New extraction media in microextraction techniques. A review of reviews

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Review Article

New extraction media in microextraction techniques. A review of reviews Vahid Jalilia, Abdullah Barkhordarib, , Alireza Ghiasvandc,d ⁎

a

Student Research Committee, Department of Occupational Health Engineering, School of Public Health and safety, Shahid Beheshti University of Medical Sciences, Tehran, Iran Department of Occupational Health Engineering, School of Public Health, Shahroud University of Medical Sciences, Shahroud, Iran c Australian Centre for Research on Separation Science (ACROSS), School of Natural Sciences, University of Tasmania, Hobart, Tasmania 7001, Australia d Department of Chemistry, Lorestan University, Khoramabad, Iran b

ARTICLE INFO

ABSTRACT

Keywords: New extraction media Microextraction techniques Review

Sample preparation is considered one of the most critical steps in the analytical process. Conventional sample preparation techniques suffers from both a lack of selectivity and consuming large amounts of organic solvents. In recent years, the development of microextraction techniques (METs) for sample preparation has led to improved analytical figures of merit including recovery, precision, linearity, limit of detection, and limit of quantification. In addition, these techniques are inexpensive, reusable, solvent-minimized, and reduce the analysis time. It is well known that, the efficiency of METs mainly depends on the choice of a suitable extraction media. Over time, many review articles have focused on the application of different extraction media in METs. This article, summarizes the review publications describing new extraction media in METs along with the different aspects and areas of application.

1. Introduction Sample preparation is one of the important steps in the analysis of samples. The objectives of this step are 1) to minimize the complexity of the sample and 2) to eliminate matrix interferences before being entered into detecting devices. However, sample preparation is the step most likely to cause problems, such as the consumption of time, cost, and low extraction yields [1,2]. For these reasons, many analysts refer to this stage as the Achilles' heel of the process of analyzing samples [3]. The current conventional sample preparation methods are not consistent with the goals of green analytical chemistry, because they consume large amounts of organic solvents and produce hazardous wastes that are disposed in the environment [4]. To meet the requirements of green analytical methods and to improve extraction efficiency, microextraction techniques (METs) have been introduced as the latest green techniques to replace conventional sample preparation and extraction methods [5]. In fact, METs have eliminated or reduced the drawbacks of conventional sample preparation approaches while still providing all of their benefits. Generally, METs are based on the miniaturization of the basic extraction modes, such as solid phase extraction (SPE) and liquid-liquid extraction (LLE) [6,7]. Even though METs can differ widely, they have common properties, e.g., they improve extraction efficiency, require less time, generally are automated, consume less hazardous solvents, and are eco-friendly [8]. It is well known that the ⁎

choice of a suitable extraction phase is one of the critical factors that affect the efficiency of METs. Currently, many sorbents and solvents are used as extraction media in METs [9]. New discoveries in materials science may provide new tools for the preparation of analytical samples. In recent years, nanostructure materials have resulted in the improvement of existing analytical procedures and the development of new procedures [10,11]. Also, the application of new solvents in liquidphase microextraction (LPME) techniques has increased remarkably because they achieve better extraction efficiency [12]. Table 1 summarizes the advantages and the drawbacks of the new extraction media described in this review. Numerous articles that have been published in recent years have reviewed the applications of new extraction media in METs (Table 2). Therefore, the aim of this paper is to present, for the first time, a comprehensive overview of review articles that have been published that are related to the application of new extraction media in METs. 2. Historical overview and principles of microextraction techniques Overall, METs can be classified into two main categories (Fig. 1): techniques based on solid phase extraction and techniques based on liquid phase extraction. METs based on solid phase include solid phase microextraction (SPME), in-tube SPME, and needle trap device (NTD)

Corresponding author. E-mail address: [email protected] (A. Barkhordari).

https://doi.org/10.1016/j.microc.2019.104386 Received 9 September 2019; Received in revised form 29 October 2019; Accepted 29 October 2019 0026-265X/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Vahid Jalili, Abdullah Barkhordari and Alireza Ghiasvand, Microchemical Journal, https://doi.org/10.1016/j.microc.2019.104386

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Table 1 Strengths and weaknesses of new extraction media. New extraction media Solid extraction media

Liquid extraction media

Advantages ■ High porosity ■ Durability (MIPs) ■ Good reusability (MIPs) ■ Thermal stability ■ Capability of being functionalized (CNTs) ■ High reproducibility (Graphene) ■ High specific surface area ■ Low-cost synthesis ■ Mechanical stability ■ Extremely small size ■ Tunable pore size (MOFs) ■ Surface modifiability ■ High fracture strength ■ Excellent conductivity ■ High adsorption capacity ■ Low cost ■ High purity ■ Thermal stability ■ Non-flammability ■ Tunable miscibility ■ Multifunctionality ■ Biodegradable component ■ Environmental friendliness ■ Negligible vapor pressure ■ High extraction capability for various analytes ■ Chemical inertness in contact with water ■ Less vaporization of extraction solvent due to its high viscosity (DESs)

Disadvantages ■ Difficulty in leaching the entire template (MIPs) ■ Leakage of template molecule (MIPs) ■ Insolubility (CNTs) ■ The polydispersity of graphene sheets (Graphene) ■ Aggregation (Graphene) ■ Moisture sensitive (MOFs) ■ Problems in obtaining uniform particle size and shape ■ Causing high pressure in NTD and consequently hamper extraction due to small particle size

■ ■ ■ ■

Preparation of ILs are difficult, costly, complicated and time consuming Possible toxicity Some of DESs at room temperature aren't liquid or are very viscous Difficulty in mass transfer (DESs)

techniques are well suited to meet requirements of the nowadays green analytical methods [9,29].

[13–15]. Different types of METs based on solid phase are presented in Fig. 2. Pawliszyn et al. introduced the SPME technique in 1990 [16]. This technique involves partitioning the analyte between the sample and the extracting phase (solid sorbent) fixed on a fused-silica fiber [17,18]. Pawliszyn et al. also introduced the in-tube SPME technique in 1997 for application in high-performance liquid chromatography (HPLC) [14]. This technique utilizes an open tubular column in the extraction phase, which leads to increased sensitivity [14,19]. Although SPME is a solvent-free technique, but it suffers from some drawbacks, such as fiber fragility, limited sorption capacity, expensive coated fiber, and memory effects [20,21]. To address these problems, Pawliszyn and colleagues developed the NTD technique in 2001 [15,20,21]. In this technique, a stainless steel needle loaded with a suitable sorbent is used for sampling and analysis of various compounds [17,22]. After sampling, the compounds are thermally desorbed by placing the sampler into the injection port of the gas chromatography (GC) [23]. The NTD technique has been successfully applied in the analysis of various samples. Among the advantages of this technique, it is solvent-free, reusable, inexpensive, and easy to automate and miniaturize [9]. As shown in Fig. 3, METs based on liquid phase can be classified into three main categories including single-drop microextraction (SDME), hollowfiber liquid phase microextraction (HF-LPME), and dispersive liquid–liquid microextraction (DLLME) [24]. In 1996, Jeannot et al. introduced SDME for organic compound analysis. In this straightforward technique, a micro-drop of the solvent is suspended from the tip of a syringe and then immersed in a sample solution in which it is immiscible or suspended in the headspace above the sample [25]. In 1999, Pedersen et al. introduced HF-LPME. In this technique, the extraction phase is placed inside a porous hollow polypropylene fiber due to its mechanical protection and capability to improve LPME stability and reliability. In addition, the porous hollow fiber prevents loss of the extraction phase into the sample [26]. DLLME is based on the use of a dispersive extraction solvent. The extraction solvent is dispersed in an aqueous sample, which enables formation of droplets of the extractant. This process increases the speed of the transfer of analytes from the sample into the extraction phase [27,28]. In all METs, the extraction process is based on the transmission of the analytes of interest from the sample into the acceptor phase (liquid or solid phase). All of these

3. New solid sorbents in microextraction techniques 3.1. Carbon nanotubes In 1991, carbon nanotubes (CNTs) were introduced by Iijima as a new member of the carbon family. Generally, CNTs can be classified into two main categories, i.e., multiwall carbon nanotubes and single wall carbon nanotubes [30,31]. Over the last few decades, these materials have become an important part of multidisciplinary research due to their unique properties and wide range of applications [32]. Their unique properties include high tensile strength, large surface area, thermal conductivity, stability and resilience, and their ability to establish different types of interactions with organic and inorganic compounds. These unique properties make CNTs suitable as a sorbent [33,34]. To date, CNTs have been the most used carbon-based nanomaterials in sample preparation techniques, and a large number of research and review papers have been published in this field. [34–36]. Zhang et al. reviewed the applications of different carbon-based nanomaterials, including CNTs, graphene, carbon nanofibers, fullerenes, carbon nanocones-disks in sample preparation. In this review, the characteristics and future trends of these materials were discussed [37]. Different techniques for the application of CNTs in SPME coatings have been reviewed by Ghaemi et al. whose review included sections that address the CNT-based coatings of SPME fibers, a comparison of the different coating methods, advantages and the disadvantages of these coating, and future perspectives of CNTs in SPME coatings [38]. The application of CNTs in separation techniques were reviewed by Pyrzynska et al. This review examine a number of application of CNTs in preconcentration and enrichment using SPE and METs [39]. Kędziora et al. focused on sorbents used in NTD technique. The extraction sorbents discussed include the commercially sorbents, synthetic sorbents such as polymers and nanoparticles. This article also reviewed the application of CNTs as sorbents in NTD [40]. Song et al. reviewed the configurations of CNT based SPME techniques and their application in environmental analysis [41]. 2

3

f

e

d

c

b

a

SPME SPME SPME, In-tube SPME SPME SPME, In-tube SPME, NTD SPME SPME, In-tube SPME SDME, DLLME, SPME SDME, DLLME SDME, DLLME DLLME SDME, HF-LPME, DLLME

MIPs, MOFs, CPs

Graphene

Graphene CNTs, MIPs, Graphene, MOFs

Different types of aerogels

ILs

MILs

DESs

ILs, DESs

Zeolites ILs ILs

METs SPME NTD SPME, LPME

New extraction media CNTs CNTs MIPs

Polycyclic aromatic hydrocarbons. Benzene, toluene, ethylbenzene and xylenes. Volatile organic compounds. Very volatile organic compounds. Semi-volatile organic compounds. Polychlorinated biphenyls.

Liquid phase

Extraction phase Solid phase

Extraction of VOCs, SVOCs, metals, biological metabolites, and cationic dyes from environmental, biological, and industrial samples Extraction of VOCs, SVOCs, hormones, estrogens, food additives, and noble metals from air, water, and biological samples Extraction of VOCs, organophosphorus pesticides, DNA sequences, PCBsf and acrylamide, organic UV filters, benzodiazepines, and phthalates from environmental, biological, and food samples Extraction of PAHs, organic pollutants, pharmaceutical drugs, sequence specific DNA, free fatty acids, uric acid and dopamine, diclofenac, and isoprenaline from water, urine, blood, plasma, milk, cell lysate and DNA samples Extraction of triazenes, heavy metals, PAHs, parabens, estrogens, herbicides, hydrocarbons, alkylphenols, and a preservative from vegetable oil, honey, water, urine, oilseeds and aqueous samples Extraction of trace curcumin, heavy metals, benzoylurea insecticides, triazine herbicides, amoxicillin and ceftriaxone, benzophenone, and drugs from food, environmental samples, honey, vegetable oils, hospital sewage, aqueous, and biological samples Extraction of arsenic species from water, edible oils, fruit juice, urine, whole blood, serum, hair, cigarette, rice, fish, and tea samples.

Application of METs based on new extraction media Extraction of phenobarbital, metals, PAHsa, Pyrethroids, herbicides, BTEXb, and various pesticides from environmental samples Extraction of VOCsc, VVOCsd, BTEX, Phthalates, PAHs, and thiol compounds from air, water, blood, urine, plasma, and garlic samples Extraction of triazines, methadone, parabens, ofloxacin, organophos- phorouspesticides, phenolic compounds, and endosulfan from water, human plasma, environmental solid, milk, fruits, and aqueous samples Extraction of PAHs, phenolic compounds, pesticides, halogenated aromatic hydrocarbons, pharmaceutical drugs, carbamate pesticides, volatile fatty acids, and antiepileptic drug from water, human serum, pharmaceutical, and fruit juice samples Extraction of BTEX, phthalate esters, chlorophenols, diazepam, oxazepam, tricyclic antidepressants, PAHs, alcohols, and pesticides from urine, water, cosmetic, human plasma, milk, environmental solid, fruits, tea, and soil samples Extraction of parabens, PAHs, pyrethroids, and triazines from environmental, biological and food samples Extraction of BTEX, aldehydes, metals, alkaloids and flavonoids, peptides, catecholamines, antiviral drug, anabolic steroid and ibuprofen from biological samples Extraction of VOCs and SVOCse from aqueous, air, and soil samples

Table 2 Recent published articles (2017–2019) that reviewed the application of METs based on new extraction media for analysis of different analytes.

[130]

[129]

[120]

[113]

[90] [112] [111]

[9]

[63] [75]

[128]

[53]

Refs. [41] [40] [48]

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Fig. 1. Different types of microextraction techniques.

Fig. 2. Schematic presentation of different types of microextraction techniques based on solid phase.

3.2. Molecularly imprinted polymers

reviewed the applications of MIPs in METs and describe the development of these techniques. The advantages and drawbacks of each technique were also discussed along with expected trends [47]. Li et al. provided an overview of the synthesis and properties of MIPs, recent applications in the field of SPME and LPME, advantages and disadvantages of the applications of MIPs as sorbent, and forecasted trends [48]. The topic of MIP applications for SPE and SPME was also reviewed by Tamayo et al., whose research discussed the application of MIPs loaded in HPLC columns for the direct injection of crude sample extracts. This publication included different sections which address molecularly imprinted SPE and direct coupling of MIP columns to the detection system [49]. Several other articles have also discussed the application of MIPs as sorbent in METs [50–53].

Molecularly imprinted polymers (MIPs) are synthetic materials that are able to recognize specific target analytes from other closely-related compounds, which makes them suitable for used in separation processes [42,43]. In fact, MIPs are cross-linked polymers with particular binding sites for analytes of interest. Overall, these binding sites are formed from the copolymerization of crosslinking monomers and functional monomers in the presence of the print molecule, which is called the template. When the template is removed from the polymer, they become recognition sites that are supplementary to the print molecule in terms of size, shape, and functionality. So, the resulting MIP selectively rebinds the template in priority to other closely-related structures. [44,45]. In recent years, the use of MIPs as selective sorbent materials in sample preparation has increased remarkably, and it has led to analytical methods that have high selectivity. In addition, MIPs can be merged into METs without affecting their inherent selectivity and stability [46]. Using a combination of MIPs with METs offers a powerful analytical tool for fulfilling current sample preparation requirements. In the past few years, numerous review articles have been published concerning the use of MIPs as sorbents in METs. Turiel et al.

3.3. Graphene In 2004, graphene, a material derived from graphite, was introduced by Novoselov et al. [54]. Graphene is a two-dimensional carbon nanomaterial that can be synthesized by simple methods from common graphite without the need for special apparatus. This ease of synthesis greatly increases its application in different fields and allows 4

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Fig. 3. Schematic presentation of different types of microextraction techniques based on liquid phase.

graphene to be produced at a low cost [55,56]. Graphene, having many outstanding properties which can be used as sorbent such as high specific surface area and excellent chemical stability [57]. The high specific surface area in graphene, which is due to the unique nanosheet morphology of graphene, leads to a high adsorption capacity [58]. In addition, graphene can provide a strong affinity for different compounds such as drugs, pollutants and biomolecules, which have carbonbased structures [59]. The application of graphene as sorbents in sample preparation techniques has increased significantly in recent years and displayed excellent results in this field [60,61]. The application of graphene and graphene-based materials as sorbent in sample preparation techniques were reviewed by Liu et al. In this article, the use of graphene as an extractor and matrix in matrix-assisted laser desorption/ionization mass spectrometry were discussed. The authors also discussed future perspectives and possible challenges in this field. This review included sections that address synthesis and characterization of graphene and applications of graphene in SPE [62]. The application of graphene-based sorbents in modern sample preparation techniques were reviewed by Toffoli et al., whose research discussed the most important properties of graphene-based material, synthesis routes and the applications in both offline and online sample preparations techniques. The modes of METs such as stir bar sorptive extraction, and solid phase microextraction by loaded sorbent were also discussed [63]. Sajid et al. reviewed the application of graphene as sorbent in SPME technique. Some of the key advancements in different aspects of SPME such as types and designs, coating materials, and coating strategies were also discussed [64].

of separation science for extraction and enrichment of a variety of analytes, such as drugs, pollutants, metal ions, and hormones, from environmental, biological, food, and pharmaceutical samples [74]. Hashemi et al. reviewed applications of different sorbents for SPE and SPME from biological samples. This study focused on advancements and applications of SPE and SPME methods based on new nanomaterial sorbents for separation and determination of various analytes in biological samples. The role of various sorbents such as MOFs, MIP, carbon nanotubes, and graphene oxide in sample preparation techniques were discussed [75]. Bautista et al. reviewed the application of MOFs as a new generation of SPME coatings, providing a critical overview of the application of MOFs as a novel sorbent for SPME coatings. In addition, the advantages of these materials versus commercial SPME coatings in terms of stability, selectivity, and sensitivity were described [76]. The application of MOFs in sample pretreatment were also discussed by Xiong et al., who summarized the application of MOFs as sorbent in sample pretreatment techniques (including SPE and SPME) and the future prospects of MOFs for sample pretreatment [76]. 3.5. Aerogels Aerogels were first introduced by Samuel Kistler in 1932, and he synthesized various types of inorganic aerogels, including silica, alumina, tungsten oxide, ferric oxide, and stannic oxide [77]. Aerogels are synthesized by the sol-gel technique, in which hydrolysis is used to convert the precursors into a colloidal suspension (sol), which finally is converted into a three-dimensional network (gel) [78]. To date, aerogels have been used in a wide variety of application, including as insulation materials, filters, storage, sorbents, and catalysts [79–81]. These materials have unique properties, including high surface area, low density, high porosity, and thermal stability, which make them viable for the extraction of samples. Thus, numerous applications have been developed for aerogels in which they are used as sorbents [82–84]. Today, to improve extraction efficiency, various types of nanostructure materials are applied in METs including SPME, in-tube SPME, and NTD [22,85,86]. The role of aerogel-based sorbents in METs have been reviewed by Jalili et al. Various types of aerogels, including silica aerogel, carbon aerogel, graphene aerogel and hybrid aerogel were described. A history of these materials, the distinctive properties of aerogel sorbents, and their future prospects also were discussed [9].

3.4. Metal-organic frameworks In recent years, the application of a new group of hybrid materials, i.e., the use of metal-organic frameworks (MOFs), as sorbents in the preparation of samples using METs, has received increasing interest [65,66]. MOFs are crystalline three-dimensional coordination polymers, in which the structures are based on the coordination chemistry between the inorganic secondary building unit and the organic linkers [67–69]. The special properties of MOFs include high porosity, large surface area, flexibility, tunable pore size, and both thermal and mechanical stability, so they are being considered as suitable sorbents in various sample preparation techniques [70–73]. These materials have been used in the field 5

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3.6. Other solid sorbents

[104–106]. These solvents are non-flammable and non-volatile, which makes them suitable for the development of safer processes. In addition, their other properties, such as polarity and viscosity, among other chemical and physical properties, can be determined based on their cationic or the anionic constituents. The immiscibility of some ILs with water and the high solubility of organic species in ILs render them suitable solvents for the extractions of different compounds [107,108]. In recent years, the number of publications concerning potential applications for ILs during METs has increased exponentially. Vickackaite and Padarauskas reviewed the applications of ILs in METs, describing the advantages and drawbacks of using ILs as solvents or sorbents during METs. This review article also addressed the use of ILs during SPME, SDME, DLLME and HF-LPME. The compatibility between METs that utilize ILs and analytical instruments, such as GC, HPLC, and flame atomic absorption spectrometry were also described [109]. The roles played by ILs during sorptive METs were reviewed by Herrador et al., whose research discussed the advantages of using ILs during METs, such as SDME, HF-LPME, DLLME, and in-tube SPME. These advantages include the reduced consumption of organic solvents, high selectivity, increased simplicity, and extractability. Furthermore, the unique properties of ILs that can be exploited during each extraction procedure were also described [110]. The applications of ILs during METs were also reviewed by Marcinkowska et al., who discussed the properties of ILs for analytical purposes and the methods for implementing ILs during METs. In addition, examples ILs-based MET applications for the preconcentration of analytes in different samples were presented. Finally, the current trends and future perspectives with regards to this solvent was also discussed [111]. The applications of poly-ILs in METs were also reviewed by Mei et al., who provided a comprehensive review of poly-ILs and their applications during METs. For this purpose, the first part of this paper discussed the basics of poly-ILs, such as their classification, synthesis, and properties, whereas the second section of this paper discussed the applications of poly-ILs as sorbents during METs. Additionally, the current drawbacks and future prospects of using polyILs during METs were discussed [112]. In another study, the role of ILs in analytical extractions (e.g., DLLME and SDME techniques) has been discussed [113].

Zeolites are microporous, crystalline aluminosilicates with a wide range of applications, such as catalysis, petro chemistry, environmental remediation, and medicine [87]. Zeolites naturally originate in mines and can also be synthetically prepared in the laboratory. Their extraordinary properties, such as their high surface area, high adsorption capacity, selectivity, chemical and thermal stability, ion-exchange capacity, and low-cost extraction, contribute to the potential use of zeolites as sorbents for analytical chemistry purposes [88,89]. Baile et al. reviewed the application of zeolites and zeolite-based materials as sorbent during extraction and METs, including an overview of the zeolites and zeolite-based materials that have been used during extractions and METs, along with novel applications and advances [90]. Conductive polymers (CPs) are materials that exhibit highly reversible redox behaviors, with highly п-conjugated polymeric chains, and that exhibit the electronic properties of both metals and semiconductors. Their unique properties, such as multifunctionality, the ease of synthesis, and stability, make CPs suitable for use as sorbents during sample preparations [91–93]. The applications of CP-based sorbents during sample preparation techniques were reviewed by Bagheri et al., who presented a general overview of the development of METs and the application of CP-based nanomaterials and nanocomposites in METs [94]. Nanocomposites (NCs) are generated by hybridizing organic and inorganic building blocks, with at least one constituent having a dimension smaller than 100 nm. In general, NC materials demonstrate different properties (such as mechanical, electrical, electrochemical, optical, catalytic and structural properties) from those displayed by their parent constituents [95–97]. Overall, the application of NCs as sorbents in METs has resulted in increased extraction efficiencies, possibly because of the multifunctionality that results from the multiphase structure of NCs and the higher specific surface area. Ayazi et al. reviewed the application of NC-based sorbents in METs, including a comprehensive review of NC-based sorbent synthesis and their applications in METs, such as SPME, stir bar sorptive extraction, and needle trap extraction [98]. The identification of trace organic compounds in various samples is an issue of great interest. However, the direct determination of extremely low concentrations of analytes is difficult due to matrix interference and the insufficient sensitivity of analytical techniques. Thus, the separation and preconcentration of trace analytes from matrices are required [99]. Immunoaffinity sorbents can be functionalized by using antibodies specific to the molecules of interest. In fact, the high specificity and affinity of antigen-antibody interactions provide an efficient, clean, and selective extraction technique. Immunosorbents (ISs) were developed by Farjam in the nineties [100]. Today, numerous ISs are commercially available, especially for trace analyses of pesticides, toxins, or drugs in food samples [101]. The application of immunosorbents for METs were reviewed by Pichon et al., who explains some of the developments related to the application of ISs during these techniques. This review also presents different potential approaches that have been reported for the application of ISs to the extraction of analytes of interest from complex samples [102].

4.2. Magnetic ionic liquids Following ILs discovery, magnetic ionic liquids (MILs)—a new subclass of ILs—have contributed to significant advances in analytical applications. MILs are produced by incorporating a paramagnetic part into the cation or anion of the IL structure [114–116]. These solvents possess physicochemical properties similar to those of conventional ILs while also responding strongly to external magnetic fields [117]. MIL solvents are used in analytical extractions, manipulations within microfluidic devices, magnet-based sensors, and a host of other applications [118]. So far, these solvents have been applied in extraction techniques, including DLLME, and SDME. Clark et al. reviewed applications of MILs in analytical chemistry. This review explores the application of MILs in solvent-based extractions and microextractions. Structural features of MILs that influence their physicochemical and magnetic properties were also discussed [119]. The application of MILs in analytical sample preparation was reviewed by Sajid, who highlighted the applications of MILs in analytical extraction and METs and included different sections that address applications of MILs in analytical extractions and biological extractions [120].

4. Reviews focused on new solvents in microextraction techniques 4.1. Ionic liquids The term “ionic liquids” (ILs) describes liquids that have melting points below 100 °C and can be defined as organic salts that are liquid at near room temperature [103]. ILs were first introduced by Walden, who described the first stable IL, ethylammonium nitrate, in 1914. Initially, the sensitivity of ILs to moisture limited their use in different applications. In the 1990s, ILs that were stable in air and moisture were introduced, which initiated a wide range of research on these solvents

4.3. Deep eutectic solvents Deep eutectic solvents (DESs) are solvents that have properties similar to ILs, and it has been reported that they have additional advantages. To date, DESs have been used in many areas of science and technology. These solvents are produced by mixing two or more compounds and heating them to 80 °C, which is followed by freeze drying 6

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without the need for a complex purification step [121–123]. The unique properties of DESs include the possibility of having a huge number of eutectic mixtures that have different chemical properties simply by changing one or both components [124]. Despite the fact that numerous articles have been published on this topic, the use of DESs in analytical chemistry is still in its infancy. Cunha et al. reviewed the application of DESs in METs. Their review provided a critical overview of the new extraction techniques based on DESs that are being used in the analyses of food and biological and environmental samples. In addition, appraisals have been conducted to determine how DESs work in improving the extraction yields of a variety of analytes [125]. One review article described the application of DESs in a variety of extraction techniques, including LPME, SPME, microwave‐assisted extraction, ultrasound‐assisted extraction, and pressurized liquid extraction, and it also discussed various related topics, such as the applications of ILs and DESs in the development of analytical methods, the elimination of environmental contaminants, selective isolation, and the recovery of target compounds [126]. The application of DESs in analytical chemistry also was reviewed by Shishov et al., and they focused on the use of DESs in analytical chemistry for the extraction and separation of target analytes from various samples [127]. The replacement of conventional organic solvents with different solvents in LPME techniques to reduce toxic waste and to improve selectivity and extraction efficiency was reviewed by Jiwoo et al., who found that the non-conventional solvents being used for this purpose included ILs, MILs, and DESs. Jiwoo et al.’s review included an overview of the use of these new solvents 2012 to 2016 [12].

media, and evaluating the protocols required for their application can facilitate the commercialization of new extraction media. In addition, METs and their modifications are expected to be developed for more specialized applications. Declaration of Competing Interest None. References [1] R.-.J. Raterink, P.W. Lindenburg, R.J. Vreeken, R. Ramautar, T. Hankemeier, Recent developments in sample-pretreatment techniques for mass spectrometrybased metabolomics, Trends Anal. Chem. 61 (2014) 157–167. [2] R. Jędrkiewicz, A. Głowacz, M. Kupska, J. Gromadzka, J. Namieśnik, Application of modern sample preparation techniques to the determination of chloropropanols in food samples, Trends Anal. Chem. 62 (2014) 173–183. [3] B.H. Fumes, M.R. Silva, F.N. Andrade, C.E.D. Nazario, F.M. Lanças, Recent advances and future trends in new materials for sample preparation, Trends Anal. Chem. 71 (2015) 9–25. [4] S. Armenta, S. 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5. Concluding remarks METs are reliable for preconcentration and enrichment of analytes in different samples. These techniques are solvent-free or solventminimized, simple, sensitive, rapid, and high-efficient. Since the introduction of these techniques, the extraction process has been simplified, along with increasing selectivity and enhancing efficiency. Over the past few years, one of the efforts to improve METs has been the development of new extraction media with better adsorption properties and high preconcentration for analysis of different analytes. This review offers a summary of reviewed articles in order to present the application of new extraction media (solid sorbents or extraction solvents) in METs. It is obvious that the choice of a suitable extraction phase is one of the important parameters in analytes extraction efficiency from various matrices. New discoveries in materials science may provide new tools for analytical sample preparation. In recent years, solid sorbents and extraction solvents as new extraction media have been used extensively to improve the efficiency of METs. Thus, the combined use of METs and an appropriate extraction media provides a powerful tool for the sampling and analysis of different compounds. To date, various research efforts have contributed to the development of METs and new extraction media. However, there are still significant opportunities for the development of new extraction media for the separation and enrichment of target compounds. Due to the importance of extraction media in the final success of the analysis, designable structures and the ability to make hybrids of extraction media provide many opportunities to produce more efficient composites and customized extraction techniques. The sorption capabilities and improved properties of these composites as interesting extraction media will be helpful in developing analytical tools that will simplify the analytical process. Thus, considering the available equipment for the synthesis and preparation of these extraction phases, it is expected that future research should focus on the synthesis and use of new extraction media with more tailored properties in sample preparation techniques. During the next few years, there will be more applications in which new extraction media will be compared with commercial media, and this will lead to new developments, improvements, and a better understanding of these materials. In addition, preparing for such developments, establishing new extraction 7

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