0% found this document useful (0 votes)
29 views10 pages

ZnO Nanoparticles: Synthesis & Applications

This study focuses on the synthesis and characterization of zinc oxide (ZnO) nanoparticles (NPs) for applications in photocatalysis, antibacterial activity, and cytotoxicity against kidney cancer cell lines. The ZnO NPs were synthesized using a precipitation method, exhibiting a hexagonal wurtzite structure with an average crystallite diameter of 43 nm, and demonstrated high photocatalytic activity and antibacterial properties. The findings suggest that ZnO NPs have potential for various biomedical applications due to their low cytotoxicity and effective antibacterial properties.

Uploaded by

shreyashbote
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
29 views10 pages

ZnO Nanoparticles: Synthesis & Applications

This study focuses on the synthesis and characterization of zinc oxide (ZnO) nanoparticles (NPs) for applications in photocatalysis, antibacterial activity, and cytotoxicity against kidney cancer cell lines. The ZnO NPs were synthesized using a precipitation method, exhibiting a hexagonal wurtzite structure with an average crystallite diameter of 43 nm, and demonstrated high photocatalytic activity and antibacterial properties. The findings suggest that ZnO NPs have potential for various biomedical applications due to their low cytotoxicity and effective antibacterial properties.

Uploaded by

shreyashbote
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Journal of Alloys and Compounds 874 (2021) 159868

Contents lists available at ScienceDirect

Journal of Alloys and Compounds


journal homepage: www.elsevier.com/locate/jalcom

Synthesis and characterization of ZnO nanoparticles for photocatalysis,


antibacterial and cytotoxicity in kidney cancer (A498) cell lines ]]
]]]]]]
]]

Ala Manohar a,b, Junwoo Park a, Dereje Degefa Geleta a, Chintagumpala Krishnamoorthi c,

Ramar Thangam b, Heemin Kang a,b, Joonho Lee a,b,
a
Department of Materials Science and Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea
b
Institute for High Technology Materials and Devices, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea
c
Center for Nanotechnology Research, Vellore Institute of Technology, Vellore 632014, India

a r t i cl e i nfo a bstr ac t

Article history: Zinc oxide (ZnO) nanoparticles (NPs) are gaining more interest due to their multifunctional and biological
Received 17 January 2021 properties. Herein, we synthesized ZnO NPs and characterized their optical and electrical properties for
Received in revised form 30 March 2021 application in catalysis and optoelectronic devices and potential biomedical applications. The synthesis of
Accepted 4 April 2021
ZnO NPs was performed via a precipitation method, and their crystallinity, crystal structure, crystal phase
Available online 10 April 2021
purity, particle morphology, and size distribution were characterized via X-ray diffraction and transmission
electron micrographs. The crystal ligand environment, chemical purity and chemical oxidation states were
Keywords:
Oxide materials studied by Raman, infrared and X-ray photoelectron spectroscopy. Thermal stability and residual matter
Precipitation decomposition were studied by thermogravimetric analysis. Furthermore, the optical energy band gap was
Catalysis investigated by UV-Vis absorbance spectroscopy. Similarly, the photocatalytic properties were also studied
Photoelectron spectroscopies by rhodamine B degradation under UV light irradiation. Biological activities, such as antibacterial and cy­
totoxicity potentials, were explored. The synthesized ZnO crystallized in a hexagonal wurtzite structure
with an average crystallite diameter of 43 nm. Various anion ligands around Zn2+ in wurtzite were con­
firmed. The sample showed a 3.26 eV optical energy gap with a high photocatalytic activity of 99.5% in
70 min. The synthesized NPs showed high antibacterial activity against Pseudomonas aeruginosa and less
cytotoxicity to kidney cancer cell lines (A498). From this finding, we suggest that the prepared ZnO NPs
could be used for various biomedical applications.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction exciton binding energy, extensive electrochemical potential window,


significant bandgap, nontoxicity and significant electron transfer
Zinc oxide (ZnO) is a significant semiconductor that has attracted rate [4]. ZnO NPs have also been attractive to the biomedical field
important attention because of its applications in different sectors, due to their -nontoxicity, high catalytic and optical properties, bio­
such as industry, science, and technology [1]. In the last two decades, conductivity and anticancer potential [5]. The environmentally eco-
researchers have focused on the synthesis of ZnO nanoparticles friendly behavior and n-type semiconductor nature of ZnO reveal
(NPs) because of their different electrical and optical properties [2]. high photosensitivity, biocompatibility and chemical stability.
Among the various photocatalytic materials (TiO2, Fe2O3, WO3, etc.), Hence, ZnO is used in various promising applications, such as
ZnO has received significant attention in pollutant removal and transducers, antibacterial agents, photocatalytics, optoelectronics,
wastewater treatment in recent years owing to the existence of free electronic batteries, gas sensors, solar cells, biosensors, rubber fab­
electrons, and the significant number of holes created in the valence rication, food packaging, piezoelectric devices, electrodes, and
band is fewer than that of electrons generated in the conduction ceramic materials [6–11]. Compared to other nanosized semi­
band [3]. On the other hand, ZnO has been widely used in electro­ conductors, ZnO shows a wide bandgap (3.37 eV) and high excitation
chemical sensing owing to its significant chemical stability, great binding energy (60 meV) that is approximately 2.4 times higher than
room temperature thermal energy of 25 meV; thus, it has received
preferable attention in the materials research area [12]. Due to its

Corresponding author at: Department of Materials Science and Engineering, potential antimicrobial properties, ZnO NPs have been used in
Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea. shampoos (antifungal), ointments (antibiotic), creams (antiseptic),
E-mail address: [email protected] (J. Lee).

https://doi.org/10.1016/j.jallcom.2021.159868
0925-8388/© 2021 Elsevier B.V. All rights reserved.
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

tapes (surgical) and calamine lotions [13]. ZnO NPs were used in 2.2. Synthesis of ZnO nanoparticles
sunscreen products because of their spectrum (broad) protection
against UV light; additionally, Zn is an essential supplement for cell One gram of zinc acetate dihydrate [Zn (CH3CO2)2.2H2O] was
division, growth and metabolic breakdown of enzymes as well as dissolved in 50 mL of deionized water (A), and then 4 mg of NaOH
protein in humans [14]. ZnO NPs have recently attracted increasing pellets were dissolved in 50 mL of ethanol solution (B). Further,
research attention owing to their large and significant applications solutions A and B were thoroughly mixed using magnetic stirring at
in antioxidant activity and drug delivery and for biosensors and 70 °C for 3 h. The color was changed to milky white, and a precipitate
environmental remediation [15] and in electrochemical sensor ap­ was formed during the heating process. The resultant precipitate
plications, owing to their high surface area, low cost and significant was separated by centrifugation at 5000 rpm for 30 min and washed
stability [16]. three times with absolute ethanol followed by double deionized
ZnO crystallizes into three crystal phase structures (rock salt, zinc water to remove any impurities present. The final sediment was
blende and hexagonal wurtzite). Among them, the hexagonal dried on a hot plate at 60 °C for 20 min and ground into powder form
wurtzite structure is highly stable under various conditions. This using a mortar and pestle. Finally, the powder was annealed at
causes ZnO to be a preferable material for science and technology 800 °C for 4 h to obtain crystalline ZnO NPs, and a schematic illus­
applications such as the rubber industry (for shoe soles), lifeguards tration of the synthesis of ZnO NPs is shown in Scheme 1.
(at beaches), hockey pucks and tire manufacturing [13,14,17]. ZnO
NPs show the best catalyst activity in photocatalytic reactions. ZnO 2.3. Crystal characterizations
NPs can be synthesized by various physical and chemical techniques,
such as laser ablation [18], sputtering [19], ball milling [20], com­ The morphology, size, size distribution and elemental analysis of
bustion [21], hydrothermal [22], and polyol [23] techniques. In the the particles were studied by ultrahigh-resolution transmission
present study, we report the novel synthesis of synthetic ZnO NPs electron microscopy (HR-TEM; JEOL, JEM -3010). The crystal struc­
with a narrow size distribution through a precipitation method and ture of the ZnO NPs was investigated by X-ray diffraction (XRD;
their structural morphology and chemical, photocatalytic and bio­ Bruker, D8 Advance). The surface chafe of ZnO NPs was measured
logical activities. using the zeta potential. The chemical purity of the synthesized
particles was analyzed with an FT-IR spectrophotometer (FT-IR;
Shimadzu, IRAffinity −1). Crystal lattice vibrational analysis was
2. Materials and methods carried out by using a Raman spectrometer (Raman; Horiba Jobin
Yvon, LabRAM ARAMIS IR2) with a 532 nm wavelength Nd-YAG laser
2.1. Materials source. The thermal properties and sample weight loss were ana­
lyzed using thermogravimetric analysis (TGA; Netzsch -TG 209 F1
Zinc acetate dihydrate (99.99%, Sigma –Aldrich), sodium hydro­ Iris). The cation and anion oxidation states of the ZnO NPs were
xide (98%, Sigma –Aldrich), ethanol (99.5%, Samchun, South Korea), analyzed by X-ray photoelectron spectrometry (XPS; ULVAC -PHI,
Dulbecco’s modified Eagle’s medium (Hi media), dimethyl sulfoxide PHI 5000 Versa Probe). The optical energy band gap of the sample
(Hi media) and streptomycin (Hi media) were used without further was estimated using a UV-Vis spectrophotometer (UV–visible;
purification. Agilent, Cary 5000).

Scheme 1. Schematic representation of the design and synthesis of the ZnO NPs.

2
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

Fig. 1. Morphological Characterization of the ZnO NPs. (a) High-resolution TEM (HR-TEM) images at different magnifications, (b) lattice fringe (HR-TEM) profiles, (c) selected area
(electron) diffraction (SAED) patterns, and (d) energy-dispersive X-ray spectroscopy (EDX) analysis of the corresponding ZnO NPs.

2.4. Photocatalytic property of ZnO nanoparticles using a sterilized swab on the surface of Muller-Hinton agar
medium. In this experiment, three wells were made in medium, and
The photocatalytic activity of the ZnO sample was studied by then 30 µg/mL Zn NPs, streptomycin (an antibiotic) and distilled
rhodamine B (RhB) dye degradation under UV light irradiation using water were poured into separate wells. The wells were incubated for
a photoreactor (Heber Scientific, HML MP88, India) for a defined 24 h at 37 °C. Distilled water does not have any effect on bacteria;
time duration. Fifteen milligrams of ZnO photocatalyst was added to hence, it was considered a negative control. After 24 h, the formed
10 mg/mL RhB solution and stirred in the absence of light for 70 min bacterial inhibitory “zone of inhibition” dimensions around the wells
to make a homogeneous dispersion. Then, the dye solution was ir­ were measured.
radiated with UV radiation (365 nm) while stirring the solution. The
aliquots were collected through a special syringe every 10 min for 2.6. Cytotoxicity using MTT assay
70 min, and the corresponding absorption spectra were measured.
TheA498 kidney cancer cell line was cultured at 37 °C in
2.5. Antibacterial study Dulbecco’s modified Eagle’s medium (DMEM) supplemented with
10% fetal bovine serum (FBS) in an incubator. The cell viability of ZnO
The antibacterial activity of ZnO NPs was investigated against NPs was further investigated using an MTT assay against A498
Pseudomonas aeruginosa (MTCC No; 1934) and Proteus vulgaris kidney cancer cell lines. Cells were added to 96-well plates and in­
(MTCC No; 1771) using Muller-Hinton agar microbiological growth cubated for 24 h at 37 °C in a fixed humidified atmosphere of 5% CO2.
medium. First, 0.1 mL of each bacterial culture was spread equally After 24 h of incubation, the cancer cells were treated with

3
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

Fig. 2. Chemical Characterization of the ZnO NPs. (a) X-ray powder diffraction (XRD) pattern, (b) zeta potential measurements, (c) Fourier transform infrared spectroscopy (FT-IR)
analysis, (d) Raman spectrum, (e) and thermogravimetric analysis (TGA) spectrum analysis of the corresponding ZnO NPs.

100–400 µg/mL synthesized ZnO NPs and further incubated for 36 h. incubated for an additional 4 h. Finally, 200 µL of DMSO was added to
Dimethyl sulfoxide (DMSO) was used as a negative control. After each well, and the absorbance was recorded at 575 nm by using an
36 h, 20 µL of MTT solution was added to each of the 96 wells and ELISA reader.

4
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

3. Results and discussion

3.1. Morphology of ZnO nanoparticles

Transmission electron microscopy images of the ZnO NPs at


various magnifications are shown in Fig. 1a. The majority of particles
showed an elongated morphology. The average particle diameter of
the ZnO NPs is 43 nm and is equal to the crystallite diameter esti­
mated from the XRD profile broadening. The interplanar distance of
the Wurtzite-crystalline ZnO NPs is shown in a high-resolution TEM
micrograph in Fig. 1b. The D-spacing was estimated from the con­
centric bright fringes by a standard procedure, and the obtained d
-space = 2.81 Å corresponds to the (100) plane of ZnO NPs (ICDD −36
to 1451). The high-resolution TEM image of a single ZnO NP showed
a highly oriented crystalline structure with an interplanar D-space of
2.47 Å corresponding to the (101) plane. Similarly, the D-spacings
corresponding to the other fringes were assigned as the (002), (101),
(102), (110), (103) and (201) planes. Selected area electron diffraction
(SAED) profiles of the sample are shown in Fig. 1c. The elemental
composition of the ZnO NPs was studied by energy-dispersive X-ray
spectroscopy (EDX) analysis and is shown in Fig. 1d. The spectrum
shows pure ZnO crystals without any impurities. The presence of Cu
and C peaks belongs to the TEM grid (carbon-coated copper
grid) [24].

3.2. General characterizations of ZnO NPs

The X-ray diffraction pattern of the as-synthesized ZnO powder is


shown in Fig. 2a. The XRD peaks well matched the hexagonal
wurtzite crystal structure of ZnO powder given at ICDD file number
36-1451, where all the characters have their standard meaning of
crystallography. Mean lattice parameter values found to be a
= b = 8.237 Å and c = 8.321 Å. The average crystallite diameter (D) was
estimated by Scherrer’s equation and is 43 nm.
The applied electric field depended on the ZnO NPs at room
temperature, and the measured zeta potential spectrum is presented
in Fig. 2b. The surface charge of the ZnO NPs had a measured mean
value of − 26.8 mV. This result confirms the repulsion between the
particles, and the ‘-’ symbol indicates that the ZnO NPs are more
stable. The Fourier transform infrared (FT-IR) spectrum of ZnO NPs is
shown in Fig. 2c. The sample has a prominent infrared absorption
peak above 500 cm−1 energy. Other peaks are relatively small and
can be neglected for all practical cases. The other peaks correspond
to water and the other organic chemicals used in the synthesis. The
peak at 3424 cm−1 may be attributed to the surface absorbed -OH
(hydroxyl) groups and water (H2O) molecules [25–27]. The peaks at
2921 and 2636 cm−1 were attributed to the C–H stretching mode
[28]. Appeared peaks at 2298 and 2168 cm−1 are attributed to the C˭C
stretching mode. The band at 1524 cm−1 arises from the asymmetric
stretching mode of C˭O, and the peak at 1425 cm−1 arises from the
symmetric stretching mode of the carbonyl group (C–O) [29]. The
small shoulder peaks at 986 and 860 cm−1 are attributed to the C – H
out-of-plane bending group [25]. The small peak at 694 cm−1 cor­
responds to ZnO NPs [30,31].
Fig. 2d shows the Raman spectrum of the as-prepared ZnO NPs
recorded in the range of 200–1400 cm−1 at room temperature. Ac­
cording to group theory, the A1, E1 and E2 modes (optical) are pre­
sent at the point of the Brillion zone and show various frequencies in Fig. 3. Spectral characterization of the ZnO NPs. (a) X-ray photoelectron spectroscopy
infrared and Raman active regions [32,33]. Raman modes 332, 540, (XPS) and (b) Zn 2P and (c) O 1s spectra of ZnO NPs.
664, 984 and 1145 cm−1 are in the sample due to multiple-phonon
scattering [34]. The observed peaks at approximately 380 cm−1 and
the small (shoulder) peaks at 410 cm−1 correspond to transverse optical (E2) frequency mode of the wurtzite structure (C6ν symmetry
optical phonon (A1 and E1) modes, respectively [35]. The peak at group) [34].
583 cm−1 can be assigned to the longitudinal optical mode (E1) [36]. The thermogravimetric analysis (TGA) curve of the ZnO NPs is
The high-intensity peak at 437 cm−1 corresponds to the symmetry shown in Fig. 2e. The TGA curve shows 0.41% weight loss over the

5
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

Fig. 4. Spectral characterization of the ZnO NPs. (a) UV spectrum and (b) optical band gap spectrum of the ZnO NPs.

25–170 °C temperature range. This is attributed to the evaporation of 3.5. Photocatalytic study
H2O molecules [37,38]. The second weight loss of 0.54% occurred
over the temperature range of 170–300 °C, representing the loss of The photocatalytic activity of the ZnO NPs was evaluated by
the other organic residues used in the synthesis [30]. The final rhodamine B (RhB) dye degradation under UV light irradiation.
weight loss of 1.11% (between 300 and 700 °C) corresponded to the Fig. 5a shows the UV-Vis absorbance spectra of degraded dye ali­
decomposition of calcination of carbonaceous materials [39,40]. The quots taken at regular 10 min intervals. In the absence of light (in­
obtained results are close to those reported in the literature [38,41]. itial), the sample shows a broad and prominent absorption band at
~550 nm, which corresponds to RhB dye. As the photoreaction pro­
gresses, the dye concentration decreases, and hence, the absorbance
3.3. XPS analysis of ZnO nanoparticles intensity also decreases. After 70 min, the sample shows 99.5% de­
gradation of the initial absorption intensity. The degradation per­
To investigate the existing states of the elements and composi­ centage rate of RhB was calculated by using the following
tion of the synthesized ZnO powder sample, XPS measurements relation [47]:
were performed, and the results are presented in Fig. 3a-c. Fig. 3a
Ai At
(the elemental survey scan spectrum) shows the presence of zinc DegradationPercentage = X100
Ai (1)
(Zn), oxygen (O) and carbon (C) elements in the sample. Fig. 3b and c
shows the elemental spectra of the Zn and O elements, respectively. where Ai and At are the initial absorption intensity (t = 0 min) and
The obtained spectroscopic peaks related to Zn and O were from ZnO absorbance at “t” minutes, respectively. The relative change in ab­
NPs, and the obtained C small peak occurred owing to the residual sorbance intensity (A/Ai) as a function of UV irradiation time of RhB
organics present in the sample. In Fig. 3b, for the Zn 2p spectrum, the is plotted in Fig. 5b, and the corresponding first-order kinetic data
fitting peaks at 1025 and 1043 eV are related to Zn 2p3/2 and Zn 2p1/2, are shown in Fig. 5c. The first-order kinetic data show a linear curve
respectively, verifying the existence of Zn2+ [42]. Moreover, the high- with time, and a linear fit gives a chi-square value of 0.92. The
resolution spectrum of O 1s (Fig. 3c) exhibits a broad curve, which mechanism for rhodamine B dye degradation with the ZnO photo­
can be deconvoluted into three peaks: 529.11, 529.21 and 530.43 eV. catalyst under UV radiation is shown in Scheme 2. The photo­
The distinctive peak at 529.11 eV is assigned to typical lattice O in the generated electrons (e-) in the conduction band (CB) move towards
metal Zn - O framework. The peak at 529.21 eV is related to the the surface and produce superoxide (O2-) anions and HOO. radicals.
presence of other oxygen (OH and H2O) components absorbed on Holes (h+) in the valence band (VB) change to the backside of the
the synthesized ZnO NP surface. The peak at 530.43 eV is related to a catalyst surface and interact with water or hydroxide ions to gen­
larger number of defect sites with low O coordination in the na­ erate hydroxyl radicals (OH.) species. This may be attributed to the
noscale ZnO species [43,44]. efficient variation of the electron-hole pairs, which mostly play a
pivotal role in dye (RhB) degradation.

3.4. Optical energy band gap 3.6. Antibacterial activity of ZnO nanoparticles

The optical absorption spectrum of the ZnO NPs in the UV-Vis The antibacterial activity of the synthesized ZnO NPs was ana­
region is shown in Fig. 4a. The spectrum shows a prominent peak at lyzed by the Muller Hinton Agar (MHA) microbial growth medium
374 nm, which confirms ZnO compound formation [45]. Fig. 4b plate technique against selected Pseudomonas aeruginosa and Proteus
shows a Tauc plot as (αhυ)2 versus photon energy (hυ). The re­ vulgaris. The “Zone of inhibition” of Pseudomonas aeruginosa and
spective value of the bandgap is obtained by extrapolating to (αhυ)2 Proteus was carried out using the diffusion (disc) technique to detect
= 0 for the direct transition. The obtained optical energy band gap their aptitude. Synthesized ZnO NPs were vastly reactive because of
value is 3.26 eV and is in good agreement with the literature their high surface area to volume ratio vulgaris (Fig. 6a-b). Proteus
data [45,46]. vulgaris revealed a 6 mm zone of inhibition in the 30 µg/well, and

6
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

Scheme 2. Schematic diagram of the photocatalytic activities of RhB degradation over


the surface of the ZnO NPs.

(streptomycin) (Table 1). This kind of antibacterial activity of the ZnO


NPs may be suitable for the implementation of preparing food
(bioactive) packaging materials [48].

3.7. Cytotoxicity of ZnO nanoparticles

The cytotoxicity of the synthesized ZnO NPs was evaluated using


A498 kidney cancer cells at different NP concentrations, viz., 100 µg/
mL, 200 µg/mL, 300 µg/mL, and 400 µg/mL. After 36 h, a cell viability
test was conducted. We found that there was an altered morpho­
logical feature in A498 cells after treatment with different con­
centrations of ZnO NPs (vulgaris) (Fig. 6c-d). The observed
microscopic images showed that the cell monolayer structure and
morphological features of the cells did not vary in their respective
controls, where the cells were treated with 100 and 200 µg/mL ZnO
NPs. In particular, cells treated with higher concentrations (300 and
400 µg/mL) of ZnO NPs exhibited a change in their morphology. In
the presence of 100 and 200 µg/mL ZnO NPs, while the monolayer
structure was preserved, the presence of cells with an altered cel­
lular profile was detected. In the presence of 300 µg/mL ZnO NPs, the
utmost number of the cells twisted into a spherical form, the
structure of the cell monolayer was concerned with obviously no­
ticeable gaps varied by neighboring cells, and their cell viability was
calculated (Fig. 6d). As shown in Fig. 6d, the cell proliferation of A498
cells decreased with increasing ZnO NP concentrations, and the in­
hibitory concentration (IC50) value was to be 5.469 µg/mL.

3.8. Novelty and comparisons

Ruddaraju and coworkers studied the preparation of ZnO-NPs


using Annonasquamosa leaf extract and evaluated their antibacterial
activity and anticancer activity. These authors characterized the NPs
by XRD, UV-Vis, Raman and TEM. Furthermore, we compared our
XRD, TEM and antibacterial activity results with those reported by
Ruddraraju and coworkers. Compared to that work, one of the
greatest benefits of our method adopted in this work is the ease, low
cost, short time duration and viability of the ZnO NP synthesis
strategy [49].
Promod Kumar et al. investigated Rb-doped ZnO NPs prepared by
a simple combustion technique and studied their photocatalytic
Fig. 5. Photocatalytic and kinetic evaluation of the ZnO NPs. (a) UV–vis absorption
spectrum of the ZnO NPs at different time intervals (0–70 min) under UV light irra­ activity, but the antibacterial activity was not determined. In our
diation. (b) Photocatalyst evaluations of the ZnO NP extent of degradation of dye work, we evaluated two bacteria in vitro, Pseudomonas aeruginosa
(RhB) in various time interval profiles. (c) First-order kinetic profile of the ZnO NPs. and Proteus vulgaris, and compared their activities [50].
Mina Zare et al. investigated the hydrothermal synthesis of ZnO
Pseudomonas aeruginosa revealed no zone of inhibition. The max­ NPs using Thymus vulgaris leaf extract and performed photocatalytic
imum zone of inhibition obtained for Pseudomonas aeruginosa was activity, antimicrobial activity, antioxidant activity and hemolysis
5 mm, and Proteus vulgaris was 9 mm in the 30 µg/well assays. In our study, we determined the viability of ZnO NPs using an

7
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

Fig. 6. Biological activities of the ZnO NPs. The antibacterial activity against (a) Pseudomonas aeruginosa and (b) Proteus vulgaris. (c) Cytotoxicity-induced morphology. (d)
Corresponding cell viability percentage of A498 cells at the selected concentrations of the synthesized ZnO NPs.

MTT assay against A498 kidney cancer cell lines. Compared to that In the above literature studies and this study, it is revealed that
work, the synthesized ZnO NPs exhibit a narrow size distribution, using a statistical experimental strategy leads us to a rapid and de­
significant antibacterial activity, cell viability and the best photo­ pendable optimization of the preparation of significant parameters
catalyst activity through RhB dye degradation under UV light irra­ for procurement of ZnO NPs having significant size, thus optimizing
diation [51]. time and resources. The synthesized ZnO NPs can be significantly
Pavan Kumar et al. studied Beta vulgaris-based ZnO NPs and re­ capable agents for biomedical applications, mostly for the growth of
ported luminescence, photocatalytic and antioxidant properties. therapeutic plans in cancer therapy.
Their XRD study confirmed crystallite sizes of synthesized NPs to be
~53–76 nm. However, in our study, the average crystallite size of the 4. Conclusions
ZnO NPs were determined by the XRD study to be 43 nm [52].
In this study, we prepared ZnO NPs via the precipitation method.
The pure hexagonal wurtzite crystal structures were examined by X-
Table 1
ray diffraction analysis, and the average crystallite size was found to
Zone of inhibition of the ZnO NPs against Pseudomonas aeruginosa and Proteus vulgaris
bacteria. be 43 nm. In addition, the semiconducting behavior of the ZnO NP
band gap value was found to be 3.26 eV, with particle sizes of 43 nm.
Organisms Sample (Zone of inhibition) Streptomycin
Selected area electron diffraction (SAED) patterns showed a con­
Pseudomonas aeruginosa – 5 mm centric circular ring bright pattern, confirming that the prepared
Proteus vulgaris 6 mm 9 mm
nanoparticles were well crystallized. EDS measurements revealed

8
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

that the sample contains only Zn and O elements. The vibrational [12] Z.L. Wang, Splendid one-dimensional nanostructures of zinc oxide: a new na­
properties of the ZnO NPs were confirmed by FT-IR and Raman nomaterial family for nanotechnology, ACS Nano 2 (2008) 1987–1992, https://
doi.org/10.1021/nn800631r
spectroscopy measurements. The TGA investigation confirms that [13] K.S. Siddiqi, A. ur Rahman, Tajuddin, A. Husen, Properties of zinc oxide nano­
the sample has no impurity phases. The elemental analysis and particles and their activity against microbes, Nanoscale Res. Lett. 13 (2018) 141,
chemical states of the elements were confirmed by X-ray photo­ https://doi.org/10.1186/s11671-018-2532-3
[14] M. Jha, N.G. Shimpi, Spherical nanosilver: bio-inspired green synthesis, char­
electron spectroscopy. The ZnO NP photocatalytic activity was acterizations, and catalytic applications, Nano Struct. Nano Objects 16 (2018)
evaluated through RhB dye degradation under UV light irradiation. 234–249, https://doi.org/10.1016/j.nanoso.2018.07.004
The antibacterial activity was analyzed against Pseudomonas aeru­ [15] A.M. Pillai, V.S. Sivasankarapillai, A. Rahdar, J. Joseph, F. Sadeghfar, R.A. A,
K. Rajesh, G.Z. Kyzas, Green synthesis and characterization of zinc oxide nano­
ginosa and Proteus vulgaris. In addition, cell viability was investigated particles with antibacterial and antifungal activity, J. Mol. Struct. 1211 (2020)
by MTT assay to prove the cytotoxic potentials of the prepared ma­ 128107, https://doi.org/10.1016/j.molstruc.2020.128107
terials. [16] R. Sha, S.K. Puttapati, V.V.S.S. Srikanth, S. Badhulika, Ultra-sensitive non-enzy­
matic ethanol eensor eased on eeduced eraphene exide-einc exide eomposite
eodified electrode, IEEE Sens. J. 18 (2018) 1844–1848.
CRediT authorship contribution statement [17] M.M. Khan, N.H. Saadah, M.E. Khan, M.H. Harunsani, A.L. Tan, M.H. Cho,
Phytogenic synthesis of band gap-narrowed ZnO nanoparticles using the bulb
Ala Manohar: Data curation: Lead; Investigation: Lead; extract of Costus woodsonii, Bionanoscience 9 (2019) 334–344, https://doi.org/
10.1007/s12668-019-00616-0
Visualization: Lead; Writing – original draft: Lead. Junwoo Park: [18] H. Usui, Y. Shimizu, T. Sasaki, N. Koshizaki, Photoluminescence of ZnO nano­
Data curation: Supporting; Formal analysis: Supporting. Dereje particles prepared by laser ablation in different surfactant solutions, J. Phys.
Degefa Geleta: Data curation: Supporting; Formal analysis: Chem. B 109 (2005) 120–124, https://doi.org/10.1021/jp046747j
[19] W. Gao, Z. Li, ZnO thin films produced by magnetron sputtering, Ceram. Int. 30
Supporting. Chintagumpala Krishnamoorthi: Supervision: Equal. (2004) 1155–1159, https://doi.org/10.1016/j.ceramint.2003.12.197
Ramar Thangam: Validation: Supporting; Writing – review & [20] P.K. Giri, S. Bhattacharyya, D.K. Singh, R. Kesavamoorthy, B.K. Panigrahi,
editing: Supporting. Heemin Kang: Validation: Supporting; Writing K.G.M. Nair, Correlation between microstructure and optical properties of ZnO
nanoparticles synthesized by ball milling, J. Appl. Phys. 102 (2007) 093515,
– review & editing: Supporting. Joonho Lee: Funding acquisition: https://doi.org/10.1063/1.2804012
Lead; Project administration: Lead; Supervision: Lead; Writing – [21] S. Ekambaram, Y. Iikubo, A. Kudo, Combustion synthesis and photocatalytic
review & editing: Lead. properties of transition metal-incorporated ZnO, J. Alloys Compd. 433 (2007)
237–240, https://doi.org/10.1016/j.jallcom.2006.06.045
[22] J. Yu, X. Yu, Hydrothermal synthesis and photocatalytic activity of zinc oxide
Declaration of Competing Interest hollow spheres, Environ. Sci. Technol. 42 (2008) 4902–4907, https://doi.org/10.
1021/es800036n
[23] S. Lee, S. Jeong, D. Kim, S. Hwang, M. Jeon, J. Moon, ZnO nanoparticles with
The authors declare that they have no known competing fi­
controlled shapes and sizes prepared using a simple polyol synthesis,
nancial interests or personal relationships that could have appeared Superlattices Microstruct. 43 (2008) 330–339, https://doi.org/10.1016/j.spmi.
to influence the work reported in this paper. 2008.01.004
[24] K. Sood, J. Kaur, H. Singh, S. Kumar Arya, M. Khatri, Comparative toxicity eva­
luation of graphene oxide (GO) and zinc oxide (ZnO) nanoparticles on
Acknowledgments Drosophila melanogaster, Toxicol. Rep. 6 (2019) 768–781, https://doi.org/10.
1016/j.toxrep.2019.07.009
Ala Manohar was supported by a Korea University Grant. [25] T. Thirugnanam, Effect of polymers (PEG and PVP) on sol-gel synthesis of mi­
crosized zinc oxide, J. Nanomater. 2013 (2013) 1–7, https://doi.org/10.1155/2013/
362175
References [26] H. Li, J. Wang, H. Liu, C. Yang, H. Xu, X. Li, H. Cui, Sol-gel preparation of trans­
parent zinc oxide films with highly preferential crystal orientation, Vacuum 77
[1] L.L. Yang, Q.X. Zhao, M. Willander, X.J. Liu, M. Fahlman, J.H. Yang, Origin of the (2004) 57–62, https://doi.org/10.1016/j.vacuum.2004.08.003
surface recombination centers in ZnO nanorods arrays by X-ray photoelectron [27] R.F. Silva, M.E.D. Zaniquelli, Morphology of nanometric size particulate alumi­
spectroscopy, Appl. Surf. Sci. 256 (2010) 3592–3597, https://doi.org/10.1016/j. nium-doped zinc oxide films, Colloids Surf. A Physicochem. Eng. Asp. 198–200
apsusc.2009.12.160 (2002) 551–558, https://doi.org/10.1016/S0927-7757(01)00959-1
[2] D. Segets, L.M. Tomalino, J. Gradl, W. Peukert, Real-time monitoring of the nu­ [28] S. Maensiri, P. Laokul, V. Promarak, Synthesis and optical properties of nano­
cleation and growth of ZnO nanoparticles using an optical hyper-rayleigh scat­ crystalline ZnO powders by a simple method using zinc acetate dihydrate and
tering method, J. Phys. Chem. C 113 (2009) 11995–12001, https://doi.org/10. poly(vinyl pyrrolidone), J. Cryst. Growth 289 (2006) 102–106, https://doi.org/10.
1021/jp9009965 1016/j.jcrysgro.2005.10.145
[3] M. Yarahmadi, H. Maleki-ghaleh, M. Emami, Synthesis and characterization of [29] K. Saoud, R. Alsoubaihi, N. Bensalah, T. Bora, M. Bertino, J. Dutta, Synthesis of
Sr-doped ZnO nanoparticles for photocatalytic applications, J. Alloys Compd. 853 supported silver nano-spheres on zinc oxide nanorods for visible light photo­
(2021) 157000, https://doi.org/10.1016/j.jallcom.2020.157000 catalytic applications, Mater. Res. Bull. 63 (2015) 134–140, https://doi.org/10.
[4] R. Sha, S. Kumar, V. Vss, S. Badhulika, Ultra-sensitive phenol sensor based on 1016/j.materresbull.2014.12.001
overcoming surface fouling of reduced graphene oxide-zinc oxide composite [30] Y. Wang, C. Zhang, S. Bi, G. Luo, Preparation of ZnO nanoparticles using the direct
electrode, J. Electroanal. Chem. 785 (2017) 26–32, https://doi.org/10.1016/j. precipitation method in a membrane dispersion micro-structured reactor,
jelechem.2016.12.001 Powder Technol. 202 (2010) 130–136, https://doi.org/10.1016/j.powtec.2010.04.
[5] A.B. Djurišić, X. Chen, Y.H. Leung, A. Man Ching Ng, ZnO nanostructures: growth, 027
properties and applications, J. Mater. Chem. 22 (2012) 6526–6535, https://doi. [31] S. Popovic, M. Maljkovic, S. Music, D. Dragcevic, Influence of synthesis procedure
org/10.1039/c2jm15548f on the formation and properties of zinc oxide, J. Alloys Compd. 347 (2002)
[6] B. Dindar, S. Içli, Unusual photoreactivity of zinc oxide irradiated by con­ 324–332, https://doi.org/10.1016/s0925-8388(02)00792-2
centrated sunlight, J. Photochem. Photobiol. A Chem. 140 (2001) 263–268, [32] K.A. Alim, V.A. Fonoberov, M. Shamsa, A.A. Balandin, Micro-Raman investigation
https://doi.org/10.1016/S1010-6030(01)00414-2 of optical phonons in ZnO nanocrystals, J. Appl. Phys. 97 (2005) 124313, https://
[7] A. Belaidi, T. Dittrich, D. Kieven, J. Tornow, K. Schwarzburg, M. Kunst, N. Allsop, doi.org/10.1063/1.1944222
M.C. Lux-Steiner, S. Gavrilov, ZnO-nanorod arrays for solar cells with extremely [33] A. Pruna, Q. Shao, M. Kamruzzaman, Y.Y. Li, J.A. Zapien, D. Pullini, D. Busquets
thin sulfidic absorber, Sol. Energy Mater. Sol. Cells 93 (2009) 1033–1036, https:// Mataix, A. Ruotolo, Effect of ZnO core electrodeposition conditions on electro­
doi.org/10.1016/j.solmat.2008.11.035 chemical and photocatalytic properties of polypyrrole-graphene oxide shelled
[8] Q. Zhang, C. Xie, S. Zhang, A. Wang, B. Zhu, L. Wang, Z. Yang, Identification and nanoarrays, Appl. Surf. Sci. 392 (2017) 801–809, https://doi.org/10.1016/j.apsusc.
pattern recognition analysis of Chinese liquors by doped nano ZnO gas sensor 2016.09.122
array, Sens. Actuators B Chem. 110 (2005) 370–376, https://doi.org/10.1016/j.snb. [34] T.C. Damen, S.P.S. Porto, B. Tell, Raman effect in ZnO, Phys. Rev. 142 (1966)
2005.02.017 570–573 https://doi.org/10.1103%2Fphysrev.142.570.
[9] S.Z. Kang, T. Wu, X. Li, J. Mu, A facile gelatin-assisted preparation and photo­ [35] N. Ashkenov, B.N. Mbenkum, C. Bundesmann, V. Riede, M. Lorenz, D. Spemann,
catalytic activity of zinc oxide nanosheets, Colloids Surf. A Physicochem. Eng. E.M. Kaidashev, A. Kasic, M. Schubert, M. Grundmann, G. Wagner, H. Neumann,
Asp. 369 (2010) 268–271, https://doi.org/10.1016/j.colsurfa.2010.08.029 V. Darakchieva, H. Arwin, B. Monemar, Infrared dielectric functions and phonon
[10] T. Aoki, Y. Hatanaka, D.C. Look, ZnO diode fabricated by excimer-laser doping, modes of high-quality ZnO films, J. Appl. Phys. 93 (2003) 126–133, https://doi.
Appl. Phys. Lett. 76 (2000) 3257–3258, https://doi.org/10.1063/1.126599 org/10.1063/1.1526935
[11] K. Ghule, A.V. Ghule, B.J. Chen, Y.C. Ling, Preparation and characterization of ZnO [36] K.A. Alim, V.A. Fonoberov, A.A. Balandin, Origin of the optical phonon frequency
nanoparticles coated paper and its antibacterial activity study, Green Chem. 8 shifts in ZnO quantum dots, Appl. Phys. Lett. 86 (2005) 1–3, https://doi.org/10.
(2006) 1034–1041, https://doi.org/10.1039/b605623g 1063/1.1861509

9
A. Manohar, J. Park, D.D. Geleta et al. Journal of Alloys and Compounds 874 (2021) 159868

[37] A.K. Giri, A. Sinhamahapatra, S. Prakash, J. Chaudhari, V.K. Shahi, A.B. Panda, [45] M.A. Rauf, M. Owais, R. Rajpoot, F. Ahmad, N. Khan, S. Zubair, Biomimetically
Porous ZnO microtubes with excellent cholesterol sensing and catalytic prop­ synthesized ZnO nanoparticles attain potent antibacterial activity against less
erties, J. Mater. Chem. A 1 (2013) 814–822, https://doi.org/10.1039/c2ta00107a susceptible: S. aureus skin infection in experimental animals, RSC Adv. 7 (2017)
[38] M. Sudha, S. Senthilkumar, R. Hariharan, A. Suganthi, M. Rajarajan, Synthesis, 36361–36373, https://doi.org/10.1039/c7ra05040b
characterization and study of photocatalytic activity of surface modified ZnO [46] S.C. Lyu, Y. Zhang, H. Ruh, H.J. Lee, H.W. Shim, E.K. Suh, C.J. Lee, Low temperature
nanoparticles by PEG capping, J. Sol-Gel Sci. Technol. 65 (2013) 301–310, https:// growth and photoluminescence of well-aligned zinc oxide nanowires,
doi.org/10.1007/s10971-012-2936-y Chem. Phys. Lett. 363 (2002) 134–138, https://doi.org/10.1016/S0009-2614(02)
[39] S. Lan, L. Liu, R. Li, Z. Leng, S. Gan, Hierarchical hollow structure ZnO: synthesis, 01145-4
characterization, and highly efficient adsorption/photocatalysis toward congo red, [47] A. Umar, R. Kumar, G. Kumar, H. Algarni, S.H. Kim, Effect of annealing tem­
Ind. Eng. Chem. Res. 53 (2014) 3131–3139, https://doi.org/10.1021/ie404053m perature on the properties and photocatalytic efficiencies of ZnO nanoparticles,
[40] Y. Ying, T. Song, H. Huang, X. Peng, Nanoporous ZnO nanostructures for photo­ J. Alloys Compd. 648 (2015) 46–52, https://doi.org/10.1016/j.jallcom.2015.04.236
catalytic degradation of organic pollutants, Appl. Phys. A Mater. Sci. Process. 110 [48] M. Hoseinnejad, S.M. Jafari, I. Katouzian, Inorganic and metal nanoparticles and
(2013) 351–359, https://doi.org/10.1007/s00339-012-7273-z their antimicrobial activity in food packaging applications, Crit. Rev. Microbiol.
[41] D. Raoufi, Synthesis and microstructural properties of ZnO nanoparticles pre­ 44 (2018) 161–181, https://doi.org/10.1080/1040841X.2017.1332001
pared by precipitation method, Renew, Energy 50 (2013) 932–937, https://doi. [49] R. Lakshmi, S.V.N. Pammi, P.P.N. Vijay, Antibiotic potentiation and anti-cancer
org/10.1016/j.renene.2012.08.076 competence through bio-mediated ZnO nanoparticles, Mater. Sci. Eng. C 103
[42] X. Yang, H. Xue, Q. Yang, R. Yuan, W. Kang, C.S. Lee, Preparation of porous ZnO/ (2019) 109756, https://doi.org/10.1016/j.msec.2019.109756
ZnFe2O4 composite from metal organic frameworks and its applications for li­ [50] P. Kumar, A. Kumar, M. Ahmad, S. Kazim, Surface, optical and photocatalytic
thium ion batteries, Chem. Eng. J. 308 (2017) 340–346, https://doi.org/10.1016/j. properties of Rb doped ZnO nanoparticles, Appl. Surf. Sci. 514 (2020) 145930,
cej.2016.09.071 https://doi.org/10.1016/j.apsusc.2020.145930
[43] L. Hou, L. Lian, L. Zhang, G. Pang, C. Yuan, X. Zhang, Self-sacrifice template fab­ [51] M. Zare, K. Namratha, M.S. Thakur, K. Byrappa, Biocompatibility assessment and
rication of hierarchical mesoporous bi-component-active ZnO/ZnFe2O4 sub- photocatalytic activity of bio-hydrothermal synthesis of ZnO nanoparticles by
microcubes as superior anode towards high-performance lithium-ion battery, Thymus vulgaris leaf extract, Mater. Res. Bull. 109 (2019) 49–59, https://doi.org/
Adv. Funct. Mater. 25 (2015) 238–246, https://doi.org/10.1002/adfm.201402827 10.1016/j.materresbull.2018.09.025
[44] S.S. Karpova, V.A. Moshnikov, A.I. Maksimov, S.V. Mjakin, N.E. Kazantseva, Study [52] M.A.P. Kumar, D. Suresh, H. Nagabhushana, S.C. Sharma, Beta vulgaris aided
of the effect of the acid-base surface properties of ZnO, Fe2O3 and ZnFe2O4 green synthesis of ZnO nanoparticles and their luminescence, photocatalytic and
oxides on their gas sensitivity to ethanol vapor, Semiconductors 47 (2013) antioxidant properties, Eur. Phys. J. 130 (2015) 190, https://doi.org/10.1140/epjp/
1026–1030, https://doi.org/10.1134/S1063782613080095 i2015-15109-2

10

You might also like