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Graphene oxide-based probe for detecting

Cite this: Environ. Sci.: Water Res.
deltamethrin and emamectin benzoate pesticides
Technol., 2024, 10, 2162 in agricultural run-off†
Suryyia Manzoor,a Muhammad Hayat,a Hina Raza,b Noureddine Elboughdiri, *cd
Muhammad Imran Khan, e Zeeshan Ali,a Ayesha Javed,a Nadeem Raza,f
Fahad Abdulazizg and Abdallah Shanableheh

Insecticides adversely affect aquatic ecosystems due to prolonged exposure, persistent nature, and
bioaccumulation. Deltamethrin and emamectin benzoate are pesticides that can enter water resources via
fruits and vegetables, causing severe concerns to living organisms. This study focuses on fabricating a
probe for the selective solid-phase microextraction of targeted pesticides from agricultural runoff. The
sorbent was designed using the novel dual-template graphene oxide-based molecularly imprinted
organically modified silica. In this study, we investigated the effect of different parameters (time, pH, and
Received 22nd April 2024, temperature) on the efficacy of the sorbent using response surface methodology (central composite
Accepted 26th June 2024
design). The sorbent exhibited high binding capacities of 42 mg g−1 and 27 mg g−1 for deltamethrin and
DOI: 10.1039/d4ew00328d
emamectin benzoate, respectively. Percentage recoveries were 93.3% and 94.2% for deltamethrin and
emamectin benzoate, respectively. The selective detection of deltamethrin and emamectin benzoate from
rsc.li/es-water agricultural runoff was confirmed by real-sample analysis using high-performance liquid chromatography.

Water impact
The obtained analysis and results suggested that the GO-based MIormosil was capable of effectively adsorbing the desired pesticides from water samples.
Deltamethrin and emamectin benzoate are pesticides that can enter water resources due to their fruits and vegetables, causing severe concerns to living
organisms. This study focuses on fabricating a probe for the selective solid-phase microextraction of targeted pesticides from agricultural runoff.

1. Introduction
Chemicals designated as insecticides are frequently used in
a
Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, Pakistan. agriculture to safeguard crops from pests, boost crop yields,
E-mail: [email protected], [email protected], and enhance food security, as well as in households to
[email protected], [email protected] control indoor pests such as ants, cockroaches, and
b
Faculty of Pharmacy, Bahauddin Zakariya University, Multan, Pakistan.
mosquitoes.1 However, their prolonged unmanaged exposure
E-mail: [email protected]
c
Chemical Engineering Department, College of Engineering, University of Ha'il, P.
and persistent nature can cause contamination in diverse
O. Box: 2440, Ha'il 81441, Saudi Arabia environmental segments including water, soil, and air and
d
Chemical Engineering Process Department, National School of Engineers Gabes, lead to long-term effects on the ecosystem, including damage
University of Gabes, Gabes 6011, Tunisia. E-mail: [email protected]; to biodiversity and several beneficial species such as
Tel: +966549571015
e
pollinators.2 When water flows over the soil, it contaminates
Research Institute of Sciences and Engineering (RISE), University of Sharjah,
Sharjah 27272, United Arab Emirates. E-mail: [email protected],
a more significant part of the ecosystem than point sources
[email protected] such as lakes.
f
Department of Chemistry, College of Science, Imam Mohammad Ibn Saud Islamic The use of organochlorides and organophosphorus
University (IMSIU), Riyadh, Saudi Arabia. E-mail: [email protected] insecticides has significantly declined in recent years due to
g
Department of Chemistry, College of Science, University of Ha'il, Ha'il 81451,
their high toxicity and potential environmental harm.3 As an
Saudi Arabia. E-mail: [email protected]
h
Scientific Research Center, Australian University, Kuwait
alternative, synthetic pyrethroids such as deltamethrin and
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ emamectin benzoate have gained popularity for effectively
10.1039/d4ew00328d managing crop pests.4,5 Deltamethrin acts by extending the

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Environmental Science: Water Research & Technology Paper

opening of sodium channels in insects that lead to paralysis development.16,17,20,21 Furthermore, MIormosil can be tailored
and ultimately death. Emamectin benzoate, derived from to enhance stability in various conditions, including extreme
avermectin, is a macrocyclic lactone that acts as a foliar temperatures and pH ranges. Multi-template imprinting is a
pesticide by encouraging the release of aminobutyric acid. It strategy that involves using two or more template molecules
inhibits neurotransmitters, causing paralysis, which then during the synthesis of MIMs.22 This approach can result in
results in insect death.6 To combat the emerging challenge of MIormosil with multiple recognition sites, improving the
pesticide resistance, a current trend has been the use of two MIormosil selectivity and specificity towards various
or more pesticides in combination. Blending pesticides with structurally related analytes.23 Furthermore, to improve the
different mechanisms of action may have additive, binding capacity of these materials, a recent trend has been
antagonistic, or synergistic effects on a given insect species.7 the introduction of 2D materials like graphene oxide (GO)
However, their uncontrolled and regular use can cause them and its derivatives in fabricating imprinted sorbents. GO
to infiltrate the food chain and pose a health danger to provides a higher surface-to-volume ratio and enhanced
humans. For instance, the neurotoxic deltamethrin has been binding strength, favoring swift sorption dynamics towards
connected to developmental issues, olfactory dysfunction, the analyte.24,25
fibrosis, and cognitive impairment, in addition to its effects The literature presents a knowledge gap regarding the
on the neurological system.8 Due to its negative simultaneous determination of deltamethrin and emamectin
consequences, the US Environmental Protection Agency (EPA) benzoate through the imprinted sorbent. The present study
has restricted the use of this insecticide.9 thus describes a synthetic route to design graphene oxide-
Emamectin benzoate gained fame in the agriculture sector based imprinted sorbent (MIormosil) with the capability to
due to its low application volume and broad-range efficacy. simultaneously determine these two pesticides selectively in
Conversely, its long residence time with a half-life of 120 days agricultural run-off. The use of graphene oxide served to
makes it persistent, especially in agricultural run-off.10 Its enhance the sorption capacity by providing a high surface
neurotoxic nature can result in physiological alterations area and functional groups. Finally, a probe for SPME was
among various fish species, affecting their growth and fabricated to facilitate the extraction process of these
reproduction rate. Being able to damage DNA, it is also pesticides from the sample matrix, followed by HPLC. The
capable of destroying human epithelial cells and stomach physiochemical properties and extraction efficiency of the
linings through apoptosis.11–13 dual-template graphene oxide-based MIormosil have been
Consequent to the severe concerns of deltamethrin and evaluated in detail. A central composite design optimized the
emamectin benzoate, there is a dire need to develop experimental parameters through response surface
sensitive, efficient, and reliable approaches for their methodology (RSM).
determination in aquatic environments. To this end, several
techniques such as gas chromatography (GC), liquid 2. Materials and methods
chromatography-electrospray ionization mass spectrometry 2.1. Reagents
(LC-EIMS), and ultraviolet–visible spectroscopy (UV-vis) have
been employed for the determination of insecticides. 3-Aminopropyl triethoxysilane (97%), tetra ethyl ortho silicate
However, the techniques above may suffer from issues, such (98%), and HPLC grade water, standard emamectin benzoate
as interferences from complex matrixes and can result in (71%), and deltamethrin (98%) were obtained from Sigma
errors during analysis.14 Therefore, to minimize matrix Aldrich, Germany. Ethanol, methanol, hydrochloric acid
interferences, sample preparation techniques, such as solid- (37%), and sodium hydroxide were obtained from Riedel-de
phase extraction (SPE), liquid–liquid extraction (LLE), stir bar Haen, UK. Acetone (99.5%) was obtained from Analar, UK. All
sorption extraction (SBSE), liquid-phase micro-extraction chemicals in the current research were used without further
(LPME), and solid-phase microextraction (SPME), are often a purification steps.
preferable choice. The adsorbent material used in all of these
techniques is pivotal in determining a separation process's 2.2. Synthesis of molecularly imprinted ormosil and
efficiency and extraction capacity.15–18 Recently, molecularly designing the probe
imprinted materials (MIMs) have been considered as Firstly, graphene oxide (GO) was prepared by a slight
promising sorbents due to their ability to specifically modification in the Hummer's method.26 In the second step,
recognize the target compound. MIMs are artificial entities 0.1 g of graphene oxide (synthesized in the first step) was
with bio-inspired properties that bind to a target molecule suspended in 10 mL of ethanol by sonicating for 30 min in a
with high selectivity.19 round-bottom flask. To this suspension, 2.5 mL of
Molecularly imprinted ormosil (MIormosil) is a type of MIM aminopropyl triethoxy silane (APTES) and 2 mL of 0.1 M HCl
synthesized by imprinting a target molecule into a sol–gel were added, and sonicated for 1 min. Afterward, 0.8 g of
matrix. They have been shown to exhibit high stability, emamectin benzoate (dissolved in 8 mL methanol) and 0.45
physical strength, and ease of synthesis, making them an g of deltamethrin (dissolved in 5 mL acetone) were added as
attractive choice for various applications, including water template molecules. Finally, 5 mL of tetraethyl orthosilicate
monitoring, food analysis, and pharmaceutical (TEOS) was introduced to the same flask, and the mixture

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was heated at 80 °C until a hard, jelly-like ormosil (MIormosil) 2.6. Imprinting factor
was formed. Using a Soxhlet apparatus, the MIormosil was Eqn (1) was used to calculate the imprint factor (α) for
then washed with methanol and acetone to extract the deltamethrin and emamectin benzoate.
entrapped templates. Non-imprinted ormosil (NIormosil) was
also synthesized using the identical procedure, except for the qm
α¼ (1)
addition of templates, and was subsequently used for qn
comparison.
Finally, the MIormosil was coated on the surface of a 3 mm Here, the equilibrium adsorption capacity of MIormosil is qm
× 5 cm (width × height) aluminium wire to obtain a solid = mg g−1 and that of NIormosil is qn = mg g−1.
phase microextraction (SPME) probe. The total length of the
wire was kept longer (10 cm) to facilitate its holding. 2.7. Selectivity studies of MIormosil
The selectivity of the designed adsorbent was evaluated by
performing cross-reactivity assays to preferentially retain
2.3. Characterization deltamethrin and emamectin benzoate in the presence of
The morphologies of both ormosils were examined through analogs with related morphological characters. Doramectin
scanning electron microscopy ((SEM), Hitachi SU8000, Tokyo, and moxidectin were selected for emamectin benzoate, while
Japan). Before SEM analysis, thin gold films were sputter- cyhalothrin and cyphenothrin were selected for deltamethrin
coated onto samples at 15 kV for 200 s using JEOL JFC-1000E for the selectivity evaluation experiments. The same
ion sputter fine coat under vacuum (∼10−3 Torr). FTIR experimental parameters, as applied to assay emamectin
spectra (in the range of 4000 to 550 cm−1) were obtained benzoate and deltamethrin, were used for the quantitative
through a Bruker Alpha II FT-IR spectrometer (Bruker, analysis of structural analogs and the percentage recoveries
Billerica, MA, USA) equipped with an automated were calculated.
refractometer (ATR) module. The iodine adsorption number
was used to calculate the surface area. For this, 0.05 g of each 2.8. Determination of pesticides in water sample
of MIormosil and NIormosil was added to each flask, along with A 2 L volume of water sample was obtained from a nearby
10 mL of standard iodine solution, and the flasks were then agricultural land and stored at 4 °C. At the time of analysis,
stirred for 30 min. After filtration, the titration of the the water sample was filtered using a membrane filter paper
solutions was done with 0.1 N sodium thiosulfate. (pore size 0.45 μm, diam. 47 mm) to remove debris and
suspended particles. The filtered water sample was spiked
with emamectin benzoate and deltamethrin at three varying
2.4. Adsorption isotherms and kinetic studies concentrations (5, 50, and 100 μg mL−1) in three separate
The adsorption behavior of pesticides on the designed flasks, each containing 25 mL of filtered water. For SPME, the
MIormosil was evaluated using Langmuir and Freundlich SPME probe was introduced into each flask. The water
adsorption isotherms. For these adsorption experiments, 20 samples containing pesticides and SPME probes were agitated
mg of MIormosil was dispersed in different concentrations of for 15 min. The probe was then taken out, and the adsorbed
emamectin benzoate and deltamethrin solutions (e.g., 10, 20, pesticides were desorbed using methanol/acetone as solvent.
30, 40, 50, 60, 70, 80, and 90 mg L−1). The concentration of The HPLC analysis of the real water sample and sample
the pesticides in the filtrate was measured using a UV-vis containing desorbed pesticides was performed using an
(Shimadzu UV-800ENG240V, SOFT, Japan) Agilent 1100 liquid chromatograph (Palo Alto, CA, USA) with a
spectrophotometer. heated column compartment and a diode array detector. An
Similar experiments were carried out to determine the Ultra IBD 5 m 250 × 4.6 mm long C18 column was selected,
effect of time on MIormosil's capacity to bind emamectin and the mobile phase was prepared using acetonitrile/water
benzoate and deltamethrin. Further non-linear kinetic (75 : 25 v/v). A flow rate of 1 mL min−1 was maintained.
models were also applied.
2.9. Regeneration studies
Regeneration studies were carried out by dispersing 20 mg of
2.5. Response surface methodology (RSM) MIormosil in 50 mL of a 200 mg L−1 mixed standard solution
The experimental sets were developed using Stat-expert Ease's of emamectin benzoate and deltamethrin at room
design software (version 13) to assess the impact of different temperature. The concentration of the target pesticides in the
experimental factors using the response surface method filtrate was measured using a UV-vis spectrophotometer after
(RSM). The model was designed using three variables: stirring the above solution for 30 min at 100 rpm, and
concentration, pH, and time. The central composite design filtering through an HPLC-grade filter (0.45 μm). The
(CCD) was selected using 17 experimental runs to evaluate quantification of emamectin benzoate and deltamethrin was
the binding capacity. The significance of the regression executed at their respective wavelengths of maximum
results was evaluated using ANOVA. absorption (245 nm for emamectin benzoate and 265 nm for

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deltamethrin). The sorbent was then isolated using filter Thus, in the case of a non-covalent synthetic approach, the
paper after adsorption, washed several times with methanol/ formation of hydrogen bonds (like primary molecule-to-
acetone, and dried at 60 °C. The regenerated MIormosil was molecule interactions) significantly affects the template–
utilized in the next adsorption cycle, and a total of seven monomer complex strength. In the current study, graphene
adsorption–desorption cycles were performed. oxide and 3-aminopropyl triethoxy silane were selected to
provide functional groups that could effectively interact with
3. Results and discussion the templates. Furthermore, graphene oxide also enhances
the surface area of the adsorbent, leading to enhanced active
Notably, strong interaction between the template and the sites that are necessarily required for the sorption of target
monomer complex is crucial for the imprinting process. molecules. Tetraethyl orthosilicate was used as a cross-

Fig. 1 Schematic route for the (a) synthesis of MIormosil, and (b) structural representation of the reagents and prepared sorbent.

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Paper Environmental Science: Water Research & Technology

linking agent to create molecularly imprinted ormosil with existence of different physical characteristics. MIormosil is
multiple templates. Emamectin benzoate and deltamethrin thus expected to have a greater capacity to retain the target
were used as dummy templates. Fig. 1 represents the molecules (deltamethrin and emamectin benzoate) relative to
schematic diagram of the MIormosil's synthetic scheme. It is NIormosil.
also worth mentioning that NIormosil lacked specific 3.1.2. FT-IR analysis. FT-IR spectroscopy was used to
recognition, as it was synthesized without the use of a identify the functional groups present in the MIormosil and
template (deltamethrin and emamectin benzoate). NIormosil, and confirm its synthesis. Fig. 2a and b are the
FTIR spectra of the templates (deltamethrin and emamectin
benzoate). The FT-IR spectrum of deltamethrin presented
3.1. Characterization peaks at 1701 cm−1, 1489.25 cm−1 and 1113.8 cm−1 due to the
3.1.1. Surface area determination. The surface area of the carbonyl group, ring stretch absorption of CC, and
two sorbents (MIormosil and NIormosil) was calculated through aromatic stretch of C–O–C, respectively. The band at 1008.48
eqn (2):27 cm−1 was attributed to the aromatic ethers of C–O.28 In the
case of emamectin benzoate, a broad band was observed at
Surface area = 253.8[V1(Ci – Cf)] (2) 3137 cm−1 occurring due to the presence of –OH, while the
bands at 2972 cm−1 and 2928 cm−1 are possibly due to the
V1 is the initial volume of iodine in mL, Ci is the initial stretching vibrations of C–H from the aromatic ring. A
concentration of iodine, Cf is the final concentration of prominent sharp band at 1740 cm−1 appeared due to CO,
iodine, and 253.8 is the surface area of one mol of iodine. while those at 1639, 1603, and 1560 cm−1 were attributed to
The surface area of MIormosil was calculated to be 217.13 the stretching vibrations of CC from an aromatic ring or
m2 g−1 and that of NIormosil was 122.58 m2 g−1. A high surface possibly the conjugated olefins. The bands due to C–H
area of MIormosil as compared to NIormosil suggests the deformation in CH3 groups were assigned at 1452 and 1392

Fig. 2 FT-IR spectra of (a) deltamethrin, (b) emmectin benzoate, (c) NIormosil and (d) MIormosil.

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cm−1. The C–O and C–O–C bands occurred at 1160 and 1058
cm−1.29
Fig. 2c and d represent the FTIR spectra non-imprinted
and imprinted ormosils. The band at 1066 cm−1 corresponds
to Si–O–Si, while the amide group's N–H stretching appeared
at 3710 cm−1 and bending at 1515 cm−1.15 At 3498 cm−1, a
well-defined band was observed that belonged to –OH groups
from residual water due to weak H-bonding or uncondensed
silanol groups.30 The band at 2980 cm−1 specified the
presence of C–H in stretching, while the peak at 1480 cm−1
presented the existence of the C–H bending mode with sp3
hybridization.31,32 The –OH bending and C–O stretching
modes were identified at 1450–1420 cm−1 and 1248 cm−1, Fig. 4 EDX spectrum of MIormosil presenting its elemental
respectively. At 890 cm−1, the CH bending was observed. In composition.
the case of spectrum b (MIormosil), some extra peaks were
observed, which can be correlated to the presence of a
template in the imprinted sorbent (for example, at 2224 and formation of graphene oxide (Fig. 5a), having a characteristic
2021 cm−1). They most probably are caused by the CN peak at 9.2 in the 2θ region with the hkl plane (101).
stretching modes and aromatic combination bonds of the Meanwhile, the XRD pattern of MI ormosil (Fig. 5b)
templates, respectively. The NIormosil exhibited the same confirmed the presence of both silica and graphene oxide.
spectrum, excluding the peaks due to templates, which The silica peaks appeared at 22° and 26°. The spectrum
confirmed their similar chemical compositions. further reveals the amorphous nature of the designed
3.1.3. Scanning electron microscopy. A scanning electron sorbent, having a percent crystallinity of 11.6% calculated by
microscope was used to examine the morphologies of eqn (3). The amorphous nature of the composite suggests the
MIormosil and NIormosil. The SEM images (Fig. 3a and b) of increased adsorption capability of the adsorbent.
MIormosil and NIormosil revealed lumps with long, strip-shaped
structures. Additionally, irregularly shaped particles with %Crystalinity = Area of crystalline peaks/Area of crystalline
varied sizes and shapes are visible. and amorphous peaks × 100 (3)
3.1.4. Energy dispersive X-ray analysis (EDX). EDX, being a
widely used analytical technique for elemental analysis, was
selected to determine the chemical composition of the 3.2. Response surface methodology (RSM), central composite
MIormosil (Fig. 4). The spectrum confirmed the presence of design
carbon as a major element (63%) incorporated by graphene Response surface methodology is a combination of
oxide, APTES and TEOS. Oxygen, nitrogen, and silicon were mathematical and statistical approaches. It is useful for
detected with the percentage values of 29%, 3% and 5%, developing, improving, and optimizing various processes.33
respectively. The purpose of using RSM is to handle the challenges that
3.1.5. X-ray diffraction analysis. The XRD patterns of pure typically arise during batch adsorption, such as the absence
graphene oxide and MIormosil were analyzed by the X Pert of interactive effects between the variables.34 When using
HighScore Plus Software. The XRD pattern confirmed the batch binding assay optimization, one working parameter is

Fig. 3 SEM images of (a) MIormosil and (b) NIormosil.

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fit was 0.08, which further confirmed that the data's

frequency of not fitting the model was non-significant.
The final actual model in terms of COD factors for
deltamethrin is described by eqn (4)

Sqrt(R1) = +4.421 + 0.015 × Concentration + 0.010 × Time

− 0.009 × pH − 0.0002 × Concentration × Time
+ 0.0004 × Concentration × pH + 0.002 × Time
× pH (4)

Similarly, the actual factor equation for emamectin benzoate

is given below.

Sqrt(R1) = +0.551271 + 0.017244 × concentration + 0.000530

× time − 0.068106 × pH + 0.000029 × concentration
× time + 0.000671 × concentration × pH
− 0.001186 × time × pH − 0.000185
× concentration2 + 0.000023 × time2 + 0.006608
× pH2 (5)

These equations are meant to help in predicting the response

for the factors under analysis.36
It is important to look at the RSM model's “lack of fit”
because predictions that do not match the data will be
wrong or misleading. To figure out how well this criterion
works, the difference between the model's residuals was
compared. The p-value shows how likely it is that the effect
or result that was seen happened by chance alone. If the
p-value is very small (usually less than 0.05), the observed
Fig. 5 XRD spectra of (a) graphene oxide, (b) MIormosil. effect is statistically significant. The reverse will be true in
the situations when the p-value is greater than 0.05. The
analysis of variance (ANOVA) was used to test the
altered while the others are kept constant, which is not the significance and usefulness of the RSM model. The model's
case in RSM.35 RSM is an effective statistical technique used F-value (F = 58.33) and very low P-value (P = 0.0001)
in the design and optimization of experiments, and helps to indicate that the 2FI model showed the best fit for
explore the effects of different parameters on binding deltamethrin, which suggests that there is only a 0.01%
capacity while reducing the number of experimental runs chance that a model F value could occur due to noise. The
needed. The method of RSM entails constructing a non-significant lack of fit indicates that the proposed
mathematical model that depicts the relationship between model's predictability is suitable for the set of variables
the independent variables (factors) and the dependent under investigation. R 2, which is used to compare the
variable (response). In this study, the response surface empirical data and applicable equations, signifies
method was used to optimize the interaction between the agreement when it is higher than 0.8. Deltamethrin's
MIormosil adsorption conditions and pesticide removal rate. predicted and adjusted R 2 values were 0.9732 and 0.9844,
Improved performance and cost-effectiveness were observed, respectively. Moreover, the 3D graphs presented the
as the process was able to successfully remove deltamethrin interdependence of different parameters under
and emamectin benzoate, while using less adsorbent consideration and their effect on response, i.e., qe (Fig. 6).
material. Different independent variables, such as the (A) As predicted by the model, a maximum binding capacity of
amount of MIormosil, (5–100 mg L−1), (B) contact time (5–30 42 mg g−1 could be obtained under the following
min), and (C) pH (4–10) of the adsorbent with the pesticide's experimental conditions: pH 10, time 26 min, and
solution, were selected and their effects were investigated. concentration of pesticide at 100 mg L−1.
The binding capacities (qe) of the MIormosil for both target In the case of emamectin benzoate, the quadratic
pesticides were calculated from the sets of experimental model with the data's F-value (68.92) and p-value <0.0001
values using the central composite design (CCD) model indicates that the model is significant. The predicted
matrix shown in Tables S1 and S2.† (0.819) and experimental (0.97) values of R 2 for emamectin
The data for deltamethrin followed the 2FI model with a benzoate agree with each other. In this case, too, 3D
p-value of 0.0001, whereas the p-value for the model's lack of graphs were obtained to show how different factors, like

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Fig. 6 The interdependence of the three studied parameters and their effect on the binding capacity (qe): a) effect of concentration and time, b)
effect of concentration and pH, c) effect of time and pH. d) Graph between the predicted factors and actual factors of deltamethrin.

time, pH, and concentration, were interrelated with each 3.3. Selectivity studies
other and impacted the binding capacity (qe) (Fig. 7). This
model predicts that the maximum binding of 27 mg g−1 The design of the imprinted materials is essential for their
will occur when the pH is 10, the time is 14 min, and efficacy in capturing and isolating the target analyte. The
the concentration is 64 mg L−1. Additionally, the cavities within the polymeric matrix must be tailored to the
experimental values of 41.17 mg g−1 (deltamethrin) and target molecule's form, size, and chemical characteristics.37
26.85 mg g−1 (emamectin benzoate) were not too far from Therefore, the selectivity of MIormosil using a “dummy
the predicted values with an error of 0.83% and 0.55%, template” instead of the target molecule is the best option
respectively. for trace compound analysis.38 The capability of the MIormosil
In the case of real sample analysis, when simultaneous to selectively bind with emamectin benzoates was determined
determination of both pesticides was required, a compromise by comparing the percentage recoveries obtained for the
was made on time and the maximum time of 26 min was target molecule and structurally similar compounds, i.e.,
selected. doramectin and moxidectin. The existence of a cyclohexyl

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Fig. 7 The interdependence of parameters and their effect on the binding capacity (qe): a) effect of concentration and time, b) effect of
concentration and pH, c) effect of time and pH. d) Graph between the predicted factors and actual factors of emamectin benzoate.

moiety at the C-25 position may be the reason for dimethylcyclopropanecarboxylate, respectively. Fig. S1b† shows
doramectin's low cross-reactivity values. Moxidectin, one of that percentage recoveries for deltamethrin were 91.9 ± 1% (n = 3),
the milbemycins, differs structurally from emamectin 40.1 ± 2% (n = 3) for cyhalothrin, and 38.1 ± 1% (n = 3) for
benzoate, as it lacks a disaccharide group at position C-13, cyphenothrin.
and hence showed less binding. The percentage recoveries
were 96.3 ± 2% (n = 3) for emamectin benzoate, 42.1 ± 1% (n
= 3) for doramectin, and 40.2 ± 1% (n = 3) for moxidectin, 3.4. Imprinting factor
respectively, as shown in Fig. S1a.† The imprinting factor is an important parameter for
On the other hand, the cross-reactivity of deltamethrin was evaluating the MIormosil performance, as it measures the
assessed by comparing it with the structurally related compounds; selectivity of MIormosil for a target molecule compared to
λ-cyhalothrin and cyphenothrin. Deltamethrin is a cis-3-(2,2- other molecules. It is defined as the ratio of the binding
dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, whereas capacity of the MIP for the target molecule to its binding
cyphenothrin and cyhalothrin are cyano-(3-phenoxyphenyl)-2,2- capacity for a non-target molecule. A high imprinting factor
dimethyl-3-(2-methyl-1-propenyl) cyclopropane carboxylate and indicates that the MIormosil has a high selectivity for the target
cyano-3-phenoxybenzyl(R3-(2-chloro-3,3,3-trifluoropropenyl)-2,2- molecule, which can lead to improved detection and

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Fig. 8 Comparison of the binding capacities of (a) deltamethrin and (b) emamectin benzoate on MIormosil vs. NIormosil.

separation accuracy and selectivity.15 The presence of specific 3.5. Kinetic modelling
binding sites in MIormosil and nonspecific binding sites in
NIormosil may account for the difference in the binding Kinetic modeling is the development of mathematical
capacity. In Fig. 8, the specific binding sites in MIormosil models to predict and describe the behavior of complex
resulted in a higher affinity and selectivity for deltamethrin systems, while taking into account individual processes
and emamectin benzoate, whereas the nonspecific binding and interconnections. These models frequently consist of
sites in NIormosil allowed for some adsorption, albeit at a a collection of differential equations that depict the
lower capacity. From the literature, an imprinting factor value change in concentrations or attributes of the system's
greater than 1 is acceptable.39 Deltamethrin and emamectin components as a function of time. A proper kinetic model
benzoate presented imprint factors of 2.2 and 2.80, must be used for an accurate understanding of a reaction
respectively, which means that both have successful system. Kinetic models, including linear and nonlinear
imprinting of nearly similar levels. These values are models, help in explaining the adsorption mechanics and
comparable to the IF values of 2.75 and 2.01 observed for rate-limiting phases in adsorption system design.
other molecules like sulfadimethoxine and iprodione in Estimating the rate of sorbent absorption throughout the
previous studies.40,41 adsorption process is a critical part of adsorption system

Fig. 9 Non-linear fitting of (a) PFO, PSO kinetic models for the adsorption of deltamethrin, and (b) PFO, PSO kinetic models for the adsorption of
emamectin benzoate on MIormosil.

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Table 1 Adsorption kinetic parameters obtained using the PFO and PSO models for deltamethrin and emamectin benzoate on MIormosil

Sr. no. Pseudo-first-order Pseudo-second-order

Non-linear modelling R2 χ2 qe (mg g−1) R2 χ2 qe (mg g−1)
Deltamethrin 0.99 1.45 42.34 0.98 2.98 51.45
Emamectin benzoate 0.99 1.01 25.95 0.98 2.01 28.68

design.42 To investigate the kinetics of the adsorption of data and the model, and the differences between the
deltamethrin and emamectin benzoate on the surface of experimental and predicted values are small.47 The
MIormosil, the two most prevalent kinetic models (pseudo- correlation between the experimental and calculated values
first order (PFO) and pseudo-second-order (PSO)) were shows how well the model predictions match the
compared. Adsorption is described as a chemisorption experimental data.48 Both emamectin benzoate and
process in the pseudo-second-order model, but as a deltamethrin on the MIormosil demonstrated the best
physisorption in the pseudo-first-order model, which is pseudo-first order fitting with the lowest values of χ 2
based on Lagergren's kinetics.43 The adsorption process (1.01, 1.45) and the highest R 2 (0.99) value, as shown in
involves rate-limiting and rate-determining steps, Table 1. These results suggested that the adsorption of
determining efficiency and kinetics. The first step involves emamectin benzoate and deltamethrin on the MIormosil is
adsorbate molecule diffraction from the bulk solution to due to the hydrogen bonding between their functional
the adsorbent surface, using pseudo-first-order kinetics. groups and the active sites of adsorbent. As a result, the
The rate-determining step, on the other hand, involves adsorption can be assumed to follow the PFO kinetic
molecular collisions and surface interactions, determining model.
the adsorption rate using pseudo-second order.44 In this
study, non-linear models were applied to investigate the
behavior of MIormosil, as shown in Fig. 9. However, by 3.6. Adsorption isotherms
applying a nonlinear approach to the PFO and PSO Adsorption isotherms can offer decisive details, such as the
models, more accurate estimates of the rate constants and strength and specificity of the adsorption, regarding the
better predictions of the reaction's behavior over time can nature of the interactions between the adsorbate and the
be obtained.45 A low value of χ 2, a high value of R 2, and sorbent surface. By analyzing the shape and parameters of
a good correlation between experimental and calculated the isotherm, one can also determine the surface area of the
values are important criteria for evaluating the quality of sorbent, the maximum amount of adsorbate that can be
a kinetic model for adsorption studies.46 The χ 2 value adsorbed onto the surface of the sorbent (known as the
measures the goodness of fit between the experimental adsorption capacity), and most importantly, the type of

Fig. 10 Non-linear modelling of the (a) Langmuir and Freundlich isotherms for deltamethrin, and the (b) Langmuir and Freundlich isotherms for
emamectin benzoate.

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Environmental Science: Water Research & Technology Paper

Table 2 Adsorption isotherm parameters obtained using the Langmuir and Freundlich models for deltamethrin and emamectin benzoate on MIormosil

Sr. no. Langmuir Freundlich

Non-linear modeling qm (mg g−1) KL (L mol−1) R2 qm (mg g−1) n R2
Deltamethrin 45.84 0.04 0.98 41.43 2.92 0.99
Emamectin benzoate 24.9 0.232 0.98 25.80 8.66 0.99

adsorption mechanism that is occurring (such as Langmuir in the first cycle, gradually decreased as the number of cycles
or Freundlich adsorption). increased, finally reaching 91.9% for emamectin benzoate
In this study, linear Langmuir and Freundlich fitting and 93.1% for deltamethrin in 7 consecutive regeneration
models were applied for adsorption analysis, as shown in cycles (Fig. 11a and b). It was evident that the resilient GO-
Fig. 10. Various studies claim that the standard for based MIormosil would be beneficial for practical applications,
determining whether a model fits is not just R 2, but also how owing to its remarkable stability and efficiency.
closely qe cal and qe exp coincide.49 From the results, it was For the selective deltamethrin and emamectin benzoate
noticed that the Freundlich model is well-fitted for both adsorption, the limit of detection (LOD), the limit of
emamectin benzoate and deltamethrin, which can be quantification (LOQ), intraday and interday precision, as well
explained by higher R 2 values (0.99). There is another factor as percentage recovery were determined using the GO-based
in which the fit of the Freundlich model is confirmed: the MIormosil. The adsorption and desorption of deltamethrin and
closeness between the experimental and predicted values for emamectin benzoate on the surface of MIormosil were
both insecticides, as shown in Table 2. If the value of “n” lies confirmed using HPLC. The signal-to-noise ratio of HPLC
between 2 to 10, it is indicative of efficient adsorption. In the was used to determine the LOD and LOQ for emamectin
current study, the values of “n” for both pesticides were in benzoate, which were 0.31 and 0.59 μg L−1, respectively, and
the prescribed range, suggesting the sorbent's strong ability those for deltamethrin, which were 0.41 and 0.92 μg L−1. The
to recognize analytes.50 relative standard deviation (RSD) values for deltamethrin
were 3.4% (n = 6), 3.7% (n = 6), and 3.0% (n = 6), and those
for emamectin benzoate were 4.01% (n = 6), 3.9% (n = 6), and
3.7. Reusability studies 4.6% (n = 6), obtained from the interday and intraday
The reusability of MIormosil is crucial in determining its analysis.
possible applications in different domains of analytical
chemistry. In this study, the binding capacity of MIormosil for
emamectin benzoate and deltamethrin was measured 3.8. HPLC analysis of pesticides in agricultural run-off
repeatedly after each adsorption–desorption cycle. For The water samples were spiked with target pesticides at three
MIormosil, the percentage of regeneration, which started at different concentrations, i.e., 5, 50, and 100 μg mL−1 of
93.3% for deltamethrin and 94.2% for emamectin benzoate deltamethrin and emamectin benzoate, and analyzed by

Fig. 11 Regeneration studies of MIormosil for seven consecutive cycles: (a) deltamethrin, (b) emamectin benzoate.

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Paper Environmental Science: Water Research & Technology

Table 3 Comparison of the performance of various adsorbents for determining deltamethrin and emamectin benzoate

No. Sample matrix Analyte Adsorbent Method LOQ RSD Recover% Ref.
−1
1 Water Deltamethrin MOF (MIL-101(Cr)-based composite) MSPE 8–15 μg L 6.9 81.7 51
2 Water Deltamethrin Magnetic titanium dioxide MSPE 9.3 × 103 μg L−1 4 91.3 52
3 Water Deltamethrin Polystyrene-coated MNPs MSPE 12 μg L−1 4.4 88.2 53
5 Plant Emamectin benzoate g-MWCNTs d-SPE 0.050 mg kg−1 4.8–12.8 90.6 54
(D. officinale)
6 Fish Emamectin benzoate Alumina d-SPE 1 μg kg−1 19 85 55
7 Water Deltamethrin GO-MIormosil SPME 0.31 μgL−1 3.4 92.0 Current study
Emamectin benzoate 0.41 μgL−1 4.1 93.3

HPLC. The percentage recoveries for the two targets were research is higher for dual pollutants (91.9% and 93.3%).
found to be 91.9% ± 3.9% (n = 6) and 93.1% ± 4.1% (n = 6), Furthermore, the novel sorbent presented low LOQ values.
respectively. Because of their similarity, the MIormosil sorbent significantly
Given the necessity of water safety, especially in the case outperformed the templates. This is most probably due to
of agricultural run-off, as it seeps through the ground and the presence of imprinted sites in MIMs, which are
flows to become part of aquatic reservoirs, it is pertinent to considered specific for the analyte and reduce the chances of
design efficient sorbents that can adequately mitigate the non-specific binding, as is possible in other sorbents.
emerging water pollutants. Considering the imprinting MSPE: magnetic solid-phase extraction, SPME: solid phase
technique, the GO-based MIormosil-based probe thus microextraction, MWCNTs: multi-walled carbon nanotubes d-
fabricated in this work was evaluated for its ability to interact SPE: dispersive solid phase extraction.
with deltamethrin and emamectin in a water sample
collected from agricultural land. The use of a probe helped in
the swift and direct determination of pesticides, eliminating 4. Conclusion
multistep tedious steps involved in conventional SPME
A novel hybrid, dual-template GO-based MIormosil-based probe
procedures, e.g., dispersive solid phase microextraction
was designed for solid-phase microextraction, followed by
(dSPME). Fig. S2a† shows the chromatogram of a spiked real
HPLC, of deltamethrin and emamectin benzoate from
sample presenting the peaks of deltamethrin at 3 min and
agricultural run-off. The characterization results validated the
for emamectin at 3.58, while Fig. S2b† presents the
successful imprinting process. The as-prepared GO-based
chromatogram obtained after desorption of the adsorbed
MIormosil revealed the best imprinting structure, presenting
pesticides on the MIormosil (used as a sorbent for SPME in
the pseudo-first-order kinetic model as a fit for the
real water samples). The results from HPLC analysis
experimental data of deltamethrin and emamectin benzoate
suggested that the GO-based MIormosil was capable of
extraction. The Freundlich isotherm model (R 2 = 0.99) fitted
effectively adsorbing the desired pesticides from water
with the experimental data better than the Langmuir
samples.
isotherm model in describing the SPME of deltamethrin and
emamectin benzoate, demonstrating the heterogeneous
3.9. Comparative study nature of the binding sites. Using the as-prepared ormosil,
deltamethrin, and emamectin benzoate as target insecticides
Comparative studies provide insights into the differences
were selectively and simultaneously determined from the
between entities, and identify all possible factors that could
agricultural runoff. Because of the abundance of recognition
contribute to them. Here, the performance of novel GO-based
cavities on the GO-based MIormosil, the ability to recognize
MIormosil was compared with that of the MOF material MIL-
and imprint the target insecticides significantly outperforms
101 (Cr)-based composite, magnetic titanium dioxide, and
the competitors. Moreover, the method was successfully
polystyrene-coated magnetic coated nanoparticles, for
employed in seven sequential cycles, indicating its good
determining deltamethrin and emamectin benzoate.
stability, low limit of detection, and limit of quantification to
Similarly, the method (SPME) applied in this study is
realize the quantification of a minute amount of
compared with other methods, such as MSPE used in the
deltamethrin and emamectin benzoate. This study provides
literature.
an effective strategy for rapid, cost-effective, and highly
The comparative study demonstrated that the newly
selective simultaneous determination of multiple analytes in
designed sorbent presented greater selectivity towards target
agricultural runoff.
pesticides, as compared to the other sorbents (Table 3).
When compared to other sorbents, such as MOF material
MIL-101 (Cr)-based composite (81.7%), magnetic titanium Data availability
dioxide (91.1%), polystyrene-coated MNPs (88.2%), alumina
(85%) and multi-walled carbon nanotubes (MWCNTs), The data relevant to this work are presented in the
(90.6%), the percentage recoveries of the sorbent used in this manuscript.

2174 | Environ. Sci.: Water Res. Technol., 2024, 10, 2162–2176 This journal is © The Royal Society of Chemistry 2024
Environmental Science: Water Research & Technology Paper

Author contributions 12 A. Mobeen, et al., Toxicity assessment of emamectin

benzoate and its commercially available formulations in
Conceptualization: Suryyia Manzoor, Hina Raza; supervision: Pakistan by in vivo and in vitro assays, Food Chem. Toxicol.,
Suryyia Manzoor, Hina Raza; writing – review & editing: 2022, 165, 113139.
Suryyia Manzoor, Noureddine Elboughdiri, Muhammad 13 C. Niu, et al., Toxic effects of the Emamectin Benzoate
Imran Khan, Abdallah Shanableh, Nadeem Raza; exposure on cultured human bronchial epithelial (16HBE)
investigation: Muhammad Hayat, Zeeshan Ali, Ayesha Javed; cells, Environ. Pollut., 2020, 257, 113618.
formal analysis: Nadeem Raza, Noureddine Elboughdiri, 14 F. A. Momani, et al., Pesticides and herbicides, Water
Muhammad Hayat; funding: Noureddine Elboughdiri. Environ. Res., 2004, 76, 1775–1856.
15 M. Hayat, et al., Molecularly imprinted ormosil as a sorbent
Conflicts of interest for targeted dispersive solid phase micro extraction of
pyriproxyfen from strawberry samples, Chemosphere,
The authors declare no conflict of interest.
2023, 320, 137835.
16 T. Wang, et al., Synthesis of fluorescent artificial receptors
Acknowledgements with high specificity for simultaneous detection of non-
The authors are highly thankful to Higher Education steroidal anti-inflammatory drugs, Food Chem., 2023, 410,
Commission (HEC) of Pakistan and Bahauddin Zakariya 135419.
University, Multan, Pakistan for financial support. 17 F. Wang, et al., A simple approach to prepare fluorescent
molecularly imprinted nanoparticles, RSC Adv., 2021, 11(13),
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