Author’s Accepted Manuscript

Magnetic Cu-MOFs embedded within graphene

oxide nanocomposites for enhanced
preconcentration of benzenoid-containing
insecticides

Xuemei Wang, Xiaomin Ma, Pengfei Huang, Juan

Wang, Tongtong Du, Xinzhen Du, Xiaoquan Lu
www.elsevier.com/locate/talanta

PII: S0039-9140(18)30006-7
DOI: https://doi.org/10.1016/j.talanta.2018.01.004
Reference: TAL18227
To appear in: Talanta
Received date: 8 November 2017
Revised date: 27 December 2017
Accepted date: 2 January 2018
Cite this article as: Xuemei Wang, Xiaomin Ma, Pengfei Huang, Juan Wang,
Tongtong Du, Xinzhen Du and Xiaoquan Lu, Magnetic Cu-MOFs embedded
within graphene oxide nanocomposites for enhanced preconcentration of
benzenoid-containing insecticides, Talanta,
https://doi.org/10.1016/j.talanta.2018.01.004
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Magnetic Cu-MOFs embedded within graphene oxide nanocomposites

for enhanced preconcentration of benzenoid-containing insecticides

Xuemei Wang a,b,, Xiaomin Ma a, Pengfei Huang a, Juan Wang a, Tongtong Du a,

Xinzhen Du a,b, Xiaoquan Lu a,b

a
College of Chemistry and Chemical Engineering, Northwest Normal University,

b
Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, Lanzhou

730070, China

*
Corresponding author. Tel: +86-931-7973035. E-mail address: [email protected]

(Xuemei Wang)

1
Abstract

Hybrid magnetic nanocomposites based on Cu-MOFs, graphene oxide (GO), and

Fe3O4 nanoparticles (NPs) were prepared via chemical bonding approach, which GO

were used as platforms to load nanostructured Cu-MOFs and Fe3O4 NPs. The composite

features both magnetic separation characteristics and high MOFs porosity, making it an

excellent adsorbent for magnetic solid-phase extraction (MSPE). The as-synthesized

nanocomposites are characterized by XRD, TGA, SEM, TEM, nitrogen

adsorption-desorption analysis and FT-IR spectroscopy. The composites are used in

MSPE of six aromatic insecticides from various real samples prior to their

quantification by HPLC. Amount of adsorbent, extraction times, extraction temperature,

desorption times and oscillation rate are optimized. Under the optimal conditions, the

method has a relative standard deviations (RSDs) of 1.9-2.7%, and good linearity

2
(correlation coefficients higher than 0.9931). The low LOD and LOQ for six

insecticides are found to be 0.30-1.58 μg﹒L-1 and 1.0-5.2 μg﹒L-1, respectively. The

RSDs of within batch extraction are 1.6-9.5% and 3.9-12% for batch to batch extraction.

The experimental results suggest that the nanocomposites have potential application for

removal of hazardous pollutants from effluents.

Keywords: Magnetic solid-phase extraction; Preconcentration; Metal-organic

frameworks; Insecticides; High performance liquid chromatography.

1. Introduction

The extensive use of insecticides emitted into the environment is an event of public

health, which is potentially hazardous to human health due to the serious

contaminations of water, soil, and agricultural products. Insecticides enter the

ecosystem through different ways, in particular from agricultural drainage [1],

wastewater treatment plants [2] and other water resources. According to the World

Health Organization, 1.5 billion cases of diarrhea in children (leading to more than 3

million deaths) are caused by contaminated food and drinking water every year [3].

Studies have indicated that the high toxicity of insecticides is ascribed to their abilities

to irreversibly inhibit the activity of acetylcholinesterase (AChE) in the central and

peripheral nervous system, resulting in accumulation of the neurotransmitter

acetylcholine (ACh) in the body and thus cause serious harm to the human nervous,

respiratory, endocrine, and cardiovascular system, even fatal consequences[4-7].

Therefore, it is very important and significant to develop highly sensitive and reliable

3
detection and quantitative method for insecticides residues to improve the public safety

and environmental protection.

Many analytical techniques have been developed for the effective determination of

insecticides in the past decades, such as high-performance liquid chromatography

(HPLC) [8,9], gas chromatography/mass spectrometry (GC/MS) [10], electrochemical

analysis[11,12], immunochips [13,14]. However, these modern techniques are always

necessary for trace analysis. We also know that these instruments are used for

environmental and food contaminants. Hence, most of the analysis may require a

sample preparation step before an analysis depending on the sample type.

Solid-phase extraction (SPE) is a very efficient sample preconcentration technique

that has been widely used for extraction and removal of insecticides, due to the

simplicity, short extraction times, good enrichment factors and low consumption of

organic solvents [15,16]. Traditional SPE procedures are performed in specific columns,

and thus the effective interaction area between the adsorbent and analytes is limited.

Recently, a new SPE named magnetic solid-phase extraction (MSPE) has been

developed using magnetic nanomaterials as adsorbent [17,18]. In this technique, the

adsorbent is dispersed in the sample solution, and therefore the contact area between the

adsorbent and analytes is effectively enhanced. Also, the adsorbent can be easily

separated from the sample solution by an external magnetic field. However, the bare

nanoparticles have lower adsorption capabilities due to low surface area, easy

aggregation and instability of nano-sized particles, lead to low extraction efficiency [19].

Therefore, surfaces modifications of magnetic nanoparticles such as mesoporous

4
materials [20], metal-organic frameworks (MOFs) [21] and graphene/GO [22-24] have

been applied to overcome these problems.

In this study, a new magnetic nanoparticles (named as Fe3O4@SiO2-GO-MOFs) was

synthesized by covalent bonding of the GO nanosheets and silica-coated Fe3O4

(Fe3O4@SiO2) with core-shell structured, and then the GO surfaces were modified with

Cu-MOFs (Fig.1). The nanocomposites combine both advantages of the large surface

area of GO, and magnetic property of Fe3O4 without any limitations and drawbacks.

The silica shells not only protect Fe3O4 particles against oxidation and agglomeration,

but also serve as a platform to integrate the Fe3O4 particles and GO nanosheets through

covalent bond. This integration can be carried out with easy modification of silica shells

with amine groups and then chemical bonding of amines with carboxylic groups on the

GO nanosheets. The Cu-MOFs modified GO provide more active sites for adsorption

owing to the high porosity and tunability of MOFs. The material was applied as an

adsorbent in MSPE for extraction and enrichment of six benzenoid-containing

insecticides from some fruits and water samples. Remarkably, the

Fe3O4@SiO2-GO-MOFs demonstrated significant adsorption properties for six

insecticides enhanced determination.

<Insert Fig. 1>

2. Materials and methods

2.1 Materials and Chemicals

Six benzenoid-containing insecticides standards containing Imidacloprid,

5
Carbendazim, Metalaxyl, Myclobutanil, Tebuconazole and Cyfluthrin were acquired

from National Institute of Metrology (Beijing, China). Their chemical structures and

basic physicochemical properties are shown in Table S1. Copper nitrate

(Cu(NO3)2·3H2O), ferric chloride (FeCl3·6H2O), anhydrous alcohol,

1,3,5-benzenetricarboxylic acid (H3BTC), sodium acetate andydrous (NaAc), ethylene

glycol (EG), tetraethylorthosili-cate (TEOS), ammonium hydroxide (NH3·H2O) and

hydrochloric acid (HCl) were from Rionlon Bohua Pharmaceutical & Chemical Co. Ltd.

(Tianjin, China) and used directly without further purification. Glycol and 3-ammonia

propyl triethoxy silane (APTES) were purchased from Aladdin Chemical Corporation

(Shanghai, China). HPLC grade methanol was purchased from Thermo Fisher Scientific

China Ltd. (Shanghai, China). All used deionized water in the experiment was prepared

by Aquapro Water Purification System (Chongqing, China).

The stock solutions of 100 mg﹒L-1 each insecticide was prepared in deionized water

and stored in amber bottles in the refrigerator at 4 °C. The standard working solutions

were prepared by diluting the stock solution with deionized water to the required

concentration. Four water samples of sewage treatment plant were collected from

Anning, Xigu, Yanchang,Yanerwan (Domestic sewage) (Lanzhou, Gansu Province,

China). Five types of fruits (Apple, Plum, Grape, Cucumber, Spinach) were purchased

from local supermarkets. All fruit pulp and peel were chopped and homogenised in a

juicer, respectively. Tap water was from our lab. All these samples were filtrated

through 0.45 μm glass fiber membrane (Automatic Science, China) and stored in brown

glass bottles at 5 °C.

6
2.2 Instrument and chromatographic conditions

FT-IR spectra were recorded on a Digilab FTS3000 FTIR spectrometer using the

KBr wafer technique. Thermal gravimetric analysis (TGA) was performed using a TGA

2050 with a ramping rate of 5 °C﹒min-1 from 25 to 800 °C under air. The XRD

measurements were carried out on a D/max-2400 X-ray powder diffractometer (Japan,

Rigaku), using CuKα radiation (40 kV, 30 mA) source with a resolution of 0.02° and

scanning speed of 0.5 °·min-1. SEM images were recorded on a ULTRA Plus (Germany

Zeiss). TEM were conducted on Tecnai G2 F20 (FEI, USA) with an accelerating

voltage of 80 kV was used. Nitrogen adsorption-desorption isotherms were performed

at 77 K on a Quantachrome AS1Win™. The specific surface area was calculated from

the adsorption-desorption isotherm by using the Brunauer-Emmet-Teller (BET)

equation and the pore size was calculated from the adsorption isotherm by applying the

Barret-Joyner-Halenda (BJH) method. Magnetization measurements were carried out

using a Vibrating Sample Magnetometer (VSM, Lakeshore, 735 VSM Controller) under

applied magnetic field at room temperature. Oscillation in extraction procedure was

performed by a SHZ-82A environmental incubator shaker (Changzhou Guohua Electric

Co., Ltd, China).

The Agilent 1260 series HPLC-UV system (Agilent Technologies, USA) with a

variable wavelength detector and a reverse phase C18 HPLC column (5 μm, 150 mm ×

4.6 mm, Agilent, USA) were used for quantitative analysis. Mobile phase flow rate was

0.6 mL﹒min-1 and was constituted of the organic phase A (methanol) and aqueous

solution B (water), (A/B = 80:20, v/v). The wavelength of UV detection was 225 nm

7
and the sample injection volume was 20 µL.

2.3 Synthesis of the materials

2.3.1 Graphene oxide (GO) and Fe3O4 nanoparticles (Fe3O4 NPs) and silica-coated

Fe3O4 microspheres (Fe3O4@SiO2)

GO was prepared according to modified Hummers method [25]. Fe3O4 NPs were

prepared by solvothermal reduction method according to previous report [26].

Fe3O4@SiO2 microspheres were synthesized according to the modified stober method

[27].

2.3.2 Amino functionalized Fe3O4@SiO2 (Fe3O4@SiO2-NH2)

Amino functionalized Fe3O4@SiO2 (Fe3O4@SiO2-NH2) was prepared by surface

modification using APTES as the silylation agent. 0.3 g of Fe3O4@SiO2 was dispersed

in 60 mL of ethanol. Then 600 mL of APTES was added under ultrasonication, and the

reaction was allowed to proceed under mechanical stirring for 6 h at room temperature.

The resulting brown-yellow Fe3O4@SiO2-NH2 powder was collected with a magnet,

washed with ethanol and ultrapure water for several times, and drying at 60 °C under an

air atmosphere.

2.3.3 Magnetic Cu-MOFs (Fe3O4@SiO2-MOFs)

To understand the role of GO in the magnetic hybrid, magnetic Cu-MOFs was

synthesized to be compared. 3.0 g Cu(NO3)2·3H2O was dissolved in 30 mL ultrapure

water and 1.5 g H3BTC was dissolved in 30 mL ethanol. The two solutions were mixed

and stirred for 30 min. 0.15g Fe3O4@SiO2-NH2 was dispersed in the above solution

under ultrasonication for 30 min. Then the homogeneous mixture was sealed in

8
 Teflon-lined autoclave and heated at 120 °C for 12 h. The obtained blue crystals

(Fe3O4@SiO2-MOFs) were filtered, washed several times with ultrapure water and

ethanol, and then dried overnight at 60 °C under an air atmosphere.

2.3.4 Cu-MOFs

3.0 g Cu(NO3)2·3H2O was dissolved into 30 ml deionized water and mixed with 1.5

g H3BTC) dissolved into 30 ml ethanol. The resulting mixture was sealed in a

Teflon-lined autoclave. The autoclave was heated at 120 °C for 12. Afterwards, the

autoclave was cooled to room temperature. Blue solids of Cu-based MOFs were

collected and washed several times with ethanol and ultrapure water. Finally, the

resulting solid was dried at 60 °C under overnight resulting in a fine blue powder of

Cu-MOFs.

2.3.5 Magnetic Cu-MOFs embedded within GO nanocomposites

(Fe3O4@SiO2-GO-MOFs)

3.0 g Cu(NO3)2·3H2O was dissolved in 30 mL ultrapure water and stirred to form a

homogeneous blue solution (solution 1), 0.15g Fe3O4@SiO2-NH2 was dispersed in the

solution 1 under ultrasonication for 30 min. 1.5 g H3BTC was dissolved in 30 mL

ethanol and stirred to form clear colorless solution (solution 2), 4.65g GO was added in

the solution 2 under ultrasonication for 30 min. Solution 1 and 2 were mixed and

transferred quickly in Teflon-lined autoclave and heated at 120 °C for 12 h. The

obtained blue crystals (Fe3O4@SiO2-GO-MOFs) were filtered, washed several times

with ultrapure water and ethanol, and then dried overnight at 60 °C under an air

atmosphere.

9
2.4 Adsorption process of Fe3O4@SiO2-GO-MOFs

For preconcentration of insecticide, 10 mg of Fe3O4@SiO2-GO-MOFs is dispersed

into centrifuge tube with 15 mL of spiked water sample of 10 mg L-1, then the sample

solution is shaken in oscillator with 150 rpm and at 15℃. After 50 min, a magnet is

placed on the outside bottom of the centrifuge tube to collect the

Fe3O4@SiO2-GO-MOFs, and then the supernatant is discarded. After that, 200 μL

methanol is added to the tube, and is shaken and desorbed for 5 min. In the next step,

the magnet is attached to the outside bottom. The desorption solutions is collected and

20 μL of it is injected into the HPLC-UV analysis.

3. Results and discussion

3.1. Characterization results

Fig. 2 shows the FT-IR spectra of different nanocomposites. The asymmetric

stretching of the carboxylate groups in H3BTC is detected at 1515-1645 cm-1, and the

symmetric stretching of carboxylate groups in H3BTC is observed at 1378 and 1435

cm-1, in the region of 1300 - 600 cm-1, several bands are observed, and they are assigned

to the out-of-plane vibrations of H3BTC. All the characteristics peaks of H3BTC are

observed in Cu-MOFs (Fig. 2b), Fe3O4@SiO2-MOFs (Fig. 2a) and

Fe3O4@SiO2-GO-MOFs (Fig. 2d), and it indicates that the structure of MOFs is

preserved, while these peaks have not appeared in Fig. 2c. The peaks of

Fe3O4@SiO2-MOFs (Fig. 2a) and Fe3O4@SiO2-GO-MOFs (Fig. 2d) are different from

10
2500 cm-1 to 3700 cm-1, which indicates that addition of GO has an effect on the hybrid

nanocomposites. The characteristic peak of Fe-O-Fe was observed at 586 cm-1, which

implied Fe3O4 NPs are successfully introduced into the nanocomposites.

<Insert Fig. 2>

Further confirmation of the difference of nanocomposites is provided by the

powder XRD in Fig. 3. For GO, the peak at 2θ is about 9.3, which represents the

interlayer distance of 9.5 A [28]. The diffraction patterns of the Fe3O4@SiO2-MOFs

(Fig. 3b) and Fe3O4@SiO2-GO-MOFs (Fig. 3a) are similar to that observed for

Cu-MOFs (Fig. 3c), which indicates that the structure of Cu-MOFs is well preserved

and the complexes are pure powder. Fig. 3a shows a strong diffraction peak at around

26, which indicate the existence of a large number of GO. Meanwhile, several peaks

around 30, 36, and 43 are related to the characteristic peak of Fe3O4 NPs, which are

presented in Fig. 3a and 3b.

<Insert Fig. 3>

The TGA were used to evaluate the thermal stability, which reveal that all

self-made materials are stable up to 350 °C (Fig. 4a-c). A gradual weight loss (20-30%)

are observed at temperatures up to 200 °C, which is attributed to the evaporation of the

water and solvents that are incorporated into the frameworks. A large weight loss (~

40%) with a sharp exothermic peak occurs at temperatures between 300 and 400 °C,

which are ascribed to the decomposition of the organic components and the MOFs.
<Insert Fig. 4>

The morphological structures of the nanocomposites are characterized by SEM and

11
TEM (Fig. 5). The crystals of Cu-MOFs and Fe3O4@SiO2-GO-MOFs grow into

well-defined aggregates of regular octahedron frameworks approximately 10 μm in size

(Fig. 5a and 5b). The surfaces of pure Cu-MOFs are smooth and have clear edges and

corners (Fig. 5a), however, Fig. 5b indicate uniform distribution of a large number of

ball-like Fe3O4@SiO2 NPs on GO-MOFs, which is a desirable feature for magnetic

separation. In addition, the ultrafine particles and porous 3D network structures (Fig. 5b,

inset) play an important role in the mass transfer and adsorption. Fig. 5c clearly shows

the octahedron geometry of Cu-MOFs. Fig. 5d exhibit that Fe3O4@SiO2-GO-MOFs

forms a sea island structure, Fe3O4 is encapsulated by SiO2 with core-shell structured,

with Fe3O4@SiO2 and Cu-MOFs as the islands and GO as the sea, which indicate the

addition of GO prevent the aggregation of Fe3O4@SiO2 and conduce to the

homogeneous dispersion of them.

<Insert Fig. 5>

The porosity of the prepared materials is investigated via nitrogen

adsorption-desorption isotherms. The data of the surface area, pore volume and pore

size are listed in Table 1. As can be seen in Table 1, the self-made materials have

relatively high specific surface area, higher pore volume and pore. It is hypothesized

that formation and growth of the MOFs over GO surface through chemical bonding

results in formation of micro-pores which are beneficial for small molecules adsorption

[29]. The large surface area and high porosity of the prepared hybrid nanocomposites

provide many channels for pollutants adsorption and benefit their immigration into the

pores [29]. The data also imply that the synthetic methodology does not affect the pore

12
property of the MOFs.
<Insert Table 1>

The magnetic profile of the magnetic hybrid materials are verified by the

magnetization curve measured by VSM, and the results are shown in Fig. S1. The

saturation magnetization of Fe3O4@SiO2-MOFs is 2.5 emu g-1, and that of

Fe3O4@SiO2-GO-MOFs is 1.8 emu g-1. It is clear that the prepared nanocomposites are

magnetic, which can meet the requirement for magnetic separation of the adsorbent

from solution.

3.2. Optimization of MSPE conditions

In order to achieve the best adsorption efficiency of Fe3O4@SiO2-GO-MOFs, the

following parameters are optimized: (a) adsorbent amount, (b) extraction time, (c)

temperature, (d) desorption time, and (e) oscillation rate. Respective data and Figures

are given in the Electronic Supporting Material (Figure S2). The following experimental

conditions were found to give best results: (a) An amount of 10 mg of adsorbent, (b) 50

min is optimized extraction time, (b) The best extraction temperature is at 15 °C, (c)

desorption time is 5 min; (d) 150 rpm is selected in the experiment.

3.3. Validation of the method

Optimized MSPE conditions are employed to validate the analytical performance

of the method. As shown in Table 2, good linearity with satisfactory squared regression

coefficients (R2 > 0.9931) is acquired. The calibration curves for insecticides are linear

13
in the range of 20.0-1000 μg ﹒ L-1. The LOD and LOQ are calculated as the

concentration corresponding to the signals of 3 and 10 times the standard deviation of

the baseline noise, respectively. The LOD and LOQ for seven insecticides are found to

be 0.30-1.58 μg﹒L-1 and 1.0-5.2 μg﹒L-1, respectively, these data are lower than the

GB/T5749-2006 (China, Such as Carbendazim ≤ 100 µg﹒L-1), which indicate the

practicability of the method. Reproducibility is assessed using the relative standard

deviations (RSDs) of the extracted concentration for pesticides in extraction process, the

RSD values are in the range of 1.9-2.5% (n=5), illustrating the acceptable

reproducibility achieved by the proposed method. Fig. 6 shows several typical

chromatograms of direct HPLC, the MSPE method of Cu-MOFs, Fe3O4@SiO2-MOFs

and Fe3O4@SiO2-GO-MOFs and SWNTs adsorbent for spiked at 50 μg L-1 of standard

solutions. The results implied that the Fe3O4@SiO2-GO-MOFs nanocomposite has

highest extraction efficiency and enhanced preconcentration abilities for insecticides,

which is attributed to the three kinds of adsorbent (Fe3O4@SiO2-GO-MOFs) - adsorbate

(benzenoid-containing compounds) interactions mechanisms (π-π interaction,

hydrophobic interaction and hydrogen bonds).

Because Fe3O4@SiO2-GO-MOFs has benzene rings, it could be speculated that it

can strongly bound with benzenoid-containing insecticides by formation of π-π

interaction. In addition, some studies show that the complex structure of adsorbent

could bind similar functional groups of target contaminants by formation of

hydrophobic interaction. Meanwhile, hydrogen bonds may play an important role in

adsorption of organic compounds in presence of oxygenated function groups or

14
carbonyl groups. These are consistent with the reported adsorption mechanism for some

other similar compounds [30-32].

<Insert Table 2>

<Insert Fig. 6>

3.4. Practical application

To demonstrate the applicability of the Fe3O4@SiO2-GO-MOFs, four water

samples of sewage treatment plant and five fresh juices are analyzed. Because five

insecticides are only detected in Yanerwan sample, ranging from 1.27 to 5.98 μg﹒L-1,

Cdz and Mcb are not been detected, no insecticides are found in other eight samples,

therefore, recoveries and precisions of one sample is shown in Table 3. The sample is

spiked with standard solutions of insecticides at 20 μg﹒L-1 and 50 μg﹒L-1 to evaluate

the recoveries, which ranged from 81.2 to 113.1% and 84.9 to 105.8%, respectively. The

results are owing to the difference of accumulation effect of hazardous insecticides in a

different matrix. The nonpolar insecticides are more inclined to transport in complex

composition of the sample due to the adsorption of organic matter such as humus and

microorganism.
<Insert Table 3>

4. Conclusions

In this work, a magnetic Cu-MOFs embedded within graphene oxide

nanocomposites based on a simple green solvothermal method are prepared. The

chemical bonding between Fe3O4@SiO2, GO and Cu-MOFs endow the hybrid materials

15
with high chemical stability, desirable durability and excellent adsorption abilities.

Besides that, its successful application as adsorbent in MSPE combined with HPLC-UV

is tested by preconcentration of six insecticides in real samples and shows high

sensitivity, unusual adsorption properties, good reproducibility and outstanding

selectivity. It will be possible that these MOFs composites as supports can be one of the

most promising candidates for environmental pollutants separation and enrichment. The

structural diversity of MOFs can expand the application scope to related detection

schemes.

Acknowledgments

This work was generously supported by the Natural Science Foundation of China (No.

21467028, and 21327005), Program for Chang Jiang Scholars and Innovative Research

Team, Ministry of Education, China (Grant no. IRT1283), Key Laboratory of Ploymer

Materials of Gansu Province and Key Laboratory of Ecological Environment Related

Polymer Materials of Ministry of Education.

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[31] Z. Yang, N. Zhuo, S.P. Zhang, Y.Y. Dong, X.T. Zhang, J.C. Shen, W.B. Yang, Y.P.

Wang, J.Q, Chen, ACS Appl. Mater. Interfaces 7 (2015) 24446-24457.

[32] X. Wang, K. Zhao, B. Yang, T. Chen, D. Li, H. Wu, J. Wei, X. Wu, Chem. Eng. J.

306 (2016) 452-459.

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 Figures captions

Fig. 1. The fabrication process for Cu-MOFs and Fe3O4@SiO2-GO-MOFs.

Fig. 2. FT-IR spectra of the synthesized nanocomposites (a) Fe3O4@SiO2-MOFs; (b)

Cu-MOFs; (c) Fe3O4 ; (d) Fe3O4@SiO2-GO-MOFs.

Fig. 3. Powdre XRD patterns of synthesized nanocomposites (a) Fe3O4@SiO2-MOFs;

(b) Fe3O4@SiO2-MOFs ; (c) Cu-MOFs.

Fig. 4. TG curve of (a) Cu-MOFs; (b) Fe3O4@SiO2-MOFs; (c)

Fe3O4@SiO2-GO-MOFs.

Fig. 5. SEM (a) and TEM (c) images of Cu-MOFs; SEM (b) and TEM (d) images of

Fe3O4@SiO2-GO-MOFs.

Fig. 6. Chromatograms of six insecticides for the preconcentration of 50.0µg L-1

standard solution for direct HPLC(e); the Dispersive-SPE of Cu-MOFs (c) and SWNTs

(d); the MSPE method Fe3O4@SiO2-MOFs (b) and Fe3O4@SiO2-GO-MOFs (a) (a Cft1

and b Cft2 are enantiomers.)

19
Fig. 1

20
Fig. 2

21
Fig. 3

22
Fig. 4

23
Fig. 5

24
Fig. 6

25
Table 1 Some properties of self-made materials for nitrogen adsorption experiments.

Samples BET surface area (m2/g) Pore volume a(cm3/g) Pore size b (nm)

Cu-MOFs 760.2 0.43 2.27

Fe3O4@SiO2-MOFs 813.4 0.39 1.91

Fe3O4@SiO2-GO-MOFs 828.6 0.41 2.05

a
Total pore volume.
b
Average pore diameter calculated using BJH method.

26
Table 2 Analytical parameters of the proposed method (n = 5).

Regression Linear range LOD LOQ RSD

Analytes R2
equation (μg L-1) (μg L-1) (μg L-1) (%)
Idc y=0.15*x+3.85 0.9976 20-1000 0.46 1.5 1.9
Cdz y=0.01*x+1.94 0.9970 20-1000 1.58 5.2 2.5
Mtl y=0.08*x+13.88 0.9931 20-1000 0.94 3.1 2.2
Mcb y=0.12*x+15.84 0.9956 20-1000 0.30 1.0 2.3
Cft1a y=0.05*x+0.4328 0.9990 20-1000 0.55 1.8 2.1
Tbn y=0.26*x+13.45 0.9941 20-1000 0.97 3.2 2.7
Cft2b y=0.02*x+0.40 0.9984 20-1000 0.97 1.8 2.3
a
Cft1 and b Cft2 are enantiomers.

27
Table 3. Recoveries and precisions of insecticides in the analysis of environmental

water samples (n = 3).

Spike 20µg L-1 Spike 50µg L-1

Original
Sample Analyte
(µg L-1) Found Recoveryb RSD Found Recovery RSD
(µg L-1) (%) (%) (µg L-1) (%) (%)

Idc 1.87 18.1 81.2 6.7 44.3 84.9 6.5

Cdz NDa 19.3 96.5 6.3 51.2 102.4 6.9

Mtl 5.98 28.6 113.1 7.5 53.7 95.4 7.3

Yanerwan Mcb ND 20.5 102.5 5.8 52.9 105.8 5.4

Tbn 1.27 21.6 101.6 7.6 48 93.5 6.6

Cft1c 4.4 23.9 97.5 7.2 54.6 100.4 9.2

Cft2d 2.2 18.9 83.5 8.7 44.8 85.2 8.1

a.
Not detected or lower than limits of detection.
b.
Recovery: Percentage of concentration of spiked standard.
c.
Cft1 and d. Cft2 are enantiomers.

28
 Highlights

·A facile and efficient strategy for the preparation of a hybrid magnetic metal-organic

framework

·The unique materials have high adsorption capacity and enhanced preconcentration of

hazardous insecticides.

·The proposed method will be applied for determination of specific toxic pollutants in

real samples.

29
Graphical abstract

30