Chemosphere 323 (2023) 138263

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Green synthesis of zinc oxide nanoparticles using Brassica oleracea var.

botrytis leaf extract: Photocatalytic, antimicrobial and larvicidal activity
Utaiyachandran Manojkumar a, Durairaj Kaliannan b, Venkatesan Srinivasan a,
Balamuralikrishnan Balasubramanian c, Hesam Kamyab d, e, *, Zainab Haider Mussa f,
Jayanthi Palaniyappan a, Mohsen Mesbah g, ***, Shreeshivadasan Chelliapan g,
Senthilkumar Palaninaicker a, **
a
Department of Environmental Science, School of Energy & Environmental Sciences, Periyar University, Salem, Tamil Nadu, 636011, India
b
Department of Infection Biology, School of Medicine, Wonkwang University, Lksan, 54538, South Korea
c
Department of Food Science and Biotechnology, College of Life Science, Sejong University, Seoul, South Korea
d
Faculty of Architecture and Urbanism, UTE University, Calle Rumipamba S/N and Bourgeois, Quito, Ecuador
e
Malaysia-Japan International Institute of Technology (MJIIT), Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100, Kuala Lumpur, Malaysia
f
College of Pharmacy, University of Al-Ameed, Kerbala, 56001, Iraq
g
Engineering Department, Razak Faculty of Technology & Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100, Kuala Lumpur, Malaysia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• ZnO NPs were synthesized using leaves

extract of Brassica oleracea var. botrytis
by co-precipitation as a green method.
• The synthesized BO-ZnO NPs showed
around 80% degradation of methylene
blue dye under direct sunlight
irradiation.
• The synthesized zinc oxide nano­
particles exhibit antimicrobial activity
against various microorganisms.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Pouria Ahmadi Green synthesis of nanomaterials has emerged as an ecofriendly sustainable technology for the removal of dyes in
the last few decades. Especially, plant leaf extracts have been considered as inexpensive and effective materials
Keywords: for the synthesis of nanoparticles. In this study, zinc oxide nanoparticles (ZnO NPs) were prepared using leaves
Brassica oleracea var. botrytis extract of Brassica oleracea var. botrytis (BO) by co-precipitation and applied for photocatalytic/antibacterial
Zinc oxide
activity. The synthesized BO-ZnO NPs was characterized by different instrumental techniques. The UV–vis
Thiazine dye
Spectrum of the synthesized material showed maximum absorbance at a wavelength of 311 nm, which confirmed
Photocatalytic degradation
Antibacterial and larvicidal activity the formation of BO-ZnO NPs. The XRD pattern of BO-ZnO NPs represents a hexagonal wurtzite structure and the
average size of particles was about 52 nm. FT-IR spectrum analysis confirms the presence of hydroxyl, carbonyl,
carboxylic, and phenol groups. SEM images exhibited a flower like morphology and EDX spectrum confirming

* Corresponding author. Faculty of Architecture and Urbanism, UTE University, Calle Rumipamba S/N and Bourgeois, Quito, Ecuador.
** Corresponding author.
*** Corresponding author.
E-mail addresses: hesam_kamyab@yahoo.com (H. Kamyab), mesbah.mohsen@utm.my (M. Mesbah), pskumares@periyaruniversity.ac.in (S. Palaninaicker).

https://doi.org/10.1016/j.chemosphere.2023.138263
Received 1 December 2022; Received in revised form 5 February 2023; Accepted 26 February 2023
Available online 27 February 2023
0045-6535/© 2023 Elsevier Ltd. All rights reserved.
U. Manojkumar et al. Chemosphere 323 (2023) 138263

the presence of the elements Zn and O. Photo-catalytic activity of BO-ZnO NPs was tested against thiazine dye
(methylene blue-MB) degradation under direct sunlight irradiation. Around 80% of the MB dye got degraded at
pH 8 under 75 min of sunlight irradiation. Further, the study examined that the antimicrobial and larvicidal
activity of BO-ZnO NPs obtained through green synthesis. The antimicrobial study results showed that the BO-
ZnO NPs formed zones against bacterial pathogens. The results showed the formation of an inhibition zone
against B. subtills (16 mm), S.aureus (13 mm), K. pneumonia (13 mm), and E. coli (9 mm) respectively at a
concentration of 100 μg/mL of BO-ZnO NPs. The larvicidal activity of the BO-ZnO NPs was tested against the
fourth instar of Culex quinquefasciatus mosquito larvae The LC50 and LC90 values estimated through the larvicidal
activity of BO-ZnO NPs were 76.03, 190.03 ppm respectively. Hence the above findings propose the synthesized
BO-ZnO NPs by the ecofriendly method can be used for various environmental and antipathogenic applications.

1. Introduction
Synthetic dyes are considered to be the major pollutants for the
aquatic ecosystem. Currently, more than 10,000 different synthetic dyes
are used in industries (Al-Tohamy et al., 2022; Thampraphaphon et al.,
2022; Dassanayake et al., 2021). Methylene blue (MB) is the most used
synthetic dye in textile industries for coloring fabric (Mahmoud et al.,
2021; Al-Ghouti and Al-Absi, 2020). The MB dye molecules are
extremely stable and cannot be easily degraded through a conventional
wastewater treatment process (Cheng et al., 2019; Hou et al., 2018).
Also, MB dye causes severe central nervous system toxicity and seroto­
nin toxicity (Oladoye et al., 2022; Huang and Li, 2022; Alshehri and
Malik, 2019). Current approaches for handling emerging water pollut­
ants include biological processes, activated carbon adsorption, mem­
brane filtration and chemical treatments such as chlorination ozonation
and advanced oxidation processes (Castaneda et al., 2022: Nguyen et al.,
2022; Kamyab et al., 2022).
Besides this, by-product intermediates generated during the course
of the treatment process may cause a severe warning to the aquatic
ecosystem (Zdarta et al., 2022; Wei et al., 2020). In relation to this last
methodology, the application of photocatalysis is considered an effec­
tive, easy, ecological, profitable, and innovative alternative for the
removal of emerging pollutants. Also, this process does not require
chemicals and does not produce any intermediate pollutants; photo­
catalytic processes have the ability to degrade hazardous organic pol­
lutants to mineralization, whereas most of the other techniques transfer
pollutants from one place to another (Islam et al., 2019). Moreover, the
photodegradation of pollutants is an economic process; sunlight is a
copiously accessible source of energy and its irradiation can be used for
photocatalysis technique (Saad Algarni et al., 2022). Under these cir­
cumstances, photocatalysis is considered to be one of the most effective
and alternate methods for the degradation of MB dye. A number of
catalysts obtained through chemical synthesis and also plant based
synthesis have been reported to be efficient in MB degradation. How­
ever, chemical synthesis methods are costly and toxic to the environ­
ment. In contrast, green synthesis of metal oxide nanoparticles has been
found to be environmentally friendly, less expensive, and a viable
alternative for the treatment of textile effluents. Previous studies
demonstrate the importance of green synthesis of metal oxide nano­
particles from plant extracts, where oxides of metals like copper, silver,
gold and nickel, etc., cinnamon bark (ElMitwalli et al., 2020), Mentha
Longifolia (Li et al., 2021), Garcinia mangostana (Xin Lee et al., 2016),
Jatropha curcas (Ghosh et al., 2020), Celastrus paniculatus (Mali et al.,
2020), Caesalpinia bonducella (Sukumar et al., 2020), Citrus medica Linn
(Shende et al., 2015), Allium cepa and Allium sativum (Gamze, 2017),
Aloe vera (Ashraf et al., 2016), Salvia spinosa (Pirtarighat et al., 2019),
Fumaria officinalis (Huang et al., 2021), Salvia hispanica L. (Sabouri et al.,
2021), Calotropis gigantean (Din et al., 2018) and Ocimum sanctum
(Pandian et al., 2015), that has been resourcefully used for the prepa­
ration of metal nanoparticles. Several synthetic routes of ZnO nano
particles (NPs) are reported by many authors (da Silva et al., 2017; Isai
and Shrivastava, 2019; Amini and Ashrafi, 2016; Alhadhrami et al.,
2018; Nasri et al., 2021). Among these, green synthesis received great
attention from researchers due to the avoidance of toxic chemicals for
the synthesis. In line with this ZnO NPs synthesized from leaf extracts, as
explained in this study also showed defined crystal structures and good
dye degradation ability.
The plant/plant materials derived ZnO NPs such as coconut husk,
Dolichos Lablab L, Panos, Ipomoea pes-caprae (L). R. Br, were applied as a
photocatalyst for degrading many industrial pollutants. Similarly, ZnO
NPs extracted from Cinnamomum tamala have been used for photo­
catalytic degradation of MB and Metanil yellow dye and attained 99% of
dye degradation (Priyadharshini et al., 2021). Fruit extracts of Myristica
fragrans mediated nanoparticles degraded the MB dye up to 88% in 140
min (Faisal et al., 2021). The green synthesis of ZnO nanostructures
using leaf extracts of Dolichos Lablab L.had been utilized for MB dye
degradation and it attained 80% removal at 210 min (Kahsay et al.,
2019). Green syntheses of ZnO from panos extracts showed 99% of MB
dye degradation (Kaliraj et al., 2019). Cinnamomum tamala leaf extract
stabilized ZnO NPs have been used as a photocatalyst to degrade the MB
dye and attained 98% of degradation within 90 min (Narath et al.,
2021). The Leea asiatica mediated ZnO NPs achieved 81.3% of potential
dye degradation (Ali et al., 2021). Various plant leaves extracts such as,
walnut leaf, Cassia fistula, Melia azadarach and Piper betel leaf extracts
were used for the synthesis of ZnO NPs and investigated for its anti­
bacterial activity against S. aureus and E. coli (Naseer et al., 2020; Saemi
et al., 2021; Thi Tran et al., 2021). (Umamaheswari et al., 2021) Syn­
thesized ZnO nanoparticles from Raphanus sativus Var. Longipinnatus leaf
extract and evaluated its anticancer property in A549 cell lines and it
was observed that after ZnO NPs exposure, a sharp decrease in cell
viability percentage was observed and the IC50 was found to be 40
μg/mL. The antifungal studies of zinc oxide nanoparticles were also
conducted against S. sclerotiorum, R. necatrix and Fusarium along with
Cicer arietinum seed germination activity (Dulta et al., 2022).
Brassica oleracea plant is widely cultivated, its flowers were utilized
as food and their leaves are considered as agricultural waste (Gupta and
Chandra, 2020; Pankar and Bornare, 2018). B. oleracea was grown in an
area of about 452.59(000′ Ha) with a production of 8668.22(000′ tonnes)
and the productivity was about 19.15 MT/Ha (Arunkumar et al., 2020).
The leaves contribute 50% of the total production of B. oleracea var.
botrytis and are disposed of improperly. Improper disposal of leaves
generates leachates and enhances the growth of harmful microorgan­
isms (Kadam et al., 2020). Further, cauliflower leaves are rich sources of
polyphenols that are promising reducing agents for nanoparticle syn­
thesis (Kadam et al., 2020 & Cartea et al., 2010).
An extensive literature survey demonstrated that there is no research
available for ZnO NPs synthesized from BO leaves extract. In the present
investigation, BO plant leaves were selected to synthesize ZnO nano­
particles. Their antibacterial, larvicidal activity and photocatalytic
degradation ability of MB dye were investigated. Hence, combustion
synthesis of nanomaterial via ‘greener’ methods deliver a better
advantage in terms of inexpensive, free availability, and facile route to
prepare the sample. In the current study, the efficiency of BO-ZnO NPs in
dye degradation, and its antibacterial, anti-larvicidal activity were
assessed and reported.

2
U. Manojkumar et al.
Fig. 1. Schematic illustration of BO-ZnO NPs synthesis.
2. Materials and method
2.1. Chemicals
Zinc nitrate hexahydrate (Zn(NO3)2.6H2O) AR (98%), Sodium hy­
droxide (NaOH) AR (98%), Hydrochloric acid (HCl) AR (37%), Nutrient
broth and Muller Hinton agar AR, commercial tetracycline compounds
were obtained from loba (India). All the chemicals used were of AR
grade.
2.2. Preparation of Brassica oleracea var. botrytis (BO) leaf extract
BO leaves were collected from a nearby locality at Salem, Tamilnadu,
India (longitude 11 43′ 12.9′′ N and latitude 78 05′ 30.5′′ E). The collected
◦ ◦
BO leaves was washed with tap water to eradicate the adhered dust
particles and then dried under the sunlight for 28 h (4 days). The dried
BO leaves were powdered and stored for further experiments. Around
20 g of BO leaves powder was taken in a 250 mL round bottom flask
containing 150 mL of distilled water (DW) and was stirred using the
magnetic stirrer at 100 ◦ C for 30 min. Further, the extract was cooled
and filtered with Whatman No. 1 filter paper to remove the residues. The
filtrate extract was stored in a refrigerator at 4 ◦ C for the synthesis of BO-
ZnO nano material (Naseer et al., 2020).
2.3. Green synthesis of BO-ZnO NPs
The ZnO NPs were synthesized according to (Vidya et al., 2017) with
slight modification. About 5 g of Zn(NO3)2.6H2O was added to 50 mL of
the BO leaf extract and placed at 70◦ C in a water bath. The colour
change of the liquid from brown colour into a semi-solid dark brown
colour indicated the formation of BO-ZnO NPs. The semi-solid liquid was
dried in the oven for 24 h at 70◦ C. The phytochemicals present in the
biomaterials (such as plant and algae) extract can act as reducing agents
renovating the metal precursors into metal NPs. Phytochemicals mate­
rials are containing antioxidants and toxic-free chemicals; hence they
can act as both reducing and stabilizing agents (Singh et al., 2018;
Jayachandran et al., 2021). The probable reaction mechanisms for the
production of ZnO NPs are presented below (Eissa et al., 2022):
Zn(NO₃)₂ + BO leaf extract → Zn(OH)2
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Chemosphere 323 (2023) 138263
Zn(OH)2 + calcination → ZnO + H2O
Further, the dried BO-ZnO NPs materials were powdered and then
annealed at 400◦ C for 1 h to eliminate the impurities. The unabridged
synthesis method is shown in the schematic diagram Fig. 1.
2.4. Photocatalytic degradation of thiazine dye
The photocatalytic activity of BO-ZnO NPs was tested under sunlight
irradiation. The stock solution of 1000 mg/L of MB was prepared to
dissolve the stoichiometric amount of thiazine dye ( MB) in DW. This
solution was further diluted for the required working concentration
solutions ranging from 0.020 to 0.08 g/L. About 0.05 g of the photo­
catalyst was added to the 50 mL working concentration solution of MB.
A batch mode experiment was performed with these working solutions
for a predetermined time under sunlight. The absorbance spectrums of
the experimental solutions were recorded through a UV–visible spec­
trophotometer at a uniform interval time of 15 min. The percentage of
degradation was calculated using the following formula:
% degradation = C0 − Ct/C0 × 100
Where, C0 and Ct represent the initial and time-dependent concentra­
tions of the MB dye, respectively. The absorbance (Abs) is directly
proportionate to the concentration of the MB dye; then, the concentra­
tion of MB was analyzed from the measured Abs.
2.5. Antibacterial activity
The antibacterial activity of prepared BO-ZnO NPs was assessed
against bacterial pathogens, there are K. pneumonia, E. coli representing
gram negative strains and B. subtills, S. aureus representing gram positive
strains respectively. The pure culture strains were procured from the
Environmental Microbiology Division, Department of Environmental
Science, Periyar University, Salem, India. Bacterial culture was retained
in a nutrient broth (NB) medium. The experiment was performed on
Muller Hinton agar (MHA) plates and the bacterial culture was swabbed
on agar plates. Different concentrations of BO-ZnO NPs (25–100 μg/L)
were added on MHA plates by agar well diffusion method. The positive
U. Manojkumar et al.
Fig. 2. UV–Visible spectrum (A) of BO-ZnO NPs, plant extract and XRD Patterns (B) BO-ZnO NPs.
control was made using a well consisting of tetracycline alone. All the
MHA plates was incubated at 37◦ C for 24 h. After incubation, MHA
plates were examined for the presence of inhibition zones and its
diameter was measured in mm (millimeter) (Cittrarasu et al., 2021).
2.6. Larvicidal activity
The C. quinquefasciatus mosquito larvae were collected from sewage
in a nearby locality. The larvae were maintained at a temperature of 27
± 1.5◦ C with 75–85% of relative humidity under a light/dark of 12:12 h
(photoperiod) in the laboratory. Larvae were fed with powdery pup
biscuit and yeast extract in the ratio of 3:1. When the larval growth
reaches the fourth instar stage, they were used for the bioassays with
different concentrations of BO-ZnO NPs (50, 100, 150, 200 and 250 μg/
L) and crude plant extract (Manimegalai et al., 2020). The larval mor­
tality was observed after 24 h of exposure and percentage (%) mortality
was calculated from the average of replicates. The LC50, LC90, F and R2
values are calculated by using SPSS software.
Fig. 3. FTIR spectra (A) of BO-ZnO NPs before (a), after MB dye degradation (b) and BO-plant extract (c) and SEM images (B) and (C) EDX spectra of BO-ZnO NPs.
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Chemosphere 323 (2023) 138263
2.7. Characterization of nanoparticles
To confirm the occurrence of ZnO NPs from the BO leaf extract, the
co-precipitated solution was characterized in UV–vis spectrophotometer
by measuring its absorbance at 200–800 nm (Shimadzu-1800, India).
The phase purity and crystalline nature of BO-ZnO nanoparticle was
determined through an X-ray diffraction spectrometer (Rigaku Miniflex
X-ray diffractometer system) with monochromatic Cu Kα radiation,
(λCu = 1.54 Å) at 40 mA, 40 kV electric potential. The functional groups
were analyzed through an FT-IR spectrometer (Bruker Tensor 27 spec­
trophotometer) by measuring the IR (Infra-Red) spectrum in a middle
wavelength region of 4000–450 cm− 1 at a resolution of 4.0 cm− 1. The
morphology and distribution of metallic elements were analyzed
through SEM-EDX operated at 200 kV-The SEM images were then ob­
tained through JEM-2100F (JEOL) software.
3. Results and discussion
3.1. UV–visible spectra of BO-ZnO NPs
The development of BO-ZnO NPs was confirmed through the
U. Manojkumar et al.
Fig. 4. Effect of pH on MB dye degradation by BO-ZnO NPs; a) pH 6, b) pH 7, c) pH 8 and d) pH 9.
absorbance spectrum obtained from a UV–visible spectrophotometer
(200–800 nm). The maximum Abs was attained at 311 nm and the
formation of such peaks takes place due to the SPR of BO-ZnO NPs. The
wide band gap in the absorbance by the material declares the bath­
ochromic shift as proved by the UV–visible measurements Fig. 2 (A).
Similar reports of ZnO NPs formation was confirmed through UV–vis
spectrum results (Jayachandran et al., 2021). In this present study, the
absorbance peak of ZnO NPs was obtained between 310 and 360 nm of
wavelength. Similarly, the UV–Vis spectra of E. globules leaf extract
recorded the absorption peak, at 300 nm, attributing to the formation of
ZnO NPs (Barzinjy and Azeez, 2020).
3.2. XRD analysis
The synthesized BO-ZnO NPs were analyzed through an XRD pattern
to conclude the phase and crystalline nature of the sample. Fig. 2 (B)
shows the major crystalline planes (100), (101), (102), (110), (103) and
(112) showing the diffraction peak at a position 31.5, 36.08, 47.3, 56.2,
62.68 and 67.74◦ angles at 2θ range between 20 and 80◦ . The highest
intensity peak was observed at 36.08. From these results, it is evident
that the three strong planes and three weak planes peak positions fully
confirm the hexagonal wurtzite structure. The crystal plan was calcu­
lated as per the record of JCPDS, Card number: 36–1451. The crystalline
diameter size (D) was analyzed using Debye Scherer’s equation:
D= (0.9 × λ)/ (β cos θ)(Å)
Where, λ - wavelength Cu Ka 1.5406; Å, β - full width at half maximum
5
Chemosphere 323 (2023) 138263
(radiant); and θ - diffraction angle (degrees).
As per the equation, the calculated crystalline size of BO-ZnO NPs
obtained through XRD analysis was about 52 nm. The hexagonal wurt­
zite structure of synthesized ZnO NPs in the present study was struc­
turally similar to that of the previous characterization reports of
different plant extracts such as Hibiscus sabdariffa (Soto-Robles et al.,
2019), Rubus coreanus (Rupa et al., 2018) and Cassia fistula (Suresh et al.,
2015) and Linum usitatissimum extract (Alkasir et al., 2020).
3.3. FT-IR spectrometric analysis
The Fig. 3 (A) shows that the FT-IR results, demonstrating the
functional groups of the BO-plant extract, BO-ZnO NPs at pre and post
dye degradation conditions. The peak position at 3380 cm− 1 showed the
presence of a hydroxyl group at both pre and post degradation condi­
tions (Zheng et al., 2005). However, the shrunken nature of hydroxyl
peak in the sample tested after the degradation experiment denotes the
complete dye degradation (Alshehri and Malik, 2019). The BO-ZnO NPs
also showed sharp Abs peaks at 2922 cm− 1 and 2850 cm− 1 indicating
the presence of –CH2- asymmetric stretching (Park et al., 2016). The
peak at 1654 cm− 1 indicates the existence of the (carbonyl group) in the
NPs (Dauthal and Mukhopadhyay, 2013). Also, the Abs peaks obtained
at 1458 cm− 1 and 1330 cm− 1 revealed the carboxylic acid group
(=C–– O) and stretching vibration (=C– – N) for phenol and amine groups
respectively. The absorption peaks at 1032 cm− 1, 676 cm− 1, 598 cm− 1,
and 545 cm− 1 show the Zn–O metallic bond which confirmed the for­
mation of BO-ZnO NPs from the leaf extract. In addition, the peaks ob­
tained at 2920 cm− 1 and 2849 cm− 1 specify MB dye degradation by ZnO
U. Manojkumar et al.
Fig. 5. Effect of initial MB dye concentration on MB dye degradation by BO-ZnO NPs; a) 0.020 g/L, b) 0.040 g/L c) 0.060 g/L and d) 0.080 g/L.
NPs as it confirms the formation of CH2 asymmetric stretching bands.
These bands appearing at 1786 cm− 1, 1689 cm− 1, 1397 cm− 1, 1333
cm− 1, 1250 cm− 1, 1166 cm− 1, 672 cm− 1 and 562 cm− 1 confirm MB dye
degradation indicating the formation of carboxylic acids, phenols, and
ester groups.
3.4. Scanning electron microscopic analysis and energy dispersive X-ray
studies
The SEM images of BO-ZnO NPs were presented in Fig. 3 (B) (a) & (b)
under different magnifications (10 & 5 μm). The results demonstrate
that the surface morphology of BO-ZnO NPs appeared as a flower-like
structure providing a more accessible surface area for MB dye degra­
dation. Similar to this, Laurus nobilis L plant derived ZnO NPs prepared
using zinc nitrate as a precursor also showed flower like morphology and
it was explained that, in the course of synthesis, the NPs formed like
flower-shaped bundle. This agglomeration of the formed NPs is due to its
polarity and electrostatic attraction (Fakhari et al., 2019). It was also
stated that the flower-like morphology is common for ZnO NPs syn­
thesized from plant extracts like Bridelia retusa (Vinayagam et al., 2021),
Peltophorum pterocarpum (Pai et al., 2019).
The EDX spectrum of BO-ZnO NPs was shown in Fig. 3 (C). Three
major peaks, representing the elemental constitution of BO-ZnO NPs,
were found to be zinc, carbon and oxygen. The weight (%) composition
of Zn, C and O is 46.39%, 29.33% and 24.29%, respectively. The Inset
figure indicates the percentage of the aforesaid elements. The peaks of
zinc and oxygen observed along with carbon may be due to the fact that
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Chemosphere 323 (2023) 138263
these metals may act as a capping agent for NPs (Chikkanna et al., 2019;
Balaraman et al., 2022). Previous studies reported that the EDX spec­
trum of biogenic synthesized ZnO NPs confirmed the presence of ele­
ments in different weight percentages. For example, ZnO NPs
synthesized from Bridelia retusa show the weight % elemental compo­
sition of Zn, C and O to be 63.57, 9.94 and 26.49%, respectively, which
validated the existence of ZnO (Vinayagam et al., 2021). Similarly, the
EDX analyses of e Nelumbo nucifera plant extract derived ZnO revealed
the elemental composition of Zn, C and O at 80.1, 2 and 17.9%,
respectively (Narayana et al., 2020). The EDX spectra of Brassica oler­
acea L. var. italica extract derived ZnO NPs also showed the presence of
Zn, C and O to be 34.13, 32.47 and 33.4% respectively (Osuntokun et al.,
2019).
3.5. Photo-catalytic adsorption -batch mode study
3.5.1. Effect of various pH of solution on dye removal
The pH of the solution is one of the most important factors in pho­
tocatalytic degradation. The effect of pH on the photocatalytic degra­
dation of MB is shown in Fig. 4. The results obtained through batch
mode experimental study, showed that around 80% of MB dye got
degraded at 75 min under the alkaline pH (pH 8) with a catalyst dose of
0.050 g/50 mL under solar light irradiation. The percentage degradation
of MB dye at different pH 6, 7, 8 and 9, was found to be 30, 32, 80 and
46% respectively. The higher rate of MB degradation at alkaline pH
indicates that the negatively charged surface on the catalyst is favoring
the electrostatic attraction. The complete degradation of the MB dye
U. Manojkumar et al.
Fig. 6. Effect of different catalytic concentration of BO-ZnO NPs on MB dye degradation (a) 0.040 g/L (b) 0.050 g/L (c) 0.060 g/L (d) 0.070 g/L and (e) 0.080 g/L.
occurs initially under alkaline conditions within a short time. Initially,
MB degradation was observed to be slow due to the acidic pH of the dye
and its acidic nature might have stopped the hydroxyl radical formation.
The generation of the proton during the dye degradation process in­
dicates a slow degradation rate (Alkaykh et al., 2020). It has been stated
that the production of radicals is directly proportional to photocatalytic
degradation efficiency (Nosaka and Nosaka, 2016). Therefore, the acid
and neutral pH of MB (pH 6 and 7) contains a huge amount of proton
(H+); hence excess of H+ interacts with hydroxyl radicals and gives
water molecules (Diantoro et al., 2018; Zhang et al., 2020). Thus,
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Chemosphere 323 (2023) 138263
insufficient productions of hydroxyl radicals were unable to degrade the
MB in a short time. The basic nature of the (pH 8) MB dye solution
generates an excess amount of hydroxyl and superoxide radicals. Thus,
the increased levels of hydroxyl and superoxide ion formations enhance
the degradation process in a short time.
3.5.2. Effect of initial MB concentration on dye removal
The effect of initial MB concentration (between 0.020 and 0.08 g/L)
on the photocatalytic degradation of MB onto the BO-ZnO NPs was
studied. The degradation decreased with the increase in initial MB
U. Manojkumar et al. Chemosphere 323 (2023) 138263

3.5.3. Effect of different catalytic doses on dye removal

The photocatalytic activity of the catalyst was studied to optimize
the catalytic load (0.040–0.080 g), by keeping the MB dye concentration
constant (20 ppm). Fig. 6 shows the different photocatalytic doses and
its MB degradation rate (a) 0.040 g, (b) 0.050 g, (c) 0.060 g, (d) 0.070 g
and (e) 0.080 g, respectively. The percentage degradation of MB dye
increased from 78 to 93% as the catalytic dosage increased from 0.040 to
0.080 g. As compared to lower BO-ZnO NPs concentrations, 0.080 g of
the catalyst concentration attained rapid degradation in a short time.
The decrease in degradation time is directly proportional to the increase
in catalyst concentration, due to the enormous production of radicals
(Khairnar and Shrivastava, 2019; Djebbari et al., 2021; Kumar et al.,
2021; Yulizar et al., 2020; Dhir, 2020; Kim et al., 2020). The increased
degradation percentage of MB dye is maybe due to the presence of more
active sites and higher surface area in the catalyst. From the results, it
was evident that a higher dose of catalyst has a higher surface area for
the production of radicals acting towards dye degradation.

3.6. Antibacterial activity

Green synthesized BO-ZnO NPs were found to exhibit significant

Fig. 7. Antibacterial activity against various bacteria at varying BO-ZnO NPs
concentration (a) 25 μg/mL, (b) 50 μg/mL, (c) 75 μg/mL, (d) 100 μg/mL and (e)
Positive control.
concentration as shown in Fig. 5. This indicates that the degradation is
vastly dependent on the initial concentration of MB. Due to the lower
initial concentration, the ratio between the available MB molecules and
the available adsorption surface area of the catalyst is less. However, at
higher concentrations, the available adsorption surface area becomes
lower with respect to the MB molecules in an aqueous solution and
hence the removal percentage of MB depends on the initial concentra­
tion. The maximum degradation of MB dye (84%) was obtained at the
lowest concentration of 0.020 g/L. By raising the initial concentration of
MB dye from 0.02 to 0.08 g/L, the degradation gradually decreased from
85 to 0.80%. The increasing initial concentration of the dye increases the
adsorption of dye molecules on the surface of the catalyst and signifi­
cantly reduced the amount of light absorption on the surface of the
catalyst. (Reza et al., 2017; Alshehri and Malik, 2019). This may be due
to the decrease in light absorption on the catalyst surface and reduced
production of OH radicals. These OH radicals play a vital role in the
degradation of dyes. Therefore, the maintenance of the ratio of catalyst
and dye concentration was important for the photocatalytic degradation
of dyes. Hence it was concluded that the highest degradation of MB dye
was 80% at 0.02 g/L. These observations were in line with similar kind
of studies conducted elsewhere (Khodaie et al., 2013; Benhabiles et al.,
2016; Krishnakumar and Swaminathan, 2011; Behnajady et al., 2006).
antibacterial activity against gram-positive and gram negative clinical
pathogens. Fig. 7 shows the antibacterial activity of the ZnO nano­
particles. The results showed the formation of an inhibition zone against
B. subtills (16 mm), S. aureus (13 mm), K. pneumonia (13 mm), and E. coli
(9 mm) respectively at a concentration of 100 μg/mL of BO-ZnO NPs.
The inhibition zone measurements were compared with positive con­
trols and therefore, the results suggest that the BO-ZnO NPs showed
significant antibacterial activity. The bioactive compounds collectively
found in most of the Brassica species such as alkaloids, aliphatic & ar­
omatic amines, phenolic acids, glycosides, polyphenols, zeaxanthin, &
β-carotene, flavonoids, saponins, anthocyanins, terpenoids, tannins,
phytosterols chlorophyll, phytosteroids, glucosinolates, lutein and
vitamin E & C. Due to the presence of these phyto-compounds, Brassica
plants illustrate a higher rate of biological activities against various
pathogens and are also effective in treating numerous diseases in ani­
mals and humans (Nawaz et al., 2018; Abdoli et al., 2022).
Previously, several reports discussed the antibacterial potential of
ZnO NPs obtained from Catharanthus roseus leaves extract against bac­
terial pathogens like B. cereus, S. aureus, P. mirabilis, S. pyogenes,
P. aeruginosa and E. coli. Gupta et al. (2018) reported the ZnO NPs at a
higher concentration (1500 μg/mL) revealed potential antibacterial
activity against the pathogens, as displayed by the diameter of ZOI
11.09–11.74 mm, respectively (Awwad and Amer, 2020). Prepared
Ailanthus altissima fruits aqueous extract mediated ZnO NPs (500 μg/mL)
and the results exhibited the inhibition zone diameter for S. aureus (20
mm) and E. coli (18 mm). ZnO NPs synthesized from Camellia sinensis
leaves extract (20 μg/mL) exhibited antibacterial activity against
selected pathogens and the ZOI diameter was 10.3 mm against

Table 1
Larvicidal activity of BO leaf extract, BO-ZnO NPs against C. quinquefasciatus.
Instar Concentrations (ppm) Mortality (%) LC50 LC90 F value R2 value
Sample

BO leaf extract IV 50 10 ± 0 396.978 2773.00 11.083 0.811

100 16.67 ± 0.16
150 23.3 ± 0.23
200 33.3 ± 0.33
250 40 ± 0.4
BO-ZnO NPs IV 50 36.67 ± 0.36 76.035 190.025 33.650 0.899
100 53.33 ± 0.53
150 73.33 ± 0.73
200 96.66 ± 0.96
250 100 ± 1
Zinc Nitrate IV 250 53.33 ± 0.53 – – – –

LC50- Concentration lethal to 50% test population, LC90- Concentration lethal to 90% test population, (±) Standard error F-ratio, variance between the means of two
populations and R2 – Statistical fitness.

8
U. Manojkumar et al.
K. pneumonia, 3.3 mm against P. aeruginosa and 5.3 mm against S. aureus
(Senthilkumar and Sivakumar, 2014).
3.7. Larvicidal activity
The larvicidal activity was evaluated for synthesized BO-ZnO NPs
and crude BO extract. The 4th instar stage of larvae were performed for
the assays with different concentrations of BO-ZnO NPs and crude plant
extract. No mortality of larvae was observed in the control group.
Mortality increased with the increase in the concentration of the BO-ZnO
NPs and crude BO leaves extract from 50 to 250 ppm. On exposure of the
larvae for 24 h, the LC50 values and LC90 values were estimated. The
LC50 and LC90 values for BO-ZnO NPs and crude BO extract were 76.03,
396.97 and is 190.02, and 2773.00 ppm, respectively. The mortality rate
due to the existence of zinc nitrate precursor was about 53.33% at 250
ppm (Table 1). Hence, it’s clear that the BO extract synthesized ZnO NPs
possess a potential toxic effect against mosquito larvae. Similar kinds of
results were reported for the ZnO NPs extracts synthesized through
Knoxia sumatrensis (Loganathan et al., 2021), Ficus religiosa (Soni and
Dhiman, 2020).
Also (Gandhi et al., 2017), reported around 92% and 100% mortality
of mosquito larvae using M. charantia leaf extract (100 ppm) and leaf
extract synthesized ZnO NPs (10 ppm) respectively. Further, LC50 values
of 42.64 and 4.7 ppm; LC90 values of 92.95 and 8.29 ppm were reported.
In another study, ZnO NPs (30 mg/L) showed 74% mortality in
C. quinquefasciatus second instar larvae and LC50 and LC90 values were
about 0.72 and 27.79 ppm respectively (Mostafa et al., 2018).
4. Conclusions
In summary, green synthesized BO-ZnO NPs by using Brassica oler­
acea var. botrytis leaf extract exhibited better dye degradation and
antimicrobial/larvicidal activities. Herein, an alkaline condition (pH 8)
was proclaimed to be ideal for photocatalytic activity rather than acidic
and neutral pH. Around 80% of the MB dye got degraded at pH 8 under
75 min of sunlight irradiation. The hexagonal structure of BO-ZnO NPs
has a vast surface area, which supports effective light penetration and
effective charge separation. The optimum catalytic dose (50 mg) can
break the chromophoric structure in MB dye. Degradation time got
reduced due to the enormous amount of hydroxyl and superoxide radical
production. Also, BO-ZnO NPs (100 μg/mL) formed high inhibition
zones against potential bacterial pathogens. The BO-ZnO NPs and BO
extract also revealed significant larvicidal activity against mosquito
larvae. Hence the above findings propose the synthesized BO-ZnO NPs
may be used in textile wastewater treatment processes in future and also
in good agricultural waste management practices.
Credit author statement
Utaiyachandran Manojkumar: Methodology; Data Curation; Writing
- Original Draft. Durairaj Kaliannan, Hesam Kamyab: Conceptualization;
Writing, Review & editing. Srinivasan Venkatesan, Shreeshivadasan
Chelliapan, Zainab Haider Mussa, Mohsen Mesbah: Review & editing.
Balamuralikrishnan Balasubramanian, Palaniyappan Jayanthi: Review
& editing and Proofread. Senthilkumar Palaninaicker: Supervision;
Validation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The authors are unable or have chosen not to specify which data has
9
Chemosphere 323 (2023) 138263
been used.
Acknowledgement
The corresponding author gratefully acknowledges University
Research Fellowship (URF), Periyar University. The authors also
acknowledge the provision of institutional research infrastructure fa­
cilities. Finally, the authors would like to express their gratitude to
Universiti Teknologi Malaysia (UTM) for their support through Vote
Number R.K130000.7113.05E83.
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