Accepted Manuscript

Corn-like stationary phase for solid phase microextraction

prepared by electro-assisted deposition of sol-gel/silica
nanoparticles composite

Sirwan Mohammadiazar, Mehdi Maham, Fateme Hasanli

PII: S0026-265X(18)31936-2
DOI: https://doi.org/10.1016/j.microc.2019.04.012
Reference: MICROC 3826
To appear in: Microchemical Journal
Received date: 1 January 2019
Revised date: 1 April 2019
Accepted date: 3 April 2019

Please cite this article as: S. Mohammadiazar, M. Maham and F. Hasanli, Corn-like
stationary phase for solid phase microextraction prepared by electro-assisted deposition
of sol-gel/silica nanoparticles composite, Microchemical Journal, https://doi.org/10.1016/
j.microc.2019.04.012

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 ACCEPTED MANUSCRIPT
Corn-like stationary phase for solid phase microextraction prepared by electro-assisted
deposition of sol-gel/silica nanoparticles composite
Sirwan Mohammadiazar1,*, Mehdi Maham2, Fateme Hasanli3
1
Department of Chemistry, Sanandaj Branch, Islamic Azad University, Sanandaj, Iran.
2
Department of Chemistry, Aliabad Katoul Branch, Islamic Azad University, Aliabad Katoul, Iran.
3
Department of Chemistry, Tehran North Branch, Islamic Azad University, Tehran, Iran.

*Correspondence: Sirwan Mohammadiazar, Department of Chemistry, Sanandaj Branch, Islamic Azad

University, Sanandaj, Iran; Email: sirwan.mohammadi@yahoo.com; Tel: +988733184715; Fax: +9833184712.

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Abstract

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A novel solid phase microextraction (SPME) fiber was fabricated based on the

electrophoretic and electrochemical deposition of silica nanoparticles and silicon alkoxides as

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sol-gel precursors. The surface of the Cu support was initially modified by a self-assembled
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monolayer (SAM) of (3-mercaptopropyl) trimethoxysilane (3MPTS). Then, the composite

coating was electrodeposited on the modified substrate. The SEM images showed that porous
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and corn-like particles of composite were coated on the Cu wire substrate. The prepared

composite was used as SPME fiber and applied to extract some halogenated benzenes from
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aqueous solution as model compounds. Parameters affecting the extraction efficiency such as
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extraction temperature, extraction time, and ionic strength were evaluated and optimized.
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Then, the extraction efficiency of the new fiber was evaluated by determining the limit of
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detection (LOD), linear dynamic range (LDR) and relative standard deviation (RSD). Using

GC-MS determination of analytes it was found that LOD, LDR, and RSD of this method
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were between 0.1-0.6 μg L−1, 0.5-100 μg L−1 and less than 14.4 %, respectively. The thermal

stability of the fiber was investigated by thermogravimetric analysis, and finally, results show

that each fiber is usable at 280 °C (3 min) for more than 80 times. Furthermore, the proposed

fiber was successfully applied for quantification of halogenated benzenes in real water

samples.

Keywords: Solid phase microextraction; Halobenzenes; Electro-assisted; Sol-gel; Silica

nanoparticles.

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1 Introduction

Solid phase microextraction (SPME) is a fast, easy, and solvent-free sample preparation

technique based on the partitioning of target analytes between the sample matrix and a fiber

formed by dispersing small amount of extracting phase on a solid support. SPME can be used

for direct extraction of analyte(s) by immersion of the fiber into the sample or indirect

extraction by exposing the fiber to the headspace (HS) of the sample [1-4]. HS-SPME is

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preferred for the analysis of volatile analytes and complex samples owing to its simple

technical manipulation, the purity of the extract, and to protect the fiber from contaminants

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existing in the sample matrix [5, 6]. The fiber coating plays the crucial role in SPME, and

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developing novel coatings, especially porous ones are valuable to the extraction of analytes.
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Although some commercial fibers have been introduced in SPME, they have some

disadvantages such as high cost, low porosity and consequently low extraction efficiency, and
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fragility.

Recently, much attention has been focused on synthesis of nanocomposites and metal
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organic framework to be employed as SPME coatings to provide a larger surface area, good
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porosity and stability during extraction [7-14]. Also, to overcome the fiber fragility, a number
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of metallic wires such as stainless steel [1], platinum [7], copper [15], gold [16], zinc [17],
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aluminum [18] and titanium [19] have been incorporated as fiber substrates. The sol-gel

technology provides an effective methodology in the synthesis of advanced materials to

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overcome some problems of commercial SPME fibers [20-24]. Sol-gel coatings can be

prepared in the presence of precursor(s), water and acidic or basic catalysts (in most cases

trifluoroacetic acid). They are prepared under mild thermal conditions which facilitate the

incorporation of organic/inorganic components into inorganic polymeric structures by the

simplicity of operation. The electro-assisted sol-gel deposition is accomplished without a

catalyst. Liu and Walcarius [25] prepared sol–gel films by electrochemically-assisted

deposition. The catalyst of OH¯ ions will be generated by electrochemical reduction of water,
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O2, or both [25] and used as catalyst in the sol–gel condensation reactions.

Electrochemically-assisted deposition of sol-gel films has several advantages such as gelation

stage occurs independently from evaporation and drying stages and also, the thickness of the

deposited films can be controlled by tuning the deposition potential and time. To improve the

mechanical stability of the SPME coatings prepared by the electrochemically deposited

method, two techniques can be used. An intermediate layer such as the self-assembled

monolayer (SAM) of (3-mercaptopropyl)trimethoxysilane (3MPTS) can be used to bind the

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solid support on the one hand, and the sol-gel film on the other hand [26, 27]. Another

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alternative is using an easily reducible metal ion such as Cu+2, co-precipitated with the sol-gel

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film, binding both of the metal surface and sol-gel network [28].

Silica nanoparticles also have advantages, including high thermal stability, chemical
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inertness and nontoxicity [27, 28]. The present study reports the first example of a facile in-

situ electrodeposition method to prepare a novel and corn-like SPME coating through
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incorporating silica nanoparticles into the sol-gel film. The electrodeposition of the sol-gel

film using negative potentials was performed on the Cu support modified by SAM of
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3MPTS. The performance of the as-prepared coating was evaluated through extracting some
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halobenzenes in aqueous samples as model compounds.

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2 Material and methods

2.1 Materials
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The 3-(trimethoxysilyl) propyl methacrylate (3TMSPMA) and 3MPTS were obtained

from Fluka (Buchs, Switzerland). Tetraethyl orthosilicate (TEOS) and silica nanoparticles

(10-20 nm) were purchased from Aldrich (Steinheim, Germany). Water was produced by a

Milli-Q plus ultrapure Millipore 6.0 water system. All reagents, used were of analytical grade

and purchased from Merck (Darmstadt, Germany). The individual halobenzene standards

including chlorobenzene (ClBz), 2-chlorobenzotrifluoride (2ClBzTF), bromobenzene (BrBz),

benzyl chloride (BzCl) and 1,2-dichlorobenzene (1,2DClBz) were purchased from Merck

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(Darmstadt, Germany). The stock solution of halobenzenes (1000 µg mL-1) was prepared in

H2O/methanol (70:30 v/v ratio). Working solutions were prepared weekly by diluting the

stock solution in ultrapure water. Cu wires (OD ≈ 154 µm) were also prepared from home

electricity wires.

2.2 Apparatus

Halobenzenes were separated and analyzed by an Agilent GC-MS (7890B/5977A

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Agilent Technologies, USA) equipped with a split/splitless injector. Compounds were

separated on an HP-5 capillary column (30 m × 0.25 mm, 0.25 µm in film thickness). The

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MS was operated in the EI mode (70 eV). The MS instrument was programmed in the

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selected ion monitoring mode (Table 1). The injector temperature was set at 280 C, and fiber

desorption was carried out in the splitless mode for 3 min. For GC analysis, the column
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temperature program started at 50 °C for 3 min, increased by 10 °C min-1 to 110 °C and by 10
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°C min-1 to 180 °C, hold for 2 min. The injector temperature was maintained at the 280 °C

and Helium (99.999%) was used as the carrier gas.

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The electro-assisted deposition was carried out with a potentiostat/galvanostat AutoLab

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(PGSTAT 101). Surface characteristic studies of the prepared fiber coatings were done using
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the field emission scanning electron microscopy (TESCAN MIRA3 XMU, USA). The

thermal stability of the developed fiber was assessed by its thermogravimetric analysis curve
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measured on a TG 209 F1 Iris-thermogravimetric analyzer NETZSCH (Germany) under inert

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(N2) atmosphere over the temperature range of 30–600 °C (heating rate of 10 °C.min-1).

2.3 SPME fiber preparation procedure

The working electrode, i.e., Cu wire was washed prior to the film deposition with

ultrapure water, ethanol, and ultrapure water again, followed by drying at room temperature

for 2 hr. To create a self-assembled monolayer of 3MPTS on the Cu wire, it was immersed in

a solution of the 3MPTS (10-2 mol L-1 in toluene) for 2 hr. Then, the modified Cu wire was

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immersed into alkaline (NaOH 1 mol L-1) and acidic (HCl 0.1 mol L-1) solutions, each for 15

min.

The starting sols were prepared by mixing TEOS (100 µL) and 3TMSPMA (500 µL), in

a solution consisting of 7 mL ethanol, 3 mL phosphate buffer (1mmol L-1, pH=3.5)

containing KNO3 0.2 mol L-1. These sol solutions were stirred for 3 hr in a closed beaker to

achieve hydrolysis, then, 0.05 gr silica nanoparticles were added to the solution and it was

sonicated for 5 min. The films deposition was performed by applying a cathodic potential of -

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1000 mV at a three-electrode system, including Cu wire as cathode, Pt as anode and Ag/AgCl

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as reference electrode immersed into the prehyrolysed sols, for 500 s under moderated

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stirring. In order to uniform the surface charge of the working electrode, the reference

electrode was located between the working and counter electrodes. The resulting films were
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then rinsed with ultrapure water and left to dry at room temperature for 12 hr. The prepared

fiber was conditioned in the GC inlet at 280 °C for 2 hr to remove any residual solvent and
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unreacted reagents.
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2.4 SPME process

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The HS-SPME procedure was carried out by a spiked aqueous sample of 6 mL in a 10-
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mL vial placed on a magnetic stirrer. In all experiments, NaCl 20 % (w/v) was added to 6 mL
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of the spiked aqueous sample containing a magnetic stir bar. The extraction of halobenzenes

was performed by exposing the fiber to the HS of the aqueous sample for 20 min at 20 oC.
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After reaching equilibrium, the SPME probe was withdrawn from the vial and inserted into

the GC injector for 3 min at 280 °C for thermal desorption.

3 Results and discussion

3.1 The fiber preparation and characterization

The electro-assisted sol-gel coating on the Cu wire was based on the hydrolysis of

silicon alkoxide precursors at low pH, followed by applying a negative potential to the

cathode to increase the pH by reduction of oxygen, water or both:

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- -
2H2O + 2e 2OH + H 2
- -
O2 + 2 H2O + 4e 4OH

- -
O2 + 2H2O + 2e H2O2 + 2OH

All three reactions produce OH− ions near the electrode surface. The generation of OH–

ions can catalyze the condensation of the sol-gel process and lead to deposition of the

appropriate oxide film on the modified electrode surface. The electrochemical base catalyzed

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sol-gel film has several advantages. For example, the sol solution can be reused and

practically no base is used. The electro-assisted deposition of the sol-gel film can affect the

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coating morphology. The applied potential strongly affects the concentration of OH– and H2

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bubbles near the electrode surface. More negative potentials can increase the production

speed of OH– and H2 bubbles. In more negative potentials, the increased production of OH–
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causes a decrease in the average size of the grains and thus increases their density.
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Furthermore, an increase in the fiber porosity due to the increased release of H2 bubbles can

be observed in more negative potentials.

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The electrodeposited sol-gel film is cracked and flaked off after drying since there is a
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weak interaction between the sol-gel coating and the metal substrate. To increase the
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interaction between the sol-gel coating and metal substrate, the SAM of 3MPTS was used as
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an intermediate layer to bind the sol-gel film to the Cu surface. As can be seen from Fig. S1,

EDX analysis shows trace amounts of Sulphur atoms that can be attributed to the SAM of
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3MPTS molecules. Before sol-gel coating, the 3MPTS molecules were hydrolyzed and

condensed in alkaline and acidic solutions, respectively, to form a 2D network and some free

–OH functional groups on the surface as active sites to bind the sol-gel film.

The SPME fiber coating containing nanomaterials provide a remarkably high surface

area to volume ratio and highly available adsorbing sites. In the present study, to improve the

surface porosity, silica nanoparticles were added to the sol solution in an acidic environment.

Characterization of the novel fiber was performed through SEM and TG analyses. The SEM

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studies showed that the sol-gel film was coated on the Cu wire (Fig. 1A). As Fig. 1B shows,

the stationary phase had a corn-like structure.

The silica nanoparticles containing some Si-OH groups are able to gain protons at low

pH to form . Here, we propose the mechanism of preparation of corn-like stationary

phase by the adsorption of positively charged on negatively charged electrode surface

via the electrophoretic deposition of silica nanoparticles and electrochemical deposition of

the sol-gel coating, simultaneously. It should be noted that electrodeposited silica

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nanoparticles are not stable in the absence of the sol-gel film and can easily be removed by

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water.

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As Fig. 1C illustrates, silica nanoparticles adsorbed on the electrode surface, can be

grown and their size increases by the coating of the sol-gel film. As can be seen from Fig. 1D
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the size of the particles is between 28-62 nm, causing a high surface area and therefore high

extraction capacity.
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The TG analysis (Fig. 2) showed that there was no obvious weight loss between 30 and

400 oC. The good consistency and thermal stability of the fiber coating were due to the good
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thermal stability nature of sol-gel based materials and the strong adhesion of the coating to
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the substrate. Experimental results indicated that the fiber had a long lifetime (over 80 times

usability) without any decrease in extraction efficiency.

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3.2. The effect of silica nanoparticles incorporation on extraction efficiency of the fiber
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Fig. 3 shows the effect of silica nanoparticles incorporation in the sol-gel film on

extraction efficiency. As can be seen, the extraction efficiency of the prepared fiber was

enhanced more than 30% in the presence of silica nanoparticles, due to the high surface area/

volume ratio.

3.3 The study of extraction parameters

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The effect of the three main factors, including the extraction temperature, extraction

time and salt content on the extraction performance was studied and optimized. To optimize

experimental factors, a one-at-a-time approach was used for 100 ng L-1 halobenzenes under

agitated sampling conditions in the 10 mL vial containing 6 mL sample solution.

Generally, the salting out effect causes a significant decrease in the solubility of the

analytes in the donor aqueous phase and thus considerably increases the transfer of analytes

into the extractor phase; NaCl is usually used for this purpose. The effect of different

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concentrations of NaCl on the extraction performance in the range of 0-25% (w/v) was shown

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in Fig. 4A. Based on the experimental data, the best performance was achieved at 20% (w/v).

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Such a decrease of extraction efficiency for halobenzenes in NaCl concentrations over 20%

(w/v) might result from the increase of viscosity with the addition of salt, slowing down the
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extraction kinetics (the diffusion coefficient and the mass transfer rate) of the compounds.

Microextraction temperature has a double effect on extraction performance, i.e., an increase

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in temperature leads to an increase in distribution velocity and vapor pressure of analytes.

This increases the extraction performance, while at higher temperatures, the distribution
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constants of analytes between the sample and the fiber decrease since the extraction is an
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exothermic process. As Fig. 4B shows, distribution velocity affects the extraction efficiency

at temperatures below 30 °C and the distribution constant is dominant at temperatures higher

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than 30 oC. Therefore, the extraction temperature of 30 °C was selected as the optimal

temperature in further experiments.

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SPME is an equilibrium-based technique in which the amount of extracted analytes is

directly related to the extraction time. In order to optimize the extraction time, the prepared

fiber was exposed to the headspace of the sample for 10-40 min. The obtained results (Fig.

4C) showed that extraction equilibrium was obtained in 20 min. This short extraction time

was mainly due to the porous structure and thin thickness of the fiber coating, enhancing the

mass transfer of the analytes into the coating.

3.4 The study of desorption conditions

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To increase sensitivity and prevent the effect of carrying-over, desorption of the analytes

from the fiber should be sufficient. To obtain the optimized desorption conditions, different

temperatures in the range of 220-300 °C with a fixed desorption time of 3 min were used to

desorb analytes in the GC injection port. The desorption temperature highly affects the

lifetime of the prepared fiber, as a result, the lowest appropriate temperature should be

chosen. Fig. 5A shows, all the analytes are completely desorbed at 280 °C and it was chosen

as the optimized desorption temperature. In addition, monitoring the analytes carry-over

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versus desorption time exhibited that a 3 min time of desorption was sufficient to effectively

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desorb all the analytes from the SPME fiber (Fig. 5B).

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3.5 Analytical performance NU
The analytical characteristics of the SPME-GC/MS method, including relative standard

deviation, limit of detection (LOD) and linear dynamic range were determined to assess the
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method performance (Table 2). To evaluate the precision of the proposed method, single fiber

repeatability and fiber-to-fiber reproducibility were assessed by five replicate extractions of

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100 ng L-1 halobenzenes by one fiber and five different fibers produced in the same batch,
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respectively. The LOD was calculated based on signal to noise ratio of 3:1. To investigate the
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applicability of the prepared fiber coating to extract the target analytes and predict the matrix
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effect in real samples, water samples were collected from the Gheshlagh River (Sanandaj,

Iran), tap water and well water. The obtained results indicated that none of the target analytes
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is present in the actual aqueous sample. Then, the river water sample was spiked at

concentration levels of 10, 50 and 100 ng L-1 and the optimized procedure was performed to

analyze the target analytes. Table 3 shows the relative recoveries for HS-SPME of

halogenated benzenes in the spiked real samples, as a criterion to evaluate matrix effect.

Satisfactory relative recoveries ranging from 76-101% were achieved for the selected

analytes. Furthermore, the figures of merit of the proposed method were compared with those

of other methods reported in the literature. As Table 4 shows, the efficiency of the proposed
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fiber is comparable with that of other SPME fibers to extract halobenzenes from water

samples. Reusability of the SPME device is an important factor affecting the practical

application of the fiber. The recyclability studies showed that the as-prepared fiber could be

used more than 80 times without significant reduction in its performance. The excellent

stability of the fiber was attributed to the sol-gel coating and mechanical stability derived

from Cu substrate modified by SAM of 3MPTS.

[27, 31-36]

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4 Conclusions

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In this study, unbreakable SPME fibers were prepared by simultaneous deposition of

sol-gel and silica nanoparticles on the Cu wire modified by the SAM of 3MPTS as an

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intermediate layer. The well-organized SAM of 3MPTS as an intermediate layer could
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increase the mechanical strength of fiber and prolong the fiber life cycle. Incorporated silica

nanoparticles into the sol-gel film, enhances the porosity of the coating and increases the
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extraction efficiency owing to the large specific surface area. The corn-like extraction phase

was prepared by adsorption of positive charged on the negatively charged electrode

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surface via the simultaneous electrophoretic and electrochemical deposition of silica

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nanoparticles as well as the sol-gel film, respectively. The prepared sol-gel coating exhibited
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high thermal stability and strong adhesion to the fiber. The fabricated SPME fiber was used to
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extract halobenzenes as the model analytes from water samples. The extraction efficiency of

the fiber was improved more than 30% in the presence of silica nanoparticles. Under the
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optimal conditions, the suggested method showed good figures of merits over a wide

concentration range of halobenzenes. As a result, the present study introduced new and

efficient SPME fiber coating to extract organic compounds.

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[29] A.D. Guimarães, J.J. Carvalho, C. Gon Çalves, M.D.F. Alpendurada, Simultaneous

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analysis of 23 priority volatile compounds in water by solid-phase microextraction–gas

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chromatography–mass spectrometry and estimation of the method's uncertainty, Int. J.

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Environ. Anal. Chem., 88 (2008) 151-164.

[30] Y. He, Y. Wang, H.K. Lee, Trace analysis of ten chlorinated benzenes in water by
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headspace solid-phase microextraction, J. Chromatogr. A, 874 (2000) 149-154.

[31] E. Ghasemi, M. Sillanpaa, Optimization of headspace solid phase microextraction based

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on nano-structured ZnO combined with gas chromatography-mass spectrometry for

preconcentration and determination of ultra-traces of chlorobenzenes in environmental

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samples, Talanta, 130 (2014) 322-327.

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[32] V.H. Niri, L. Bragg, J. Pawliszyn, Fast analysis of volatile organic compounds and

disinfection by-products in drinking water using solid-phase microextraction–gas

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chromatography/time-of-flight mass spectrometry, J. Chromatogr. A, 1201 (2008) 222–227.

[33] G. Zhang, Z. Li, X. Zang, C. Wang, Z. Wang, Solid-phase microextraction with a

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graphene-composite-coated fiber coupled with GC for the determination of some halogenated

aromatic hydrocarbons in water samples, J. Sep. Sci., 37 (2014) 440–446.

[34] M. Farjaminezhad, M. Saber Tehrani, P. Aberoomand Azar, S. Waqif Hussain, S.

Bohlooli, Polyvinylimidazole/sol–gel composite as a novel solid-phase microextraction

coating for the determination of halogenated benzenes from aqueous solutions, J. Sep. Sci.,

37 (2014) 1475-1481.

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Figure Captions

Fig. 1. The SEM images of electrochemically deposited sol-gel fibers at different

magnifications: (A) 200X (B) 3000X, (C) 30000X and (D) 60000X.

Fig. 2. TGA curves (continuous line) and its DTA curves (dotted line) for the proposed fiber

coating.

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Fig. 3. Comparison of extraction efficiency of the fibers prepared by electrodeposited sol-gel

film and silica nanoparticle incorporation in the electrodeposited sol-gel film, extraction

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conditions: concentration of halobenzenes 100 ng L-1, extraction temperature: 30 ◦C,

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extraction time: 20 min, salt content 20% (w/v).

Fig. 4. The effect of extraction parameters on the performance of prepared fiber, (A) salt
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content, conditions: concentration of halobenzenes 100 ng L-1, extraction temperature: 30 ◦C,
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extraction time: 20 min, (B) extraction temperature, conditions: concentration of

halobenzenes 100 ng L-1, extraction time: 20 min, salt content 20% (w/v), (C) extraction time,

conditions: concentration of halobenzenes 100 ng L-1, salt content: 20% (w/v), extraction
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temperature: 30 ◦C.
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Fig. 5. The effect of desorption parameters on the performance of prepared fiber, (A)

desorption temperature, (B) desorption time, conditions: concentration of halobenzenes 100

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ng L-1, extraction time: 20 min, salt content 20% (w/v), extraction temperature: 30 ◦C.
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Table 1: Retention times and selected ions of compounds studied by GC–MS

Compound Retention time (min) Selected ions (m/z)

ClBz 4.79 55, 71, 112

2ClBzTF 6.06 75, 130, 180

BrBz 6.59 51, 77, 156

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BzCl 8.22 65, 91, 126

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1,2DClBz 8.61 75, 111, 146

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Table 2. Method validation parameters for each halobenzene, using the proposed SPME-GC/MS.

DLR RSD (%) n=5 LOD

Analyte Regression Equation r2
(µg L-1) Single fiber Fiber-to-fiber (ng L-1)
repeatability reproducibility
ClBz 0.002-0.100 y=8412.12x+2371 0.9984 10.1 6.2 0.5

2ClBzTF 0.0005-0.100 y=12843.21x+4261 0.9994 14.4 8.7 0.1

BrBz 0.002-0.100 y=9345.25x+2366 0.9972 9.6 10.2 0.5

BzCl 0.002-0.100 y=8967.51x+2137 0.9989 7.9 3.7 0.6

1,2DClBz 0.0005-0.100 y=14732.37x+3216 0.9996 11.7 3.9 0.1

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Table 3. Relative recoveries (%) and RSD values (%) after HS-SPME of selected halobenzenes using
the sol-gel/silica nanoparticle composite fiber and GC-MS.

Relative recoveries (%) ( RSD %)

Analyte
Real sample 10 ng.L-1 50 ng.L-1 100 ng.L-1

Qeshlagh River 64.3 (8.5) 78.5 (6.8) 95.3 (6.3)

CBz tap water 73.2 (4.5) 82.7 (6.4) 91.7 (7.2)
well water 68.4 (9.1) 84.1 (6.7) 93.2 (7.9)

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Qeshlagh River 86.1 (9.4) 94.4 (8.6) 93.4 (5.4)
2CBzTF tap water 79.2 (6.3) 89.3 (7.9) 94.2 (5.5)

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well water 83.3 (8.4) 78.7 (6.3) 103.4 (5.7)

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Qeshlagh River 76.7 (8.8) 101.3 (9.5) 96.1 (4.4)
BBz tap water 84.1 (7.4) 89.4 (8.5) 102.7 (6.6)
well water 69.2 (8.0)
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94.3 (9.3) 96.4 (7.5)

Qeshlagh River 93.5 (10.1) 88.6 (7.4) 95.3 (9.9)

BzCl tap water 83.8 (9.1) 93.2 (6.3) 104.2 (5.7)
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well water 79.4 (6.5) 83.7 (8.7) 97.4 (10.0)

Qeshlagh River 76.4 (11.5) 83.3 (7.6) 91.8 (7.99)

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1,2DCBz tap water 67.9 (6.6) 84.2 (9.4) 104.1 (8.4)

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well water 86.4 (7.0) 66.5 (9.1) 89.4 (8.6)

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Table 4. A comparison of the present SPME with silica nanoparticle incorporated sol-gel film for analysis of

halobenzenes in water samples with other SPME fibers.

RSD (%)
LOD
Analyte Method Fiber coating Single fiber Fiber-to-fiber Ref.
(ng L-1)
repeatability reproducibility
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ClBz SPME-GC/MS CAR/PDMS 140 9.1 - 29

1,2DClBz SPME-GC/MS PDMS** 6 5.2 - 30

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ClBZ 1×10-2 3.5 3.6
SPME-GC/MS ZnO nanorods 31

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1,2DClBz 1×10-2 4.8 4.1

ClBZ 63 1.4 -

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SPME-GC/MS DVB/CAR/PDMS*** 32
1,2DClBz NU 22 6.7 -

ClBz 1000 4.5 14.9

1,2DClBz SPME-GC/FID Graphene composite 500 4.2 7.9 33

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BrBz 1000 7.2 9.6

ClBZ 1×10-1 9.2 15.0

1,2DClBz 175×10-4 5.5 11.0

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BrBz SPME-GC/MS Polyvinylimidazole 75×10-3 9.1 14.0 34

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1×10-1
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BzCl 8.0 10.6

2ClBzTF 135 ×10-4 7.0 7.3

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ClBz 0.5 10.1 6.2

1,2DClBz 0.1 11.7 3.9

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Sol-gel/Silica nanoparticle This

BrBz SPME-GC/MS 0.5 9.6 10.2
composite work
BzCl 0.6 7.9 3.7

2ClBzTF 0.1 14.4 8.7

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Carboxen/Polydimethylsiloxane
**
Polydimethylsiloxane
***
Divinylbenzene/Carboxen/Polydimethylsiloxane

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Highlights

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 Porous and unbreakable solid phase microextraction fiber was prepared.

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Silica nanoparticles and sol-gel film were electrochemically co-deposited.

 Novel coating was applied for extraction of some halobenzenes from aqueous

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solution.
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Figure 1
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