the cells [66,67].

Figure 14 
                  (a) The colony of cultured Aspergillus niger fungal strain; (b) Aspergillus niger-treated with the ZnO/β-CD/nicotinic acid nanocomposite material at different concentrations in methanol (20 and 40 µL).
Figure 14

(a) The colony of cultured Aspergillus niger fungal strain; (b) Aspergillus niger-treated with the ZnO/β-CD/nicotinic acid nanocomposite material at different concentrations in methanol (20 and 40 µL).

3.6 Photocatalytic degradation mechanism

The photocatalysis mechanisms are described via the photodegradation of MB by the ZnO/β-CD/nicotinic acid nanocomposite material in the presence of UV-Vis light and air [59,68,69,70,71,72,73]. It can be explained as follows: In the photocatalysis process at a 587 nm wavelength, 1.0 × 10−4 M MB dye was mixed with 40.0 mg of the ZnO/β-CD/nicotinic acid nanocomposite material. The solution mixture of MB and the ZnO/β-CD/nicotinic acid nanocomposite vessel was photo-irradiated under UV/visible light; the ZnO composite is excited. Due to the excitation of the composite material, photo-induced pairs of electrons and holes (e + h+) are formed. These electrons or holes are captured by the aqueous solution of MB dye and radicals like OH˙ and O2 ˙ are generated, which decolourized the blue colour of MB [73,74]. The active sites of the ZnO composite catalyst are covered by the MB dye and degradation products, which compete with the H2O and OH˙ to be adsorbed on the same sites; as a result fewer OH˙ radicals are formed and high degradation efficiency is observed [75]. A specific amount of light radiation is used by the MB dye molecules and less amount of photons reach the surface of the catalyst to generate OH˙ radicals [74,76].

The MB dye enters into the holes of the ZnO/β-CD/nicotinic acid composite (which binds with ZnO centrally) surface and absorbs radiation of light for excitation. An electron rapidly excites the MB dye to the conduction band of ZnO. Along with the OH˙ radical, another important radical, the superoxide anion radical (O2 ˙), is illuminated from the ZnO nanocomposite. Thus, the excited MB dye with the ZnO/β-CD/nicotinic acid composite material undergoes the photocatalytic degradation reaction [77,78]. The mechanism reaction is as follows:

(5) ZnO/β-CD/nicotinic acid + h υ ZnO/β-CD/nicotinic acid ˙ + e + h +

(6) e + O 2 O 2 ˙

(7) h + + H 2 O O ˙ H

(8) MB + O ˙ H de-colourized blue colour

(9) MB + O 2 ˙ de-colourized blue colour

In summary, in the presence of light and air, the ZnO/β-CD/nicotinic acid nanocomposite material generates holes and electrons. They react with water and form ˙O2 and ˙OH radicals, which are used in the photocatalysis or in the photodegradation process of MB at pH 6 of the solution. In an acidic medium, the rate of degradation was high in comparison with the basic medium because the negatively charged hydroxyl radicals easily degrade the cationic dye. At a constant time interval, the activity of the ZnO/β-CD/nicotinic acid nanocomposite material decreases because of the formation of a layer of OH that coats the surface of the catalyst, which could be washed with ethanol and distilled water. After drying the solid nanocomposite, it can again be reused for the next catalysis reaction cycle. After each cycle, the activity of the catalyst for degradation is slightly decreased and after the 5th cycle, it would be around 90%. These ZnO/β-CD/nicotinic acid nanocomposites are also used as antibacterial or growth inhibitors against E. coli and S. aureus bacterial strains. At high optical density, the nanocomposites damaged the cell membranes of S. aureus. As a result, at high optical density, colony growth was not observed; for E. coli it did not show any result. The ZnO/β-CD/nicotinic acid nanocomposite produced a clear ZOI for S. aureus but for E. coli, no clear region was observed around the wells. Similar to antibacterial activity, the Zn/β-CD/nicotinic acid nanocomposite showed antifungal activity for the A. niger fungal strain.

4 Conclusion

Here, we synthesized ZnO/β-CD/nicotinic acid nanocomposites using the co-precipitation method with aq. solvent. The reaction between both precursors in the presence of water generated OH ions for precipitation. The synthesized ZnO/β-CD/nicotinic acid nanocomposite was characterized, and the average XRD crystallite size was 50 nm as calculated using the Scherrer formula. It also showed a remarkable photocatalytic property with MB. The ZnO/β-CD/nicotinic acid composite showed good catalytic efficiency in the degradation of MB at pH 6 in comparison with ZnO. The blue colour of MB was decolourized at a constant time interval. After 190 min, the blue colour of the solution became colourless. This process provided easy recovery of the nanocomposite catalyst by centrifugation and separation. The catalytic activity was again regained in consecutive steps. The degradation efficiency was around 90%. Due to the generation of ˙O2 and ˙OH radicals by the ZnO/β-CD/nicotinic acid nanocomposite material, it was also used as antibacterial or growth inhibitors against S. aureus bacterial strains, but it did not show any antibacterial effect against E. coli. It was also used as an antifungal growth inhibitor for A. niger fungal strains. The prepared materials also showed the efficacy of anticancer activity towards MCF-7 cell lines.

Acknowledgements

The authors extend their appreciation to the Researchers Supporting Project number (RSPD 2023R739), King Saud University, Riyadh, Saudi Arabia for funding this work.

  1. Funding information: This research was funded by the Researchers Supporting Project number (RSPD2023R739), King Saud University, Riyadh, Saudi Arabia.

  2. Author contributions: Mohammed S. Alqahtani and Rabbani Syed: writing – original draft, writing – review and editing, methodology, formal analysis; Mudassar Shahid and Jilani Purusottapatnam Shaik: writing – original draft, formal analysis, visualization, project administration; Rabbani Syed: funding and resources.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: All the data are available in the manuscript.

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Received: 2023-03-23
Accepted: 2023-05-31
Published Online: 2023-07-25

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  23. Characterisation of carbonate lake sediments as a potential filler for polymer composites
  24. Evaluation of nano-selenium biofortification characteristics of alfalfa (Medicago sativa L.)
  25. Quality of oil extracted by cold press from Nigella sativa seeds incorporated with rosemary extracts and pretreated by microwaves
  26. Heteropolyacid-loaded MOF-derived mesoporous zirconia catalyst for chemical degradation of rhodamine B
  27. Recovery of critical metals from carbonatite-type mineral wastes: Geochemical modeling investigation of (bio)hydrometallurgical leaching of REEs
  28. Photocatalytic properties of ZnFe-mixed oxides synthesized via a simple route for water remediation
  29. Attenuation of di(2-ethylhexyl)phthalate-induced hepatic and renal toxicity by naringin nanoparticles in a rat model
  30. Novel in situ synthesis of quaternary core–shell metallic sulfide nanocomposites for degradation of organic dyes and hydrogen production
  31. Microfluidic steam-based synthesis of luminescent carbon quantum dots as sensing probes for nitrite detection
  32. Transformation of eggshell waste to egg white protein solution, calcium chloride dihydrate, and eggshell membrane powder
  33. Preparation of Zr-MOFs for the adsorption of doxycycline hydrochloride from wastewater
  34. Green nanoarchitectonics of the silver nanocrystal potential for treating malaria and their cytotoxic effects on the kidney Vero cell line
  35. Carbon emissions analysis of producing modified asphalt with natural asphalt
  36. An efficient and green synthesis of 2-phenylquinazolin-4(3H)-ones via t-BuONa-mediated oxidative condensation of 2-aminobenzamides and benzyl alcohols under solvent- and transition metal-free conditions
  37. Chitosan nanoparticles loaded with mesosulfuron methyl and mesosulfuron methyl + florasulam + MCPA isooctyl to manage weeds of wheat (Triticum aestivum L.)
  38. Synergism between lignite and high-sulfur petroleum coke in CO2 gasification
  39. Facile aqueous synthesis of ZnCuInS/ZnS–ZnS QDs with enhanced photoluminescence lifetime for selective detection of Cu(ii) ions
  40. Rapid synthesis of copper nanoparticles using Nepeta cataria leaves: An eco-friendly management of disease-causing vectors and bacterial pathogens
  41. Study on the photoelectrocatalytic activity of reduced TiO2 nanotube films for removal of methyl orange
  42. Development of a fuzzy logic model for the prediction of spark-ignition engine performance and emission for gasoline–ethanol blends
  43. Micro-impact-induced mechano-chemical synthesis of organic precursors from FeC/FeN and carbonates/nitrates in water and its extension to nucleobases
  44. Green synthesis of strontium-doped tin dioxide (SrSnO2) nanoparticles using the Mahonia bealei leaf extract and evaluation of their anticancer and antimicrobial activities
  45. A study on the larvicidal and adulticidal potential of Cladostepus spongiosus macroalgae and green-fabricated silver nanoparticles against mosquito vectors
  46. Catalysts based on nickel salt heteropolytungstates for selective oxidation of diphenyl sulfide
  47. Powerful antibacterial nanocomposites from Corallina officinalis-mediated nanometals and chitosan nanoparticles against fish-borne pathogens
  48. Removal behavior of Zn and alkalis from blast furnace dust in pre-reduction sinter process
  49. Environmentally friendly synthesis and computational studies of novel class of acridinedione integrated spirothiopyrrolizidines/indolizidines
  50. The mechanisms of inhibition and lubrication of clean fracturing flowback fluids in water-based drilling fluids
  51. Adsorption/desorption performance of cellulose membrane for Pb(ii)
  52. A one-pot, multicomponent tandem synthesis of fused polycyclic pyrrolo[3,2-c]quinolinone/pyrrolizino[2,3-c]quinolinone hybrid heterocycles via environmentally benign solid state melt reaction
  53. Green synthesis of silver nanoparticles using durian rind extract and optical characteristics of surface plasmon resonance-based optical sensor for the detection of hydrogen peroxide
  54. Electrochemical analysis of copper-EDTA-ammonia-gold thiosulfate dissolution system
  55. Characterization of bio-oil production by microwave pyrolysis from cashew nut shells and Cassia fistula pods
  56. Green synthesis methods and characterization of bacterial cellulose/silver nanoparticle composites
  57. Photocatalytic research performance of zinc oxide/graphite phase carbon nitride catalyst and its application in environment
  58. Effect of phytogenic iron nanoparticles on the bio-fortification of wheat varieties
  59. In vitro anti-cancer and antimicrobial effects of manganese oxide nanoparticles synthesized using the Glycyrrhiza uralensis leaf extract on breast cancer cell lines
  60. Preparation of Pd/Ce(F)-MCM-48 catalysts and their catalytic performance of n-heptane isomerization
  61. Green “one-pot” fluorescent bis-indolizine synthesis with whole-cell plant biocatalysis
  62. Silica-titania mesoporous silicas of MCM-41 type as effective catalysts and photocatalysts for selective oxidation of diphenyl sulfide by H2O2
  63. Biosynthesis of zinc oxide nanoparticles from molted feathers of Pavo cristatus and their antibiofilm and anticancer activities
  64. Clean preparation of rutile from Ti-containing mixed molten slag by CO2 oxidation
  65. Synthesis and characterization of Pluronic F-127-coated titanium dioxide nanoparticles synthesized from extracts of Atractylodes macrocephala leaf for antioxidant, antimicrobial, and anticancer properties
  66. Effect of pretreatment with alkali on the anaerobic digestion characteristics of kitchen waste and analysis of microbial diversity
  67. Ameliorated antimicrobial, antioxidant, and anticancer properties by Plectranthus vettiveroides root extract-mediated green synthesis of chitosan nanoparticles
  68. Microwave-accelerated pretreatment technique in green extraction of oil and bioactive compounds from camelina seeds: Effectiveness and characterization
  69. Studies on the extraction performance of phorate by aptamer-functionalized magnetic nanoparticles in plasma samples
  70. Investigation of structural properties and antibacterial activity of AgO nanoparticle extract from Solanum nigrum/Mentha leaf extracts by green synthesis method
  71. Green fabrication of chitosan from marine crustaceans and mushroom waste: Toward sustainable resource utilization
  72. Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)
  73. The enhanced adsorption properties of phosphorus from aqueous solutions using lanthanum modified synthetic zeolites
  74. Separation of graphene oxides of different sizes by multi-layer dialysis and anti-friction and lubrication performance
  75. Visible-light-assisted base-catalyzed, one-pot synthesis of highly functionalized cinnolines
  76. The experimental study on the air oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid with Co–Mn–Br system
  77. Highly efficient removal of tetracycline and methyl violet 2B from aqueous solution using the bimetallic FeZn-ZIFs catalyst
  78. A thermo-tolerant cellulase enzyme produced by Bacillus amyloliquefaciens M7, an insight into synthesis, optimization, characterization, and bio-polishing activity
  79. Exploration of ketone derivatives of succinimide for their antidiabetic potential: In vitro and in vivo approaches
  80. Ultrasound-assisted green synthesis and in silico study of 6-(4-(butylamino)-6-(diethylamino)-1,3,5-triazin-2-yl)oxypyridazine derivatives
  81. A study of the anticancer potential of Pluronic F-127 encapsulated Fe2O3 nanoparticles derived from Berberis vulgaris extract
  82. Biogenic synthesis of silver nanoparticles using Consolida orientalis flowers: Identification, catalytic degradation, and biological effect
  83. Initial assessment of the presence of plastic waste in some coastal mangrove forests in Vietnam
  84. Adsorption synergy electrocatalytic degradation of phenol by active oxygen-containing species generated in Co-coal based cathode and graphite anode
  85. Antibacterial, antifungal, antioxidant, and cytotoxicity activities of the aqueous extract of Syzygium aromaticum-mediated synthesized novel silver nanoparticles
  86. Synthesis of a silica matrix with ZnO nanoparticles for the fabrication of a recyclable photodegradation system to eliminate methylene blue dye
  87. Natural polymer fillers instead of dye and pigments: Pumice and scoria in PDMS fluid and elastomer composites
  88. Study on the preparation of glycerylphosphorylcholine by transesterification under supported sodium methoxide
  89. Wireless network handheld terminal-based green ecological sustainable design evaluation system: Improved data communication and reduced packet loss rate
  90. The optimization of hydrogel strength from cassava starch using oxidized sucrose as a crosslinking agent
  91. Green synthesis of silver nanoparticles using Saccharum officinarum leaf extract for antiviral paint
  92. Study on the reliability of nano-silver-coated tin solder joints for flip chips
  93. Environmentally sustainable analytical quality by design aided RP-HPLC method for the estimation of brilliant blue in commercial food samples employing a green-ultrasound-assisted extraction technique
  94. Anticancer and antimicrobial potential of zinc/sodium alginate/polyethylene glycol/d-pinitol nanocomposites against osteosarcoma MG-63 cells
  95. Nanoporous carbon@CoFe2O4 nanocomposite as a green absorbent for the adsorptive removal of Hg(ii) from aqueous solutions
  96. Characterization of silver sulfide nanoparticles from actinobacterial strain (M10A62) and its toxicity against lepidopteran and dipterans insect species
  97. Phyto-fabrication and characterization of silver nanoparticles using Withania somnifera: Investigating antioxidant potential
  98. Effect of e-waste nanofillers on the mechanical, thermal, and wear properties of epoxy-blend sisal woven fiber-reinforced composites
  99. Magnesium nanohydroxide (2D brucite) as a host matrix for thymol and carvacrol: Synthesis, characterization, and inhibition of foodborne pathogens
  100. Synergistic inhibitive effect of a hybrid zinc oxide-benzalkonium chloride composite on the corrosion of carbon steel in a sulfuric acidic solution
  101. Review Articles
  102. Role and the importance of green approach in biosynthesis of nanopropolis and effectiveness of propolis in the treatment of COVID-19 pandemic
  103. Gum tragacanth-mediated synthesis of metal nanoparticles, characterization, and their applications as a bactericide, catalyst, antioxidant, and peroxidase mimic
  104. Green-processed nano-biocomposite (ZnO–TiO2): Potential candidates for biomedical applications
  105. Reaction mechanisms in microwave-assisted lignin depolymerisation in hydrogen-donating solvents
  106. Recent progress on non-noble metal catalysts for the deoxydehydration of biomass-derived oxygenates
  107. Rapid Communication
  108. Phosphorus removal by iron–carbon microelectrolysis: A new way to achieve phosphorus recovery
  109. Special Issue: Biomolecules-derived synthesis of nanomaterials for environmental and biological applications (Guest Editors: Arpita Roy and Fernanda Maria Policarpo Tonelli)
  110. Biomolecules-derived synthesis of nanomaterials for environmental and biological applications
  111. Nano-encapsulated tanshinone IIA in PLGA-PEG-COOH inhibits apoptosis and inflammation in cerebral ischemia/reperfusion injury
  112. Green fabrication of silver nanoparticles using Melia azedarach ripened fruit extract, their characterization, and biological properties
  113. Green-synthesized nanoparticles and their therapeutic applications: A review
  114. Antioxidant, antibacterial, and cytotoxicity potential of synthesized silver nanoparticles from the Cassia alata leaf aqueous extract
  115. Green synthesis of silver nanoparticles using Callisia fragrans leaf extract and its anticancer activity against MCF-7, HepG2, KB, LU-1, and MKN-7 cell lines
  116. Algae-based green AgNPs, AuNPs, and FeNPs as potential nanoremediators
  117. Green synthesis of Kickxia elatine-induced silver nanoparticles and their role as anti-acetylcholinesterase in the treatment of Alzheimer’s disease
  118. Phytocrystallization of silver nanoparticles using Cassia alata flower extract for effective control of fungal skin pathogens
  119. Antibacterial wound dressing with hydrogel from chitosan and polyvinyl alcohol from the red cabbage extract loaded with silver nanoparticles
  120. Leveraging of mycogenic copper oxide nanostructures for disease management of Alternaria blight of Brassica juncea
  121. Nanoscale molecular reactions in microbiological medicines in modern medical applications
  122. Synthesis and characterization of ZnO/β-cyclodextrin/nicotinic acid nanocomposite and its biological and environmental application
  123. Green synthesis of silver nanoparticles via Taxus wallichiana Zucc. plant-derived Taxol: Novel utilization as anticancer, antioxidation, anti-inflammation, and antiurolithic potential
  124. Recyclability and catalytic characteristics of copper oxide nanoparticles derived from bougainvillea plant flower extract for biomedical application
  125. Phytofabrication, characterization, and evaluation of novel bioinspired selenium–iron (Se–Fe) nanocomposites using Allium sativum extract for bio-potential applications
  126. Erratum
  127. Erratum to “Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)”
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