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Trends in Analytical Chemistry, Vol. 34, 2012

Towards greater mechanical, thermal and chemical stability in solid-phase microextraction

Habib Bagheri, Hamed Piri-Moghadam, Mehrnoush Naderi
Solid-phase microextraction (SPME) is a fast, solvent-free technique, which, since its introduction in the 1990s, has been increasingly applied to sample preparation in analytical chemistry. Conventional SPME bers are fabricated by making a physical bond between the usual silica substrate and the polymeric coatings. However, some applications are limited, as the lifetime and the stability of conventional SPME bers cannot meet the demands of analyzing relatively non-volatile compounds with more polar moieties. There have been attempts to analyze less volatile compounds by increasing the thermal, physical and chemical stability of the bers. In this review, we present some new developments in the use of sol-gel technology, molecularly-imprinted polymers (MIPs) and electrochemical deposition to prepare thermally-stable, chemically-bonded, unbreakable SPME bers. 2012 Elsevier Ltd. All rights reserved.
Keywords: Coating polymer; Electrochemical deposition; Modifier; Molecularly-imprinted polymer (MIP); Polarity; Polymerization; Sample preparation; Sol-gel technology; Solid-phase microextraction (SPME); SPME fiber

1. Introduction
Habib Bagheri*, Hamed Piri-Moghadam, Mehrnoush Naderi Environmental and BioAnalytical Laboratories, Department of Chemistry, Sharif University of Technology, P.O. Box 113659516, Tehran, Iran

Corresponding author. Tel.: +98 21 66165316; Fax: +98 21 66012983; E-mail:

Solid-phase microextraction (SPME) is an innovative technique that was introduced in early of 1990s [1]. In SPME, sampling, extraction and preconcentration are performed in single step. SPME is simple, fast, solvent free and cost effective. In SPME, a small amount of extracting phase, dispersed on a solid support, is exposed to the sample for a well-dened period of time. Afterwards, a partitioning equilibrium between the sample matrix and extraction phase is reached. If this option is selected for analysis, convection conditions do not affect the sample amount extracted. Another option is to utilize short time preequilibrium extraction, and, if convection or agitation is constant, the amount of analyte extracted is related to time. Then, desorption of analytes should be performed as fast as possible to avoid any possible peak broadening. In GC, the rapid desorption happens inside the high temperature injection port, while, in HPLC, the fast desorption is achievable using a mobile phase with strong eluting power. SPME is an alternative to liquid-liquid extraction (LLE) and solid-phase extraction (SPE), and, in contrast to them, is

regarded as a non-exhaustive extraction technique. Although the use of SPME bers is increasingly popular, their relatively low recommended operating temperature (generally in the range 240 280C), their instability and swelling in organic solvents (greatly restricting their use with HPLC), ber breakage, and loss of coatings are obstacles to the analysis of some chemicals. Except for ber breakages, the others are due to the physical bonds between the coatings, the extracting phase, and the solid substrates. Low operating temperature and loss of coatings affects the performance and the life-times of the bers. Preparation of chemicallybonded SPME bers has been the center of attention for many researchers to overcome some of these problems.

2. Preparation of bers using sol-gel technology 2.1. Fundamentals of sol-gel technology Inorganic polymerization, better known as the sol-gel process, is a general method for preparing oxides by the wet route at room temperature. Sol-gel technology provides a resourceful approach to synthesize


0165-9936/$ - see front matter 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2011.11.004

Trends in Analytical Chemistry, Vol. 34, 2012


inorganic polymer and organicinorganic hybrid materials under extraordinarily mild conditions, so it can be used to obtain products of various sizes, shapes and formats (e.g., bers, lms, monoliths and monosized particles). This technology has found increasing applications in many areas, and, in analytical chemistry, it is used to prepare SPME bers. Sol-gel technology, developed by Malik and co-workers [2,3], can be an excellent alternative to conventional coating-preparation methods, due to its inherent advantages and performance. These include a single-step manufacturing process, material homogeneity at the molecular level, chemical bonding between the sorbent and the fused-silica surface, high thermal and solvent stability, and the porous structure of the hybrid material. Moreover, sol-gel organicinorganic hybrid materials provide desirable sorptive properties that are difcult to achieve using purely organic or inorganic materials. Fig. 1 shows the chemical transformations occurring during the main steps of the sol-gel process. Precursor, coating polymer, catalyst and deactivating agent (non-polar bers) are required for preparation of SPME sol-gel-based bers. Moreover, the functionality of the solid support is one of the main issues in preparing SPME bers using sol-gel technology. 2.2. Sol-gel technology for preparing SPME bers Research concerning the preparation of new SPME bers includes three sol-gel-based features in selecting (i) precursors, (ii) coating polymers, and (iii) modiers to achieve bers with specic physical capabilities and the desired polarity and selectivity. 2.2.1. Precursors. Sol-gel-based non-polar SPME bers were introduced by Malik et al. [2,3] to improve the performance of traditional bers. The protective polyimide coating was removed from a 1-cm end segment of a 200-lm o.d. fused-silica ber, and the exposed outer surface was coated with a bonded sol-gel layer of poly(dimethylsiloxane) (PDMS). They used methyltrimethoxysilane (MTMOS) as a precursor for preparing the chemically-bonded PDMS ber. Because of chemical bonding between the sol-gel PDMS coating and the fused-silica SPME bers, sol-gel-coated PDMS bers exhibit thermal stability greater than conventionallycoated PDMS bers. The sol-gel PDMS bers can be routinely used up to 320C (and higher) without any signs of bleeding, whereas conventionally-coated PDMS bers begin to bleed around 200C. Enhanced thermal stability of sol-gel-coated bers can overcome the sample-carryover problem often encountered in SPME of polar solutes with conventional PDMS bers. Sol-gel coatings possess a porous structure and reduced coating thickness that enhances extraction and mass-transfer rates in SPME. High-temperature conditioning of sol-gel-coated PDMS bers led to consistent

improvement in peak-area repeatability for SPME-GC analysis. Enhanced thermal stability allowed the use of higher injection-port temperatures for efcient desorption of less-volatile analytes and should extend the range of analytes that can be handled by SPME-GC techniques. Mackenzie explained that the sol-gel network originating from an alkyl derivative of tetraalkoxysilane (TAOS) precursor possesses a more open structure and can effectively minimize the stress during drying and cracking [4]. This is the reason for the choice of MTMOS as a precursor instead of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS). One of the most important advantages of the sol-gel route is the possibility of designing the material structure and properties through proper selection of the sol-gel precursor and other building blocks. Due to the great importance of the precursor to selectivity, allyloxy bisbenzo 16-crown-5 trimethoxysilane was rst used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) coating for SPME [5]. The extraction efciencies of the new coating for organophosphorous pesticides (OPs) were studied. The new crown-ether ber presented a larger response to OPs than the commercial bers when they were used to extract OPs from an aqueous solution at the same concentration and the same extraction conditions. An ultrathin phenyl-functionalized SPME ber coating was developed by sol-gel deposition to control the thickness of the ber coating [6]. PTMOS and MTMOS were the sol-gel precursors used at different proportions, together with different water contents, catalysts and reaction times. The lm thickness was in the range 0.2 1 lm and could not be increased by multi-coating processes, and, apparently, a dense, non-porous microstructure was obtained. This coating exhibited a strong hydrophobic character, as shown by the capability of extraction of long-chain and polar aromatic compounds, comparable to that of 100 lm PDMS and 65 lm carbowaxdivinylbenzene (CWDVB). Although the sol-gel technique has overcame some signicant shortcomings of SPME and capillary-microextraction (CME) techniques by providing an effective means of chemical immobilization for sorbent coatings, a narrow window of pH stability in silica-based materials should have been resolved. In 2004, Malik et al. [7] prepared sol-gel TiO2PDMS-coated capillaries and showed the possibility of using them in on-line CMEHPLC operation. This led to a signicant improvement in pH stability and extraction sensitivity. Sol-gel TiO2 PDMS-coated microextraction capillaries possess excellent pH stability and retain their extraction characteristics intact, even after prolonged treatment with highly alkaline (pH 13) NaOH solution. Direct chemical bonding of the coating to capillary inner walls provides these coatings with excellent solvent resistance, and makes sol-gel TiO2PDMS-coated capillaries very suitable for



Trends in Analytical Chemistry, Vol. 34, 2012

Figure 1. Chemical transformations occurring during the main steps of the sol-gel process.

on-line sample preconcentration in CME-HPLC analysis, as they were used effectively in the extraction of different classes of analytes with good sensitivity and run-to-run repeatability. Low-ppb and sub-ppb level limits of detection (LODs) were achieved for PAHs, ketones, and alkylbenzenes in CME-HPLC analysis using the sol-gel TiO2PDMS-coated microextraction capillaries in conjunction with UV detection (Fig. 2). A novel zirconia-based hybrid organicinorganic solgel coating was also developed for CME (in-tube SPME) in 2005 [8]. Zirconia possesses much better alkali resistance than other metal oxides (e.g., alumina, silica, and titanium). It is practically insoluble within a wide pH range (114) [911]. Zirconia also shows outstanding resistance to dissolution at high temperatures [12,13]. Besides the extraordinary pH stability, excellent chemical inertness and high mechanical strength are two other attractive features. Alhooshani et al. [8] used zirconium (IV) butoxide as the precursor and silanolterminated poly(dimethyldiphenylsiloxane) (PDMDPS) as the coating polymer. Alumina, due to its high surface area, mechanical strength, and thermal and chemical stability, has been widely used in sample purication and analytical separations. The surface chemistry of alumina is quite dif-

ferent from that of silica. Based on references reported, silica has a weak Brnsted acidity due to the silanol groups, while alumina provides Lewis acidity and basicity as well as low concentration of Brnsted-acid sites. Both Brnsted and Lewis acidbase characteristics are responsible for the chromatographic performance of alumina. Compared to silica, alumina is capable of both ion and ligand exchange. The ligand-exchange ability of alumina originates from the presence of Lewis-acid sites on the surface (i.e. coordinatively unsaturated Al3+, and water molecules or other easily displaced ligands coordinatively bonded to the sites). Lewis basic analytes containing polar functional groups (e.g., carboxylic, phenolic-OH or amino groups) can substitute for the surface hydroxyl group or coordinated water molecules and form complexes with the metal ions of the oxide surface, so ligand-exchange interaction can play an important role in selective extraction of these compounds by alumina-based hybrid materials. Preparation of alumina-based hybrid organicinorganic sol-gel sorbents from a highly reactive precursor, aluminum sec-butoxide, and a sol-gel-active organic polymer (hydroxyl-terminated polydimethylsiloxane) was reported in 2006 by Liu [14]. The selectivity and the efciency of this novel ber were investigated by analyzing polar

Figure 2. (A) Hydrolysis of titanium (IV) isopropoxide, and (B) polycondensation of hydrolysis product, titanium hydroxide.


Trends in Analytical Chemistry, Vol. 34, 2012


functional compounds (e.g., fatty acids, phenols, alcohols, aldehydes and amines). Although SPME sol-gel bers are becoming increasingly popular and can overcome the chemical and thermal instability of traditional bers, the easy breakage of SPME sol-gel bers is a major drawback. Although use of fused silica as substrate has many advantageous, it is also responsible for ber breakage. In recent years, preparation of unbreakable bers was the focus of many researchers. In 2006, the rst unbreakable SPME ber fabricated by sol-gel deposition was reported by Azenha et al. [15]. They used titanium wire as a new, unbreakable substrate and showed that, under suitable conditions, alkoxysilanes and hydrosilanes can form Ti-O-Si bonds. Before the deposition, titanium wire was immersed in 1 M NaOH for 1 h to increase the number of surface titanol groups and nally washed successively with 0.1 M HCl, water, and methanol. Then, PDMS was chemically bonded to the Ti wire by sol-gel technology. A ber with MTOMS precursor on the NiTi alloy as substrate was also prepared by Carasek et al. in 2008 as an unbreakable ber [16,17]. They described the use of zirconium oxide electrolytically deposited onto an NiTi alloy as a new substrate for sol-gel reactions. Electrolytically-coated ber with ZrO2 (NiTiZrO2) was proposed as an efcient, unbreakable substrate for poly(ethylene glycol) SPME coating using sol-gel reactions. Wires of NiTi were used as a support for electrodeposition of ZrO2. NiTi wires previously electrodeposited with ZrO2 were dipped into NaOH 1.0 mol L1 solution for 1 h for their surface activation, followed by neutralization by rinsing with hydrochloric acid 0.1 mol L1 and deionized water. This activation leads to a greater

exposure of the silanol groups to the silica rod, favoring chemical bonding between the support and the polymeric coating, which, in turn, leads to greater thermal stability of the ber. The applicability of the proposed NiTiZrO2PDMS ber was evaluated through extraction of benzene, toluene, ethylbenzene and o-xylene (BTEX) from the headspace of aqueous samples (Fig. 3). Recently, Bagheri et al. [18,19] developed a new way to prepare unbreakable CME and SPME bers. They used self-assembled monolayers (SAMs) to functionalize the substrate. SAMs are ordered monomolecular lms, which are spontaneously formed from immersing a solid substrate in a solution containing amphifunctional molecules. The amphifunctional molecule has a head group, which usually has a high afnity for the solid surface, a tail (typically an alkyl chain), and a terminal group that can be used to control the surface properties of the resultant monolayer. The molecular forces between the tails are primarily responsible for the order of the monolayer. The most extensively studied SAMs are silanes, which are used to modify hydroxyl-terminated surfaces, and organosulfur compounds. The afnity of sulfur for gold, platinum, copper and silver could therefore be used. There are several processes for preparation of unbreakable bers. First, Au wires with length 2 cm and thickness 240 lm, were prepared and immersed in piranha solution (H2SO4:H2O2, 3:1, v/v) for 10 min at 80C. Afterwards, the wires were washed with acetone in an ultrasonic bath for 10 min. The prepared Au wires were immersed in the solution of 3-(mercaptopropyl) trimethoxysilane (3MPTMOS) in ethanol with concentration of 103 mol L1 for 12 h. Afterwards, to introduce amino functionality to the surface, the modied

Figure 3. NiTiZrO2 surface-bonded sol-gel PDMS coating.



Trends in Analytical Chemistry, Vol. 34, 2012

gold substrates were dipped in a solution of 1.2 mL 3-TESPA in ethanol with concentration of 103 mol L1 and 30 lL triuoroacetic acid (TFA) and 20 lL water for 12 h. Next, the substrates were placed in an oven at 120C for 30 min. These two operations were repeated for three cycles to form a layer of 3-TMSPA on the ber. Then, 1 mg oxidized multi-wall carbon nanotubes (MWCNTs) were dispersed in a 1 mL sodium dodecylsulfate (SDS) solution (1%) for 30 min under sonication to prepare the MWCNT suspension. The pretreated bers were immersed in the MWCNT suspension for 4 h in a hot water bath (70C), then placed in a 120C oven for 30 min. This procedure was repeated three times until the coating reached the desired thickness. Finally, the coated ber was conditioned under the ow of dry nitrogen prior to the SPME experiments. Bagheri et al. also used the SAM-sol-gel technique to prepare unbreakable CME for on-line extraction of compounds in conjunction with high-performance liquid chromatography (HPLC) [19]. The inner surface of a copper tube, intended to be used as an HPLC loop, was electrodeposited by metallic Cu followed by the SAMs of 3MPTMOS. Then, polyethylene glycol (PEG) was chemically bonded to the OH sites of the SAM already covering the

inner surface of the copper loop using sol-gel technology. The homogeneity and the porous surface structure of the SAM and sol-gel coatings were examined using the scanning electron microscopy (SEM). Different precursors, which have been used in sol-gel SPME along with their advantages and disadvantages, are summarized in Table 1. 2.2.2. Coating polymers and modiers. Wang et al. [26] used PEG as the main sol ingredient to prepare a novel high-performance SPME ber in 2000. It showed a high sample capacity for both polar and non-polar compounds. After that, several attempts were made to obtain bers with different characteristics using different coating polymers and modiers. Crown ethers have been widely used as chromatographic stationary phases by other researchers, due to their good selectivity originating from their cavity structure and the strong electronegative effect of heteroatoms on the crown-ether ring. In 2001, Zeng et al. [27] used three crown ethers containing hydroxyl groups as a modier to coat the fused-silica rods using sol-gel technology, and the bers were investigated by extraction of aromatic amines from

Table 1. Different precursor and their advantages Precursor Methyltrimethoxysilane (MTMOS) Allyloxy bisbenzo 16-crown-5 trimethoxysilane Ultrathin phenylfunctionalized Titanium (IV) isopropoxide Zirconium(IV) butoxide Advantages Overcome problems associated with cracking and shrinkage of TEOS Overcome lack of enough selectively of precursors such as MTMOS and TEOS for extraction of organophosphorous pesticides Capability of extraction of long chain and apolar aromatic compounds pH-resistant It is practically insoluble within a wide pH range (114), outstanding resistance to dissolution at high temperatures, excellent chemical inertness and high mechanical strength High surface area, mechanical strength, thermal and chemical stability Both polar and nonpolar analytes were efciently extracted from aqueous samples on the same sol-gel dendrimer capillary and provided excellent detection sensitivity It is a bifunctional reagent, contains both methacrylate and alkoxysilane groups The cyanopropyl moiety in sol-gel CN-PDMS coatings provided effective extraction of highly polar analytes such as free fatty acids, alcohols, and phenols without requiring derivatization, pH adjustment or salting out procedures Selective for analysis of aromatic compounds, High porosity Impart polar moiety into the coating network for the extraction of polar compounds Disadvantages Lack of selectivity Ref. [2,3]


Having a dense, non-porous microstructure

[6] [7] [8]

Aluminum sec-butoxide Phenyl-terminated dendrimer with a triethoxysilyl root 3-(Trimethoxysilyl)propyl methacrylate (TMSPMA) 3-Cyanopropyltriethoxysilane

Lack of selectivity, tree-like branched architecture makes it difcult for coating modier and other stationary phases

[14] [20]

[21] [22]

Anilinemethyltriethoxysilane (AMTEOS) 3-(trimethoxysilyl) propyl amine (TMSPA)

[23] [24,25]


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aqueous samples with headspace SPME. These bers exhibited high thermal and solvent stability. The sol-gelderived hydroxydibenzo-14-crown-4-coated ber demonstrated the best afnity for several aromatic amine derivatives. The extraction ability showed no signicant decline after it was used 150 times. Open crown ether is also a type of non-cyclic polyether compound. The structural units of open crown ether are similar to that of cyclic polyether crown ethers. Open crown not only possesses the selectivity of crown ether, but also is easily synthesized and is non-toxic [28]. Calixarenes are regarded as the third generation of supramolecules next to crown ethers and cyclodextrins. They are a class of cyclic oligomers prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions. Considering the outstanding capacity of the calixarene as receptors, mainly based on their variable chemical modication potential and their conformational pliability allowing a kind of induced t to the shape of suitable guest molecules, a sol-gel-coated calix[4]arene ber was rst developed by Zeng et al. [2932]. Carbon-based materials are regarded as good sorbents and have been widely used in trapping and separating organic compounds. There are also some reports about using carbon materials as SPME bers {e.g., polycrystalline graphites [33], modied pencil lead [34], activated carbon [35]}. Hydroxyfullerene as a novel coating was also reported [36]. Fullerene has a unique spherical shape, a conjugated three-dimensional p-electronic system, is used as stationary phase for LC and GC, and has shown a wide range of operational temperatures, good thermal stability and good selectivity for aromatic compounds, especially exhibiting strong afnity for planar polychlorinated biphenyl (PCB) molecules. In recent years, ionic liquids (ILs) have gained popularity in a number of elds, due to their perceived advantages over traditional solvents. They are considered green because they are remarkably less hazardous than their conventional counterparts, due to negligible vapor pressures, low ammability, good thermal stability, tunable viscosities, low corrosion tendencies, and varying degrees of solubility with water and organic solvents. IL-mediated sol-gel sorbents was rst reported by Malik et al. [37,38] for CME. ILs were used as co-solvents and as porogens in the sol-gel system. The advantages of using ILs as solvents for reactions include their ability to be recycled, high thermal stability, and the improved stability of reactants in ILs. The advantages of ILs as porogens, instead of organic molecules in sol-gel systems, include the effect that the cation and the anion portions of the IL have on pore structure and distribution, and the ability of ILs to decompose from sol-gel systems without leaving residues behind. Their investi-

gation revealed that, for PDMS sol-gels, the addition of a phosphonium-based IL, trihexyltetradecylphosphonium tetrauoroborate (TTPT), slowed down gelation by about 1.5 h in comparison with the sol-gel that did not contain the IL. The slower gelation in the IL-mediated sol-gels can be attributed to the increased viscosity of the sol solution due to the addition of the IL. It is reasonable to assume that the IL did not play a role in extractions, since the thermal decomposition temperature of TTPT is 190C, and the IL-mediated sol-gel PDMS microextraction capillaries were heated in an inert environment to 300C. It can therefore be safely assumed that, during thermal conditioning, the IL had decomposed and the decomposition products were at least partially removed from the capillary with the purging helium ow. The preconcentration abilities of the two types of solgel PDMS capillaries (PDMS-IL and PDMS-no IL) were also compared to determine the effect of the IL on the resulting sol-gel coating. Results showed that the sol-gel PDMS-IL coating provided signicantly greater extraction capability than the PDMS-no IL. This, in turn, translated into lower LODs for the sol-gel PDMS-IL microextraction capillary. Malik et al. [37,38] also prepared IL-mediated polar sol-gel microextraction capillaries: PEG, polyTHF, and BMPO in conjunction with BMPT (NButyl-4-methylpyridinium tetrauoroborate) and TTPT. The PEG-IL sol-gel coating appeared to be more porous than its counterpart prepared without IL. Sol-gel coatings with greater porous morphology obtained with the help of ILs can be expected to provide better performance in extraction. Bonded IL polymeric material for SPME GC analysis was reported by Shirey et al. [39]. In this work, attention was devoted to the extraction of hydrophilic and polar compounds (e.g., short-chain alcohols and amines). For this purpose, completely new and different ILs were prepared and tested as coatings for SPME. To reduce contamination and/or loss of adsorbent, the different IL derivatives were covalently bonded to silica microparticles that were subsequently used to prepare a porous, mechanically strong ber coating. Both headspace and immersion techniques were tested to evaluate the capabilities of the newly developed bonded IL-based sorbents with a large variety of polar solutes. Four new IL were prepared and bonded onto 5 lm silica particles for use as coatings in SPME. Two ILs contained styrene units that allowed for polymerization and greater carbon content of the bonded silica particles. Two polymeric ILs differing by their anion were used to prepare two SPME bers that were used in both headspace and immersion extractions and compared to commercial bers. In both sets of experiments, ethyl acetate was used as an internal standard to take into account coating volume differences between the bers. The polymeric IL bers are very efcient in headspace SPME for short-chain alcohols. Immersion SPME could also be used with the IL bers for



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short-chain alcohols as well as for polar and basic amines that can be extracted at pH 11 without damage to the IL-bonded silica particles. The sensitivities of the two IL-based bers differing by the anion were similar. The mechanical strength and the durability of the polymeric IL bers were reported to be excellent. Nowadays, reaching lower LODs is one the main challenges, and much research has been focused on it. CNTs are a new type of carbon material rst found in 1991 by Iijima [40]. It can be described as a graphite sheet rolled up into a nanoscale tube of single-wall carbon nanotubes (SWCNTs) or with additional graphite tubes of MWCNTs. Because of their unique geometrical structure, CNTs exhibit excellent mechanical and thermal properties. For example, the highly developed hydrophobic surface of CNTs showed strong sorption property towards various compounds compared with a planar carbon surface [41]. MWCNTs have been characterized as superior sorbent for removing dioxins for environmental protection. CNTs have a curved surface, so they are expected to show a stronger binding afnity for hydrophobic molecules compared with a planar carbon surface. Furthermore, the internal pores of the CNTs are large enough to allow molecules to penetrate. A large sorption surface is also available on the outside and in the interstitial spaces within the nanotube bundles. All these indicate that CNTs have a great ability to physically adsorb hydrophobic organic pollutants. MWCNT-coated bers for SPME were rst introduced by Yan et al. [42] to extract polybrominated diphenyl ethers from water and milk samples before gas chromatography (GC) with electron-capture detection. A novel MWCNT-bonded fused-silica ber for SPME GC analysis of phenols in water samples was also reported by Jiang [43]. Fig. 4 shows the preparation process of MWCNT-SPME bers. Table 2 shows different

coating polymers and modiers that have been used in sol-gel-based SPME.

3. Preparation of bers with molecularlyimprinted polymers (MIPs) 3.1. Fundamentals of the MIP method The principle of molecular imprinting was inspired by Fischers lock-and-key metaphor. In the rst step, the selected key molecule is mixed with lock building blocks. The building blocks and the key are allowed to associate with each other, rmly or loosely. The complexes so formed between the key and the building blocks are subsequently glued together in order to x the buildingblock positions around the key. Removing the molecular key then leaves a construction which, if everything works properly, is selective for the original key. In molecular imprinting, molecules are used to create the marks or imprints, normally within a network polymer. A number of expressions have been used in the past to describe the present technology (e.g., enzyme-analogue built polymers, host-guest polymerization, template synthesis or template polymerization, creation of footprints, and preparation of specic adsorbents). In molecular imprinting, the key molecules described above can be denoted by a variety of expressions [e.g., templates (T), template molecules, target molecules, analytes, imprint molecules, imprint antigens or print molecules], any of which is frequently encountered. The lock building blocks are normally called functional monomers (M), although polymers have also been used as imprinting building blocks. The molecular glue used to x the key-building block complexes is almost always perceived as a crosslinker (X) or a crosslinking monomer. The entire imprinting procedure is performed in a

Figure 4. Preparation process of the multi-walled carbon nanotube (MWCNT)/ber.


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Table 2. Different coating polymer and modifier and their advantages Coating polymer or modier Polyethylene glycol (PEG) Crown ethers Advantages High sample capacity for both polar and non-polar compounds Good selectivity resulting from its cavity structure and the strong electronegative effect of heteroatoms on the crown ether ring Outstanding capacity Chemical resistance and low cost High partition coefcients (381 for benzene and 1340 for o-xylene) Wide operational temperature, good thermal stability and good selectivity for aromatic compounds, especially exhibited strong afnity for planar PCB molecules Low LOD High extraction efciency, excellent mechanical strength and durability (extraction at pH 11 without damage) Has high hydrophobic doughnut-shaped cavity Excellent SPME characteristics For the extraction of both non-polar and polar organic compounds High surface area, higher enrichment factor High surface area, high extraction efciency, thermal stability [26] [27,28] Ref.

Calixarenes Polycrystalline graphites (pencil lead and glassy carbon) Activated carbon Fullerene

[2932] [33,34] [35] [36]

Ionic liquid-mediated sol-gel Bonded ionic liquid SPME

[37,38] [39]

Permethylated-b-cyclodextrin Amphiphilic and hydrophilic oligomers Single and multi-wall carbon nanotubes (CNTs) Nanocomposites

[44] [45]

[42,43,4649] [5054]

solvent that can be denoted porogen, since one of its functions is to ll the space between the aggregated network polymers so as to induce a porous construction [55]. 3.2. MIP-based SPME The combination of MIP and SPME technique provides a powerful sample-preparation tool in terms of selectivity, simplicity, and exibility. The rst attempt to use MIP in CME (in-tube SPME) was reported by Mullett et al. [56]. An automated, online MIP-SPME method was developed for the determination of propranolol in biological uids and showed improved selectivity compared to in-tube stationaryphase materials, so overcoming the limitations of then existing SPME coating materials. Preconcentration of the sample by the MIP adsorbent increased the sensitivity, yielding low LODs. Koster et al. [57] reported the rst work dealing with the use of MIP coatings on SPME bers. A silica SPME ber was silanized, followed by in-situ synthesis of the MIP on the external surface of the ber. They prepared the MIP-based SPME ber using clenbuterol as a template and demonstrated the possibility of selective extraction of brombuterol. This ber was brittle and the MIP coating stripped during withdrawal of the ber in the needle.

Djozan et al. [58,59] used a monolithic MIP with SPME for selective extraction of diacetylmorphine and analogous compounds. This was the rst publication of MIP-SPME followed by GC. The ber prepared was monolith and exible enough to be placed in a homemade syringe and inserted into a GC or a GC-MS injection port. The MIP was prepared through thermal radical copolymerization of MAA and EDMA in the presence of DAMO as template, and acetonitrile (ACN) and azobis(isobutyronitrile) (AIBN) were also used as solvent and initiator, respectively. For preparation of bers, the pre-polymer solution was poured into a test tube and capillary home-made glass as mold was inserted into tube and the mixture was cured. Polymeric monolith was then withdrawn from the mold. Pulling out MIP and non-imprinted polymer (NIP) bers from capillary homemade glass used two methods: (1) the capillaries were immersed in 40% hydrouoric acid (HF) for 2 h, and, after dissolving the glass capillary, the polymeric bers were washed with distilled water; (2) the bers were mechanically withdrawn from mold. Djozan et al. also compared the extraction efciency of MIP with that of NIP. A novel MIP-coated SPME ber that could be coupled directly to HPLC was prepared by Hu et al. [60,61]. Prior to the coating procedure, the bers were silylated by



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immersing them into a 10% (v/v) 3-(methacryloxy) propyltrimethoxysilane solution in acetone at room temperature for 1 h. Fig. 5 shows the pretreatment of fused silica and the MIP-coating process. A simple approach for preparation of bisphenol A (BPA) MIP-coated SPME bers was developed by Tan et al. [62]. A capillary was inserted into a larger bore capillary to form a sleeve as mold. The prepolymer solution, which comprised BPA, acrylamide (AM), 3(trimethoxysilyl)propyl methacrylate (TRIM), AIBN and ACN, was introduced into the interspace between the two capillaries, followed by polymerization under UV photoirradiation. The larger bore capillary was etched away with hydrouoric acid after the polymerization (Fig. 6). A carbon monolith was also prepared by Feng et al. [63] and applied as the SPME ber. The carbon monolith was synthesized via a polymerizationcarbonization method, styrene and divinylbenzene being adopted as precursors and dodecanol as a porogen during poly-

merization. The resultant monolith had a bimodal porous substructure, narrowly distributed nano-skeleton pores and uniform textural pores or through pores. The carbon monolith was directly used as an extraction ber for the extraction of phenols followed by GC-MS. The resulting carbon monolith was demonstrated to be a favorable SPME ber for extracting phenols as model analytes, while high extraction capacity, shorter extraction time and long lifespan could be achieved.

4. Electrochemically-prepared SPME bers 4.1. Oxidized metal-based SPME bers In 2001, Djozan et al. [64] reported an anodized aluminum wire as an SPME ber. Aluminum wires were anodized by direct current in a solution of sulfuric acid at room temperature and were conditioned at 300C for 30 min. These bers were used for the extraction of some aliphatic alcohols, BTEX and petroleum products from

Figure 5. Preparation of molecularly-imprinted polymer, solid-phase microextraction (MIP-SPME) ber.


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Figure 6. Preparing molecularly-imprinted polymer (MIP)-coated solid-phase microextraction (SPME) bers.

gaseous samples. The results obtained proved the ability of anodized aluminum wire to be a ber for sampling organic compounds from gaseous samples. This behavior could be due to the porous layer of aluminum oxide, which is formed on metal surfaces. This ber was rm, inexpensive, durable and simple to prepare. Djozan et al. also reported anodized zinc wire as an SPME ber [65]. Zinc oxide is an interesting metal oxide and can be produced easily. It has considerable adsorptive and catalytic behavior. For preparation of ber, zinc metal with high purity was washed with dilute detergent solution and distilled water. The wire was used in three forms: (1) polished wire without ZnO wire; (2) wire oxidized in air; and, (3) anodized zinc wire. Type (1) ber was prepared with mechanical polishing before use. Type (2) ber was prepared with exposure to air for a long time. A thin layer of ZnO was formed in this way. For preparation of type (3) ber, the zinc wire was anodized in a stainless-steel cell containing 0.2 M NaOH solution as electrolyte at a controlled potential of 20 V for 20 min. The zinc wire and cell wall were used as the anode and cathode, respectively. Comparison of these bers showed that the ZnO layer formed on the surface of zinc wire has a major role in adsorption of the analytes with these bers. However, when the zinc wire was anodized, the extraction efciency was increased dramatically. The thickness and the porosity of the oxide layer were increased substantially during the anodizing process. In-loop SPME coupled with HPLC using this method was also reported by the same authors [66,67]. 4.2. Conductive polymer-based SPME bers Conductive polymers are organic materials that generally possess an extended conjugated p-electron system along a polymer backbone. They are versatile materials

in which molecular/analyte recognition can be achieved in different ways, including: (1) incorporation of counter ions that introduce selective interaction of counter ions; (2) use of the inherent and unusual multifunctionality (e.g., hydrophobic, acidbase and pp interactions, polar functional groups, ion-exchange, hydrogen bonding, electroactivity) of the polymers; (3) introduction of functional groups to the monomers. These materials can be easily synthesized in both aqueous and non-aqueous medium, chemically and electrochemically; there are various types of dopant and additives for use in synthesis. All these conditions and varieties affect the chemical, mechanical, morphological and electronic properties of the polymers. These polymers can be synthesized from a wide range of commercial monomers, which could lead to many polymers having different properties. Application of SPME for extraction of ionic species has been limited since the neutral charge of commercially available SPME coatings result in a low coating/sample partition coefcient and poor analyte recoveries. To overcome this difculty, chemical modication of the sample or ber surface by derivatization or addition of complexing agents (e.g., crown ethers) has been developed to increase the extraction efciency [68]. These reactions can require expensive, toxic reagents and produce unstable products, and the procedures are often time consuming and labor intensive. Electrochemically-aided control of SPME (EASPME) using a conducting polymer for ionic species has been developed by Ceylan et al. [69] as the extraction phase to address the above issues. This work described the use of an SPME method with poly(3-methylthiophene) coated platinum micro-ber electrodes to extract arsenate ions from aqueous solutions without derivatization. The bers were fabricated by cycling the working electrode between 0.20 and +1.7 V (versus Ag/AgCl) in an ACN



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solution containing 50 mM 3-methylthiophene monomer and 75 mM tetrabutylammonium tetrauoroborate (TBATFB) electrolyte. All electrochemical procedures (extraction and expulsion) were conducted in a threeelectrode system. After fabrication, the conducting polymer lm was immersed in the sample solution and converted to its oxidized, positively charged form by applying a constant potential of +1.2 V with respect to

the Ag/AgCl reference electrode. Arsenate ions migrated into the lm to maintain electroneutrality. Upon subsequent reversal of the potential to 0.60 V versus Ag/ AgCl, the polymer lm was converted to its reduced, neutral form, and the arsenate ions were expelled into a smaller volume (200 lL) of de-ionized water for analysis using ow injection with inductively coupled plasma mass spectrometric (ICP-MS) detection. Fig. 7 shows the

Figure 7. Mechanism of polymerization of monomers (e.g., thiophene and pyrrole).


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mechanism of polymerization of monomers, such as thiophene and pyrrole. Pawliszyn et al. [70] also coated polypyrrole (PPy) and poly-N-phenylpyrrole (PPPy) on the surface of metal wires by an electrochemical method. These coated wires have been used for SPME of volatile organic compounds. They also reported polypyrrole-coated capillary in-tube SPME coupled with LC-electrospray ionization mass spectrometry for the determination of b-blockers in urine

and serum samples [71]. Due to the inherent multifunctional properties of PPy, primarily pp interactions, baseacid interactions, and interactions from polar groups and hydrogen bonding, PPy coating can be used for SPME of a large range of analytes. The rst example of coupling SPME to ion chromatography (IC) was reported by Pawliszyn et al. [72]. The two new coatings showed different selectivities to various organic compounds (e.g., the PPPy coating had

Table 3. Summary of some applications of fibers Fiber type Sol gel-based Analytes Polycyclic aromatic hydrocarbons (PAHs) Organophosphorus pesticides (OPs) Phenols (Halophenols, Dimethylphenols, cresol, . . .) Aldehydes Ketones Alkylbenzenes Amines Estrogens Polychlorinated biphenyls(PCBs) Esters Bisphenol A (BPA) Polybrominated diphenyl ethers (PBDEs) Alcohols Fatty acids Antiestrogens Haloanisoles Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) Propranolol Clenbuterol Diacetylmorphine Triazine Tetracyclines Bisphenol A (BPA) 8-Hydroxy-2 0 -deoxyguanosine 17b-Estradiol Electrochemically assisted Oxidized metals-based Alkylbenzenes, alcohols Thiophenols Phenol and biphenyl L-Dopa and L-Dopamine Arsenate ions VOCs b-blockers Inorganic anions Cationic analytes Phenols Organochlorine pesticides PCBs PAHs Fluoxetine and noruoxetine enantiomers Matrix Water samples Water samples Water samples Water Water Water Water Water Water samples samples samples samples samples samples Ref. [2,7,8,19,20,22,30,45,54,76] [5,18,25] [2,6,14,16,20,22,24, 31,38,43,50,55,78] [6,8,14,20,22,37,38,51] [15,20,22,37,38,51] [6,7,15,17,23,26,28,30,51,52,78] [14,22,27,29,30,36,38,50] [45] [36] [16,21,28,32,79] [45] [42,44] [14,20,21,37,38] [14,21,22,38] [77] [80] [49,53]

Water and beer Water samples Water and milk Water and beer Water and beer Biological samples Cork stopper Urine


Urine and plasma Urine Water samples Water, rice, onion, soy bean, corn, lettuce and soil Chicken feed, chicken muscle and milk Water, urine and milk Urine Fish Gaseous samples Gaseous samples n-Hexane Aqueous solutions Water samples Water samples Urine and serum Water samples Water samples Water samples Water samples Water samples Water samples Human plasma

[56,82] [57] [58] [59,60] [61] [62] [81] [83] [64] [65] [66] [67] [69] [70] [71] [72] [73] [74,47] [75] [84] [85] [86]

Conductive polymers-based



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better selectivity to aromatic compounds than the PPy coating, due to the phenyl group incorporated into the polymer). This demonstrated that the selectivity of the coating can be modied by introducing a new functional group into the polymer. A metal wire (platinum, gold or stainless steel) was inserted into the needle of a Hamilton syringe and attached to the plunger. Polypyrrole (PPy) was directly prepared onto the surface of the working electrode from a 0.1 M tetrabutylammonium perchlorateACN solution containing 0.1 M corresponding monomer. A constant deposition potential (1.0 V) was applied using a potentiostat. In 2002, Ceylan et al. [73] used EASPME conductingpolymer-lm material for extraction of cationic analytes. They used a PPy lm with sulfated b-cyclodextrin (SbCD) as the dopant anion. The resulting poly(pyrrole-sulfated b-cyclodextrin) (PPy-SbCD) lm contained a very large excess of the sulfate anion sites, far above that necessary as the counter ions compensating the positive charge of the cation radicals of oxidized PPy. The SbCD molecules are permanently trapped in the PPy matrix and made it a high-capacity cation-exchanger lm. In 2005, an aniline-based polymer was electrochemically prepared and applied as a new ber coating for SPME by Bagheri et al. [74]. A platinum wire was inserted into the needle of a homemade syringe and attached to the plunger. The polymer lm was directly electrodeposited on the platinum-wire surface in sulfuric-acid solution using a CV technique. Electrochemical deposition was performed using a three-electrode CV system by oxidation of 0.1 M aniline solution in 1.0 M H2SO4 under the nitrogen atmosphere. Prior to the polymerization procedure, the platinum-wire surface was chemically cleaned in acetone using an ultrasonic bath for 15 min and was subsequently washed with distilled water. The platinum wire (1 cm 240 mm i.d.) was used as the working electrode; a platinum rod and an Ag/AgCl electrode were employed as the counter electrode and the reference electrode, respectively. The CV system was operated using a scan rate of 25 mV/s at a potential range of 0.650.9 V, and the number of scans was set at 10. The ber was then washed by distilled water so that unwanted chemicals (e.g., monomers and the supporting electrolyte) were removed. The ber was dried under a gentle stream of nitrogen, preheated at 80C for 30 min and then inserted into a GC injector at 200C for 1 h while the helium gas was owing. The prepared ber was successfully applied for extraction of some priority phenols from water samples. In 2009, Zhao et al. [47] reported a novel MWCNT polyaniline composite lm-coated platinum wire for headspace SPME-GC determination of phenolic compounds. The electrodeposited coating had a porous structure, with high specic surface area and adsorption capacity, so it had high extraction efciency for phenolic 138

compounds. Due to chemical binding between the Pt substrate and the coating, and the interaction of polyaniline with the MWCNTs, the probe also showed high thermal stability (up to 320C) and excellent re-usability. In addition, the probe had the advantages of easy preparation and low cost. Polyphosphate-doped polypyrrole coated on steel ber was also reported by Noroozian et al. [47]. The process of electrodepositing polyphosphate-doped PPy on steel ber was very simple and inexpensive. The coating produced showed much greater thermal stability than PPy coatings doped with other counter ions. The thermal stability of PPy/polyphosphate was even greater than that of PDMS, PA, and Carbowax/PDMS commercial coatings commonly used. These characteristics made possible the SPME/thermal desorption of highly involatile compounds. The coating also showed long lifetime with excellent adhesion onto the steel surface. Some typical applications of the prepared bers by the mentioned methods are shown in Table 3. 5. Conclusion and future trends Nowadays, preparing unbreakable, chemically and thermally stable SPME bers, overcoming the main problems of conventional bers, has been attained using new techniques (e.g., sol gel, MIP and electrochemically assisted). These techniques can create chemical bonds between coating polymers and substrates. Unbreakable bers can also be prepared by metal substrates that are already functionalized by different techniques (e.g., SAMs). SPME bers prepared by sol-gel methods are not selective to target analytes, and bers obtained by the MIP technique do not have such rigid, strong structures as bers prepared by sol-gel methods, which is easier, more controllable and cheaper than the MIP technique, so coupling these methods together seems to be a new trend in SPME bers. Preparing sorbents by the sol-gel MIP technique will probably be the focus in future for synthesizing selective, stable bers under the mild conditions that might be used for relatively complex biological samples. References
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