zno nanoparticle synthesis

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ORIGINAL RESEARCH article

Synthesis of zinc oxide nanoparticles by ecofriendly routes: adsorbent for copper removal from wastewater.

• 1 Laboratório de Materiais e Compostos Inorgânicos (LabMat), Departamento de Química, Universidade Estadual Do Centro-Oeste, Guarapuava, Brazil
• 2 Chimie des Interactions Plasma-Surface (ChIPS), Research Institute for Materials Science and Engineering, Université de Mons, Mons, Belgium
• 3 Research Group on Carbon Nanostructures (CARBONNAGe), Université de Namur, Namur, Belgium
• 4 Laboratório Nacional de Luz Síncrotron (LNLS), Centro Nacional de Pesquisa em Energia e Materiais (CNPEM), Campinas, Brazil

Zinc Oxide nanoparticles have been synthesized by two simple routes using Aloe vera (green synthesis, route I) or Cassava starch (gelatinization, route II). The XRD patterns and Raman spectra show that both synthesis routes lead to single-phase ZnO. XPS results indicate the presence of zinc atoms with oxidation state Zn 2+ . SEM images of the ZnO nanoparticles synthesized using Cassava starch show the presence of pseudo-spherical nanoparticles and nanosheets, while just pseudo-spherical nanoparticles were observed when Aloe vera was used. The UV-Vis spectra showed a slight difference in the absorption edge of the ZnO particles obtained using Aloe vera (3.18 eV) and Cassava starch (3.24 eV). The ZnO nanoparticles were tested as adsorbents for the removal of copper in wastewater, it is shown that at low Cu 2+ ion concentration (~40 mg/L) the nanoparticles synthesized by both routes have the same removal efficiency, however, increasing the absorbate concentration (> 80 mg/L) the ZnO nanoparticles synthesized using Aloe vera have a higher removal efficiency. The synthesized ZnO nanoparticles can be used as effective and environmental-friendly metal trace absorbers in wastewater.

Introduction

The fast growth of the human population and the further development of industries have direct consequences on the environment, leading to the depletion of natural resources, with an emphasis on freshwater resources. The disposal of industrial, agricultural and domestic waste often contains heavy metals that are toxic to humans and other living species with long-term intake. Among these, copper is one of the most abundant pollutants in wastewater ( Ali et al., 2016 ), widely used in electroplating industries ( Rafiq et al., 2014 ), welding processes, agricultural processes, plumbing material, and electrical wiring ( Ali et al., 2016 ), its high consumption results in the presence of high amounts of this element in wasterwater. The toxic effects of this heavy metal, caused by bioaccumulation, can cause lung cancer, brain, liver, and kidney health problems, among others ( Aksu and Işoǧlu, 2005 ; Saleh, 2017 ). Therefore, it is crucial for the protection of the environment and for human health to remove this metal from industrial wasterwaters before it is disposed of.

Different techniques for the removal of copper from wastewaters have being proposed ( Fu and Wang, 2011 ), among them we can cite precipitation ( Negrea et al., 2008 ), electrocoagulation ( Dermentzis et al., 2011 ), filtration ( Kebria et al., 2015 ) and ion exchange ( Da̧browski et al., 2004 ). However, most of these methods are expensive and prove ineffective in removing heavy metals in trace concentrations. In this context, the adsorption method has stood out, due to its low-cost, ease of use ( Pan et al., 2003 ; Rafiq et al., 2014 ; Ali et al., 2016 ) and the possibility of recycling the adsorbent. Considering the importance of treating wastewater with ion removal at trace levels, in this work, ZnO (Zinc oxide) nanoparticles were used as an adsorbent. ZnO nanoparticles have been reported as good adsorbent of positive metal ions in wastewater ( Singh et al., 2011 ; Wang et al., 2013a ). The Zinc oxide is a type-n material belonging to the semiconductor group of II-VI, has a band-gap of 3.37 eV. It is one of the most widely studied oxides due to its singular physicochemical properties, that include high chemical stability, and wide light absorption range. Zinc oxide has been announced as active material in a myriad of applications such as antifungal ( Kavyashree et al., 2015 ; Sharma and Ghose, 2015 ), drug delivery ( Yuan et al., 2010 ; Chen et al., 2013 ), antibacterial ( Jones et al., 2008 ; Applerot et al., 2009 ), photocatalysts ( Banerjee et al., 2012 ; Lee et al., 2016 ), gas sensors ( Rai and Yu, 2012 ; Waclawik et al., 2012 ) and antioxidant ( Kumar et al., 2014 ). Due to its interesting properties and high applicability, various techniques have been reported for the ZnO synthesis ( Kolodziejczak-Radzimska and Jesionowski, 2014 ).

In this work, in addition to the use of ZnO nanoparticles as a copper ion adsorbent, it is described two low-toxicity routes to synthesize ZnO particles, which are easy to reproduce. The route I uses Aloe vera as an additive while route II uses Cassava starch. The use of these natural additives makes the synthesis more environmentally friendly, due to their high chemical reactivity and high combustion power, reducing the calcination temperature often used in the synthesis of the oxide, in addition, to act as complexing gelling. Aloe vera (Aloe barbadensis Miller) is a perennial plant belonging to the Liliaceae family, it consists mainly of glycoproteins, anthraquinones, saccharides, and others low-molecular-weight substances ( Choi and Chung, 2003 ); inside the leaves, there is a mucilaginous gel produced by the parenchymatous cells. Cassava starch, however, is a polysaccharide of biological, non-toxic, inexhaustible biocompatible, and biodegradable source ( Visinescu et al., 2011 ). The use of Starch and Aloe vera in the synthesis of ZnO nanoparticles has been reported ( Sangeetha et al., 2011 ; Khorsand Zak et al., 2013 ; Thirumavalavan et al., 2013 ; Carp et al., 2015 ; Kavyashree et al., 2015 ), however, here we propose simple routes with fewer steps for the synthesis of ZnO nanoparticles.

Experimental

All the chemicals used were of analytical grade. Zinc nitrate hexahydrate (Zn(NO 3 ) 2 ·6H 2 O, 98%) was purchased from Dynamic and copper nitrate trihydrate (Cu(NO 3 ) 2 ·3H 2 O, 99%) was purchased from Vetec (Sigma-Aldrich). All solutions were prepared with deionized water. Natural Cassava starch in the form of colloidal suspension was used as fuel. Aloe vera leaves were harvested in the São José region of Parana-Brazil. To obtain the extract of Aloe gel, about 200 g of Aloe vera leaves were washed with deionized water and the internal mucilaginous gel was extracted. Afterward, the mucilaginous gel was crushed using a pistil and a ceramic mortar to obtain the complete extract. Finally, the solution was washed, filtered and the resulting Aloe vera gel broth extract was stored under refrigeration (2°C).

Synthesis of Zinc Oxide

Two different routes, both easy to reproduce, were used for synthesizing Zinc oxide nanoparticles. In the route I (green synthesis), adapted from Sangeetha et al. (2011) , Aloe vera (AL) gel broth extracts at the concentration (90%) were prepared with distilled water, the volume was made up to 100 ml. Subsequently, zinc nitrate (9.40 g) was dissolved in the aloe extract solution under constant magnetic stirring (120 min.) and left at rest for 12 h. The suspension was calcined in a muffle furnace at temperatures (750 °C) for 1 h. In the route II (gelatinization method): first starch (ST) was extracted from 100 g of natural Cassava starch in 300 ml of distilled water under mechanical stirring for 2 h. It was then sieved, and in the colloidal starch suspension was added 9.40 g of zinc nitrate. After 60 min of mechanical stirring (600 rpm), the suspension was calcined in a muffle furnace at a temperature of 750 °C for 1 h ( Primo et al., 2019 ). The ZnO nanoparticles obtained were named Zn-AL (route I) and Zn-ST (route II).

Characterization Techniques

X-ray powder diffraction profile was performed at the Brazilian Synchrotron Light Laboratory (LNLS, using XRD1 beamline, 12 keV energy, λ = 1.033 Å, 2θ of 0°-80°) ( Carvalho et al., 2016 ). Scanning electron microscopy images were recorded using a JEOL-JSM-7500F Field Emission Scanning Electron Microscope operated 15 kV, the spatial resolution was 2.5 nm. The Raman spectra were recorded using a Micro-Raman system, Senterra Bruker Optik GmbH), λ = 532 nm, laser power 5 mW, time 10 s, resolution 4 cm −1 . The optical diffuse reflectance was measured (UV-VIS-NIR Spectrophotometer CARYb5G, Varian) in the range of 300–800 nm. Zeta potential was recorded using ZETASIZER NANO ZS90 (MALVERN), model ZEN 1,010 at 25°C. The zeta potentials of the nanoparticles were determined from their electrophoretic mobilities according to Smoluchowski's equation ( O'Brien and Hunter, 1981 ); the pH of these nanoparticles was adjusted between 3 and 11 using HCl or NaOH solutions. The chemical composition was evaluated by X-ray photoelectron spectroscopy (XPS) (Versaprobe PHI 5,000 from Physical Electronics, equipped with a monochromatic Al Kα X-ray source). The XPS spectra were collected at a take-off angle of 45° with respect to the electron energy analyzer and the spot size was 200 μm. Pass energy (PE) of 20 eV was used for the high-energy resolution spectra (Zn 2p, O 1s, and C 1s). The spectra were analyzed using the CASA-XPS software.

The metal ion solutions were analyzed using a Varian TM SpectrAA® 220 Flame Atomic Absorption Spectrometer (FAAS). The FAAS was equipped with an air-acetylene burner. The hollow cathode lamp was set at 4 mA and the analytical wavelength was adjusted at 324.8 nm. The slit size was adjusted to 0.2 nm. The standard curve was drawn by using copper standard solutions. After the adsorption, the ZnO nanoparticles were characterized concerning their composition by energy dispersive X-ray spectrometer (EDX) from Shimadzu, model EDX-7000, containing a Rh tube, operating at 50 and 15 W. The crystalline phases were identified by powder X-ray diffraction (XRD) performed on a Bruker model D2 Phaser with Cu Kα radiation (λ = 1.5418 Å), with scan in 2θ from 10° to 90° and step rate of 0.2°/s. The zeta potential was recorded using ZETASIZER NANO ZS90 from MALVERN, model ZEN 1010. The electronic spectra of the powdered pigments samples were measured on the range of 400–900 nm with a UV-Vis Ocean Optics spectrophotometer model USB-2000.

Adsorption Measurements

To investigate the efficiency of the ZnO nanoparticles as adsorbents for the removal of copper metal ions from water, an adsorption test was performed. The parameters: contact time; initial pH and initial metal ion concentration were investigated. The adsorption experiments were carried out in conical flasks containing 25 mL of copper solution with an initial concentration ranging from 40 to 120 mg L −1 . To this end, 250 mg of the ZnO particles were added, and the solutions were kept under continuous shaking for 240 min in a heating bath at 25°C. To study the adsorption kinetics and the pH parameters, 50 mg L −1 of a solution containing Cu (II) and the same amount of ZnO particles was prepared; its pH was adjusted using 0.1 HCl and 0.1 NaOH solutions. The resulting solutions were centrifuged at 1,200 rpm for 15 min. The ion concentration measurements were performed before the adsorption test without the presence of the adsorbent and after 4 h of adsorption in a flame atomic absorption spectrometer (FAAS).

The amount of Cu 2+ ion adsorbed at the end of the adsorption experiment and the ion percentage removal (%) by the ZnO nanoparticles were calculated applying Equations (1, 2), respectively:

where q is the amount of ion adsorbed by the adsorbent in mg g −1 , C o is the initial ion concentration in contact with the adsorbent (mg.L −1 ), C f is the ion concentration (mg.L −1 ) after the batch adsorption process, m (g) is the mass of adsorbent and V (L) is the volume of ion solution.

Test Leaching of Nanoparticles

To check the stability of the nanoparticles a method adapted from ( Rafiq et al., 2014 ) was used. Thus, 50 mL of simulated sample was treated separately with 250 mg of ZnO synthesized. The initial pH of the experiment was 4 or 6 and the contents were allowed to remain in contact for 240 min while maintaining the temperature at 25°C. After centrifugation and filtration, the residue was washed with deionized water followed by oven drying at 60°C.

Results and Discussion

Characterization of the zinc oxides nanoparticles.

Figure 1A presents the X-ray diffractograms of the zinc oxides nanoparticles obtained after heat treatment at 750°C for 60 min. The crystalline phase is identified by the presence of the characteristic peaks of the Wurtzite ZnO phase ( Kisi and Elcombe, 1989 ), belonging to the compact hexagonal system with a space group P63mc to the crystallographic chart [JCPDS, #PDF01-070-8070]. Additional peaks were not detected, evidencing that the single-phase ZnO was successfully obtained regardless of the synthesis route used and the precursors were completely decomposed. The XRD patterns allowed to determine the average crystallite size of the ZnO nanoparticles, estimated by Scherrer's equation {D = 0.9λ/(B cosθ)} ( Hedayati et al., 2015 ), with the average size of 43.3 nm for Zn-AL and 44.9 nm for Zn-ST. According to these results, the crystalline size is affected by the polysaccharide used in the synthesis, at the same calcination temperature.

Figure 1. (A) XRD pattern and (B) Raman spectrum of the ZnO samples.

Figure 1B shows the Raman spectra of the samples indicating the characteristic wurtzite phase peaks, corroborating with the XRD patterns. The predominant bands are at 99 cm −1 (mode E 2 low) and 437 cm −1 (mode E 2 high). The E 2 low mode is attributed to the vibrations of zinc sublattice in ZnO and E 2 high mode is assigned to the oxygen vibration ( Cuscó et al., 2007 ; Stanković et al., 2012 ), the strong E 2 high mode indicates the high crystallinity of the oxide ( Jothilakshmi et al., 2009 ), the same vibrational mode has been identified for the zinc oxide nanoparticles obtained via the Starch-assisted synthetic route, reported by Carp et al. (2015) . The bands at 380 and 408 cm −1 correspond to the first-order optical modes A 1 (TO) and E 1 (TO), bands at 202 and 330 cm −1 are characteristic of second-order modes 2E 2 low and E 2 high—E 2 low, caused by multiphonon processes. The bands located at 573 and 584 cm-1 are assigned to A1(LO) and E1(LO) modes, these bands are associated to the presence of structural defects in the ZnO structure, being the E 1 (LO) mode strongly affected ( Cuscó et al., 2007 ).

Figures 2A,B shows the SEM images for Zn-AL, which consists of pseudo-spheres, and non-uniform hexagonal particles. For Zn-ST, uniform spherical particles are formed ( Figures 2C,D ). The two samples show particle aggregation, related to the self-assembly effect ( Khorsand Zak et al., 2013 ). The Zn-AL particles tend to agglomerate in plaques ( Figure 2A ), this was attributed to the Aloe vera gel acting as a sacrifice complexant in the formation of the ZnO nanoparticles during the combustion ( Kavyashree et al., 2015 ). The two synthesis routes (Aloe vera and Cassava starch) have polysaccharides as fuel for the formation of ZnO nanoparticles; their formation mechanism can be described by the “egg-box” model ( Kavyashree et al., 2015 ). Therefore, their difference in morphology can be associated with the complex polymeric network of each polysaccharide. Aloe vera gel consists of a combination of organic chains, such as soluble polysaccharides, monosaccharides, proteins, amino acids, among others ( Choi and Chung, 2003 ). The colloidal suspension of Cassava starch is more homogeneous and less complex because it consists basically of amylopectin and amylose leading to the formation of uniform particles, since the Zn (II) ions occupy the “egg-box” more efficiently, with more regular distance. The Aloe vera gel presents a greater variation in its natural components than Cassava starch, affecting directly the shape and reproducibility of ZnO nanoparticles.

Figure 2 . SEM image (A) 4,000x (B) 8,000x Zn-AL; and (C) 4,000x (D) 8,000x Zn-ST.

The chemical environment of the zinc and oxygen atoms were analyzed using X-ray photoelectron spectroscopy (XPS). The O 1s and Zn 2p XPS core-level spectra are shown in Figure 3 . The binding energy of the XPS data was calibrated using the C 1s peak at 284.6 eV ( Das et al., 2010 ). The O 1s spectrum was fitted with three components centered on 530.2 ± 0.1, 531.4 ± 0.6, and 532.3 ± 0.7 eV, for both samples ( Figure 3A ). The low binding energy component located at 530.2 ± 0.1 eV is attributed to O 2− ions participating in the Zn-O bond in the wurtzite structure of the hexagonal Zn 2+ ions of ZnO ( Chen et al., 2000 ; Al-Gaashani et al., 2013 ). The component centered at 531.4 ± 0.6 is associated with photoelectrons emitted from O 2− ions in oxygen-deficient regions in the matrix of ZnO ( Chen et al., 2000 ). The high binding energy component located at 532.7 ± 0.7 is reported to be associated with oxygen species adsorbed on the surface of the ZnO, such a -CO 3 , H 2 O, or O 2 ( Sangeetha et al., 2011 ; Visinescu et al., 2011 ). The Zn 2p high-resolution XPS spectra show the 2p doublet ( Figure 3B ) with components centered at 1020.6 eV (Zn 2p 3/2 ) and 1043.5 eV (Zn 2p 1/2 ). For both samples, the binding energy difference between these core levels is 23.0 eV, reference value denoting the presence of zinc in Zn 2+ oxidation state ( Chen et al., 2000 ; Das et al., 2010 ), the chemical state is confirmed by the Zn LMM Auger data ( Figure 3C ).

Figure 3 . XPS spectra of (A) O 1s. (B) Zn 2p and (C) Zn LMM Auger of the ZnO samples.

Figure 4 shows the optical characterization of the ZnO nanoparticles synthesized using Aloe vera (Route I) and Cassava starch (Route II). It can be observed in Figure 4A an increase in the reflectance at wavelengths larger than 380 nm, this can be attributed to the direct band-gap of ZnO due to the electron transitions from the valence band to the conduction band (O 2p Zn 3d ) ( Kavyashree et al., 2015 ), with a lower percentage of reflectance for Zn-AL (~65%). The band energy gaps (E GAP ) of the samples were calculated using the Kubelka-Munk method ( Cuscó et al., 2007 ), the E GAP were determined by linear extrapolation of the curve [F(R) x E]2 vs. energy (E) in ( Figure 4B ), with values: 3.24 eV (Zn-ST) and 3.18 eV (Zn-AL), similar values have been reported in ( Khorsand Zak et al., 2013 ; Carp et al., 2015 ) for zinc oxides obtained with Starch. The variation in the optical gap of the ZnO nanoparticles can be associated with a variation in the average particle size and morphology. The synthesized ZnO nanoparticles exhibit a slight red shift in the absorption edge ( Figure 4A ), this increase in the response range toward the visible radiation region can be explored in the future as photocatalysts with visible light activity ( Stanković et al., 2012 ).

Figure 4. (A) Diffuse reflectance spectra and (B) Kubelka-Munk curves of ZnO samples.

Copper Ion Removal by ZnO Particles

Zeta potencial (ζ) vs. ph.

Figure 5 shows the obtained ζ-potential values as a function of pH for Zn-AL and Zn-ST. The zeta potential allows evaluating if the particles in the colloidal state show chemical stability. A high ζ-potential generates electrostatic repulsion, preventing particles flocculation and aggregation ( Rodrigues et al., 2020 ); this range of ζ-potential is located below −30 mV or above +30 mV. When the pH <6, the ZnO surface charge shows a strongly positive ζ potential value equal to + 30 ± 2 mV for Zn-ST and +24 ± 2 mV for Zn-ST. Increasing the pH, the point of zero charge (pH PZC ) is reached at 8.8 and 9.4 for Zn-AL and Zn-ST, respectively. These values are in accordance with the values of the literature pH PZC for ZnO ( Adair et al., 2001 ; Tso et al., 2010 ). By further increasing the pH ≥ pH PZC the ZnO nanoparticles exhibit negative surface charge values.

Figure 5 . Zeta potential as a function of pH and point of zero charge (pH PZC ) for the Zn-AL and Zn-ST samples.

Effect of pH on Adsorption

In the absorption study, the pH is an important factor that affects the surface charge of the adsorbent and the degree of ionization of the ions affects the adsorption capacity. The adsorption study was carried at different pHs (2–6), because the copper ion precipitates as Cu(OH) 2 at pH ≥ 6 ( Bagheri et al., 2014 ). The effect of the pH in the adsorption of the heavy metal by the ZnO is shown in Figure 6 . The removal of the Cu (II) ions is strongly dependent on pH, with percentage of removal > 95% for all evaluated pH, reaching the maximum adsorption at pH of 4 for Zn-AL.

Figure 6 . Effect of the pH on the adsorption of the Cu (II) ions by the Zn-AL and Zn-ST oxides.

The removal of Cu (II) on surface of ZnO, can be explained in terms of the adsorbent pH PZC (point zero charge), for values of the pH < pH PZC the adsorbent surface is protonated and positively charged, while for pH > pH PZC the active sites are deprotonated and the charge is negative ( Kikuchi et al., 2006 ; Bagheri et al., 2014 ). Thus, increasing the pH, the competition between H + and Cu 2+ decreases by the reduction of the repulsive force. However, in this study, the adsorption at pH < pH PZC was observed ( Figure 5 ), indicating that, the adsorption of metallic ions on the surface of ZnO may occur via non-electrostatic interaction. When the ZnO particles are exposed in water, hydroxyl groups will be formed ( Wang et al., 2010 ; Le et al., 2019 ), becoming adsorptive active sites removing metal ions by reacting with OH − on the ZnO surface ( Bagheri et al., 2014 ). Thus, the mechanism of ion adsorption can be explained by the model of complexing of ion adsorption in hydrated solids ( Faur-Brasquet et al., 2002 ; Bagheri et al., 2014 ), in which the Cu (II) ions interact with the active groups (OH − ) on the oxide surface:

Therefore, with an increase in the pH of the solution, the amount of active sites on the ZnO surface increases, becoming more favorable to the adsorption of the metallic ion, thus resulting in a greater removal efficiency. The decrease in the removal of Cu (II) ions at pH 6 ( Figure 6 ), can be associated to their precipitation occurring from pH ≥ 6, and thus forming complexes that are not adsorbed by the ZnO adsorbents.

The isotherm and adsorption kinetics studies were performed without pH (pH ~ 6) adjustment. The stability of ZnO nanoparticle was checked after the adsorption experiment at pH 4 and 6. For pH4 the dried samples weight 253.2 mg and 252.8 mg, and for pH6 they weight 252.4 mg and 252.1 mg for Zn-AL and Zn-ST, respectively. The small increase in the weight compared to the initial one (250 mg) can be associated to the absence of adsorbent leaching.

Effect of Initial Metal Ion Concentration

Figure 7 shows the effect of the initial metal concentration on the percentage of the Cu (II) removal. The studies were carried out at optimized contact time and temperature at 25 o C. The results show that the percentage of removal decreases for increasing the initial concentration for both Zn-AL and Zn-ST. At low concentrations the metal ions are adsorbed by specific sites, with the increase in the concentration of Cu (II) ion occurs a saturation of these active sites, and the exchange sites are filled ( Rafiq et al., 2014 ). Conversely, the amount of copper adsorbed per gram of adsorbent (q e ) increased with the increase in the initial concentration of Cu ions, due to the Cu (II) ion adsorption capacity on the available adsorbent.

Figure 7 . Effect of initial concentration on adsorption and equilibrium amount adsorbed of Cu (II) ion in Zn-AL and Zn-ST.

Adsorption Isotherms

The Cu (II) ion adsorption isotherms of Zn-AL and Zn-ST are presented in Figure 8 . The results show that in the Zn-AL the saturation was not effectively reached, while the Zn-ST shows saturation when the initial concentration of 100 mg L −1 and 120 mg L −1 were investigated.

Figure 8 . Adsorption of Cu (II) ions into ZnO samples at 25 °C.

Adsorption of Cu (II) ions into Zn-AL and Zn-ST data were adjusted according to the Langmuir and the Freundlich isotherm models and their correlation parameter are presented in Table 1 . The Langmuir model is applicable in systems with ideal homogeneous surface adsorption ( Azizian and Bagheri, 2014 ; Jing et al., 2018 ). This isothermal model is generally defined as monolayer saturation capacity and the maximum adsorption capacity of the adsorbent for a particular adsorbate ( Jaerger et al., 2015 ). The Freundlich model, on the other hand, reproduces better a heterogeneous system ( Jaerger et al., 2015 ). The Langmuir isotherm in the linear form is given as (Equation 3):

where q e (mg g −1 ) is the amount of ions adsorbed per unit mass of ZnO at equilibrium; K L (L mg −1 ) is the Langmuir constant related to the affinity of the binding sites; q max (mg g −1 ) is a parameter related to the maximum amount of Cu (II) per unit weight of ZnO.

Table 1 . Parameters of the Langmuir isotherms and the Freundlich for adsorption of Cu (II) ions into ZnO samples.

The Freundlich isotherm is an empirical model and is commonly used for low concentrations of adsorbate ( Jaerger et al., 2015 ). The linearized form of the Freundlich isotherm is given as (Equation 4):

where K F (mg L −1 ) is the Freundlich constant; n is a parameter related to the intensity of adsorption and the system heterogeneity. K F and n are the Freundlich constants determined from the intercept and slope of the straight line of the plot ln q e vs. ln C e .

The correlation coefficients ( r 2 ) obtained by the Langmuir isothermal model were well-fitted as shown in Table 1 . The adsorption process consists of monolayer adsorption of Cu (II) ions at the ZnO nanoparticles surface, this is observed for the nanoparticle synthesized by both routes. Another important property obtained analyzing the Langmuir isothermal is the maximum adsorption capacity (q max ). The values of q max for Zn-AL and Zn-ST were 20.42 and 10.95 mg g −1 , respectively. The maximum adsorption values obtained in this study are relatively low compared with data reported in the literature ( Table 2 ) ( Azizian and Bagheri, 2014 ; Jing et al., 2018 ). However, in the present study, the interest is in the removal of low concentrations, and saturation was not observed for both Zn-AL and Zn-ST as adsorbent. The ZnO nanoparticles produced by both routes have good characteristics as Cu (II) ion adsorbent showing a percentage of removal near to 98% for low metal concentration ( Figure 7 ) indicating that the synthesized nanoparticles are potential adsorbent of metal traces in wastewater.

Table 2 . Reported adsorption capacities (mg g −1 ) of copper using Zinc Oxide as adsorbent.

Effect of Contact Time

Figure 9 shows the effect of contact time on the Cu (II) adsorption. The adsorption of copper by ZnO nanoparticles was investigated as a function of contact time in the range between 5 min and 240 min with 50 mg L −1 initial ZnO concentration. The value of the copper removal gradually increases with the time until the equilibrium is reached within 120 min. No significant increase occurred between 180 and 240 min until the adsorption equilibrium was reached. Both Zn-AL and Zn-ST reached the Cu (II) ion adsorption equilibrium at 150 min. The pseudo-first-order model is widely used in solute adsorption in a liquid solution and is represented by Equation (5):

where q t (mg g −1 ) is the amount of Cu (II) adsorbed at time t (min) and k 1 is the rate constant of the pseudo-first-order adsorption (min −1 ). The pseudo-second-order kinetics equation is based on the adsorption capacity and is represented in Equation (6):

where k 2 (g mg −1 min −1 ) is the pseudo-second-order adsorption rate constant.

Figure 9 . Progressive removal of Cu (II) ions from aqueous solutions using Zn-AL and Zn-ST as adsorbent.

Table 3 shows the values of the kinetic parameters obtained for the removal of Cu (II) ions in Zn-AL and Zn-ST. As observed ( Figure 10 and Table 3 ), the adsorption data adjusted better to the pseudo-second-order kinetic model, since the linear correlation coefficients r 2 2 are above 0.99 for all Cu (II) ion solutions at 25 o C. The q e data obtained experimentally are closer to those obtained by the pseudo-second-order model, this fact indicates that the adsorption process is dependent on both the quantity of Cu (II) ions and ZnO sites available ( Almeida et al., 2010 ; Jaerger et al., 2015 ). These results agreed with the report on the adsorption of metals in ZnO by Rafiq et al. (2014) and Kumar et al. (2013) .

Table 3 . Kinetic parameters for Cu (II) removal using Zn-AL and Zn-ST as adsorbent.

Figure 10 . Kinetic parameters for Cu (II) removal using Zn-AL and Zn-ST as adsorbent.

Equation (7) describes a model of the effect of the intraparticle diffusion on adsorption based on the theory proposed by Weber and Morris:

where k i is the rate constant (mg g −1 t −0.5 ) and values of C i give information regarding the thickness of the boundary layer.

When the adsorption mechanism follows the intraparticle diffusion process k i can be obtained from q t vs. t 0.5 plot. In this study, the data displayed multilinear graphs, governed by two steps as shown in Figure 11 . This fact indicates that the adsorption process involves more than one mode in the adsorption of the Cu (II) ion by the ZnO nanoparticles. The linear segment of the adsorption curve is attributed to the immediate adsorption occurring at sites available on the oxide surface. While the second linear portion refers to the adsorption in the final stages of the adsorption equilibrium, where the intraparticle diffusion process begins to decrease and reach a plateau due to the low concentration of remaining Cu (II) ions or because the maximum adsorption by the adsorbate is achieved ( Rafiq et al., 2014 ; Jaerger et al., 2015 ). The results of the intraparticle diffusion for Cu (II) ions in both Zn-AL and Zn-ST oxides suggest that the adsorption is controlled initially by the external mass transfer, followed by the mass transfer by the intraparticle diffusion until reaching equilibrium ( Almeida et al., 2010 ; Jaerger et al., 2015 ). These steps agree with the decrease in the diffusion rate going from k i1 > k i2 corroborating with the increase in the thickness of the limit layer C i1 < C i2 ( Rafiq et al., 2014 ) as observed in Table 4 .

Figure 11 . An intraparticle diffusion model for Cu (II) removal using Zn-AL and Zn-ST as adsorbent.

Table 4 . Intra-particle diffusion constants for Cu (II) removal using ZnO as adsorbent.

Characterization of Cu/ZnO Nanoparticles

After the adsorption assay, the samples at pH 4 and 6 were dried at 60 °C in an oven-dry for 12 h and characterized. The chemical composition data (EDXRF) evince the incorporation of the Cu (II) ions in both Zn-AL and Zn-ST nanoparticles following their surface adsorption ( Table 5 ).

Table 5 . Compositional chemical analysis data by EDXRF (% element).

Figure 12 shows the XRD patterns recorded on the ZnO nanoparticles before and after the Cu (II) metal ions removal. It can be seen that the diffraction peaks recorded on the samples after the adsorption correspond to the majority of peaks of the ZnO hexagonal Wurtzite crystal phase (XRD recorded on the Zn-AL and Zn-ST samples before adsorption). However, in the XRD patterns recorded after adsorption, the CuO phase can be observed in both routes (I and II) samples and for different pHs. The diffraction peaks of CuO were indexed to the monoclinic Tenorite crystal phase of CuO (JCPDS, #PDF 96-901-6327). Moreover, similar to the CuO Bragg peaks the ZnO peaks slightly shift to lower diffraction angles compared to that of the ZnO recorded before adsorption, indicating the substitution of Zn 2+ by Cu 2+ ions in the crystal lattice ( Mukhtar et al., 2012 ). According to ( Wang et al., 2010 ), the hydrated Cu (II) or Cu(H 2 O) 6 2+ can react with the OH − groups and form Cu-O weak bounds through a Lewis interaction, in addition, the adsorbed copper ions can partially hydrolyze leading to the formation of Cu-OH and, consequently, the formation of Cu-O-Cu on the surface of ZnO, thus denoting the Tenorite phase of CuO formed on the surface of ZnO. The crystallite sizes after the adsorption were calculated using Scherrer's equation ( Hedayati et al., 2015 ), the obtained value were: 16.31 nm (Zn-AL, pH 4), and 36.22 nm (Zn-AL, pH 6); and 20.18 nm (Zn-ST, pH 4), and 31.89 nm (Zn-ST, pH 6).

Figure 12 . XRD pattern before adsorption of copper solution 50 mg L −1 , pH 4, and 6: (A) Zn-AL and (B) Zn-ST.

Figure 13 shows the UV-Vis absorbance spectra of ZnO samples before and after Cu (II) adsorption. A broad peak in the visible region centered at 720 nm can be observed after the adsorption of copper. This peak can be assigned to the Cu (II) d-d transition ( Li et al., 2013 ), indicating, the adsorption of Cu (II) ions by the ZnO nanoparticles (Zn-ST and Zn-AL), verifying the XRD results.

Figure 13 . Electronic absorption spectra (visible) of ZnO before the adsorption of copper solution 50 mg L −1 , pH 4 and 6: (A) Zn-AL and (B) Zn-ST.

Conclusions

ZnO nanoparticles have been successfully synthesized by an eco-friendly procedure based on a polysaccharide, without using any surfactant, organic solvent and at low calcination temperature. The type of polysaccharide used as fuel influences on the morphology and optical property of the synthesized nanoparticles (Zn-AL and Zn-ST). Cu (II) adsorption tests showed a low experimental (q max ) value, however saturation was not observed on both synthesized (route I and route II) ZnO adsorbents in the 4 h study period. For both samples (Zn-AL and Zn-ST) at a concentration of 40 mg L −1 of copper ions, there was a high removal value of R%>95% indicating that the synthesized nanoparticles have the potential to be used in the treatment of wastewater, especially in the removal of metal ions at low concentrations. The XRD analysis of the samples after Cu (II) adsorption indicates the formation of the Tenorite phase on the ZnO nanoparticles surface regardless of the pH used in the adsorption experiment, denoting the formation of a secondary phase in the ZnO structure. Accordingly, the two ZnO synthesis routes favor controlling the surface charge, phase, crystallite size, modulating solids for specific applications (photocatalysis, sensor, pigments).

Data Availability Statement

The raw data supporting the conclusions of this article will be made available by the authors, without undue reservation.

Author Contributions

JP performed the methodology, conceptualization, investigation, and wrote the manuscript with input from CB, FA, and SJ. CB, SA, and JP performed XPS measurement and analysis. AS-C and J-FC performed the SEM measurement. VT investigation and formal data analysis of XRD. SJ performed of adsorption tests and discussion. J-FC, CB, and FA supervision. VT, CB, and FA funding acquisition and project administration. All authors contributed to the article and approved the submitted version.

This work was supported by CNPq, CAPES, Finep, Fundação Araucária, and Founds de la Recherche Scientifique (FNRS—No. 2019/V 6/5/006—JG/JN−296). This research used resources of the Brazilian Synchrotron Light Laboratory (LNLS), proposal implemented XRD1 #20190063, line XRD1/LNLS/CNPEM.

Conflict of Interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Acknowledgments

JP thanks CAPES for a graduate scholarship. CB is a Research Associate of the FRS-FNRS, Belgium. The authors are grateful to Ketlyn W. Borth for XRD measurements, Dr. Sueli P. Quináia, and Ms. Mariane Butik for FAAS measurements, and Dr. Rafael Marangoni for the adsorption tests (UNICENTRO).

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Keywords: zinc oxide, starch, aloe vera, copper ion, water treatment

Citation: Primo JdO, Bittencourt C, Acosta S, Sierra-Castillo A, Colomer J-F, Jaerger S, Teixeira VC and Anaissi FJ (2020) Synthesis of Zinc Oxide Nanoparticles by Ecofriendly Routes: Adsorbent for Copper Removal From Wastewater. Front. Chem. 8:571790. doi: 10.3389/fchem.2020.571790

Received: 11 June 2020; Accepted: 26 October 2020; Published: 27 November 2020.

Reviewed by:

Copyright © 2020 Primo, Bittencourt, Acosta, Sierra-Castillo, Colomer, Jaerger, Teixeira and Anaissi. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY) . The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

*Correspondence: Carla Bittencourt, carla.bittencourt@umons.ac.be

Disclaimer: All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article or claim that may be made by its manufacturer is not guaranteed or endorsed by the publisher.

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Zinc oxide nanoparticles: synthesis, characterization, modification, and applications in food and agriculture.

Graphical Abstract

1. Introduction

2. structure, 3. preparation method, 3.1. conventional synthesis methods, 3.2. biological/green synthesis methods, 3.3. physical synthesis methods, 3.4. a non-conventional method, 4. modifications, 5. common tools and techniques for characterization, 5.1. uv-vis spectrophotometer (uv-vis), 5.2. x-ray diffractometer (xrd), 5.3. fourier transform infrared spectroscopy (ft-ir), 5.4. atomic force microscopy (afm), 5.5. scanning electron microscopy (sem), 5.6. transmission electron microscopy (tem), 5.7. x-ray photoelectron spectroscopy (xps), 6. morphological impacts, 7. advantages and possible risk, 7.1. advantages, 7.2. possible risk, 7.3. regulations, 8. applications, 8.1. role in agriculture, 8.2. as antimicrobial agent against food-borne pathogens, 8.3. role in food processing and storage, 8.4. role in food packaging, 8.5. role in food flavor, 9. summary and future perspectives, author contributions, data availability statement, conflicts of interest.

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Share and Cite

Zhou, X.-Q.; Hayat, Z.; Zhang, D.-D.; Li, M.-Y.; Hu, S.; Wu, Q.; Cao, Y.-F.; Yuan, Y. Zinc Oxide Nanoparticles: Synthesis, Characterization, Modification, and Applications in Food and Agriculture. Processes 2023 , 11 , 1193. https://doi.org/10.3390/pr11041193

Zhou X-Q, Hayat Z, Zhang D-D, Li M-Y, Hu S, Wu Q, Cao Y-F, Yuan Y. Zinc Oxide Nanoparticles: Synthesis, Characterization, Modification, and Applications in Food and Agriculture. Processes . 2023; 11(4):1193. https://doi.org/10.3390/pr11041193

Zhou, Xian-Qing, Zakir Hayat, Dong-Dong Zhang, Meng-Yao Li, Si Hu, Qiong Wu, Yu-Fei Cao, and Ying Yuan. 2023. "Zinc Oxide Nanoparticles: Synthesis, Characterization, Modification, and Applications in Food and Agriculture" Processes 11, no. 4: 1193. https://doi.org/10.3390/pr11041193

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• Biochem Biophys Rep
• v.17; 2019 Mar

Synthesis and characterization of zinc oxide nanoparticles by using polyol chemistry for their antimicrobial and antibiofilm activity

Pranjali p. mahamuni.

a Centre for Interdisciplinary Research, D.Y. Patil University, Kolhapur, India

Pooja M. Patil

Maruti j. dhanavade.

b Department of Microbiology, Shivaji University, Kolhapur, India

Manohar V. Badiger

c CSIR, National Chemical Laboratory, Pune, India

Prem G. Shadija

Abhishek c. lokhande.

d Department of Materials Science and Engineering, Chonnam National University, Gwangju, Republic of Korea

Raghvendra A. Bohara

e CURAM, Center for Research in Medical Devices, National University of Ireland Galway, Ireland

Associated Data

The present investigation deals with facile polyol mediated synthesis and characterization of ZnO nanoparticles and their antimicrobial activities against pathogenic microorganisms. The synthesis process was carried out by refluxing zinc acetate precursor in diethylene glycol(DEG) and triethylene glycol(TEG) in the presence and in the absence of sodium acetate for 2 h and 3 h. All synthesized ZnO nanoparticles were characterized by X-ray diffraction (XRD), UV visible spectroscopy (UV), thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy(FESEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) technique. All nanoparticles showed different degree of antibacterial and antibiofilm activity against Gram-positive Staphylococcus aureus (NCIM 2654)and Gram-negative Proteus vulgaris (NCIM 2613). The antibacterial and antibiofilm activity was inversely proportional to the size of the synthesized ZnO nanoparticles. Among all prepared particles, ZnO nanoparticles with least size (~ 15 nm) prepared by refluxing zinc acetate dihydrate in diethylene glycol for 3 h exhibited remarkable antibacterial and antibiofilm activity which may serve as potential alternatives in biomedical application.

• • Synthesis of Zno NPs of different size & shape by tuning polyol/catalyst/reaction time.
• • Shape and size control were possible by varying these parameters.
• • Antibacterial and antibiofilm activity were studied against Staphylococcus aureus and Proteus vulgaris.
• • Comparative study revealed DEG synthesis for 3 h in absence of sodium acetate showed maximum antibacterial/biofilm activity.

1. Introduction

Biofilms are the complex communities of microorganisms attached to any biological or non-biological surface that remain enclosed in self-produced hydrated polymeric matrix [1] , [2] . Microorganisms in biofilm transcribe genes that are different from the genes transcribed by planktonic bacteria [3] . The cells in the biofilm are inherently protected from phagocytosis, develops high resistance to antibiotics which make them difficult to treat [4] , [5] , [6] , [7] . Both Gram-positive and Gram-negative bacteria can form the biofilm on various medical devices such as catheters, prosthetic joints, endotracheal tubes, heart valves, contact lenses and ortho-dental instruments [8] . In this regard, Staphylococcus aureus and Proteus vulgaris are biofilm-forming pathogens on medical implants able to produce severe biofilm-associated infections such as urinary tract infection, musculoskeletal infection and respiratory tract infection [9] . It has been estimated that the maximum bacterial infections treated in hospitals are associated with bacterial biofilm [6] . In fact, the number of implant-associated infections near about 1 million/year in the US alone and their direct medical costs exceed $3 billion annually [10] .

The problem of biofilm-related infections could be resolved by removal of biofilm physically or removal of implants which is not feasible economically. Other methods like use of depolymerase enzyme and the use of bacteriophages could be used to control biofilm formation [11] . Recent reports suggest that several synthesized antimicrobial peptides (AMPs) are able to interact with the membrane through penetration or dissolving the biofilms [12] , [13] . Alternatives to these conventional methods which recommend, recent developments in nanotechnology that have been proven to be an efficient approach to control biofilm formation [14] .

The ability of nanomaterials for biofilm disruption has been reported. For example, Simona and Prodan et al investigated the effect of glycerol iron oxide nanoparticles for biofilm inhibition produced by Pseudomonas aeroginosa [15] . Among nanosized metal oxides, zinc oxide (ZnO) has gained much more attention due to its interesting properties such as high surface to volume ratio, low cost and long-term environmental stability [16] , [17] . According to Sirelkhatim et al. and Dhillo et al., it is already reported by several studies that ZnO nanoparticles are non-toxic to human cells and toxic to bacterial cells. Toxicity studies showed that DNA in human cells do not get damaged by zinc ions. This fact made ZnO nanoparticles biocompatible to human cells [16] , [18] , [19] .

Various methods have been used to prepare zinc oxide nanoparticles suchas hydrothermal [20] , [21] , [22] , [23] , solvothermal methods [24] , [25] ,microemulsion [26] , sol-gel [27] , [28] and thermal decomposition of precursors [29] , [30] .

According to Raghupathi et al. and Applerot et al., ZnO nanoparticles exhibit a maximum degree of antibacterial activity with the decrease in particle size [7] , [31] . Method of synthesis of nanoparticles strongly affects the size and shape of nanoparticles, which determines the properties of nanoparticles [32] , [33] .

Fievet, Lagier, and Figlarz first introduced the use of polyols for the synthesis of small particles termed as “polyol process” or “polyol synthesis.” The polyol synthesis allows the formation of ZnO nanoparticles with excellent crystalline quality and controlled morphology. Its peculiarity lies in the properties of polyols like high boiling point (up to 320 °C), high dielectric constant, the solubility of simple metal salt precursors and coordinating properties for surface functionalisation preventing agglomeration [34] , [35] . Also, the presence of weak base sodium acetate in the reaction controls the nucleation process and assembly process through which nanoparticles with different morphology can be obtained [36] .

In the present investigation, we have synthesized ZnO nanoparticles by applying different approaches, (i) regular synthesis in polyols, (ii) in presence of sodium acetate, (iii) increasing reaction time. We have employed different strategies to synthesize ZnO nanoparticles. The synthesis method mainly involves reflux of zinc acetate dihydrate precursor in diethylene glycol (DEG) and triethylene glycol (TEG) in the presence and in absence of weak base sodium acetate for varied reaction time. The effect of these two polyols, presence and absence of sodium acetate and reaction time on size and morphology of synthesized ZnO nanoparticles is presented. These nanoparticles were studied for their antimicrobial and antibiofilm activity against Staphylococcus aureus (NCIM 2654) and Proteus vulgaris (NCIM 2813).

2. Materials and methods

2.1. materials.

All chemicals used here were of analytical grade and used without further purification. All chemicals were purchased from Loba fine chemicals, Mumbai, India. The media have been procured from Himedia Laboratories Pvt. Ltd, Mumbai, India. Distilled water was used in the all experiments. The microorganisms, Gram-positive ( Staphylococcus aureus NCIM 2654) and Gram-negative ( Proteus vulgaris NCIM 2613) were collected from the National Collection of Industrial Microorganisms (NCIM), Pune, India.

2.2. Synthesis of ZnO nanoparticles

ZnO nanoparticles were prepared by refluxing precursor zinc acetate dihydrate (0.1 M) in diethylene glycol and triethylene glycol at 180 °C and 220 °C respectively. Reaction time varied for 2 and 3 h with and without sodium acetate (0.01 M). Before refluxing, the solution was kept on a magnetic stirrer at 80 °C for 1.5 h. After completion of reflux action, the samples were centrifuged at 8000 rpm for 15 min and washed with distilled water and ethanol for three times. Further, it was dried at 80 °C for overnight ( Table 1 , Table 2 ).

TGA results of ZnO samples (1) DEG 2 h, (2) DEG 2 h with sodium acetate, (3) DEG 3 h, (4) DEG 3 h with sodium acetate, (5) TEG 2 h, (6) TEG 2 h with sodium acetate, (7) TEG 3 h, (8) TEG 3 h with sodium acetate.

% weight loss and remaining residue for all ZnO samples are given in Table 3 . From table listed above it was observed that, DEG 3 h(3) and TEG 3 h with sodium acetate (8) shows minimum weight loss and maximum final residue.

Reaction conditions used for synthesis of Zinc oxide nanoparticles.

Calculated crystallite size of ZnO NPs are listed below.

Where, D = crystallite size, λ = X-ray wavelength, β = FWHM of diffraction peak and θ = .

angle of diffraction.

2.3. Reaction mechanism of ZnO formation

By considering the chemicals involved in the hydrolysis process, the mechanism of the ZnO nanoparticles formation is proposed as follows.

Formation of metal oxides proceeds in 2 steps: hydrolysis reaction and condensation reaction. Hydrolysis reaction is water dependent, absence of water in the reaction leads into failure of occurrence of next step of reaction that is condensation reaction which will not form any product. Also, due to presence of excess amount of water, particles start to agglomerate and give large sized particles with large distribution. So the hydrolysis ratio is considered as an important factor which affects the size and morphology. ( Scheme 1 ).

Schematic representation of synthesis of DEG and TEG mediated ZnO nanoparticles.

Hydrolysis ratio is the ratio of number of moles of metal ions to number of moles of water. Alkaline ratio also considered an important factor affecting size and morphology. Amel Dalklaoui et al reported the effect of increasing alkaline ratio on morphology which showed the change in morphology from irregular and anisotropic forms to spherical form. Alkaline ratio is the number of moles of sodium hydroxide to metal which is attributed to the effect of OH - ions on morphology. Also the concentration of precursor and temperature of the reaction affects the morphology of particles. In the present investigation, concentration of precursor, hydrolysis ratio and alkaline ratio is kept constant throughout the all synthesis processes of ZnO.

First, the reaction between zinc acetate dihydrate and DEG/TEG leads to esterification that forms (Zn-OH) 2 . Further dehydration of (Zn-OH) 2 results into formation of ZnO nanoparticles. The basic approach for addition of sodium acetate was the addition of excess acetate ions that gives different particle morphologies than the particles synthesized in absence of sodium acetate. Sodium acetate causes a weak hydrolyzation, which controls the release rate of OH − [36] , [37] , [38] , [39] , [40] , [41] , [42] .

2.4. Characterization of nanoparticles

The X-ray diffraction studies of ZnO NPs were carried out using Rigaku 600Miniflex X-ray diffraction instrument (XRD) with Cukα radiation (λ = 1.5412 Å) in the scanning range of 10 0 -80 0 . To confirm the absorbance of ZnO NPs and to observe the changes in the absorbance caused due to variations in reaction conditions, UV–visible (UV–vis) spectra were carried in the wavelength range of 200–600 nm using Agilent Technologies Cary 60 UV–vis. In order to identify the characteristic functional groups present on the surface of the ZnO, Fourier transform infrared (FTIR) spectra of all samples were recorded by using JASCO INC 410,Japan,in a range of 400–4000 cm −1 . Thermal gravimetric analysis(TGA) was carried out to observe thermal stability of ZnO on instrument PerkinElmer STA-5000. All samples were heated from 50 to 900 °C at the rate of 10 °C/min. The surface morphology of all synthesized ZnO were studied by field emission scanning electron microscopy(FESEM) and transmission electron microscopy(TEM). Elemental analysis was performed by energy dispersive X-ray (EDX) spectroscopy (JSM-6701F, JOEL, Japan).

2.5. The antimicrobial assay

Antimicrobial study of different ZnO NPs was performed by agar well diffusion method. The relative activities of these samples were studied against both Gram-positive Staphylococcus aureus (NCIM 2654) and Gram-negative Proteus vulgaris (NCIM 2613) bacteria. In this method, in each well 1 mg/ml concentration of all ZnO NPs was inoculated on nutrient agar plates which were previously seeded by 100 µl of 24 h old bacterial inocula. ZnO samples were sonicated for 15 min in distilled water before inoculation. Then the plates were incubated at 37 °C for 24 h for the growth of microorganisms. Antimicrobial activity was observed by measuring the inhibition zone diameter (mm).

2.6. Determination of minimum inhibitory concentration

The determination of minimum inhibitory concentration was performed in sterile Muller –Hinton broth at concentration of nanoparticles ranging from 10 mg to 50 mg/ml against two pathogens Gram positive Staphylococcus aureus (NCIM 2654) and Gram negative Proteus vulgaris(NCIM 2613) bacteria. The assay was carried out in 96 well plates by using tryptic soy broth medium. In brief, 200 µl volume of tryptic soy medium was added in each well and inoculated with 24 h old 10 µl of bacterial inocula. One well was maintained without addition of nanoparticles, used as a control. The microplates were incubated at 37 °C for 24 h. After incubation OD was recorded at 600 nm. From graph, minimum inhibitory concentration and % of inhibition at each concentration was determined.

2.7. Antibiofilm activity

Antibiofilm activity was done by using microtiter plate method. For this, Staphylococcus aureus (NCIM 2654) and Proteus vulgaris (NCIM 2613) were inoculated in sterile tryptic soy broth and incubated for 24 h at 37 °C. Then samples were centrifuged at 5000 rpm and pellet was suspended in phosphate buffer(pH 7.0) 1 mg/ml stock of all ZnO samples were prepared. In brief, 200 µl medium with known concentrations of ZnO were inoculated with 10 µl of bacterial suspension and incubated for 24 h at 37 °C. After incubation, the wells were drained, washed with phosphate buffer saline(PBS),fixed with cold methanol, and then stained with 1% crystal violet for 30 min. Biofilm formed in wells was resuspended in 30% acetic acid. The intensity of suspension was measured at 570 nm and % of biofilm inhibition was calculated by using equation given below [8] .

3. Results and discussion

3.1. x-ray diffraction studies.

Fig. 1 A and B represents diffractograms of ZnO NPS.The XRD of all the samples having 2θ values with reflection planes at 31.72° (100), 34.39° (002), 36.23° (101) and 47.44° (102) corresponds to JCPDS Card No. 36-1451. So,all diffraction peaks fit well with hexagonal wurtzite structure of ZnO, which proves that ZnO was successfully synthesized by polyol hydrolysis method [43] .

(A) XRD of DEG 2 h(a), DEG 2 h with sodium acetate(b), DEG 3 h(c), DEG 3 h with sodium acetate(d), (B) TEG 2 h(a), TEG 2 h with sodium acetate(b), TEG 3 h(c), TEG 3 h with sodium acetate(d).

The crystallite sizes of ZnO NPs were calculated from FWHM of the most intense peak using the Debye–Scherrer formula (Eq. (1) ), given below:

3.2. UV–vis spectroscopy analysis

In order to observe the UV spectroscopy of synthesized ZnO nanoparticles, they were sonicated in distilled water for about 15 min and UV spectra were recorded Supplementary data Fig. 1 A and B shows the UV–vis absorption spectra of the ZnO nanoparticles synthesized by using DEG and TEG. The absorption peak was recorded in each spectrum in range of 360–380 nm which is a characteristic band for the pure ZnO.Absence of any other peak in the spectrum confirms that the synthesized products are ZnO only [17] . ( Fig. 2 , Fig. 3 ).

FESEM micrographs of (a) DEG 2 h, (b) DEG 2 with sodium acetate, (c) DEG 3 h, (d) DEG 3 h with sodium acetate, (e)TEG 2 h, (f) TEG 2 h with sodium acetate, (g) TEG 3 h, (h) TEG 3 h with sodium acetate.

Representative TEM images of (a) DEG 2 h, (b) DEG 2 h with sodium acetate, (c) DEG 3 h, (d) DEG 3 h with sodium acetate, (e)TEG 2 h, (f) TEG 2 h with sodium acetate, (g) TEG 3 h, (h) TEG 3 h with sodium acetate.

It is reported that the intensity of absorption peak in UV–visible spectrum is related with particle size of nanoparticles. As the particle size decreases, absorption peak shifts towards lower wavelength that is blue shift. As in case of DEG mediated synthesized ZnO nanoparticles, DEG 2 h sample shows absorption peak at 366 nm while DEG 2 h sample with sodium acetate show absorption peak at 368 nm. Similarly remaining all samples show blue shift with decrease in particle size which interpret that the intensity of the absorbance peak shows slight blue shift with decrease in particle size. The type of polyols used, temperature and reaction time have effect on absorption peak [44] , [45] .

3.3. Field emission scanning microscopy (FESEM)/energy dispersive X-ray spectroscopy (EDX)

Morphology of all ZnO nanoparticles synthesized by using DEG and TEG were studied by images obtained by FESEM and TEM. Fig. 4 , Fig. 5 clearly shows that the zinc oxide nanoparticles obtained by refluxing diethylene glycol and triethylene glycol for 2 h and 3 h in presence and in absence of sodium acetate have uniform shape and size with different morphology. Image depicts addition of sodium acetate, use of different polyol and change in reflux time from 2 h to 3 h offers difference in morphology from oval to rod shape with average particle size of ~ 15 to 100 nm. FESEM and TEM analysis reports DEG refluxed for 3 h in absence of sodium acetate exhibited least particle size of ~ 15 nm.

Antibacterial activity of DEG and TEG mediated synthesized ZnO NPs (1 mg/ml) against Gram-positive Staphylococcus aureus(NCIM 2654) (A)and Gram-negative Proteus vulgaris(NCIM 2613) (B), In plate (I) and (III) samples inoculated are(1)DEG 3 h, (2) DEG 3 h with sodium acetate, (3) DEG 2 h, (4) DEG 2 h with sodium acetate and in plate (II) and (IV) samples inoculated are(1)TEG 2 h with sodium acetate, (2) TEG 3 h, (3) TEG 3 h with sodium acetate, (4) TEG 2 h.

% of inhibition of all ZnO samples at different concentrations of all ZnO nanoparticles against Staphylococcus aureus(NCIM 2654) (A) and Proteus vulgaris(NCIM 2613) (B), (1) DEG 3 h, (2) DEG 3 h with sodium acetate, (3) TEG 3 h, (4) TEG 3 h with sodium acetate, (5) TEG 2 h, (6)TEG 2 h with sodium acetate, (7) DEG 2 h, (8) DEG 2 h with sodium acetate.

The difference observed in the morphology of the ZnO nanoparticles depends upon release rate of OH – ions. In presence of sodium acetate release rate of OH - ions becomes slow due to its weak hydrolyzing ability of acetate ions, which affects on condensation and nucleation process. So particles show elongated rod shaped morphology [38] .

The elemental analysis of all ZnO nanostructures was performed by EDX spectroscopy. The Supplementary Fig. 2 shows the EDX of all synthesized ZnO nanoparticles which reveals presence Zn and O that indicate the synthesis of pure ZnO nanoparticles. The impurity free nanoparticle exhibits the promising anti-microbial and antibiofilm activity.

3.4. Fourier Transform Infrared Spectroscopy (FT-IR) analysis

In Supplementary data Fig. 3 A and B , FTIR spectrum of ZnO nanoparticles synthesized in DEG and TEG showed characteristic peak at ~ 3443 cm −1 , which was assigned to stretching vibrations of hydroxyl group [46] , [47] and the peaks at ~ 2922 cm −1 were assigned to –CH stretching showing presence of CH 2 ,CH 3 groups [48] . The 2 peaks at about ~ 1586 cm −1 and ~ 1412 cm −1 were assigned to symmetric and asymmetric C˭O stretching [49] . The peak position at 1125 cm −1 were assigned to –CH deformation showing –CH 2 , CH 3 bending. Due to inter atomic vibrations, metal oxides generally exhibit absorption bands in fingerprint region below 1000 cm −1 . [50] . In the infrared region, the peaks at around 415–480 cm −1 corresponds to ZnO which show the stretching vibration of Zn-O [51] . This observation indicate that, DEG/TEG molecules get adsorbed on synthesized ZnO nanoparticles [48] . The differences in the particle sizes may lead to different wavenumber and frequencies are consistent to the reported literature [52] .

3.5. Thermogravimetric analysis

The thermal decomposition behaviour and presence of adsorbed polyols of all ZnO samples were observed by TGA analysis. All samples were heated from 50 to 900 °C at the rate of 10 °C/min. The Supplementary data Fig. 4A and B shows the thermal decomposition of DEG and TEG mediated synthesized ZnO nanoparticles respectively. The two successive decompositions were observed in all samples. The initial weight loss observed was due to the evaporation of surface adsorbed water and moisture occurred in range of 145–270 °C [53] and further 2ndstage of decomposition was observed in the range of 452–490 °C due to loss of adsorbed DEG/TEG molecules in all samples and which was confirmed by FTIR [54] .

3.6. Applications of ZnO NPs

3.6.1. antimicrobial activity.

From the results in Table 4 , it was observed that among all ZnO nanoparticles the smallest ZnO nanoparticles synthesized in DEG for 3 h showed significant zone of inhibition against Staphylococcus aureus(NCIM 2654) and Proteus vulgaris(NCIM 2613).

Diameter of zone of inhibition by ZnO against Staphylococcus aureus and Proteus vulgaris .

The intensity of antibacterial activity is size dependent. Intensity of antibacterial activity is inversely proportional to the size of nanoparticles, so nano-sized ZnO show good antibacterial activity than bulk ZnO [55] , [56] . The intensity of inhibition by nanoparticles depends upon small size, shape and large surface area to volume ratio, as it affects on the interaction with membrane of microorganisms. Yamamoto et al reported, study of antibacterial activity of different sized ZnO nanoparticles (10–50 nm), which showed better antimicrobial property than bulk ZnO (2 µm) [57] , [58] . According to Pratap et al., ZnO synthesized by using green route Coriandrum sativum leaf extract exhibit antibacterial activity at concentration more than 100 mg/ml [59] . Sharmila et al., demonstrated antibacterial activity of ZnO nanoparticles (22–93 nm) synthesized through green route Bauhinia tomentosa leaf extract, which showed antibacterial activity against Gram positive and Gram negative bacteria [60] . Several reports suggest that the action of ZnO on bacterial species is due to release of reactive oxygen species (ROS) species and zinc ions. Generated ROS species, that is, hydrogen peroxide (H 2 O 2 ), OH - (hydroxyl radicals), O 2 −2 (peroxide) and zinc ions from ZnO nanoparticles bind to the negative surface of the cell membrane, leading to disruption of the cells followed by leakage of inner cellular material that causes cell death [61] .

In the present study, our interest was to synthesize particles with different morphologies and to study their size dependent antibacterial activity. Out of all synthesized ZnO nanoparticles, DEG 3 h sample with least particle size (~ 15 nm) exhibited comparatively remarkable antibacterial activity against both bacteria. It’s small size and it’s high surface area to volume ratio may helped for more interaction with bacterial cell, than other ZnO NPs with greater size, this could be the reason why these nanoparticles exhibited significant antibacterial activity than other synthesized nanoparticles.

3.6.1.1. Quantitative antimicrobial assay

From the above results, it was concluded that minimum inhibitory concentration for all samples was in range of 10–20 µg/ml. It was revealed that among all samples DEG 3 h sample showed significant % of inhibition for Staphylococcus aureus(NCIM 2654) as compared to Proteus vulgaris(NCIM 2613).  For Staphylococcus aureus and Proteus vulgaris it showed 32.67% and 22.38% of inhibition at 50 µg/ml concentration respectively. ( Fig. 6 , Fig. 7 )

% of biofilm inhibition of all ZnO samples at different concentrations of all ZnO nanoparticles against Staphylococcus aureus(NCIM 2654) (A) and Proteus vulgaris(NCIM 2613) (B), (1) DEG 3 h, (2) DEG 3 h with sodium acetate, (3) TEG 3 h, (4) TEG 3 h with sodium acetate, (5) TEG 2 h, (6) TEG 2 h with sodium acetate, (7) DEG 2 h, (8) DEG 2 h with sodium acetate.

Antibacterial and antibiofilm action of ZnO on bacteria.

3.6.1.2. Antibiofilm activity by microtiter plate

Effect of all synthesized ZnO nanoparticles on biofilm formation on Staphylococcus aureus (NCIM 2654) and Proteus vulgaris(NCIM 2613) was shown in figure 11 A and B. These graphs indicate that all ZnO samples synthesized by using DEG and TEG inhibited the activity of biofilm formation. Out of all synthesized ZnO nanoparticles, ZnO synthesized by refluxing DEG for 3 h without sodium acetate showed significant % of inhibition in Staphylococcus aureus as compared to Proteus vulgaris at each concentration. All ZnO samples showed increased % of inhibition with increase in concentration. At 250 µg/ml concentration of ZnO synthesized by DEG refluxed for 3 h exhibited maximum 67.3% and 58.18% biofilm inhibition against Staphylococcus aureus and Proteus vulgaris.

Staphylococcus aureus and Proteus vulgaris are pathogens that have ability to form biofilm on medical implants associated with chronic infections. These infections are difficult to irradicate due to resistant nature of biofilm [62] . Action of antimicrobial agents against biofilm associated infections is not that much effective due to inability of penetration into network of biofilm. To overcome this problem application of nanoparticles for inhibition of antibiofilm is efficient [4] , [63] .

In present study, by using different strategies we have synthesized ZnO nanoparticles with different morphologies in which ZnO nanoparticles synthesized by refluxing DEG for 3 h in absence of sodium acetate proved to be efficient nanoparticle with remarkable antibiofilm activity than other synthesized ZnO nanoparticles with size greater than these particles. These results revealed that smaller nanoparticles exhibited significant inhibition of biofilm than larger nanoparticles.

4. Conclusion

In the present investigation, we have synthesized ZnO nanoparticles by applying different approaches, i) regular synthesis in polyols, ii) In presence of sodium acetate, iii) increasing reaction time. We showed that it is possible to control shape and size of nanoparticles through these approaches. XRD analysis revealed the phase purity. The synthesized nanoparticles have crystallite nature having hexagonal wurtzite structure. UV spectroscopy showed that absorption edges was shifted to a shorter wavelength showing blue shift due to decrease in crystal size. FTIR and TGA analysis presented that DEG and TEG molecule adsorbed on ZnO nanoparticles. The prepared all ZnO nanoparticles posses antibacterial and antibiofilm activity against Staphylococcus aureus and Proteus vulgaris. The most interesting observation found in present study is that, all synthesized nanoparticles showed nicely organized oval and rod shaped morphology with different size. In case of nanoparticles synthesized by using polyol DEG, it was observed that, addition of sodium acetate and increase in reflux time from 2 h to 3 h changes morphology of nanoparticles from oval to rod shape, while in case of nanoparticles synthesized by using polyol TEG all particles show rod shaped morphology and increase in size with addition of sodium acetate and increase in reflux time from 2 h to 3 h which highlights the role of sodium acetate in change of morphology. Out of all particles, ZnO synthesized by refluxing zinc acetate precursor in DEG for 3 h in absence of sodium acetate with particle size ~ 15 nm showed maximum activity against Staphylococcus aureus and Proteus vulgaris than other synthesized ZnO nanoparticles. This study showed that the antimicrobial and antibiofilm efficacy of ZnO nanoparticles increases with decreasing particle size. We have demonstrated that applying different approaches affects on the size and shape of nanoparticles, these findings provide better understanding of ZnO nanoparticles that can serve as a potential antibacterial and antibiofilm agent in biomedical application.

Acknowledgements

The corresponding author is thankful for D.Y. Patil University for financial support (DYPU/R&D/190) and financial support from the Irish Research Council under the Government of Ireland Postdoctoral fellowship Grant GOIPD/2017/1283. The funding agencies are highly acknowledged.

Appendix A Supplementary data associated with this article can be found in the online version at doi:10.1016/j.bbrep.2018.11.007

Appendix B Supplementary data associated with this article can be found in the online version at doi:10.1016/j.bbrep.2018.11.007

Appendix A. Transparency document

Supplementary material

Appendix B. Supplementary material

Facile synthesis and electrochemical analysis of TiN-based ZnO nanoparticles as promising cathode materials for asymmetric supercapacitors

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• Published: 27 September 2021

Biosynthesis of zinc oxide nanoparticles using Phoenix dactylifera and their effect on biomass and phytochemical compounds in Juniperus procera

• Abdalrhaman M. Salih 1 ,
• Fahad Al-Qurainy 1 ,
• Salim Khan 1 ,
• Mohamed Tarroum 1 ,
• Mohammad Nadeem 1 ,
• Hassan O. Shaikhaldein 1 ,
• Abdel-Rhman Zakaria Gaafar 1 &
• Norah S. Alfarraj 1  

Scientific Reports volume  11 , Article number:  19136 ( 2021 ) Cite this article

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• Biological techniques
• Biotechnology

Biosynthesized nanoparticles have played vital role recently, as suggested to be alternative to physical and chemical methods. In this study, biosynthesis of zinc oxide nanoparticles (ZnO NPs) were carried out using leaf extracts of Phoenix dactylifera L. and Zinc nitrate. The effect of ZnO nanoparticles on biomass and biochemical parameters was investigated. Biosynthesized ZnO nanostructure was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–visible spectrophotometer and Fourier transform infrared spectroscopy (FTIR). Which resulted in spherical shape with size ranging between 16 to 35 nm of Biosynthesized ZnO nanoparticles and UV absorption beak at 370.5 nm with clear peaks of functional groups. The impact of different concentrations (0.0 mg/L, 80 mg/L and 160 mg/L) of biosynthesized ZnO nanoparticles on biomass and bioactive compounds production of Juniperus procera in vitro was investigated. The results showed that, biosynthesized ZnO NPs (80 mg/L and 160 mg/L) concentrations were boosted the growth of J. Procera with significantly compared to non-treated plants in vitro. The highest concentration (160 mg/L) of ZnO NPs was enhanced the growth of plant at beginning period, one month later shoots became yellow and callus turned to be brownish. Moreover, the influence of ZnO NPs on phytochemical compounds in callus of Juniperus procera was examined using GC–MS analysis. The differences among treatments were recoded . Overall, zinc oxide nanoparticles substantially improved the growth of shoots and callus with increasing of biochemical parameters such as chlorophyll a, total phenolic and flavonoids contents, besides the total protein and, SOD, CAT and APX activity. ZnO NPs might be induced some phytochemical compounds as well as inhibit.

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Introduction.

Nanotechnology has become a new field of research, that dealing with synthesis of nanomaterials and nanoparticles for their applications in various fields such as catalysis, electrochemistry, biomedicines, pharmaceutics, and food technology, etc. 1 , 2 , 3 , 4 . The particles within the size less than 100 nm are known as nanoparticles (NPs) and it would be divided into different classes depend on their shapes and size as fullerenes, ceramic NPs, metal NPs and polymeric NPs 5 , 6 . There are many methods have been used for fabrication of nanoparticles, which include chemical and physical methods such as photochemical, radiation, chemical precipitation methods. These methods are non-environmental friendly due to the use of toxic, combustible, and hazardous chemicals and extremely expensive 7 , 8 . In contrast, plant extracts, fungi, and microbes mediated the synthesis process of NPs, it consider to be a suitable alternative method to non-environmental methods 9 , 10 , 11 . This method has been called ‘green synthesis or biosynthesis’ which is a less hazardous process than physical and chemical synthesis methods and low-cost 12 . It has been reported that, biosynthesized Zinc oxide nanoparticles are eco-friendly, which is provide many advantages such as antimicrobial activity against microorganisms, drug delivery and anticancer therapy as well 13 . A few studies have been conducted and tested the role of biosynthesized zinc oxide nanoparticle on plants biomass and bioactive compounds production in vitro. For example, ZnO NPs with low concentrations, it stimulated the callus growth and pointed out the nanoparticles role in regeneration, decontamination, organogenesis, callus induction and activated a protein that has a vital role in growth recounted by 14 , 15 . Previous studies have been provided evidence for NP-mediated modulation of plant secondary metabolism, beside that the studies provide an indirect link between secondary metabolism and reactive oxygen species 16 . The exposure of plants to NPs, has the potential to induce secondary metabolites of plants, and it act as phytoalexins to protect plants from biotic and abiotcs stress 16 , 17 . Juniperus procera is medicinal plant, widely spread throughout southern part of Saudi Arabia, and it is indigenous to the mountains of eastern Africa from east Sudan to Zimbabwe, and southwest of the Arabian Peninsula 18 . Juniperus procera is a source of natural drugs with potential for antimicrobial, anticancer, insecticidal antioxidant activities 19 , 20 , 21 . In nature, plants produce secondary metabolites as a protection mechanism. On the other hand, secondary metabolites can be produced and improved using micro propagation technique which is a reliable approach. Moreover, mass propagation is a rapid approach for production of important secondary metabolites 22 , 23 , 24 . Furthermore, plants have an important natural products have been used by human as condiments and flavorings and for treating health disorders and preventing diseases, including epidemics 25 . So far, natural products have made the basis for many useful agrochemicals, pharmaceuticals, and can be a alternative source for bioactive compounds to control several diseases in both crops and humans 26 , 27 . To our knowledge, there are no reports to date involving zinc oxide nanoparticles effect on biomass and bioactive compounds of J. Procera in vitro . Therefore, the main objective of the present study was to synthesis zinc oxide nanoparticles biologically, and to investigate their effect on biomass and bioactive compounds production from Juniperus procera in vitro. In this present study different characterization techniques such as TEM, XRD, FTIR and UV–Visible were used to investigate the formation of ZnO nanoparticles. Whereas, the effect of biosynthesized ZnO NPs on biomass and bioactive compounds of J. Procera in vitro was tested by the estimation of the total protein content and enzymes activity, and total phenolic content, flavonoids, and bioactive compounds.

Material and methods

Biosynthesis of zno nps.

Leaves of Phoenix dactylifera were collected from botanic garden, Dept. of Botany and Microbiology, King Saud University, with full permission has obtained from institute. The extract was prepared by drying leaves at room temperature and washed in distilled water, 5 g of this powder was homogenized completely in 100 ml Milli-Q water and extracted at ≤ 80 °C for 20 min. The resultant was filtered using Whatman filter papers No. 1. Then, extract was stored at 4 °C and used for generating biosynthesized zinc oxide nanoparticles. Zinc nitrate (99.999%) was purchased from Sigma. The synthesis of ZnO NPs was carried out by taking a 0.05 M of zinc nitrate in 100 ml Milli-Q water. Then, 2:2 (v/v) of leaf extract and zinc nitrate to obtain a mixture solution in a round-bottom flask, and incubated with constant stirring (100 rpm) at 40 °C for 24 h. The solution was cooled to room temperature and filtered using Whatman filter papers No. 1. The precipitate was washed with deionized water and absolute ethanol for several times using centrifugation (5000 rpm for 5 min), and dried in an oven at 60 °C for 24 h. Finally, the product was calcined at 600 °C for 3 h 28 .

Characterization of ZnO NPs

The surface morphology and particle size of the ZnO nanostructure were investigated using transmission electron microscope (TEM). The crystalline structure of ZnO NPs was determined using X-ray diffractometer with Cu Kα radiations (λ = 1.5406 Å) operated at voltage of 40 kV and current of 15 mA. Fourier transmission infrared (FTIR) spectra of the powder was recorded using a Fourier transmission infrared spectrometer (Perkin Elmer) in the range of 5000–100 cm −1 . Room temperature optical absorption spectrum was recorded in the range of 200–800 nm using a UV–Vis spectrophotometer (UV-1800, SHIMADZU, Japan).

Plant material

Juniperus procera was in vitro regenerated by protocol which has made and developed in our laboratory, previously 29 with full permission has obtained from institute. Firstly, cutting about 1 cm contained at least one axillary of J. procera were used as explants for in vitro propagation.

Media preparation and nanoparticles treatment

Woody Plant Media (WPM) with supplement of Plant Growth Regulators (PGRs) 2,4-D and BAP (0.5 µM), sucrose as carbon source (30 g/L), 7 g/L of agar, and the pH was adjusted to 5.7. Then, Biosynthesized ZnO NPs different concentrations (0.0 mg/L, 80 mg/L and 160 mg/L) were added to the media before autoclaving at 121 °C for 20 min. Then, for each treatment triplicate with four explants per jar were cultured under laminar conditions. The jars were incubated in growth chamber at 25 °C ± 1, with 14/10 h illumination periods for 70 days.

Chlorophyll determination

Chlorophyll content in the leaves of J. procera was carried out with a mixture of acetone and water at a ratio of 80% − 20% (v/v). 0.1 g of fresh leaves homogenized in 2 ml acetone solution 80%. Then, were stored at − 4 °C for 24 h. The mixture was centrifuged at 13000 rpm for 10 min. Absorption was measured at 663 and 645 nm using a UV-1800 spectrophotometer (Shimadzu, Japan). Estimation of chlorophyll a, b was carried out using Arnon method 30 .

Estimation of the total protein content and enzymes activity

300 mg of callus were homogenized in liquid nitrogen and dissolved in 100 mM sodium phosphate buffer (pH 7.4) containing 1% PVP, and 0.5% (v/v) Triton-X 100. Then, homogenate was centrifuged at 20,000rmp for 20 min at 4 °C. Supernatant was collected and storetd at − 20 for determination of protein by Nano drop and specific activities of antioxidant enzymes were extracted and estimated as the methods described by 31 .

Superoxide dismutase (SOD, EC 1.15.1.1) activity was estimated using the method of Marklund and Marklund 32 . The reaction mixture has contained 1 mL of 0.25 mM pyrogallol, 1.9 mL of 0.1 M sodium phosphate buffer (pH 7.4), and 100 μL of enzyme extract. The absorbance was measured at 420 nm. The SOD activity (U g − 1 protein) was defined as the amount of enzyme needed for 50% inhibition of pyrogallol oxidation.

The catalase (CAT, EC 1.11.1.6) activity was estimated by measuring the absorbance at 240 nm, as per the method described by 33 . 1 mL of 0.059 M H2O2 in 0.1 M sodium phosphate buffer (pH 7.4), 1.9 mL of distilled water, and 100 μL of enzyme extract. The CAT activity was expressed as unit g − 1 of protein.

Ascorbate peroxidase (EC 1.11.1.11) activity was determined as the methods described by 34 . The reaction medium contained 1 mL of 0.1 M sodium phosphate buffer (pH 7.4), 1 ml distilled water, 100 µL ETDA (0.1 mM), hydrogen peroxide (100 µL), and an enzyme extract (100 µL). The absorbance was recorded at 290 nm, with 3 replicates.

Proline measurement

Proline was extracted following the method described by 35 . Liquid nitrogen has been used to grind fresh sample (0.5 g) and the product was extracted in 10 ml of 3% aqueous sulfo-salicylic acid. The mix was centrifuged and 2 ml of supernatant was added to 2 mL ninhydrin plus 2 mL glacial acetic acid. The mixture was boiled at 100 °C for 1 h, then the reaction was stopped by transferring the tubes to an ice bath for 5 min. Subsequently, 6 ml of toluene was added, mixed vigorously for 15 s and the absorbance of the upper phase was read at 520 nm. The proline content was expressed in μg/g fresh weight.

Estimation of the total flavonoids

Estimation of the total flavonoids in the callus of J. procera extracts was carried out using the method describe by 36 . 0.5 mL of methanol extract, a volume of 0.5 mL of 2% AlCl3 water solution was added. After 24 h at room temperature, the absorbance was measured at 420 nm. A calibration curve was constructed, using quercetin (50–0400 µg/ml) as standard. Total flavonoid contents were expressed as quercetin (mg/g.dry wt.) using the following equation based on the calibration curve (y = 0.0014x + 0.0595).

Estimation of total phenolic content

The total phenolic content of the callus of J. procera extract was determined by using Folin-Ciocalteu reagent following method described by Ainsworth 37 . Gallic acid was used as a reference standard calibration curve. A volume of 0.5 mL of the plant extract (100 µg/mL) was mixed with 2 mL of the Folin-Ciocalteu reagent (diluted 1:10 with de-ionized water) and were neutralized with 4 mL of sodium carbonate solution (7.5%, w/v). The reaction mixture was incubated at room temperature for 30 min. The absorbance of the resulting blue color was measured at 765 nm using UV–VIS spectrophotometer (SHIMADZU, UV − 1800). The total phenolic contents were determined from the linear equation of a standard curve prepared with Gallic acid. The content of total phenolic compounds expressed as mg/g gallic acid equivalent (GAE) of dry extract.

Preparation of callus extracts for GC–MS analysis

50 mg of callus of J. procera were lyophilized before grinding. Then, has been extracted in 2.0 ml of methanol of 99.98% using Tissue Layser LT (Qiagen.) Voltage 24VDC/ power 40 VA for 2 h at 25 °C. The organic and aqueous phases were separated by centrifugation at 5000 rpm for 15 min. Then, supernatant was filtered using 0.45 µm nylon syringe before injected into GC–MS analysis.

Statistical analysis

All experiments were done in triplicate and the results were reported in the figures and tables are the average of three replicate ± standard deviations. The statistical software SPSS (version 20) one-way ANOVA was used for evaluating statistical significance and at ( P  < 0.05).

Legal statement

The collection of plant materials which are used in this study complies with relevant institutional, national, and international guidelines and legislation. Seeds and seedlings of the date palm and African pencil cedar were collected and provided by Botany and Microbiology Department (Garden and Herbarium Unit), College of Science, King Saud University (KSU) with full permission to collect plant materials by accepting the terms and conditions of national and international standards.

Results and discussion

Biosynthesis and characterization of zno nanoparticles.

The synthesis of biosynthesized ZnO NPs was carried out by taking 2:2 (v/v) of leaves extract of and zinc nitrate solution to obtain a mixture solution in a round-bottom flask, and incubated with constant stirring (100 rpm) at 40 °C for 24 h. The color of the reaction mixture was changed to yellow after 30 min of incubation time. The changing of color during the incubation time is the first sign of ZnO NPs formation. Then, the obtained biosynthesized ZnO Powder was submitted to various analytical techniques for characterization and to ascertain their shape, size and functionalization. The biosynthesized ZNO powder was dissolved in Milli-Q water to detected the UV-Visible spectra by using SHIMADZU SPECTROPHOTOMETER (UV-1800) in the range of 200–800 nm. The UV–Visible analysis showed that an absorption peak at 370.5 nm (Fig.  1 a). No another major peak shifts had been observed during reactions and optimization. According to 38 the range of UV spectrum for ZnO NPs was 368 nm. Moreover 39 , has been stated that, UV spectrum for ZnO NPs was observed at 375 nm. Additionally, many researchers reported that, UV Spectra of green zinc oxide nanoparticles is fluctuated between 360–380 nm. The shape and size of biosynthesized ZnO nanostructures was investigated using transmission electron microscope (TEM). TEM image of ZnO nanoparticles showed that, the particle size is ranged from 17 to 36 nm (Fig.  1 b). XRD spectra of the biosynthesized ZnO powder was detected by X-ray diffractor, which resulted in different crystal planes such as (100), (002), (101), (102), (110), (103), (200), (112), (201), (004) and (202) were assigned to the 2θvalues of XRD 31.57°; 34.26°; 36.05°; 47.34°; 56.47°; 62.75°; 67.82°; 68.0°; 72.0°; 76.0° and 81.0° which showed hexagonal phase of zinc oxide and good crystallinity of the products (Fig.  1 c). These presented planes are match well with the quartzite ZnO hexagonal structure having JCPDScard No. 36-1451 which was reported by 40 (Fig.  1 c). The FTIR analysis was performed to identified the chemical groups presented in the biosynthesized ZnO nanostructure. The band recorded at 675 cm −1 indicated that biosynthesized ZnO NPs well formed, the band at 876 cm −1 (C–Cl) with a stretch type of vibration, 1470 cm −1 (C=C) stretch mode of vibration, 1600 (N–H) bending vibration and 3200 to 3550 cm −1 attributed to the O–H mode of vibration and bending modes of the absorbed water. The obtained spectrum of FTIR analysis is represented in (Fig.  1 d).

( a ) UV-Visible absorption spectrum of the biosynthesized ZnO NPs (from 200 to 800 nm) band at 370.5 nm ( b ) TEM image of the biosynthesized ZnO NPs. Bar 100 nm ( c ) XRD Patterns of the biosynthesized ZnO NPs (from 10 to 85 2theta (°)) and ( d ) FTIR Spectrum of biosynthesized ZnO NPs (from 600 to 4000 cm −1 ).

The effect of biosynthesized ZnO NPs on biomass of J. Procera

The effect of different concentrations (0.0 mg/L, 80 mg/L and 160 mg/L) of biosynthesized ZnO nanoparticles on biomass of J. procera growth in vitro was investigated after 70 day of growth. The obtained results indicated that, biosynthesized ZnO NPs concentrations (80 mg/L and 160 mg/L) were enhanced the growth of J. Procera significantly compared to non-treated plants (Fig.  2 a,b). While, among ZnO NPs concentrations, the treatment of 80 mg/L biosynthesized ZnO NPs had the best biomass fresh weight (2.3 g) compared to 160 mg/L treatment (1.5 g) (Fig.  2 a,b). Obviously, the addition of biosynthesized ZnO NPs to the plants media has improved regeneration of shoots and callus formation substantially. This result supported by physiological characterization which revealed that, ZnO NPs were increased the amount of chlorophyll a (Fig.  2 c) and total protein content (Fig.  3 a) significantly compared to the control. In case of Chl b no significant result was recorded among different treatments (Fig.  2 d).These findings were in accordance with 41 who stated that, the presence of ZnO NPs was incorporated into plant hormone such auxin and improved plants growth. Chlorophyll an increased with significant result under ZnO NPs at 80 mg/L compared to control. Whereas at level (160 mg/L) was decreased significantly compared to control (Fig.  2 c). May be due to toxic level of ZnO NPs, while no significant differences were recorded in case of chlorophyll b. The highest concentration (160 mg/L) of Biosynthesized ZnO NPs was enhanced growth of Plants at beginning, one month later the color of callus turned into brownish and shoots were changed to yellowish (Fig.  2 a). Might be due high dose of zinc oxide nanoparticle, its seemed to be toxic. Although, zinc is an essential mineral at higher concentrations this metal is toxic mentioned by 42 . Moreover, ZnO NPs at high concentration inhibited the expression of genes involved in chlorophyll synthesis and photosystem structure 43 . Our findings in agreement with 44 who has been reported that, plants treated with ZnO NPs nanoparticles showed significant growth compared to the control. Moreover, it was reported that, ZnO NPs play a major role in the increase in biomass, nutrients in wheat 45 . So far, ZnO NPs with low concentrations, it stimulated the callus growth and pointed out the nanoparticles role in regeneration, decontamination, organogenesis, callus induction and activated a protein that has a vital role in growth recounted by 14 , 15 . In turn, zinc oxide nanoparticles have potential to enhancement the growth and yield of crops 46 , 47 . A few studies have been focused on phytotoxicity and toxicological effect of ZnO NPs on plants. In general, studies with NPs indicated a certain degree of phytotoxicity, especially at high concentrations 48 . Exposure plants to NPs have induced reactive nitrogen species 49 . Moreover, the highly concentration of ZnO NPs in the rhizosphere solution and root surface could potentially impact the ryegrass growth stated by 50 . Recent studies have shown that plant growth, development and physiology are significantly affected by nanoparticles. Finally, the lowest values of plants biomass were recorded in non-treated plant (Fig.  2 a,b).

( a ) Plants growth under different treatments of biosynthesized ZnO NPs ( b ) Biomass of plants under different treatments of biosynthesized ZnO NPs (g) ( c ) Chl a under different treatments of biosynthesized ZnO NPs (mg/ml) and ( d ) Chl b under different treatments of biosynthesized ZnO NPs (mg/ml). The data are presented the average of parameters ± SD. a,b,c Means within the same column with different superscripts differ significantly ( P  < 0.05).

( a ) Total protein contents under different concentration of ZnO NPs ( b ) SOD activity under different concentrations of ZnO NPs ( c ) CAT activity under different concentrations of ZnO NPs and ( d ) APX activity under different concentrations of ZnO NPs.

The impact of ZnO NPs on Protein contents and enzymes activity of callus of J. procera in vitro

Total protein contents.

The total protein of callus of J. procera was determined using Nano drop. The results showed that, there were significant differences in total protein contents among callus treated with different concentrations of ZnO NPs. While, among the ZnO NPs treatments, the highest concentration of biosynthesized ZnO NPs (160 mg/L) has given the highest level of total protein (Fig.  3 a and Table 1 ). In accordance, ZnO nanoparticles have increased protein content in tomato even under salt stress, stated by 41 . Moreover 51 who has been reported that, ZnO nanoparticles have a positive effect on protein content of callus of Nicotiana tabacum . ZnO NPs cause a great effect on expression of some genes encoding certain proteins, it could be caused turn on or turn off the expression of some genes reported by 52 . Also, it is suggested that ZnO nanoparticles might be provide the plants with bio-available Zn ion at cellular level.

Superoxide dismutase

The influence of ZnO nanoparticles on SOD activity in callus of J. procera under different treatments was investigated as an important scavenger for reactive oxygen species (ROS). SOD activity was induced by highest levels (160 mg) of ZnO NPs in the medium compared to untreated control significantly (Fig.  3 b and Table 1 ). It has been stated that, zinc oxide nanoparticles was increased the activity of SOD in Punica granatum callus 53 which is in agreement with our findings in this study. This may be due to The regulations in SOD in response to stress which might be caused by nanoparticles, SOD is well-known as powerful ROS Scavenger.

The effect of ZnO NPs on CAT activity in callus of J. procera exposed to different levels of ZnO NPs was evaluated. The result indicates that; the activity of CAT was stimulated with the increased levels of ZnO NPs significantly compared non-treated-control. On the other hand, callus was significantly affected by ZnO nanoparticles. Additionally, the result showed that CAT activity in the case of NPs represented strong correlations with ZnO NPs (Fig.  3 c and Table 1 ). In this context 53 , who has been reported that, zinc oxide nanoparticles were increased the CAT activity in callus of pomegranate.

Ascorbate peroxidase

APX activity was assessed as it catalyzes the hydrogen peroxide dependent oxidation of ascorbate in callus under different treatments of ZnO nanoparticles. The results reveled that, the increasing ZnO NPs levels were increased APX activity significantly compared to non-treated callus. Moreover, under ZnO NPs treatments, APX activity showed a strong positive association ZnO NPs concentrations (Fig.  3 d and Table 1 ). APX activity was induced by zinc oxide nanoparticle and has strong association with ZnO NPs concentrations reported by 53 .

Proline (Pro) accumulation is physiological response in many plants to a wide range of abiotic and biotic stresses and can be a reactive oxygen species scavenger 54 . The examined of pro in this study showed that, the ZnO NPs have increased the level of pro in callus of J. procera significantly compared to non-treated plants. The increasing of the pro has strongly correlation with the increasing of nanoparticles (Fig.  4 and Table 1 ). ZnO nanoparticles might be induced plant to form proline. It has been reported that, the addition of ZnO NPs to plants have increased proline contents significantly 55 .

The effect of different concentrations of ZnO nanoparticles on proline in callus of J. procera.

Total flavonoids

Flavonoids are secondary metabolites with antioxidant activity, the potency of which depends on the number and position of free OH groups 56 . Flavonoids have many biological activities such as the treatment of asthma, bronchitis and cardiovascular disease, the improvement of peripheral blood flow and reduction of cerebral insufficiency 57 . Here, in this study, the estimation of total flavonoid content of callus extract of J. procera was carried out by using Uv-spectrophotometer and quercetin as calibration curve (y = 0.0014x + 0.0595, R2 = 9839) (Fig.  5 a and Table 1 ). The results showed that, biosynthesized zinc oxide nanoparticles have increased the total flavonoids in treated callus of J. procera significantly compared to non-treated callus (Fig.  5 b). ZnO nanoparticles could be cause stress to the plants which lead to accumulation of flavonoids to act as scavengers. Higher content of flavonoids and phenol was observed in ZnO NPs as compare to crude extract was reported by 58 .

( a ) Quercetin standard curve ( b ) the impact of Zno nanoparticles on total flavonoids (mg/g dry.wt).

Total phenolic contents

Phenols are excellent oxygen radical scavengers because the electron reduction potential of the phenolic radical is lower than the electron reduction potential of oxygen radicals 59 , 60 , and also because phenoxyl radicals are generally less reactive than oxygen radicals 61 . Therefore, phenolic compounds can scavenge reactive oxygen intermediates without promoting further oxidative reactions 59 . The total phenolic content in callus of J. procera was determined using Uv-spectrophotometer and Gallic acid was used as a reference standard calibration curve (Fig.  6 a). This result indicates that, ZnO NPs nanoparticles at highest level have induced the formation of phenolic content significantly compared control (Fig.  6 b and Table 1 ). During the stress caused by heavy metals, phenolic compounds act as metal chelators and accumulated. Hence, increases in antioxidant activity of plants exposed to NPs, is mainly due to the increase in phenolic compounds, which are ROS scavengers 62 .

( a ) Gallic acid standard curve. The standard curve is used to estimate phenolics (gallic acid equivalents) in a 200-mlsample. ( b ) Total phenolic content under different treatments of biosynthesized ZnO NPs.

The effect of biosynthesized ZnO NPs on bioactive compounds production

In nature, plants produce bioactive compounds as a protection mechanism against abiotic and biotic stress, and attraction or signaling. Phytochemicals have been used by human as condiments, flavorings and for treating health disorders and preventing diseases including epidemics. The availability of some phytochemicals constituents from its current natural sources are limited. Hence, alters and inducers agents are needed to increase the productivity of bioactive compounds or even to generate new ones. As in nature, plants produce these products as repose to stress. Therefore, plants have been exposed to different concentrations of biosynthesized zinc oxide nanoparticles. The effect of ZnO NPs on bioactive compounds in callus of J. procera was investigated. The differences have been observed among the treatments. The main phytochemical compound in methanol extract of callus of J. procera under different ZnO nanoparticles concentrations is ferruginol (Table 2 and Figs.  7 , 8 and 9 ). To date, there are no reports comparing the effect of biosynthesized ZnO NPs on the production and accumulation of bioactive compounds in callus of J. procera. The result indicates that, nanoparticles have impacted on secondary metabolites production and was significantly affected. Nanoparticles could be promoting formation of some phytochemicals as well as inhibit others. Moreover, plants develop resistance to metal stress by altering phytochemicals accumulation and certain antioxidant enzymes to counteract oxidative damages of cellular components and biomolecules caused by highly reactive free radicals 63 . The effect of nanoparticles on plant secondary metabolism still obscure 16 . Therefore, it is a priority to understand the impact of nanoparticles on secondary metabolites which might be helped in production process and it can be used as promotors.

GC–MS analysis chromatograms of non-treated callus of J. procera.

GC–MS analysis chromatograms of callus of J. procera under treatment of ZnO NPs (80 mg/L).

GC–MS analysis chromatograms of callus of J. procera under treatment of ZnO NPs (160 mg/L).

In summary, it could be concluded that, the addition of biosynthesized ZnO nanoparticles to the media of plants in vitro had played vital role in biomass production. ZnO nanoparticles had greater and more-responsive effect on the J. procera shoots and calli growth and physiological indices compared to non-treated plants. Which resulted in higher growth of callus, shoots, chlorophyll, total protein content, total phenols and flavonoids contents and enzymes activity. Obviously, this study showed that, ZnO nanoparticles simultaneously induced growth promoting or factor can cause oxidative stress effects in the plant cells depends on concentrations of ZnO nanoparticles. However, our knowledge of the influence of nanoparticles on living systems is mostly inconsistent to date. The increasing number of studies on nanoparticles has been focused on nanoparticles bio-availability with respect to their concentration. Moreover, the influence of nano material is widely investigated under in vivo systems, as elicitors accompanied by biotic or abiotic conditions. But the effect of nanoparticles on bioactive compounds production in vitro is requested to be developed and validated. Therefore, we suggested that, the effect of nanoparticle on bioactive compounds should be to elucidated. The result of current study could be concluded that, the nature of nanoparticle-derived Zn ions might have had a more significant effect when other factors are taken into consideration, such as doses, particle size, particle and concentration and growth media. Further, the study which is designed and presented in this paper can be extended to involve quantification of bioactive compounds and biosynthesis pathways of the important phytochemical compounds can be tested under ZnO nanoparticles treatment, which might be lead to better understanding of the effect of nanoparticles on antioxidant systems of plants.

Data availability

The data used or analyzed during the present study are available from the corresponding author/KSU.

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The authors extend their appreciation to Researchers supporting project number (RSP-2021/73) at king Saud University, Riyadh, Saudi Arabia.

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Abdalrhaman M. Salih, Fahad Al-Qurainy, Salim Khan, Mohamed Tarroum, Mohammad Nadeem, Hassan O. Shaikhaldein, Abdel-Rhman Zakaria Gaafar & Norah S. Alfarraj

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A.M.S. was responsible for the conceptualization and has significantly contributed to all sections; A.M.S., S.K. and M.N. proposed and planned the work; A.M.S., H.S., N.S.F., A.G. methodology; M.T. analyzed the Data and performed the Figures; A.M.S. writing—original manuscript; F.A. supervised the work. The author(s) read and approved the final manuscript.

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Salih, A.M., Al-Qurainy, F., Khan, S. et al. Biosynthesis of zinc oxide nanoparticles using Phoenix dactylifera and their effect on biomass and phytochemical compounds in Juniperus procera . Sci Rep 11 , 19136 (2021). https://doi.org/10.1038/s41598-021-98607-3

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Green Synthesis of Copper Sulphide Nanoparticles Using Extracts of Syzygium cumini , Azadirachta indica , and Cascabela thevetia

• 28th International Conference on Nuclear Tracks and Radiation Measurements
• Published: 03 September 2024

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• KM Srishti Barnwal 1 ,
• Yukti Gupta 1 &
• Neena Jaggi 1  

Nanotechnology is a burgeoning modern technology due to the remarkable properties of nanoparticles. However, the escalating use of toxic reagents during the chemical synthesis of nanoparticles has become a major concern for environmental safety and human and animal health. Regarding this problem, the notion of integrating nanotechnology with green synthesis is increasingly attracting the attention of researchers. This particular study aims at the green synthesis of copper sulphide (CuS) nanoparticles S1, S2, and S3 utilizing the leaf extracts of Azadirachta indica (neem) , Syzygium cumini (jamun) , and Cascabela thevetia (kaner), respectively. The prepared leaf extract of neem is rich in quercetin, whereas extracts of jamun and kaner leaves contain gallic acid, which serves as a reducing agent during the formation of nanoparticles. The prominent and sharp peaks of x-ray diffraction (XRD) patterns match well with ICDD card no. 06-0464, which confirms the hexagonal phase of covellite CuS. Scanning electron microscopy (SEM) images reveal the formation of spherical-shaped CuS nanoparticles with mild agglomeration. The presence of Cu and S as the only elements in the synthesized samples is confirmed by energy-dispersive x-ray analysis (EDX). The occurrence of various stretching and bending vibrational modes is observed via Fourier transform infrared (FTIR) spectroscopy. Furthermore, the obtained FTIR spectra of S1, S2, and S3 evince the formation of CuS nanoparticles and the presence of bioactive compounds. The UV-Vis absorption data of the prepared samples reveal that their band gap energies lie within the range of 1.5–1.7 eV. The photoluminescence (PL) spectra of S1, S2, and S3 display decreased intensity, which could be due to the reduced recombination rate of charge carriers. The CuS nanoparticles synthesized with neem leaf extract exhibit relatively smaller crystallite size, wider band gap of 1.7 eV, and a lower recombination rate of charge carriers.

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Acknowledgments

Author KM Srishti Barnwal is grateful to the Director of the National Institute of Technology, Kurukshetra, for providing the fellowship. The author also appreciates the support from Dr. Ashish Gupta, Department of Physics, NIT Kurukshetra. The author is grateful to Dr. Sanjeev Aggarwal, Director Ion Beam Centre, Kurukshetra University, Kurukshetra, for providing the XRD facility. The author also acknowledges the Department of Chemistry, Kurukshetra University, Kurukshetra, for providing the FTIR facility.

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KM Srishti Barnwal, Yukti Gupta & Neena Jaggi

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KM Srishti Barnwal: conceptualization, methodology, investigation, formal analysis, writing—original draft. Yukti Gupta: conceptualization, methodology, investigation, formal analysis, writing—review and editing. Neena Jaggi: supervision, validation, writing—review and editing. KM Srishti Barnwal and Yukti Gupta have contributed equally to this work.

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Barnwal, K.S., Gupta, Y. & Jaggi, N. Green Synthesis of Copper Sulphide Nanoparticles Using Extracts of Syzygium cumini , Azadirachta indica , and Cascabela thevetia . J. Electron. Mater. (2024). https://doi.org/10.1007/s11664-024-11387-0

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Received : 27 December 2023

Accepted : 14 August 2024

Published : 03 September 2024

DOI : https://doi.org/10.1007/s11664-024-11387-0

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