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Introduction of a new and safe synthesis procedure

Cite this: RSC Adv., 2023, 13, 21673
for Ni-MOF-I in aqueous solution and its
application for the extraction of some pesticides
from different beverages†
Mir Ali Farajzadeh, *ab Nastaran Khoshnavaz,a Sakha Pezhhanfara
and Mohammad Reza Afshar Mogaddam cd

For the first time, this research introduces an analytical application of Ni-MOF-I, which was used as an
adsorbent in a dispersive micro solid phase extraction procedure followed by dispersive liquid–liquid
microextraction for the extraction and preconcentration of seven pesticides from different fruit juices.
Also, Ni-MOF-I was synthesized by a new and green method with many advantages over the previously
published synthesis procedures. For example, effortless and green synthesis, no need for autoclaves and
ovens, and elimination of organic solvent usage are the main highlights. The synthesized Ni-MOF-I was
characterized by applying nitrogen adsorption/desorption, energy-dispersive X-ray, scanning electron
microscopy, Fourier transform infrared spectrophotometry, and X-ray diffraction analyses. The studied
pesticides were extracted and preconcentrated by the proposed method. Then, the extracted analytes in
the sedimented organic phase were injected into a gas chromatography-flame ionization detector.
Acceptable analytical results such as low limits of detection (0.15–0.60 mg L−1) and quantification (0.50–
Received 23rd May 2023
Accepted 11th July 2023
2.0 mg L−1), reasonable extraction recoveries (51–80%), high enrichment factors (255–400), satisfactory
relative standard deviation values of 4.8–7.2% (intra-day precision, n = 6) and 5.3–7.5% (inter-day
DOI: 10.1039/d3ra03441k
precision, n = 4), and wide linear ranges were obtained. The proposed method can be introduced as an
rsc.li/rsc-advances effective analytical technique based on Ni-MOF-I for the analysis of different pesticides in fruit beverages.

diseases. Despite the mentioned advantages, pesticides may

1. Introduction put the human body at considerable danger of diseases, cause
The request for fruit-based beverages in the juice market is irrecoverable harm, and persist in the environment and cause
considerably increasing over recent years due to them containing the contamination of fruits, vegetables, and surface waters
an abundance of different phytochemicals and having valuable because of their environmental stability, capability to bio-
potential for strengthening human health.1–3 In addition to the accumulate, and toxicity.5,6 The residue of pesticides is out of the
mentioned positive factors, juices can be harmful for human consumer's control.7 Therefore, based on the aforementioned
health because of various pesticides that might be present and information, it becomes imperative to develop highly sensitive,
abundance of additive sugar.4 Pesticides are one of the main reliable, and selective analytical methods to analyze pesticide
inputs, which are utilized to eradicate various pests in house- residues in foods to decrease the possible dangers for human
holds and agriculture, heighten the output and quality of crops, society. These days, various types of analytical techniques such as
decrease the energy cost, and restrict many vector-borne gas chromatography (GC),8,9 and high performance liquid chro-
matography (HPLC)10,11 are used to determine pesticide residues
in food samples including juices. Usually, these methods have
a
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, great selectivity with low detection limits and high sensitivity,12
Tabriz, Iran. E-mail: [email protected]; [email protected]; Fax: but most samples cannot be injected directly into them because
+98 41 33340191; Tel: +98 41 33393084
b
of some limitations like the low concentration of analytes, having
Engineering Faculty, Near East University, Mersin 10, 99138 Nicosia, North Cyprus,
a complex matrix, and the intrinsic limitation of aqueous solu-
Turkey
c
Food and Drug Safety Research Center, Tabriz University of Medical Sciences, Tabriz,
tions in injection into GC instrument.3 The amounts of pesticide
Iran residues in various environments are usually under the limit of
d
Pharmaceutical Analysis Research Center, Tabriz University of Medical Sciences, detection (LOD) of many analytical instruments, so it is necessary
Tabriz, Iran to integrate sample preparation steps with instrumental analysis
† Electronic supplementary information (ESI) available. See DOI: in order to concentrate the pesticides, reduce the LODs, and
https://doi.org/10.1039/d3ra03441k

© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 21673–21684 | 21673
RSC Advances Paper

acquire a reliable signal while utilizing different analytical MS. Ma et al.33 extracted and preconcentrated four pesticides
instruments for analyzing pesticides.13 More than 80% of the including fenpyroximate, chlorfenapyr, pronil, and usilazole
analysis time is dedicated to the extraction, preconcentration, in environmental water samples using magnetic MIL-101 in
and preparation steps. For this reason, the critical part of most magnetic solid phase extraction procedure and analyzed by
analytical procedures is sample preparation step.14 Methods of HPLC-diode array detector (DAD). Chahkandi et al.34 extracted
sample preparation should be able to isolate the matrix from the some organophosphorus pesticides including diazinon, phos-
analytes15 and transfer them into a phase which is suitable for alone, fenthion, fenitrothion, and profenofos from fruit juices
injection into the analysis system by extracting the targeted and water samples applying magnetic potassium substituted
analytes from the sample matrix.16 Moreover, they should be eco- hydroxyapatite and analyzed by GC-ame ionization detector
friendly, time-saving, inexpensive, and simple.13 The two coven- (FID). Michel et al.35 extracted ten fungicide, insecticide, and
tional sample preparation methods which are applied for herbicide residues in vegetables, fruits, and cereal using LLE,
determining the pesticide residues in fruit juices are solid phase SPE, and matrix solid phase dispersion. Determination was
extraction (SPE) and liquid–liquid extraction (LLE).17 Beside the performed by reversed-HPLC-DAD. Shamsipur et al.36 used SPE
advantages they contain, they have some serious disadvantages coupled with DLLME and GC-MS for the extraction and deter-
such as high-volume use of organic solvents in the case of LLE mination of 20 pesticide residues from fruit juice, honey, milk,
and cartridge obstruction in the case of SPE.18,19 To overcome and water. Wang et al.37 developed an ultrasound-assisted
these issues, Anastassiades et al.20 introduced an alternative DLLME method based on solidication of oating organic
method over conventional SPE named dispersive solid phase droplets followed by GC-FID for the extraction and determina-
extraction (DSPE) in which the adsorbent is straightly dispersed tion of some pesticides including pyridaben, triazophos, es-
into the sample solution instead of being loaded as the cartridge. fenvalerate, buprofezin, and l-cyhalothrin in water samples.
Various kinds of materials have been utilized as solid adsorbents This research has two main novel aspects. The rst one is the
like graphene, carbon nanotubes, metal–organic frameworks introduction of a new, facile, and safe synthesis procedure for
(MOFs), silica nanoparticles, mesoporous silica, etc.21 Recently, Ni-MOF-I which is done in aqueous solution. This approach is
dispersive micro solid phase extraction (DmSPE) which is the effortless, green, and needs no special synthesis instruments
miniaturized modication of DSPE has been widely developed22 such as autoclaves, ovens, and toxic solvents such as N,N-
in which it needs less than 500 mg of solid adsorbent.4 In dimethylformamide. The second aspect is the utilization of Ni-
comparison to DSPE, DmSPE has simpler operation, and is more MOF-I for the rst time in a sample preparation process for the
economic due to the utilization of lower sorbent weights. These extraction of different pesticides from juices through DmSPE-
make the approach economical and environmentally- DLLME procedure and their analysis using GC-FID.
friendly.22,23 However, the main drawback of this method is the
low value of enrichment factors (EFs) because of consuming mL-
level of elution solvent. To solve this issue a combination of 2. Experimental
DmSPE with dispersive liquid–liquid microextraction (DLLME) is 2.1. Chemicals and solutions
required which is an affordable and simple extraction method All the target compounds (chlorpyrifos, haloxyfop-R-methyl,
and results in high EFs.24–26 The main drawback of DLLME is the oxadiazon, diniconazole, clodinafop-propargyl, fenpropathrin,
limitation of its direct application in complex matrices due to the and fenoxprop-P-ethyl) with purity >98% were procured from Dr
extraction of the co-extractives that interfere on the analysis Ehrenstorfer (Agsburg, Germany). Sodium sulfate, potassium
process.27 Considering the advantages of DmSPE and DLLME, chloride, sodium chloride, sodium hydroxide, acetonitrile
simultaneous use of these two methods can make more benets (ACN), acetone, hydrochloric acid (37%, w/w), and methanol
like the achievement of high EFs, efficient sample clean up, and (analytical grade) were obtained from Merck (Darmstadt, Ger-
low LODs and limits of quantication (LOQs).25 MOFs are a novel many). 2-Propanol was acquired from Caledon (Georgetown,
class of hybrid porous materials and a new type of three- Canada). Deionized water was supplied from Ghazi Co. (Tabriz,
dimensional coordination polymers formed by organic ligands Iran). Extraction solvents including 1,1,2-trichloroethane (1,1,2-
and metallic clusters through coordination bonds.28,29 Owing to TCE), 1,1,1-trichloroethane (1,1,1-TCE), 1,2-dibromoethane
their tailorable polarity, structure exibility, high and tunable (1,2-DBE), and carbon tetrachloride were purchased from
porosity, good thermal stability, uniform cavities, adsorption Janssen (Beerse, Belgium). To synthesize the adsorbent, nick-
capacity, and high surface area, MOFs have been used in drug el(II) chloride hexahydrate (NiCl2$6H2O), 1,4-benzenedicarbox-
delivery, photovoltaic materials, catalysis, gas purication and ylic acid (1,4-BDCA), and concentrated ammonia solution (25%,
separation, gas storage systems, biomedicine, as adsorbents in w/w) were purchased from Merck (Darmstadt, Germany). A
analytical sample preparation methods, sensors in electroana- mixture standard solution including 250 mg L−1 of each pesti-
lytical and spectroscopy methods, and the stationary phases of cide was provided in methanol and diluted using deionized
chromatographic columns.29–31 water for daily-used solutions of interest.
Many papers were reported in literature regards pesticide
residues analysis in different matrices. Barrek et al.32 separated
residual pesticides from olive oil by size-exclusion chromatog- 2.2. Samples
raphy. Aer the extraction, eleven pesticides were separated and Four commercial fruit juices including mango (the content of
analyzed by HPLC-mass spectrometry (MS) and 20 others by GC- 200 mL juice includes sodium (13 mg), potassium (75 mg), total

21674 | RSC Adv., 2023, 13, 21673–21684 © 2023 The Author(s). Published by the Royal Society of Chemistry
Paper RSC Advances

carbohydrates (28 g), sugar (26.25 g), vitamin A, vitamin C, utilizing a Mira 3 microscope (Tescan, Czech Republic). A
calcium, iron, and natural mango puree), pineapple (the Fourier transform infrared (FTIR) spectrophotometer (Bruker,
content of 200 mL juice includes sodium (22 mg), potassium (71 Billerica, USA) was utilized in the range of 400–4000 cm−1 for
mg), total carbohydrates (27.5 g), sugar (27.5 g), vitamin A, obtaining the FTIR spectrum of the adsorbent applied in the
vitamin C, calcium, iron, and natural pineapple puree), apple present investigation. A BELSORP-mini II (BEL, Japan) analyzer
(the content of 200 mL juice includes sodium (23 mg), potas- was used to carry out nitrogen adsorption/desorption analysis
sium (201 mg), total carbohydrate (26 g), vitamin A, vitamin C, for getting information about average pores diameter, pores
calcium, iron, and natural apple puree), and peach (the size, and surface area of the MOF.
contents of 200 mL juice includes sodium (22 mg), potassium
(125 mg), total carbohydrate (28 g), sugars (26.25 g), vitamin A, 2.4. Synthesis of Ni-MOF-I
vitamin C, calcium, iron, and natural mango puree) were
In this study, Ni-MOF-I was synthesized through a new green
purchased from a local store in Tabriz (Iran). The brand of all
procedure. In comparison to the previously reported synthesis
the commercial fruit juices used in this study Sun Ich. In
method38 the developed approach is more economic, time-
addition, in order to evaluate the juices of fresh fruits, two fresh
saving, and needs no expensive and special synthesis instru-
fruits including apple and orange were purchased. A juicer was
ments. Also, this synthesis process is environmentally friendly
used to extract the juices of these fruits. For separating the juice
and not harmful for human health because unlike the previous
from its scum, centrifugation was done at 6000 rpm for 5 min.
synthesis method in which dimethylformamide was utilized as
All the mentioned juices were diluted at a ratio of 1 : 1 with
the reaction solvent, deionized water was used instead. This
deionized water prior to carrying out the extraction method on
synthesis method entails the subsequent steps:
them.
(a) Initially, 0.80 g of 1,4-BDCA was added as the ligand to
5.0 mL of concentrated ammonia solution and put on a stirrer.
2.3. Apparatus Deionized water (20 mL) was slowly added until the solution
became clear. Then, the solution was poured into a burette.
Chromatographic analysis and separation of the pesticides were
(b) 1.14 g of NiCl2$6H2O was dissolved in 100 mL of deion-
carried out by a Shimadzu 2014 gas chromatograph (Kyoto,
ized water in an Erlen mayer ask. Aerward, the ask was put
Japan) equipped with a split/splitless injector and an FID. A
into a water bath set at 80 °C.
split ratio of 1 : 10 and a sampling time of 1 min were adjusted.
(c) The solution inside the burette was added dropwisely into
The temperatures of the injection port and FID were set at 300 °
the ask under stirring at 300 rpm. Aer nishing the content
C during the analysis. The initial temperature of the column
of the burette, a lid was put on the ask and continued stirring
oven was held at 60 °C for 1 min, then programmed at a rate of
for 1 h. Then, the ask was let to cool down at room tempera-
18 °C min−1 to 300 °C, and held for 3 min to complete the
ture. The formed light green precipitate was Ni-MOF-I. Then,
separation run. Chromatographic separation was attained on
the content of ask was transferred into glass tubes and then
a Zebron capillary column (95% dimethyl, 5% diphenyl poly-
were centrifuged at 6000 rpm for 5 min. Aerwards, the
siloxane) (30 m × 0.25 mm i.d, a lm thickness of 0.25 mm)
supernatant was decanted. The product remaining at the
(Phenomenex, Torrance, CA, USA). Helium (99.999%, Gulf Cryo,
bottom of the tubes was vortexed with 5 mL of deionized water
Dubai, United Arab Emirates) was used as the make up and
for 5 min, centrifuged at 6000 rpm for 5 min, and the super-
carrier gases. A ow rate of 30 mL min−1 and linear velocity of
natant was decanted. This process was repeated for 5 times
30 cm s−1 were adjusted for the make up and carrier gases,
until the product was completely washed and the decanted
respectively. The required hydrogen as the fuel of FID was
phase was neutralized. At the end, the obtained product was
provided by a hydrogen generator (OPGU-1500S, Shimadzu,
poured on a watch glass to dry at room temperature. The yield of
Japan) which was set at the ow rate of 30 mL min−1. Addi-
the MOF according to the adopted synthesis method was
tionally, the air ow rate was set to be 300 mL min−1. For
68.41%.
injection of the standards and extracted samples into GC-FID,
Eventually, the synthesized Ni-MOF-I was subjected to FTIR,
a 1.0 mL microsyringe (zero dead volume, Hamilton, Switzer-
XRD, nitrogen adsorption/desorption, EDX, and SEM analyses
land) was utilized. A Metrohm pH meter, model 654 (Herisau,
and aer that it was applied as an adsorbent in the extraction
Switzerland) was utilized for pH adjustment. Phase separation
procedure.
during the extraction process was accomplished by a Hettich
centrifuge, model D-7200 (Kirchlengern, Germany). A magnetic
heater-stirrer (Heidolph MR 3001 K, Germany) was applied in 2.5. Extraction procedure
providing the MOF. An L46 vortex (Labinco, Breda, the Neth- 2.5.1. DmSPE. Initially, into a 10 mL glass test tube, 5 mL
erlands) was utilized for vortexing. The synthesized MOF's X-ray sample solution (see Section 2.2) or deionized water spiked with
diffraction (XRD) pattern was attained by applying a Siemens 150 mg L−1 of each analyte was added and 1.065 g Na2SO4 was
D500 diffractometer (Siemens AG, Karlsruhe, Germany) at dissolved in it. Thereupon, 20 mg of Ni-MOF-I, as the adsorbent,
a voltage of 35 kV. It was performed at the rate and scan range of was added into the mentioned solution. In the following, it was
1° min−1 and 4–73°, respectively. Surface characterization of the vortexed for 5 min to adsorb the pesticides onto Ni-MOF-I
synthesized MOF was also accessed by energy-dispersive X-ray particles. Aerwards, to settle down the suspended particles of
(EDX) and scanning electron microscopy (SEM) analyses the MOF at the bottom of the tube, centrifugation was performed

© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 21673–21684 | 21675
RSC Advances Paper

Fig. 1 Schematic figure of the developed extraction procedure.

at the speed of 6000 rpm for 5 min. Aer discarding the super- desorption, EDX, and SEM. By comparing the obtained results
natant, 1.0 mL of ACN was used to desorb the analytes from Ni- with the results reported previously,38,39 it was concluded that
MOF-I particles. In order to provide efficient contact between the synthesized adsorbent is Ni-MOF-I.
ACN and the adsorbent particles for efficient elution of the XRD is an inuential and essential analysis for diagnosing
analytes, vortexing was performed for 5 min. At the end, the and validating the creation of the required crystalline
mixture of the adsorbent particles and elution solvent was compound. For this purpose, XRD analysis was done in the
centrifuged at 6000 rpm for 5 min and the obtained supernatant range of 4–73°. The outcome XRD pattern of Ni-MOF-I is shown
was applied in the following DLLME step as a disperser solvent. in Fig. 2a. Same peaks are observed at 2q values of around 10,
2.5.2. DLLME. In a 10 mL conical bottom glass test tube, 12, 16, 18, 19, 24, 28, and 29°. Based on the attained XRD
5 mL aqueous solution of Na2SO4 (0.5 mol L−1) was added. Then, pattern, some acute and distinct peaks are observed which is
the ACN phase obtained from the DmSPE step, was mixed with 17 the reason for the crystalline structure and successful formation
mL of 1,2-DBE (extraction solvent). Thereupon, it was quickly of Ni-MOF-I. Furthermore, the perfect match between the ob-
injected into the Na2SO4 solution by using a 5 mL glass syringe. tained pattern and the previously reported pattern32 veries the
The formation of the cloudy state indicated that DLLME was successful synthesis of Ni-MOF-I in this research.
done correctly. Then, the cloudy solution was centrifuged at FTIR spectrometry was also applied to identify the formation
6000 rpm for 5 min. Eventually, 1 mL of the sedimented organic of the intended MOF. Fig. 2b shows the FTIR spectrum of the
phase at the bottom of the test tube was injected into the GC-FID. synthesized Ni-MOF-I. Two absorption peaks at 1576.52 and
Fig. 1 demonstrates the overall schematic of the applied extrac- 1379.49 cm−1 are related to the symmetric and asymmetric
tion and preconcentration procedure. stretching vibration of the –COO– functional group of the ligand
coordinated to the metallic center. The presence of peaks at
2.6. Calculation of EF and extraction recovery (ER) 460.02, 607.00, and 677.49 cm−1 are ascribed to the formation
of the metal–oxygen bond between the carboxylic group of 1,4-
ER and EF were utilized to appraise efficiency of the extraction
BDCA and Ni (Ni–O). The peaks at 1501.48 and 3432.38 cm−1 are
in various experimental conditions. The equations used to
attributed to the stretching vibration of CH and OH, respec-
calculate their values are written below.
tively. Also, the peaks at 761.05 and 815.05 cm−1 are related to
Csed the C–H and C]C bonds present in the ligand section of the
EF ¼ (1)
C0 synthesized MOF. According to the above-mentioned results
  and their perfect agreement with the previously published FTIR
nsed Csed  Vsed Vsed spectrum of the desired MOF,33 it reveals that Ni-MOF-I
ER ¼  100 ¼  100 ¼ EF   100 (2)
n0 C0  Vaq Vaq synthesis was done correctly.
The morphology of the surface of the synthesized MOF can
The ratio of pesticide concentration in the extraction solvent be investigated by SEM. So, high resolution image of the MOF
(Csed) to the pesticide concentration in the initial sample solu- which is shown in Fig. 2c, was obtained to attain the surface
tion (C0) is described as EF. The ER is the ratio of the extracted morphology of Ni-MOF-I. As can be observed, the Ni-MOF-I
pesticide amount (nsed) to its initial amount (no) multiplied by shows a layer-cuboid morphology with plain surface which
100. Moreover, the term Vsed indicates volume of the settled provides an appropriate adsorption surface for the investigated
organic phase in DLLME and Vaq shows the initial aqueous pesticides.
sample volume. EDX analysis was applied to reveal the presence of elements in
the structure of the synthesized MOF and also to obtain infor-
mation about the MOF's purity. The results are shown in Fig. 2d.
3. Results and discussion As can be clearly noticed, there are some main and sharp peaks
3.1. Characterization of Ni-MOF-I corresponding to C, O, and Ni which conrm the presence of
To identify the synthesized MOF, some characterization anal- composing elements in Ni-MOF-I. No appearance of peaks related
yses were performed such as FTIR, XRD, nitrogen adsorption/ to other elements is the proof of the purity of the synthesized

21676 | RSC Adv., 2023, 13, 21673–21684 © 2023 The Author(s). Published by the Royal Society of Chemistry
Paper RSC Advances

Fig. 2 XRD pattern (a), FTIR spectrum (b), SEM image (c), EDX data (d), and BET plot (e) of Ni-MOF-I.

MOF. The EDX analysis reveals that the surface of Ni-MOF-I and 12.503 m2 g−1 for the surface area of the MOF. The
contains 17.61% nickel, 44.01% oxygen, and 38.38% carbon. mentioned data were obtained from the BET data.
To get information regarding the surface area, average pores
diameter, and total pores volume of Ni-MOF-I, nitrogen
adsorption/desorption analysis was applied (Fig. 2e). The 3.2. Optimization of parameters in DmSPE
results of the analysis were reported as follows: 0.055 cm3 g−1 3.2.1. Evaluation of Ni-MOF-I weight. The adsorbent weight
for total pores volume, 17.641 nm for average pores diameter, in adsorbent-based methods has a signicant effect on the

© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 21673–21684 | 21677
RSC Advances Paper

Fig. 3 Evaluation of Ni-MOF-I weight. Extraction conditions: DmSPE

procedure: aqueous solution, 5 mL deionized water containing
1.0 mol L−1 Na2SO4 spiked with 150 mg L−1 of each analyte without pH
adjustment; vortex time in adsorption step, 5 min; desorption solvent
(volume), ACN (1.0 mL); vortex time in desorption step, 5 min; and
centrifugation speed and time, 6000 rpm and 5 min, respectively.
DLLME procedure: aqueous phase, 5 mL deionized water without pH
adjustment and salt addition; extraction solvent (volume), 1,2-DBE (31
mL); centrifugation rate, 6000 rpm; and centrifugation time, 5 min. The
error bars show the minimum and maximum of three repeated
determinations.

Fig. 4 Study of ionic strength in DmSPE. (a) Salt type and (b)
extraction efficiency because the amount of the adsorbent has concentration of Na2SO4. Extraction conditions: are the same as those
a direct effect on the amount of the adsorbed analytes. For used in Fig. 3, except 20 mg of Ni-MOF-I was used.
evaluating this parameter, various amounts of Ni-MOF-I (5, 10,
15, 20, 25, 30, and 40 mg) were investigated. As illustrated in
Fig. 3, 20 mg of the MOF indicates the most efficient perfor- studied. The illustrated conclusions in Fig. 4b show that ER
mance compared to the tested weights in this research. Reducing values are heighten with increasing concentration of Na2SO4
the adsorbent weight from 20 mg decreases ER values because of from 0.5 to 1.5 mol L−1 and then reduced by increasing Na2SO4
the lack of adequate surface area to adsorb the analytes. Also, the concentration over 1.5 mol L−1. Because the concentrations less
little reduction of ERs in the amounts above 20 mg of the than 1.5 mol L−1 are insufficient for salting-out of the pesti-
adsorbent occurs due to the adsorbent particles agglomeration cides, the efficiency is low and at the higher salt concentration
and not being dispersed efficiently into the aqueous phase. (2.0 mol L−1) due to salting-in effect, ERs are reduced. As
Accordingly, the weight of 20 mg was considered as the optimum a result, 1.5 mol L−1 Na2SO4 was chosen as the optimum
amount of the adsorbent for the rest of the optimization steps. concentration in the further steps.
3.2.2. Study of ionic strength. The aqueous phase ionic 3.2.3. Optimization of solution pH. Because the pesticides
strength in the DmSPE step is one of the effective factors which and adsorbent stability may be varied at different pH values,
should be optimized. Salt addition enhances the aqueous phase variation of the solution pH in DmSPE can be a noteworthy and
ionic strength and it may enhance the method ER values by effective parameter on the resulted ER values. So, it is vital to
reducing the analytes solubility in the aqueous solution which evaluate the impact of the solution pH on the extraction effi-
leads to enhancement of the analytes partition onto the sorbent ciency. To appraise this factor, the solution pH was adjusted in
surface which is named salting-out effect. Also, salt addition the range of 3–11 (at 2-unit intervals) by adding 1 mol L−1 of
can have an adverse effect on the extraction procedure in which NaOH or HCl solution. Fig. S1† shows that the highest ER values
the aqueous phase viscosity enhances by salt addition, which are attained in neutral pH. The diminution of ERs in alkaline or
avoids the analytes migration from the aqueous phase onto the acidic pHs can be because of: (1) the instability of the adsorbent
adsorbent and decreases ERs. This effect is named salting-in at highly acidic or alkaline pHs, and (2) the decomposition of the
effect. To evaluate the effect of this parameter in the present analytes at the mentioned pHs. Since the samples pH utilized in
research, three different solutions each containing 1.0 mol L−1 this research was about 7 aer dilution with deionized water, the
of KCl, NaCl, and Na2SO4, separately were prepared and nally further steps were conducted without pH variation.
the results were compared with the results of saltless solution. 3.2.4. Study of adsorption time. Appropriate adsorbent
As shown in Fig. 4a, in Na2SO4 solution the highest extraction dispersion into the aqueous solution containing the analytes
efficiency is obtained compared to the other solutions. So, increases the collisions between pesticides and MOF particles
Na2SO4 was chosen as the salting-out agent and then in order to which leads to heighten the pesticides adsorption onto the
appraise the impact of Na2SO4 concentration, several concen- adsorbent particles. Therefore, studying the effect of vortexing
trations of Na2SO4 containing 0.5, 1.0, 1.5, and 2.0 mol L−1 were time of the adsorption stage is critical. In this research, to

21678 | RSC Adv., 2023, 13, 21673–21684 © 2023 The Author(s). Published by the Royal Society of Chemistry
Paper RSC Advances

achieve the optimum value, different vortexing times (1.0, 3.0, over 1.0 mL of ACN in the DLLME step cause diminution of the
5.0, 7.0, 9.0, and 11.0 min) were investigated. According to the aqueous solution polarity and enhancement of the analytes
presented results in Fig. S2,† 5 min vortexing has the highest ER solubility in the aqueous phase. So, the transfer of the analytes
values and was considered as the optimum vortexing time for into the extraction solvent is reduced. Finally 1.0 mL ACN was
the further steps. selected as the elution/disperser solvent for the further tests.
3.2.5. Optimization of the type and volume of elution/ 3.2.6. Optimization of desorption time. Vortexing was
disperser solvent. In this research, elution solvent is applied employed for desorbing the pesticides from the surface of the
for the analytes desorption in DmSPE and also this is one applied MOF in the desorption step. Several vortexing times
component of DmSPE which is in common with DLLME because including 1.0, 3.0, 5.0, 7.0, 9.0, and 11.0 min were tested to identify
it is used as a disperser solvent in DLLME. So, according to the time with the highest desorption efficiency. The obtained data
aforementioned facts, this solvent has considerable effects on in Fig. S3† conrm that 5 min vortexing is sufficient to desorb the
both steps and this fact reveals the necessity of choosing pesticides from the adsorbent surface and it was chosen as the
a proper elution/disperser solvent. An appropriate elution/ optimum vortexing time for the further investigations.
disperser solvent is a solvent that is miscible in both organic
and aqueous phases. Also, it has to be able to desorb the ana- 3.3. Optimization of parameters in DLLME
lytes successfully from the surface of Ni-MOF-I. For this inten-
3.3.1. Study of extraction solvent type and volume.
tion, 1.0 mL of different solvents which possess these traits like
Choosing the best extraction solvent is very important and vital
ACN, 2-propanol, methanol, and acetone were examined. As
in DLLME. This solvent should have several properties
shown in Fig. 5a, the best ERs are attained by employing ACN
including ability to extract the pesticides as much as possible,
compared to the other used solvents. So, ACN was chosen as
being water-immiscible and miscible with the elution/disperser
optimum elution/disperser solvent for the upcoming steps.
solvent, demonstrating favorable chromatographic behavior,
Aerwards, to assess the impact of ACN volume, several
capability of forming a stable cloudy state in the presence of
volumes of this solvent (0.5, 1.0, 1.5, and 2.0 mL) were tested.
ACN, and to be sedimented at the bottom of the test tube aer
The nal results in Fig. 5b illustrate that 1.0 mL of ACN has the
centrifugation due to its higher density than water. The solvents
highest extraction efficiency compared to the other volumes.
such as 1,2-DBE, carbon tetrachloride, 1,1,1-TCE, and 1,1,2-TCE
The reason for the reduction of ERs in the lower volume (0.5
are the extraction solvents which have the aforementioned
mL) of ACN is based on two facts: (1) inability to desorb the
properties and were used for optimization in this experiment. In
adsorbed analytes from the adsorbent surface, and (2) decient
order to attain a constant sedimented phase volume (10 ± 0.5
formation of the cloudy state in DLLME stage. Also, the volumes
mL) in each experiment, the volumes of 27, 22, 28, and 25 of 1,2-
DBE, carbon tetrachloride, 1,1,2-TCE, and 1,1,1-TCE were
utilized, respectively. According to the results shown in Fig. 6
1,2-DBE has the highest extraction efficiency and therefore was
opted as the optimal extraction solvent. Extraction solvent
volume is an effective parameter in DLLME because this
parameter directly affects the sedimented organic phase
volume, LODs, EFs, and ERs of the analytes. To evaluate this
parameter impact, different volumes of 1,2-DBE including 26,
31, 36, and 41 mL were examined. It is worth mentioning that
when the volume of 1,2-DBE increased, ERs enhanced and EF
values decreased due to dilution effect. By heightening the

Fig. 5 Optimization of type (a) and volume (b) of elution/disperser Fig. 6 Study of extraction solvent type. Extraction conditions: are the
solvent. Extraction conditions: are the same as those used in Fig. 4, same as those used in Fig. 5, except 1.0 mL ACN was used as the
except 1.5 mol L−1 Na2SO4 was used. elution solvent.

© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 21673–21684 | 21679
RSC Advances Paper

extraction solvent volume, the sedimented organic phase In order to study this factor, the MOF was subjected to repetitive
volume enhanced and dilution of the analytes occurred into it. extraction cycles. Before repeating the extraction, the used
Also, in volumes less than 26 mL, the sedimented organic phase adsorbent was eluted twice (each time by 0.5 mL of ACN) and
volume was less than 10 mL which was too low to collect and vortexing for 5 min to prevent carry-over. Based on the obtained
handle and led to a decrement in the method repeatability. data, the adsorbent showed proper adsorption ability of the
Based on the obtained data in Fig. S4,† the optimum volume of analytes aer three cycles without signicant variations in the
the extraction solvent was 26 mL. ERs. The results showed that Ni-MOF-I is a sufficient adsorbent
3.3.2. Optimization of aqueous solution pH. To evaluate for utilization in repetitive extraction cycles.
the impact of this parameter on the extraction efficiency in
DLLME stage, the pH of the aqueous solution was adjusted at
3.5. The interaction mechanisms among the pesticides and
3.0, 5.0, 7.0, 9.0, and 11.0 by using 1 mol L−1 of NaOH or HCl
Ni-MOF-I
solution. By analyzing the obtained results in Fig. S5,† it becomes
vivid that the solution with neutral pH has the highest extraction The adsorption of the pesticides on the MOF with appreciable
efficiency. This results can stem from the fact that strict acidic or ERs is due to the adsorptive interactions among the pesticides
basic pHs play a signicant role in decomposition of the and Ni-MOF-I. By considering the chemical structures of Ni-
analysts. So, in the following, deionized water without pH MOF-I and studied pesticides, it can be concluded that a non-
adjustment was used as the aqueous phase in DLLME step. covalent interaction called p–p stacking happens among the
3.3.3. Impact of ionic strength. As mentioned before, MOF's ligand and the cyclic sections of fenoxaprop-P-ethyl,
aqueous solution ionic strength is an effectual factor on the ERs fenpropathrin, clodinafop propargyl, oxadiazon, haloxyfop-R-
of the analytes. To investigate this issue, different solutions methyl, and chlorpyrifos. Halogen bond is another signicant
containing different salts including KCl, NaCl, and Na2SO4 intermolecular interaction which is based on the noncovalent
(0.50 mol L−1 of each) were used as the aqueous phase in interaction among a Lewis base, p-system, or an anion and the
DLLME step and the nal outcomes were compared to the halogen atom in another compound. In this research, halogen
saltless solution. The experimental results in Fig. S6(a)† illus- bonds emerge between the oxygen atoms of Ni-MOF-I and
trates that Na2SO4 had the highest effect in enhancement of the chlorine in chlorpyrifos, oxadiazon, and fenoxaprop-P-ethyl,
extraction efficiency. So, the further experiments were con- and also uoride and chlorine in clodinafop propargyl and
ducted by applying Na2SO4 as the optimum salt. Aer opting the haloxyfop-R-methyl. Based on the descriptions mentioned
type of salt, the impact of salt concentration should be evalu- above, efficient adsorptive intermolecular bonds are formed
ated. For this purpose, several concentrations of Na2SO4 among Ni-MOF-I and the studied pesticides.
including 0.50, 1.0, 1.5, and 2.0 mol L−1 were appraised.
Comparing the obtained data (Fig. S6(b)†) shows that 3.6. Method validation
0.50 mol L−1 of Na2SO4 resulted in better ERs. At the concen-
A sign of the success of a new method is its obtained analytical
trations above 0.50 mol L−1, due to the increase in the solution
gures of merit such as LOQ, LOD, EF, ER, relative standard
viscosity and preventing the migration of pesticides from the
deviation (RSD), linear range (LR), and coefficient of determi-
aqueous phase into the extraction solvent, the ERs dwindled.
nation (r2). The abstract of the above-mentioned quantitative
Hence, 0.50 mol L−1 was chosen as the optimum salt
parameters is given in Table 1. The EFs and ERs of this
concentration.
approach were in the ranges of 255–400 and 51–80%, respec-
tively. The RSD values were computed at the concentration of 50
3.4. The reusability of Ni-MOF-I mg L−1 of each pesticide. The RSDs for intra- (n = 6) and inter-
One of the effective factors in evaluating the efficiency of an day (n = 4) precisions were in the ranges of 4.8–7.2 and 5.3–
adsorbent is its reusability in the repetitive extraction processes. 7.5%, respectively. The LOQ and LOD calculations were based

Table 1 The obtained figures of merit for the proposed analytical method

RSDe (%)

Analyte LODa LOQb LRc r2 d Intra-day Inter-day EF  SDf ER  SDg

Chlorpyrifos 0.60 2.0 2.0–500 0.996 5.6 6.0 375  25 75  5

Haloxyfop-R-methyl 0.30 1.0 1.0–500 0.996 5.1 5.9 380  15 76  3
Oxadiazon 0.30 1.0 1.0–500 0.995 4.8 5.3 390  15 78  3
Clodinafop-propargyl 0.15 0.50 0.50–500 0.998 7.2 7.5 255  20 51  4
Clodinafop propargyl 0.25 0.85 0.85–500 0.997 6.2 7.2 350  10 70  2
Fenpropathrin 0.25 0.85 0.85–500 0.995 5.9 7.1 400  15 80  3
Fenoxaprop-P-ethyl 0.30 1.0 1.0–500 0.997 5.0 5.8 360  20 72  4
a
Limit of detection (S/N = 3) (mg L−1). b Limit of quantication (S/N = 10) (mg L−1). c Linear range (mg L−1). d Coefficient of determination. e Relative
standard deviation at a concentration of 50 mg L−1 of each analyte for intra- (n = 6) and inter-day (n = 4) precisions. f Enrichment factor ± standard
deviation (n = 3). g Extraction recovery ± standard deviation (n = 3).

21680 | RSC Adv., 2023, 13, 21673–21684 © 2023 The Author(s). Published by the Royal Society of Chemistry
Paper RSC Advances

Table 2 Study of matrix effect in the juice samples spiked at different concentrations. All samples were diluted with deionized water at a ratio of
1:1

Mean relative recovery  standard deviation (n = 3)

Pineapple Fresh orange

Analytes Fresh apple juice Peach juice juice Apple juice Mango juice juice

All samples were spiked with each analyte at a concentration of 30 mg L−1

Chlorpyrifos 95  2 97  2 94  3 97  2 92  2 96  2
Haloxyfop-R-methyl 97  2 93  3 96  3 92  2 91  2 91  2
Oxadiazon 96  3 90  3 90  3 90  4 93  4 92  2
Diniconazole 91  2 92  4 91  3 91  3 90  3 97  2
Clodinafop-propargyl 94  3 88  4 93  2 92  2 95  2 96  2
Fenpropathrin 93  2 98  4 94  3 93  3 92  4 93  2
Fenaxaprop-P-ethyl 90  4 94  3 92  4 95  3 89  3 90  3

All samples were spiked with each analyte at a concentration of 60 mg L−1

Chlorpyrifos 95  3 93  2 94  2 97  3 92  3 96  2
Haloxyfop-R-methyl 90  4 90  3 91  2 92  2 89  2 91  3
Oxadiazon 91  2 96  2 92  2 87  3 93  2 89  3
Diniconazole 93  3 92  3 96  2 95  2 85  3 98  3
Clodinafop-propargyl 92  3 87  4 89  2 89  3 94  4 99  2
Fenpropathrin 94  4 98  3 93  2 93  3 92  4 94  2
Fenaxaprop-P-ethyl 97  3 89  2 95  2 91  2 90  3 97  3

on signal-to-noise ratios of 10 and 3, respectively. The LOQ and

LOD values of this method were in the ranges of 0.50–2.0 and
0.15–0.60 mg L−1, respectively. Calibration curves were plotted at
different concentrations of pesticides utilizing standard solu-
tions. The r2 values for this method were greater than or equal
to 0.995 which indicate the good linearity of the method. The
LRs were in the range of 2.0–500 mg L−1. Low LOD, LOQ, and
RSD values, wide LRs, and applying little amounts of organic
solvents and Ni-MOF-I are the main privileges of this current
procedure.

3.7. Analysis of real samples

In this research, the applicability of the method was evaluated
by analyzing four commercial fruit juices including mango,
pineapple, apple, and peach juices and two fresh orange and
apple juices. For this purpose, deionized water and the fruit
juices were spiked at 30 and 60 mg L−1 of each pesticides,
extracted in the optimum conditions, and eventually the ob-
tained sedimented phase injected into GC-FID. The achieved Fig. 7 Typical GC-FID chromatograms of: (a) standard solution
relative recoveries of the samples compared with deionized (250 mg L−1 of each pesticide in methanol), (b) aqueous standard
solution at a concentration of 150 mg L−1 of each pesticide, (c) pineapple
water are summarized in Table 2. As it can be deduced from the
juice, (d) fresh orange juice, (e) peach juice, (f) fresh apple juice, (g)
obtained results, the analyzed juices matrices have no signi- mango juice, and (h) commercial apple juice. In all cases, except chro-
cant effect on the present method. Therefore, this method can matogram (a) the proposed method was performed and 1 mL of the
be used as an efficient and appropriate method for the sedimented phase was injected into the separation system. Peaks
extracting and analyzing the studied pesticides in the afore- identification: (1) chlorpyrifos, (2) haloxyfop-R-methyl, (3) oxadiazon, (4)
clodinafop propargyl, (5) fenpropathrin, and (6) fenoxaprop-P-ethyl.
mentioned samples. Fig. 7 indicates the GC-FID chromato-
grams of a standard solution (250 mg L−1 of each pesticide)
which was directly injected, the extracted standard aqueous
solution (containing 150 mg L−1 of each pesticide), and the 3.8. Method comparison
extracted unspiked juices under the optimum conditions. Table 3 contains comparison of the analytical characteristics
According to the chromatograms, it can be seen that the chro- (EF, ER, LOD, RSD, and LR) of the proposed method in this
matograms of the real samples do not show traces of the pres- research and other previously reported methods for analyzing
ence of any of the surveyed pesticides.

© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 21673–21684 | 21681
RSC Advances Paper

Table 3 Comparison of the introduced method with some other methods used for analysis of the studied pesticides

Method Sample LODa LOQb LRc r2 d RSDe (%) EFf ERg (%) Ref.

DSPE-DLLME-GC-FIDh Fruit juices 0.32–0.76 1.10–2.60 1.1–2000 0.994–0.999 4.6–8.4 680–840 68–84 40
HF-LPME-GC-MSi Water 0.3–0.8 1.0 1–5000 0.997–0.999 6–9 134–240 — 41
SBSE-SFOD-GC-MSj Tomato juice 0.007–0.014 0.023–0.047 0.037–2000 0.998 6–9 — 76–90 42
HS-SPME-GC-MSk Wine 0.1 0.4 0.5–150 0.995 13.5 — — 43
DmSPE-DLLME-GC-FIDl Fruit beverages 0.15–0.60 0.50–2.0 2.0–500 0.995–0.997 4.8–7.2 255–400 51–80 Present method
a
Limit of detection (mg L−1). b Limit of quantication (mg L−1). c Linear range (mg L−1). d Coefficient of determination. e Relative standard deviation.
f
Enrichment factor. g Extraction recovery. h Dispersive solid phase extraction-dispersive liquid–liquid microextraction-gas chromatography-ame
ionization detection. i Hollow ber-liquid phase microextraction-gas chromatography-mass spectrometry. j Stir bar sorptive extraction-
solidication of oating organic droplet-gas chromatography-mass spectrometry. k Headspace-solid phase microextraction-gas chromatography-
mass spectrometry. l Dispersive micro solid phase extraction-dispersive liquid–liquid microextraction-gas chromatography-ame ionization
detection.

the mentioned pesticides. According to this table, the present analytical methodology, synthesis methodology, MOF
method has comparable LRs with most of the other methods. synthesis, analytical analysis, and writing the manuscript.
Also, the RSDs are comparable with or lower than those attained Sakha Pezhhanfar: analytical methodology, synthesis method-
for the mentioned methods. Moreover, the EFs and ERs of the ology, MOF synthesis, and editing the manuscript. Mohammad
studied approach are comparable with those of the other Reza Afshar Mogaddam: analytical methodology.
mentioned techniques. In addition, the proposed method LOQs
and LODs are lower than or comparable with the reported
methods data, except for one method in which mass spec- Conflicts of interest
trometry has been used as the detector instead of FID which is
The authors declare that they have no competing interests.
intrinsically more sensitive than FID. Eventually, it can be said
that this method is an effective and efficient analytical approach
due to high EFs, reasonable ERs, low LODs and LOQs, applying Acknowledgements
little amount of Ni-MOF-I as the adsorbent, and green synthetic
procedure of the MOF. The authors are thankful to the University of Tabriz for nancial
support.

4. Conclusions
For the rst time in this research, Ni-MOF-1 was synthesized
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21684 | RSC Adv., 2023, 13, 21673–21684 © 2023 The Author(s). Published by the Royal Society of Chemistry