trac volume 77, march 2016, pages 23–43

8/19/2019 TRAC Volume 77, March 2016, Pages 23–43

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Accepted Manuscript

Title: Modern trends in solid phase extraction: new sorbent media

Author: Justyna Płotka -Wasylka, Natalia Szczepańska, Miguel de la Guardia,Jacek Namieśnik

PII: S0165-9936(15)30055-8DOI: http://dx.doi.org/doi: 10.1016/j.trac.2015.10.010Reference: TRAC 14568

To appear in: Trends in Analytical Chemistry

Please cite this article as: Justyna Płotka -Wasylka, Natalia Szczepańska, Miguel de la Guardia,Jacek Namieśnik , Modern trends in solid phase extraction: new sorbent media, Trends in

Analytical Chemistry (2015), http://dx.doi.org/doi: 10.1016/j.trac.2015.10.010.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a serviceto our customers we are providing this early version of the manuscript. The manuscript willundergo copyediting, typesetting, and review of the resulting proof before it is published in itsfinal form. Please note that during the production process errors may be discovered which couldaffect the content, and all legal disclaimers that apply to the journal pertain.


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Modern trends in solid phase extraction: new sorbent media

Justyna Płotka -Wasylka a,* , Natalia Szczepańska a , Miguel de la Guardiaª, JacekNamieśnik a

a Department of Analytical Chemistry, Faculty of Chemistry, Gdansk University of Technology, 11/12 Narutowicza Street, 80-233 Gdansk, Polandª Department of Analytical Chemistry. University of Valencia 50 DrMoliner Street 46100 Burjassot (Valencia)Spain*corresponding author: [email protected]

Highlights Review provides an updated summary of the formats/devices and trapping media used

in SPE. Discussion on the present limitations and expected future trends of these trapping

media is introduced. The main advantages of new sorbents is their high selectivity and enrichment

capability. Application of SPE for the extraction of different kind of matrices is summarized.

AbstractBased on the recently published literature, this review provides an update of the most

important features and application of formats and devices employed in solid phase extraction(SPE). Special attention was paid on new trapping media proposed in SPE prior theh h l i b d h f d i l i l di b


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It is well known, that monitoring of compounds present in samples at trace/ultra-tracelevel usually requires a preliminary step of isolation and/or enrichment of analytes becauseanalytical techniques are not sensitive enough for direct determination of trace compounds incomplex materials. So, main goals of sample preparation techniques are:

preconcentration of the analytes to a level above the limit of detection of theanalytical instrument,

isolation of the analytes from the original sample matrix and/or matrixsimplification

removal of interferences and elimination of sample constituents that are

strongly sorbed in the chromatographic column.Solid-phase extraction (SPE) plays a crucial role in sample pretreatment, replacing theclassic liquid – liquid extraction (LLE), in biological, food and environmental analyses. SPE isrecognized as beneficial alternative to LLE, because it overcomes many drawbacks of latertechnique [2]. It provides low solvent consumption, low intrinsic costs and reduction of processing time. Moreover, it is possible to automated whole process. Furthermore, SPE doesnot requires separation of phase as required for LLE, what results in elimination of errorsassociated with variable/inaccurately measured extract volumes, one of the main causes oferror found in analysis of extracts obtained by LLE [2].The fundamentals of SPE, including aspects of method development and applicabilityto organic and inorganic analytical problems have been thoughtfully discussed and reviewedin the literature [1]. Among other aspects of SPE, significant efforts have been made todevelopment and characterization of new formats and advanced sorbent materials to improveselectivity or specificity towards target analytes, higher sorptive capacity and enhanced physicochemical or mechanical stability.

This review provides an updated summary of the most important features andli i f f d i ll i di d i S lik d


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methodological solutions used in the field of SPE contributing to an increase in the greennature of the stage of preparing samples for analysis.

2.1. Car tr idgesCartridges constitute a traditional solid phase configuration. Although a wide range of

different kinds of solutions is available, it is by far the most frequently chosen format byanalytical chemists for the isolation and enrichment of analytes present in various kind ofsamples with different levels of content [4]. The SPE cartridges or tubes are small polypropylene or glass open-ended syringe barrels filled with adsorptive medium of varioustypes. Compared to those made of plastic, glass tubes have much better physicochemical properties and, in particular, a greater solvent resistance, which eliminates the possibility ofsample contamination by low molecular weight components and additives used to produce polypropylene tubes [5]. Despite this clear advantage, the solution is still far less frequentlychosen, mainly because of the high cost of production which results in an increased price perunit.

A layer of sorption bed in both, glass and plastic tubes, is located between two polyethylene or stainless frits [4,6]. The obtention of the highest extraction efficiency

depends primarily on the selection of a suitable stationary phase, which provides anopportunity to stop all analytes as well as to select the appropriate volume of the column. Thisresults in a situation where there is a very wide range of different types of columns withdifferent solid phases and sizes available in the market today. The volume of commerciallyavailable open cartridges ranges from 1 to 60 mL [7].In the case of extraction of analytes fromsamples of small volumes, the smaller ones with volumes of 1 mL or 3 mL, containing from30 mg to 4 g of sorbent, are usually chosen, and for large volume samples, the so-called largereservoir cartridges (LRC) of volumes of 10 mL up to even 150 mL, filled with as much as75 f i h il bl [7 8] I i b i h i h d i


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Another design of SPE, which in recent years has gained in popularity amonganalytical chemists, is the extraction disk. Disks were made available for commercial purposes from1989 by 3M in an attempt to redress limitations inherent in cartridges,especially in regard to isolation and enrichment of analytes from environmental samples ofhigh volume [13]. Scientific literature uses different names to describe a methodologicalsolution in which the particles of sorbent are embedded in the membrane. The most frequentlyused names are:SPE disks, extraction disks or membrane-extraction disks [14].

The sorption materials used and the operating principle of both, columns and disks, arethe same. Analytes present in the sample are adsorbed by the particles of filling and after theyare released with a small amount of solvent. The differences between these twomethodological solutions are mainly due to a different packing of the bed and the structure ofthe particles [13,14].

The sorbent particles embedded in the disks are much smaller than those used forfilling the cartridges. The typical diameter of the particles used for filling disks is 8 µm,whereas in the case of the cartridges it is 40 µm [13]. The use of a filler characterized by asmall diameter resulted in an increased extraction efficiency as well as made it possible toeliminate some of the disadvantages experienced with the use cartridges. The most significant

ones are mainly [12, 15]: the possibility of increasing the flow rate of the sample, thereby reducing time neededto perform the entire analysis

the increase of the contact surface, the uniformity and density of the bed thus reducingthe risk of loss of analytes

the reduction of void volume the reduction of the volume of the bed (mass of sorbent) resulting in the reduction of

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In addition to the size and the type of sorbent material it is also possible to introducethe overall classification of disks based on the way to package the stationary phase. Amongthe commonly available extraction disks, one can distinguish those in which [14]: sorbent is immobilized in polymer or glass fibers

sorbent is packed between two glass fiber filters.The disks in which the sorbent particles are immobilized between the microfibers of

polytetrafluoroethylene (PTFE) or glass can be found in the literature under the name ofmembrane-extraction disk or SPE membranes [18].These disks are used much like filter paperwhich unfortunately involves the nead of use special filtration apparatus [15].An alternative

solution to eliminate this disadvantage is undoubtedly the new laminar disk known asSpeedisk introduced in 1998 by J. T Beker. In this system, a thin layer of the sorption bed isfixed between two layers of plastic grids and glass-fiber filters [4]. Table 1 summarizes someinformation on the characteristics of extraction disks commonly used in analytical practices.

According to data shown in Table 1, speedisks have a greater active surface, whilespecial design of the disks allows achieving a higher value of the sample flow whichcontributes to increase the recovery of analytes. Unfortunately, the change of the design,despite of the fact that it contributed to the acceleration of analytes enrichment, also resultedin an increased void volume [4, 13].Another achievement of in this field which helps to eliminate the problem associatedwith the large void volume is the use of extraction disks in cartridge barrels knows asSpeedisk columns. This solution is a combination of a classical column and an extractiondisk. In this type of methodological approach, a thin bed of sorption is placed between twoglassfiber filters with another layer of polypropylene prefilters of graded density foradditional protection against pollution [23]. The use of protective filters contributed to thereduction of clogging risks of the columns and thus enabled the elimination of the samplefil i C l il bl f i l ll l f l


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compared to conventional SPE cartridges [28]. Without the need for centrifugation or solventevaporation, SPE-PT can be readily automated and the resultant eluents directly injected intoa gas or liquid chromatography [29]. Currently there is a wide range of tips offered bydifferent manufacturers characterized by volume of tips (from 1 to 200 µL) and volume oftrapping material placed inside [30]. Due to the fact that the SPE-TP is designed for micro-scale extraction and concentration, this solution became widely used primarily in genomic, proteomic and metabolomic studies for purification and concentration of proteins and peptides[28]. However, it has recently been increasingly used in environmental analysis for the.isolation of drugs from food samples [31] and biological fluids [32], fungicides from tapwater and grape juice [33].

2.4. M ul ti -well SPE platesIn addition to the aforementioned miniaturization of analytical instruments, a greener

nature of operations and activities in the analytical laboratory can be achieved also throughthe automation and robotization of work. The introduction of automated methods to analytical practice contributed to a best control over the sample and solvent manipulation, increased precision and accuracy as compared with manual methods [4] as well as the reduction of the

amount of laborious and time-consuming operations. An example of the introduction ofautomation at the stage of preparation of samples for analysis is the multi-well SPE plates.The first publication which describes the use of multi-weel format for isolation and

enrichment of analytes was published in 1996 [34]. Since then, an increasing interest in thistype of methodological solution has been observed. This format occurs with 96, 384 and even1536 wells, which enable fast and simultaneous preparation of a huge amount of samples in ashort period of time [27, 34].According to data published in the specialized literature, the 96-well format is much more frequently chosen by analytical chemists. In this system, standard

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2.5. Comparison and application of formats and devices used in SPEThere are many performance criteria for SPE devices and formats depending upon the

objective of the extraction. These characteristics were listed above, together with theirimportance and their determinants. Often a performance criterion of a SPE device isdetermined by the sum of several properties of its components and associated systems. Thesame properties are taking into account in order to choose the appropriate format/device for a particular application. In Table 2, comparison of formats and devices used in SPE is presented, while in Table 3, information on application of selected formats/devices aresummarized.

3. New type of sorbents used in SPE

Trapping media in SPE have aroused increasing interest in research on sample preparation, as they have key roles in obtaining high clean-up and enrichment efficiency intrace analysis in complex matrices. The applicability of SPE is mainly determined by the

trapping medium used in the extraction column.Generally, sorbents for SPE can be divided in three categories: inorganic oxides, low-specific sorbents, and compound-specific and class-specific sorbents [15, 51].

Due to the nature of adsorptive inorganic oxides sorbents as well as nature of theanalyte-adsorbent interactions, developments in this class of sorbents (e.g. silica, aluminia,magnesium silicate) is rather limited [52]. The second group of sorbents includes surface-modified silica as well as porous polymers materials such as polystyrene-divinylbenzeneresins and carbon-based materials. Among them, surface-modified silica have the broader

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3.1. N anostructur ed mater ial s

Novel nanomaterials with unique properties have been introduced for their use in SPE,additionally than traditional unspecific sorbents. Nanoparticles (NPs) are extensively used inseveral fields of science, including analytical science [52, 103]. Due to their unique behavior, based on their particle size at the nanometer scale as well as their utility in miniaturization, NPs are ideal SPE sorbents what is described in several review papers [95, 103]. Nanustructures can be applied as sorbents in two configurations [103]:

modified materials based on chemically bonded microparticles (mainly by a covalent bond), directly used as raw materials.

The main advantages of nanoparticles are easy derivatization procedures, a high surface-to-volume ratio, and unique thermal, mechanical and electronic properties. The most important products of this sorbent group are carbon-based nanomaterials and electrospun nanofibers(NFs)

3.1.1. Carbon nanomater ials

Since the discovery of fullerene C60 in 1985 [104], the development of carbon-basednanomaterials has been one of the most important trends in solid phase extraction . Recently,a large number of these materials has been investigated as sorbents in sample pretreatments.These materials include: fullerenes, graphene, carbon nanotubes, carbon nanocones-disks andnanohorns, carbon nanofibers, as well as their functionalized forms [105]. Examples ofcarbon nanostructures are presented in Figure 2.

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a large specific surface area (theoretical value 2630 m2/g ) which allows to highsorption capacity,

availability of both sides of the planar sheets of graphene for molecule adsorption; it can be easily modified with functional groups, especially via graphene oxide thathas many reactive groups (the functionalization may further enhance the selectivity ofSPE)

it can be synthesized from graphite without use of metal catalysts, thus it is easier toobtain pure material.Despite these potential advantages, less attention has been paid to the SPE applications

of graphene as compared with GO. It may be due to its drawbacks. Primarily, graphene isinsoluble and hard to disperse in all solvents due to strong van der Waals interactions that canalso hamper sorption of organic compounds or metal ions [107]. On the contrary, GO containslarge quantities of oxygen atoms on its surface as hydroxyl, epoxy, carbonyl groups,therefore, GO possesses much more hydrophilic properties than graphene, thus, can formstable colloidal suspensions [107]. GO forms hydrogen bonding or electrostatic interactionwith organic compounds or metal ions what results from rich functional groups on his surface.Graphene oxide contains many polar moieties, therefore, it has more polar character thangraphene, which is generally considered a non-polar, hydrophobic sorbent with strong affinityfor carbon-based ring structures. Due to these properties, G can be applied as a sorbent innormal phase (NP) SPE for preconcentraion of compounds that contain oxygen- and/ornitrogen-functional groups and metal species, while GO can be applied in reverse-phase (RP)SPE [107].

Both, G and GO have many potential applications in analytical chemistry asextraction sorbents. Information of these application are presented in Table 4.


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synthesized are C60 bound silica but also C18- and C30-silica were used [65]. Application offullerenes in SPE are presented in Table 4.

3.1.1.3. Carbon nanotubes

Carbon nanotubes (CNTs), discovered in 1991 [110], usually have a diameter in the rangefrom a few tenths to tens of nanometers and lengths up to several micrometers [106]. CNTsare allotropic forms of carbon containing tubular structures which can be formed in two ways[106]:

by a single rolled graphite lamella in a cylinder, i.e. single-walled CNTs (SWCNTs), by several concentrically arranged CNTs arranged around a common axis, i.e. multi-

walled CNTs (MWCNTs).Depending on their diameter and helicity of the graphitic sheet, CNTs can be either metallicor semi-conducting.

The most frequent analytical applications of CNTs concern metal and other analyteSPE and are based on multi-walled nanotubes in contrast with single-walled nanomaterials.This happened despite of the fact that SWCNTs are smaller than MWCNTs in diameter andhave a higher surface area per volume unity, therefore high efficiency of extraction could berealized. The lower SPE applications of SWCNTs in comparison with MWCNTs may resultfrom the following issues:

the synthesis work in order to obtain only single-walled nanotube is a complex process;

SWCNTs have been demonstrated to be more resistant to acid treatments thanMWCNTs; thus, the acidic oxidation conditions for the introduction of hydroxyl,carboxyl and carbonyl functionalization are more favorable in MWCNTs than in


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sing two strategies presented in Figure 3. Information on these CNTs is summarized in Table5.

The specific structures and electronic properties of CNTs allow them to interactstrongly with organic compounds, via non-covalent forces including hydrogen bonding, electrostatic forces,ð – ð stacking, hydrophobic interactions and van der Waalsforces. Mentioned interactions and hollow and layered nanosized structures make CNTsuseful as sorbents. CNTs have been employed for extraction of organophosphorous,organochloride and multi-class pesticides, sulfonylureas, triazines and many othercompounds. Furthermore, CNTs are used for the enhancement of sensitivity and selectivity of primary methods for metal species extraction and preconcentration in diverse samples [68].Recent applications of CNTs for removal and enrichment of organic and inorganiccompounds are presented in Table 4.

3.1.1.4. Carbon nanocones, nanodisks, nanofibers and nanohorns

Carbon nanocones, nanohorns, nanofibers and nanodisks are rapidly evolving assorptive materials and (pseudo)stationary phases in modern separation sciences due to their

unique mechanical and physicochemical properties as well as large chemically active surfaceareas [105]. Description of these carbon nanostructured are presented in Table 6. Taking into account application of the aforementioned carbon nanostructures,

nanofibers are the most commonly used as SPE sorbents. Graphene or CNTs, tend toaggregate, which hampers their application in a flow-through packed-bed mode due to anundue pressure drop and deteriorated retention efficiency [106]. Due to the fact that carbonnanofibers have significantly larger dimensions than grapheme and CNTs, they can overcomethis drawback without coating, functionalization or decoration [106] that was perfectly


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electrospun NF-based SPE sorbents, it is necessary to take into consideration several parameters , the most important being:

chemical composition of the polymeric material, the procedure of electrospinning, and mechanical strength.

Fabricated SPE devices that employ electrospun NFs as a sorbent bed are mainly based on polystyrene or nylon 6 polymers, thus, classification of electrospun NF-SPE devicescan be proposed as follows [3]:

polystyrene type (characterized by relatively low mechanical strength), and

nylon type (characterized by relatively high mechanical strength).The electrospun sorbents were used in SPE of some organic and inorganic species.Information on application of this type of sorbent is presenter in Table 4.

3.1.3. Dendrimers

Dendrimers are an unique class of spherical polymeric macromolecules formedthrough a nanoscale hierarchical self-assembly process. They are characterized by highly branched, three-dimensional architecture with high functionality [77, 95]. There are manytypes of dendrimer and the smallest is several nanometers in size. Dendrimers are used inmany fields of science due to its their high capacities for encapsulating drugs and pollutantsincluding heavy metals, PAHs and dyes [77]. Dendrimer functionalized mesoporous silica provides an effective route to preparing highly efficient sorbents for SPE by combing theadvantages of dendrimers with the ease separation of solid supports [77]. In addition, it isnecessary to provide a mesoporous silica support with larger pores to perform such


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Generally, specific aptamers towards a target analyte can be produced by in-vitromethod known as systematic evolution of ligands by exponential enrichment (SELEX). See

Figure 6 in which it can be seen that a random pool of sequences of oligonucleotides is dopedwith the analyteof interest, and the sequences that bind to the target are selected throughiterative cycles of separation of aptamer/target complex, isolation of template aptamers andamplification by PCR [52, 120]. A positive aspect of this process is that overall process isautomatable. Moreover, rational amounts of high-specific aptamers for the desired analyte ofinterest can be obtained. Analytes can range from small molecules (nolecular weight from 100D) to large biomoleculec or even whole cells and viruses [52].

Several efficient selection methods, including non-SELEX, cell-SELEX, automated-microfluidic SELEX, and SELEX were developed in order to improve aptamers to make themsuitable for biological and biomedical applications. Additionally, SELEX techniques can bechemically modified what allow to improve their binding properties and to broaden range ofanalyte of interest.

Due to the inherently high affinity and selectivity associated with aptamers, amptamer-functionalized materials seem to be ideal SPE sorbents for selective extraction, separation,

purification, and enrichment of trace targets from complex samples, especially biologicalsamples and therefore, there have attracted the attention of scientists. Different type ofaptamer-functionalized materials including aptamer-functionalized affinity column, aptamer-functionalized magnetic SPE (AFMM), aptamer-functionalized surface-affinity SPE (AFSA-SPE) have been developed. There are summarized and described in Table 7.

The aptamer-based SPE technique has been successfully applied, and somerepresentative applications are summarized in Table 4. The technique has been used for theselective extraction of cocaine from plasma [87] and for extraction of tetracyclines from


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After antibodies are obtained, they are covalently bonded onto appropriate sorbents.The selected sorbents should met the following criteria:

should have large sized pores due to the large size of antibodies; should be hydrophilic in order to avoid any non-specific interaction, should be pressure-resistant for use in on-line systems.

Taking into account commonly used sorbents, only silica-based ones meet the threeaforementioned requirements, therefore, in order to reduce the time for the preparation step,the use of commercial silicas, already modified with appropriate functional groups, arestrongly recommended [120].

Extraction with immunosorbents can be combined with liquid chromatography, in both, off-line and on-line modes, thus providing a totally automated device. The high degreeof purification obtained using these systems permits an efficient coupling with GC/MS orLC/MS. Several class-selective immunosorbents have been optimised for the trapping of pesticides and priority industrial organic pollutants (See Table 4). Immunosorbents are robust,and validation studies using certified reference materials have demonstrated their reliability[120].

3.2.3. M olecularl y impr in ted polymers (M I P)

Molecular imprinting is a method used for producing synthetic polymers with predetermined molecular recognition properties. Molecularly imprinting technology is basedon the formation of a complex between an analyte (template) and a functional monomer[122]. A large excess of a cross-linking agent is required to form a three-dimensional polymernetwork. After polymerization process, the template is removed from the polymer leavingspecific recognition sites complementary in size, shape and chemical functionality to the


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MIPs presents many advantages but the most importants for SPE are their highselectivity and affinity for the target molecule used in the imprinting procedure. MIPs in

comparison to biological systems, including nucleic acids and proteins, present higher physical robustness, resistance to elevated pressure and temperature, strength and inertnesstowards bases, acids, organic solvents and metal ions. Moreover, MIPs are less expensiveto be synthesized and the storage life of the polymers can be very high thus kipping theirrecognition capacity also for several years at room temperature [122]. Information onapplications of MIPSPE are presented in Table 4.

Acrylate-based MIPs became a popular choice as selective/specific sorbents for SPE

and nowadays, applications of these conventional MIPs are focused on the large and complexmolecules. However, some other interesting new developments have been reported. Forexample, the molecular imprinting was carried out towards the grafted macromolecule PMAAusing creatinine as template and with ethylene glycol diglycidyl ether as crosslinker by rightof the intermolecular hydrogen bonding and electrostatic interaction between the graftedPMAA and creatinine molecules [124]. According to the authors, the thin MIP layersupported on an inorganic support gave materials with improved thermal and mechanical

properties, and faster rebinding kinetics of analytes.Production of acrylate-based MIPs in aqueous media can be impossible because watermolecules in the polymerizing media interfere in the process by forming strong non-covalentinteractions with the template and or the functional monomer blocking coordination betweenthese reagents [52, 124]. However, the preparation of water-compatible polyacrylate MIP has been reported [125]. Preparation of MIP microspheres occurred by nanoparticle-stabilizedemulsion (Pickering emulsion) polymerization. During the polymerization, the amount of the porogen used affected the stability of the Pickering emulsion and also the specific molecular


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trapping of non-vinylated chelating ligand via imprinting of binary/ternary mixedligand complexes of metal ions with non-vinylated chelating agent and vinyl ligand.

Traditional IIP have poor site accessibility to the target ions due to the fact that thefunctionality is completely embedded by high cross-linking density in the polymer matrices[90]. To overcome the problem associated with accessibility by imprinting on the matrixsurfaces, efforts have been made and as a result IIPs of high selectivity as well as easy siteaccessibility for specific ions have been proposed. Nowadays, the surface-imprintingtechnique attracted extensive research interest due to the fact that IIPs prepared by using thisimprinting technique had many advantages including fast adsorption kinetics, goodaccessibility to the target species, complete removal of templates, low mass-transferresistance and easy preparation. The surface-imprinting technique in combination with a sol-gel process has been successfully used for the imprinted coating of silica gel and magnetic particles. From the other side, there is a limitation associated with the specific recognitionsites on the surface of magnetic particles which restricts the amount of binding sites.However, this could be improved with the support of mesoporous-silica materials with high pore volume, large surface area, good biocompatibility, easily modified surface properties,and uniform pore size distribution [90].

3.3. Metal-organic frameworks as solid-phase sorbentsMetal-organic frameworks (MOFs) are a new type of hybrid inorganic – organic

microporous crystalline materials, self-assembled straightforwardly from ions of metal withorganic linkers via coordination bonds [52, 95]. MOFs have unique properties including:

large surface area in the range 1000-10400 m2/g, uniform pore structure with specific pore size,


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as the nature of the barrier and the surface structure of the sorbent, these materials can beclassified as follows [95]:

mixed-functional phases and dual-zone materials; internal surface reversed-phase packings; shielded hydrophobic phases; semi-permeable surfaces; and polymeric materials.

These types of RAM have been successfully applied in SPE for the extraction ofenvironmental and biological samples in recent years. Nowadays, RAMs are usually applied

in coupling with MIPs. The later have specific recognition sites for the small molecule, whileRAM can exclude large molecules. Therefore, it is ideal to combine the characteristics both ofthem for extraction of trace target molecules with low molecular mass in real samples. TheRAM-MIPs have been applied in the biological, environment and food sample analysis [100].

4. Summary Nowadays, SPE is a well-established technique and, due to its advantages over other

alternatives for sample preparation, has been applied for the analysis of numerous differentclasses of compounds in a variety of matrices. The introduction of new sorbents as well ashighly selective chromatography modes, the development of new experimentalconfigurations to adapt SPE to specific situations and the improvement of automatic devicesundoubtedly allowed to the increasing application of SPE in different fields of chemicalanalysis.


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The main advantages of new sorbents is their high selectivity and enrichmentcapability. New techniques and methods of synthesis are increasingly being developed for the

new sorbents with continuously improved selectivity and other improved features. It can beconcluded that each type of the sorbents developed in the last years has its own advantages.Moreover, they are characterized by specific parameters. Comparison of selected sorbentstogether in the point of environmental impact are presented in Table 8.Significantly, extensive development of combined SPE sorbents by coupling variouscomponent/materials as well as their characteristic can rapidly advance in SPE. Thedevelopment of highly selective as well as easy-to-use sorbents with a simplified procedureand a reduction of risks of errors are the main objectives of companies involved in new SPEmaterials and methods. Obviously, there will never be an universal SPE method due to thefact that the sample pretreatment depends strongly on the analytical demand. On the contrary,there will always be a demand for rapid, selective, reliable and sensitive procedures.

The application of new SPE sorbents may significantly reduces the duration of theanalysis by reducing the number of steps in the extraction procedure, and providing thesimultaneous isolation and enrichment of analytes, and it facilitates the separation of thesorbent with analytes adsorbed on the surface. Moreover, the application some of these new

sorbents (e.g. magnetic NPs) can reduce the use of organic solvents, and thus the generationof toxic and dangerous wastes that is in accordance with the principles of green chemistry.

Acknowledgements

The research is funded by the Polish Ministry of Science and Higher Education within the“Iuventus Plus” program in years 2015−2017, Project No. IP2014 037573.


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Figure 1. The milestones in the development of methodological solutions contributing to animprovement in the green nature of the sample preparation step.


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Figure 5. Schematic representation of MSPE.


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RNA;4 Addition of the target analyte to the nucleic-acid pool; 5 Washing of non-specific orlow-affinity binding nucleic-acid molecules; 6 Isolation of RNA/DNA – target complexes; 7

Amplification by RT-PCR/PCR; 8 After enough cycles 1 to 7, the desired amount of specificRNA/DNA can be isolated and characterized [52].


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Table 1. Comparison of some aspects of SPE disks commonly used in analytical practices.Type of disk

Membrane extraction disk Speedisk Disk in cartridgecolumn

Sorbentembeddedmethod

Immobilized in PTFEfibres

Immobilizedinglass fibres

Immobilized betweentwo layers of glass-

filters

Immobilized between two layers

of glass-fibresfilters and

additional filtersTrade name Empore SPE disk [14,19,20] ENVI, SPEC SPE

disk [21]BakerbondSpeedisk

[12,14, 22]BakerbondSpeediskcolumn[12,16,22]Membrane

format

Standard

density

High

densityWeight ofsorbent [mg]

4-15 -15 10-200 10-200

Diskdiameter[mm]

25-90 25-90 47-90 50 4-10

Thickness [mm] 0,75 0,5 1 0,5-1Particle diameter[µm]

40-55 8-12 30 10 25

Max. extraction

flow [mL/min]

100 - - 200 1-10

Table 2. Comparison of formats and devices used in SPEFormat Advantages Disadvantages Application

cartridges -possibility of preparing in laboratory-possibility of combining several columns-low cost

-Small cross-sectional area- slow flow rate- channelling- high void volume-plugging

Disks -small volume of elution solvents -smaller breakthrough volume Environmentalanaly


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Table 3. Information on application of selected SPE formats/devicesFormat ofSPE

Extractionmaterial

analytes Sampletype

Finaldetermination

Recovery[%]

Ref

Extractiondisk

Multiwalledcarbonnanotubes

Atrazinesimazine

water GC/MS 87-110 17

cartridge Carbonnanocones

chlorophenols water GC/MS 98.8 – 100.9 38

cartridge amino-modifiedactive carbon

quercetin herbs HPLC/UV 98,75-104,69

39

cartridge zirconia-coatedsilica

GlyphosateGlufosinate bialaphos

Serumand urine

UPLC – MS/MS 62,9-73,582,0-115,182,7-119,8

40

cartridge molecularlyimprinted polymers

theophylline serum HPLC/UV 79,1-83,7 41

Extractiondisk

C18-silicamodified byoxime ligands

Copper (II) ions water FAAS 98,2-102 42

Pipette tip Ionic liquid

molecularlyimprinted polymers

dicofol celery GC/ECD 86.6- 101.9 43

Pipette tip Graphene oxide sulfonamides Sewage,Riverwater

LC/FD 90.4-108.2 44

Pipette tip Graphene oxide Okadaic aciddinophysistoxin-1gymnodimine

shellfish UPLC-MS/MS 75.38-92.60

45

III


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35

Table 4. Information on application of different SPE-sorbentsSorbent type Analyte Matrice Detection Recovery [%] LOD RefGraphene, graphene oxideG Pb environmental water and vegetable

samplesFAAS 95.3 – 100.4 0.61 µg/L [53]

G GSH human plasma Fluorescence

Spectrophotometer

92 – 108 0.01 nM [54]

GO chlorophenoxy acidherbicides

River and sea water CE 93.3-102.4 0.3-1.5 ng/L [55]

RGO-silica fluoroquinolones Tap and river water LC-FLR 72-118 - [56]sulfonated graphene sheets PAHs Rivew water GC-MS 81.6-113.5 0.8-3.9 ng/L [57]FullerenesC60-NaDDC Pb Rain water GC-MS 92-100 4 – 15 ng/L [58]C60 Cd Water, oyster tissue, pig kidney and

bovine liverAAS - 0.3 ng/mL [59]

C60 Mercury (II),methylmercury(I) andethylmercury(I)

Sea, waste and river waters GC-MS 80-105 1.5 ng/L [60]

C60 Organometallic compounds Aqueous solution GC-MS - 5 – 15 ng/mL [61]C60 Metal dithiocarbamates Grain samples FAAS 92-98 1 – 5 ng/mL [62]C60 BTEX Sea, waste, ground, rain, lake,

drinking and river watersGC-MS 94-104 0.04 – 0.05 µg/L [63]

C60, C70 Aromatic and non-aromatic N-nitrosomonas

Swimming, waste, well, drinkingand river waters

GC-MS 95-102 4 – 15 ng/L [64]

C60-bounded silica Amadori peptides Human serum MALDI-TOF MS - - [65]Carbon nanotubesOMWCNT, OSWCNT Organophosphorous

pesticidesSeawater GC-FID 79 – 102 0.07-0.12 µg/L [66]

MWCNTs sulfonylurea herbicides Soil HPLC-DAD 76 – 93 0.5 – 1.2 ng/g [67]MWCNTs Atrazine and simazine Water GC-MS - 2.5-5.0 pg/mL [17]As-grown, oxidized and

modified CNTs

Ni (II), Pb (II) Lake sediment, municipal sludge ETAAS 92.1 – 102.0 10-30 ng/L [68]

As-grown MWCNT Fe (III), Cu (II) Mn (II), Pb(II)

Mineral and tap waters FAAS 96-100 3.5-8.0 µg/L [69]

Carbon nanocones, nanodisks, nanofibers and nanohornscarbon nanocones/disks chlorophenols water GC-MS 98.8 – 100.9 0.3 – 8 ng/mL [38]carbon nanocones/disks toluene, ethylbenzene,

xylene isomers and styreneWater GC-MS 92 0.15 ng/mL [70]

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36

single-walled carbonnanohorns

PAHs water GC-TOF-MS 21-96 30-60 ng/L [71]

Carbon nanofibers Chlorotriazine, anddealkylated metabolites

Crude soil, water (tap, well andcreek)

LC-DAD 83.5-105 0.004-0.03 ng/mL [72]

Electrospun NFsnylon6 nanofibers mat- based SPE

docetaxel rabbit plasma HPLC-UV 85 2 ng/mL [73]

PFSPE (with PS) trazodone Human plasma HPLC-UV 94.6 – 105.5 8 ng/mL [74]PS/G NF aldehydes human exhaled breath condensates HPLC-VWD 79.8 - 105.6 4.2-19.4 nmol/L [75]Carbon NFs from soot aromatic amines wastewater HPLC-UV 70-108 0.009 – 0.081 µg/L [76]Dendrimersdendrimer-functionalizedKIT-6

acid drugs Urine HPLC-UV 85.7 – 113.9 0.4 – 4.6 ng/mL [77]

DPS Nucleobases, nucleosides Standard solution LC-DAD - - [78]PPID-SG Platinum nickel alloy FAAS - 0.014 μg/mL [79]Magnetic nanoparticlesFe3O4@SiO2-C18 Puerarin Rat plasma HPLC-UV 85.2 - 92.3 0.05 µg/mL [80]CTAB coated Fe3O4 mefenamic acid Plasma, urine HPLC-UV 92 – 99 0.087- 0.097

ng/mL[81]

magnetic-MWCNTs-PVAcryogel phthalate esters Packaged food GC-FID 70-118 26.3-36.4 ng/mL [82]

Fe3O4@SiO2-C18 Lidocaine Rat plasma HPLC-UV-VIS-DAD 89.4 – 92.3 0.01 µg/mL [83]ImmunosorbentsmAbs-Sepharose-CNBr gelmAbs: PYs5#14, PYs5#21,PYs5#33

Pyraclostrobin apple juice and red grape must HPLC-UV 98.5-101.6 250 µg/L [84]

F(ab)2-succinimidyl silica particlesFab fragments obtainedfrom a polyclonal IgGantibody againstEndomorphins 1 and 2(End1 and End2).

opioid peptides Human plasma CE-MS - End1: 0.5 ng/mLEnd2: 5 ng/mL

[85]

polyclonal antibodyagainst PA to CNBr-activated Sepharose 4B

Phenylethanolamine A feed, meat and liver HPLC-UV 89.48 – 104.89 48.7 ng/mL [86]

Aptamer-functionalized sorbentsstreptavidin activated Cocaine Post-mortem blood HPLC-DAD 90 - [87]

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37

agarose, cyanogen-bromideactivated sepharosessDNA antitetracycline tetracycline human urine and plasma ESI-IMS 82.8-86.5% 0.019- 0.037

µg/mL[88]

Streptavidin-poly(TRIM-co-GMA)

Thrombin Human serum HPLC-UV-VIS - 4 nm [89]

Ion imprinted polymersFe(III)-imprinted amino-functionalized silica gelsorbent

Fe(III) Standard solution ICP-AES >95 0.34μg/L [90]

Rh(III) ion-imprinted polymer

Rh(III) geochemical reference sample RLS >90 0.024 ng/mL [91]

Pb(II)-imprinted polymeric particles

Pb(II) Food samples FAAS 97.6-100.7 0.42 ng/mL [92]

Molecularly imprinted polymersFuntional monomer: MAACross-linker: ethylenedimethacrylatePorogen: butanone and N-

heptanePolyrazation type: precipitation polymerization

Dimethomorph ginseng GC-µ-ECD 89.2 – 91.6 0.002 mg/kg [93]

Functional monomer:DEAEMACross-linker: (EDMA)Polaryzation type: bulk polaryzation

bioactive naphthoquinones Plant extracts HPLC-UV-VIS - - [94]

Functional monomer:grafted PMAA/ SiO2 Cross-linker: EGGETemplate: creatinine

creatinine Standard solution UV/visspectrophotometer

- - [95]

Metal-organic frameworksMOF MIL-101(Cr) PAHs environmental water HPLC-PDA 81.3-105.0 2.8-27.2 ng/L [96]MOF MIL-53, MIL-100,and MIL-101

Peptides, proteins Biological samples MALDI-TODF-MS - - [97]

MIL-53(Al) Fe aqueous solution XRD 98.2-106.2 0.9 μM [98]MIL-101 organochlorine pesticides Water samples GC-MS 87.6-98.6 0.0025/0.016 ng/m [99]

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38

LRestricted-access materialsRAMs-MIPstemplate molecule:malathion pro-hydrophilic co-monomer:GMA

organophosphorus pesticides

honey GC-FPD 90.9 – 97.6 0.0005 – 0.0019µg/mL

[100]

XDS-RAM basic drugs Human plasma LC-UV-VIS 94.2-98.2 - [101]MC-WCX-RAM basic drugs Human plasma LC-UV 96.7-104.9 - [102]AAS, atomic absorption spectrometry; CE, capillary electrophoresis; CTAB, cetyltrimethylammoniumbromide; DEAEMA, 2-diethylaminoethyl methacrylate; DPS, polymer-modified silica; EDMA, ethyleneglycol dimethacrylate; EGGE, thylene glycol diglycidyl ether; ESI-IMS, electrospray ionization-ion mobility spektrometry; ETAAS,electrothermal atomic absorption spectrometry; FAAS, flame atomic absorption spectrometry; FLR, fluorescence detector; G, graphene; GMA, glycidilmethacrylate; GO,graphene, oxide; GSH, glutathione; ICP-AES, inductively coupled plasma atomic emission spectrometry; MAA, methacrylic acid; mAbs, monoclonal antibodies; MC-WCX-RAM, methylcellulose-immobilized weak cation-exchange silica-based restricted-access material; MIL, Mate´rial Institut Lavoisier; OMWCNT, oxidized multi-walledcarbon nanotubes; OSWCNT, oxidized single-walled carbon nanotubes; PAHs, polycyclic aromatic hydrocarbons; PFSPE, packed-fiber solid-phase extraction; PPID-SG,G4.0 poly(propyleneimine) dendrimer immobilized silica gel; PS, polystyrene; PS/G, polystyrene/graphene; PVA, polyvinyl alcohol; RGO, reduced graphene oxide; RLS,resonance light-scattering method; VWD, variable wavelength detector, XDS, cation-exchange sorbent-restricted access material

Page 38 of 41


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Table 5. Information on the different types of CNTs used as SPE sorbent [111]Type of CNTs Description Characteristicas-grown CNT Obtained after synthesis and purification.

Consist of one or more perfect graphenelayers rolled up as one or several(concentric) cylinders. The end of thecylinders is capped with a semi-sphere offullerene structure.

Have nonpolar bonds and high length todiameterratio.Are insoluble in most organic solvents andaqueous solutions.Have a high tendency to spontaneousaggregation which imposes greatlimitations on their use in SPE.Weak sorbents for metal ions due to theirhigh hydrophobicity and their lack offunctional groups in surfaces.

Oxidized CNT Obtained by oxidation of CNTs whichintroduces hydroxyl, carbonyl andcarboxyl groups in the nanotube surface.Oxidation is commonly carried out withacidic treatment by reflux with HNO3,H2SO4, HCl or mixtures.

Good solubility and dispersion of CNTs inaqueous solutions.High solubility of the material and producing bonded surface oxygen-containing radicals that have the ability toretain a variety of metals at an appropriate pH.

Functionalized CNT Functionalization made by binding aseries of functional groups to the CNTsidewalls by means of different chemicalreactions or physical interactions.

Improved solubility and selectivity.

Chemical fun ctionali zation The formation of covalent bonds between the functional groups and thecarbon atoms of the CNTs. This linkagecan take place directly in the sidewalls ofthe as-grown CNTs (sidewallfunctionalization) or by means of the

Chemical defect functionalization is themost preferred approach when compared tothe sidewall option.A great variety of CNT-derivatives withhigh selectivity for metal species have beensynthesized.Allfunctionalizations achieve useful groups


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Table 6. Information on carbon nanocones, nanodisks, nanofibers and nanohorns Carbon nanomaterials Descriptionnanocones They consist of curved graphite sheets with one or more pentagonal rings, defining

a conical apex, which is extended by a rolled-up graphene sheet into a largerconical structure.Only five diskrete pentagonal disklinations can define the tip of the carbon cone(six pentagons yield a nanotube), which results in five predicted cone angles[112,113].

nanohorns Single-walled carbon nanohorns with about 40 – 50 nm in tubule length and about2 – 3 nm in diameter are derived from SWNTs and ended by a five-pentagonconical cap with a cone opening angle of ~20o [114, 115].

nanodisks Disk-shaped graphene stacked atop each other, therefore yielding into the welldefined graphitic structures.Carbon nanodisks are not produced as a sole entity and are often present withmaterials such as carbon nanocones and carbon black. Carbon nanodisks, whichcould be considered to be a nanocone with a zero degree cone apex angle, occur in70% by weigh. Carbon nanocones, with defined cone apex angles of 19.2, 38.9,60, 84.6 and 112.9 degrees, occur in 20% by weight [114].

nanofibers Carbon nanofibers are solid carbon fibers with lengths in the order of few micronsand diameters below 100 nm. They have a relatively high specific surface, anduniform mesoporous magnitude and distribution. Carbon nanofibers is reported upto 1877 m2 g−1 of a specific surface area, among the highest ever reported fornano-structured materials. Carbon nanofibers could be easily available on a largescale and their surface properties can be modified with chemical treatments tosatisfy some special needs [106].

Table 7. Information on the selected aptamer-funtionalized SPE


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Table 8. Comparison of selected sorbentsType ofsorbent

sorbent Amount ofsorbent

[mg]

Amount ofelutingsolvent

Extractiontime

Type ofanalysis

Preparation of sorbent Reuse ofsorbent

Toxicity ofsorbent

EC50/LC50[mg/L]

Ref.

Amount ofsteps

Environmantalnuisance

Magneticnanoparticles

Fe3O4@SiO2-C18

12-100 80 ul-5 ml +++ Off-line, on-line

- - No data [128],[129]

Carbonnanomaterials

Graphene 20-30 0,3-05 ml +++ Off-line on-line - - - - - - Acute toxicityV. fischeri

1,92

[55, 106,107, 147]

Grapheneoxide

25-100 2 -4ml ++ Off-line on-line -- - - Chronic toxicity D. magna

0,4

[55, 130,142, 148]

MWCNT 0,33 -150 6 -25 ml ++ Off-line on-line - -- - Chronic acute D. magna

22,75

[71, 131,143, 149]

SWCNE 2-200 100 ul – 1ml

+++ Off-line on-line -- -- Chronic acute D. magna

2,42

[71, 111,149]

Fullerene 60-100 150 ul - 1ml++

Off-line on-line

-- -- Acute toxicity D. magna> 35

[64, 133,149, 153]

CNF 2,5-100 1 ul -5ml ++ Off-line on-line - -- Chronic toxicity RBE 4 cells

7,6

[73, 132,144, 150]

Aptamer-functionalizedsorbents

Amino-modifiedMNPs

8-20 200ul- 2ml

+ Off-line on-line - - - - - No data [120, 134,135, 151]

MIP 15-5003ml-15ml

++ Off-line on-line - -- No data [136-138,145]

MOF 4-150 200 ul + Off-line on-line - -- No data [99, 139,140, 146]

IIP 30-200 2-8 ml ++ Off-line -- -- No data [99, 141,154]

+++ short extraction time ++medium extraction time +long extraction time---a lot of steps/ environmentally unfriendly process -- medium number of steps/environmentally friendly process -small number of steps/environmentally friendly process

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trac volume 77, march 2016, pages 23–43

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