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

Author: Justyna Potka-Wasylka, Natalia Szczepaska, Miguel de la Guardia,
Jacek Namienik
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DOI:
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S0165-9936(15)30055-8
http://dx.doi.org/doi: 10.1016/j.trac.2015.10.010
TRAC 14568

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Trends in Analytical Chemistry

Please cite this article as: Justyna Potka-Wasylka, Natalia Szczepaska, Miguel de la Guardia,
Jacek Namienik, 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.
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Modern trends in solid phase extraction: new sorbent media

Justyna Potka-Wasylkaa,*, Natalia Szczepaskaa, Miguel de la Guardia, Jacek
Namienika
a

Department of Analytical Chemistry, Faculty of Chemistry, Gdansk University of Technology, 11/12

Narutowicza Street, 80-233 Gdansk, Poland
Department of Analytical Chemistry. University of Valencia 50 DrMoliner Street 46100 Burjassot (Valencia)
Spain
*corresponding author: plotkajustyna@gmail.com
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.

Abstract
Based 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 the
chromatography analysis, based on the use of nanostructured materials, including carbon
nanomaterials, electrospun nanofibers,dendrimes and magnetic nanoparticles, molecular
recognition sorbents, as aptamers, immunosorbents, molecular imprinted polymers, ion
imprinting polymers, metal-organic frameworks and restricted access materials. Discussions
on the present limitations as well as expected future trends of the new trapping media in
sample preparation for the improvement of the analytical determinations were made.
Moreover, application of SPE for the extraction of different kind of materials; such as
biological, environmental, pharmaceutical and food samples was summarized.

Keywords:
Solid phase extraction, green analytical chemistry,new sorbent materials,
nanomaterials,aptamers, immunosorbents, imprintedpolymers, metal-organic frameworks,
restricted access materials
1. Introduction
Modern analytical chemistry offers many techniques as well as instruments for
determination of analyte of interest in different kind of matrices. However, they are still some
goals to achieve including [1]:
Reduction or elimination of the consumption of chemical substances such as solvents,
reagents, additives, and others);
Proper management of analytical waste;
Minimalization of energy consumption; and
Operator safety ensured.

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It is well known, that monitoring of compounds present in samples at trace/ultra-trace

level usually requires a preliminary step of isolation and/or enrichment of analytes because
analytical techniques are not sensitive enough for direct determination of trace compounds in
complex materials. So, main goals of sample preparation techniques are:
preconcentration of the analytes to a level above the limit of detection of the
analytical instrument,
isolation of the analytes from the original sample matrix and/or matrix
simplification
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 the
classic liquidliquid extraction (LLE), in biological, food and environmental analyses. SPE is
recognized as beneficial alternative to LLE, because it overcomes many drawbacks of later
technique [2]. It provides low solvent consumption, low intrinsic costs and reduction of
processing time. Moreover, it is possible to automated whole process. Furthermore, SPE does
not requires separation of phase as required for LLE, what results in elimination of errors
associated with variable/inaccurately measured extract volumes, one of the main causes of
error found in analysis of extracts obtained by LLE [2].
The fundamentals of SPE, including aspects of method development and applicability
to organic and inorganic analytical problems have been thoughtfully discussed and reviewed
in the literature [1]. Among other aspects of SPE, significant efforts have been made to
development and characterization of new formats and advanced sorbent materials to improve
selectivity 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 and
application of formats/devices as well as trapping media used in SPE, like nanostructured
materials, including carbon nanomaterials, electrospun nanofibers, dendrimers, magnetic
nanoparticles and molecular recognition sorbents, together with metal-organic frameworks
and resticted access materials, employed prior chromatography analysis. Discussion on the
present limitations as well as expected future trends of the new trapping media in sample
preparation for better advancement is introduced. Moreover, application of SPE for the
extraction of different kind of matrices such as biological, environmental, pharmaceutical and
food samples is summarized.
2. The formats and procedures in SPE
Introduction of 12 principles of green chemistry to laboratory practice undoubtedly
proved to be a driving force in the search for new methodological solutions to ensure the
increase in quality of results while improving environmental friendliness. Since the
development of the concept of solid-phase extraction of target analytes, a significant progress
in this technology has been observed, including simplification, automation and
miniaturization of the original concept. SPE formats currently used in laboratory practice are
completely different from the method proposed in 1951 by Braus and co-workers, which was
based on the introduction of up to 1.2-1.5 kg of granular activated carbon into an iron cylinder
[3]. An undoubted progress that has been made in both, the research on the adsorption process
and the production of a wide range of new classes of materials able to trapping various kinds
of analytes, enabled the development of practical solutions for obtaining high rates of
recovery and enrichment with a significant reduction in the amount of sorption materials used
and organic solvents. Figure 1 shows schematically the changes undergone over the years by

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methodological solutions used in the field of SPE contributing to an increase in the green
nature of the stage of preparing samples for analysis.
2.1. Cartridges
Cartridges 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 by
analytical chemists for the isolation and enrichment of analytes present in various kind of
samples 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 various
types. Compared to those made of plastic, glass tubes have much better physicochemical
properties and, in particular, a greater solvent resistance, which eliminates the possibility of
sample contamination by low molecular weight components and additives used to produce
polypropylene tubes [5]. Despite this clear advantage, the solution is still far less frequently
chosen, mainly because of the high cost of production which results in an increased price per
unit.
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 an
opportunity to stop all analytes as well as to select the appropriate volume of the column. This
results in a situation where there is a very wide range of different types of columns with
different solid phases and sizes available in the market today. The volume of commercially
available open cartridges ranges from 1 to 60 mL [7].In the case of extraction of analytes from
samples of small volumes, the smaller ones with volumes of 1 mL or 3 mL, containing from
30 mg to 4 g of sorbent, are usually chosen, and for large volume samples, the so-called large
reservoir cartridges (LRC) of volumes of 10 mL up to even 150 mL, filled with as much as
75g of stationary phase, are available [7,8]. It is obvious that, given the current trends in
analytical chemistry, cartridges of the smallest possible volumes are preferred. Choosing a
solution that contains a reduced weight of sorption material results in the reduction of the
amount of organic solvents used at the stages of conditioning, washing and eluting and also
reduces the time needed for the whole analysis by shortening or eliminating the sorbent
drying process.
The liquid phase can be passed through the column by the gravitational force or by the
use of positive pressure using syringes, air or nitrogen lines, a vacuum flask or a centrifuge
(dynamic method) [9]. An important advantage for choosing this format of the SPE is the
capacity to prepare a highly selective tool for the isolation and enrichment of analytes in the
laboratory. In addition, based on the use of special endings, it is possible to combine several
columns filled with the same or different types of stationary phases [7,9]. The use of two
different sorption materials increases the extraction efficiency and the rate of recovery of
target analytes. This solution was successfully applied to the determination of total polycyclic
aromatic compounds in contaminated soils [10] and pesticide residues in food samples [11].
By observing the current development trends of modern analytical chemistry, one can
easily notice that a very important factor is the search for methods aimed at reducing labour
and time-consuming operations performed in laboratories as well as reducing energy consume
per one analytical cycle. It is not difficult to guess that the aforementioned trends were also
introduced in preparation of samples for analysis. Currently, there is a wide range of methods
available enabling the use of a single set for the isolation and enrichment of analytes from
different samples at the same time [9, 12].
2.2. Disks

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Another design of SPE, which in recent years has gained in popularity among
analytical 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 of
high volume [13]. Scientific literature uses different names to describe a methodological
solution in which the particles of sorbent are embedded in the membrane. The most frequently
used names are: SPE disks, extraction disks or membrane-extraction disks [14].
The sorption materials used and the operating principle of both, columns and disks, are
the same. Analytes present in the sample are adsorbed by the particles of filling and after they
are released with a small amount of solvent. The differences between these two
methodological solutions are mainly due to a different packing of the bed and the structure of
the particles [13,14].
The sorbent particles embedded in the disks are much smaller than those used for
filling the cartridges. The typical diameter of the particles used for filling disks is 8 m,
whereas in the case of the cartridges it is 40 m [13]. The use of a filler characterized by a
small diameter resulted in an increased extraction efficiency as well as made it possible to
eliminate 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 needed
to perform the entire analysis
the increase of the contact surface, the uniformity and density of the bed thus reducing
the 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
the quantity of solvents used for elution and shortening of the drying time of disks
the reduction of channeling
In addition to the high flow rates and the high cross-section area of extraction disk,
there is also a decreased risk of plugging by suspended particulate matter present in the
original sample [14]. The possibility to skip the filtration step ,which is necessary in case of
isolation and enrichment of analytes when using cartridges, resulted in the extended use of
disks in the analysis of water samples and suspensions.
The undoubted progress made in the understanding of adsorption mechanisms and the
use of new classes of materials for trapping various types of analytes resulted in a great
variety of modifications of the original solution available in the market today, with different
phase materials and diameters. Available data from literature indicate that the diameter of the
disks used in all kind of analyses ranges from 4 mm to 96 mm [4, 14].As in the case of the
SPE columns, the size of the disk used for the isolation of analytes is determined by the
volume of the sample, hence the small-diameter disks are frequently used in clinical, forensic
and pharmaceutical analysis and large-diameter ones in environmental analysis [16]. The
most frequently used disk size is 47 mm, which is suitable for standard methods used for the
analysis of water samples with volumes from0.5 to 1L [4]. The SPE sorbent most commonly
employed for the extraction of polar compounds is the octadecyl-modified silica and styrene
divinylbenzene (DVB) for analytes characterized by low polarity. However, the scientific
literature on the use of a new generation of sorbents as a stationary phase has terribly
increased in the last years including: single and multiwalled carbon nanotubes and polymers
modified with various functional groups [17]. Due to a great variety of sorbents available,
selective extraction of interest substances is possible and thus, SPE disks have many fields of
application in various analytical areas of interest [14].

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In addition to the size and the type of sorbent material it is also possible to introduce
the overall classification of disks based on the way to package the stationary phase. Among
the 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 of
membrane-extraction disk or SPE membranes [18].These disks are used much like filter paper
which unfortunately involves the nead of use special filtration apparatus [15].An alternative
solution to eliminate this disadvantage is undoubtedly the new laminar disk known as
Speedisk introduced in 1998 by J. T Beker. In this system, a thin layer of the sorption bed is
fixed between two layers of plastic grids and glass-fiber filters [4]. Table 1 summarizes some
information on the characteristics of extraction disks commonly used in analytical practices.
According to data shown in Table 1, speedisks have a greater active surface, while
special design of the disks allows achieving a higher value of the sample flow which
contributes 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 resulted
in an increased void volume [4, 13].
Another achievement of in this field which helps to eliminate the problem associated
with the large void volume is the use of extraction disks in cartridge barrels knows as
Speedisk columns. This solution is a combination of a classical column and an extraction
disk. In this type of methodological approach, a thin bed of sorption is placed between two
glassfiber filters with another layer of polypropylene prefilters of graded density for
additional protection against pollution [23]. The use of protective filters contributed to the
reduction of clogging risks of the columns and thus enabled the elimination of the sample
filtration step. Currently available for commercial purposes are small columns of a volume
ranging from 1 to 6 mL containing from 10 to 200 mg of a wide variety of sorption materials
[24].
Additionally than reported advantages of the use of disks, analytes adsorbed on the
surface of disks can be analyzed directly from their surface. To do it, laser desorption by
Fourier transform mass spectrometry (FT-MS) and matrix-assisted laser desorption /ionization
mass spectrometry (MALDI-MS) have been used [25]. In addition to their original purpose,
the disks can also be used for special applications, e.g. passive sampling or storage of analytes
[14].
2.3. Pipette tips
Miniaturization of devices and integration of analytical systems are some of the efforts
made to make analytical chemistry as environmentally friendly as possible. An example of the
application of such measures during the preparation of samples is SPE pipette tips (SPE-PT)
introduced commercially in 1989 [26]. Basically, this solution can be described as a
miniaturized version of a conventional SPE in which the absorbent material is packed inside
plastic micropipette tips. Analytes are extracted by repeated aspiration and desorption of the
sample solution using single channel and multichannel pipettors [27]. SPE pipette tips
immediately gained recognition among analytical chemists and are nowadays one of the most
promising methods, primarily because the reduction in the amount of absorbent material
contributed significantly to reduce the amount of organic solvents used which lowered the
costs, while the possibility to integrate extraction and purification in the same step shortened
the time needed to perform the entire analysis.
Based on the research focusing on the comparison of the effectiveness and efficiency
of different methods used it can be concluded that SPE-PT guarantees higher recovery rate as
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compared to conventional SPE cartridges [28]. Without the need for centrifugation or solvent
evaporation, SPE-PT can be readily automated and the resultant eluents directly injected into
a gas or liquid chromatography [29]. Currently there is a wide range of tips offered by
different manufacturers characterized by volume of tips (from 1 to 200 L) and volume of
trapping material placed inside [30]. Due to the fact that the SPE-TP is designed for microscale 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 tap
water and grape juice [33].
2.4. Multi-well SPE plates
In addition to the aforementioned miniaturization of analytical instruments, a greener
nature of operations and activities in the analytical laboratory can be achieved also through
the 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 of
automation 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 this
type of methodological solution has been observed. This format occurs with 96, 384 and even
1536 wells, which enable fast and simultaneous preparation of a huge amount of samples in a
short period of time [27, 34].According to data published in the specialized literature, the 96well format is much more frequently chosen by analytical chemists. In this system, standard
microtiter plates are used. Each of wells has small 0,65 mL or 2,5 mL SPE cartridges filled
with 3-200 mg of sorbent. Sorption layer may be loosely packed or may be embedded in a
membrane of the extraction disk [4, 5, 11]. In some solutions polypropylene (PP) pre-filters
were also used. Additional filters enabled achieving a faster flow rates and reduced the risk of
clogging [5].
Considering the method and the amount of sorbent, commercially available, multi-well
plates can be divided into two types: fixed and flexible ones. Fixed plates have a fixed volume
of columns and a fixed quantity of the solid phase. The liquid phase can be passed through the
column by gravitational forces or by using negative pressure created by a vacuum flask or a
centrifuge [4]. The solution, unfortunately, is not very popular among the researchers because
these small packed bed wells have different flow characteristic, masses and volumes as
compared with traditional SPE cartridges. So, they require some adjustment of the operating
conditions. Moreover, during the analysis only few columns may be used, which results in a
significant increase in the cost of the entire analysis [24]. To overcome some of the
aforementioned disadvantages of performing method development on fixed multi-well SPE
plates, manufactures have introduced a more-flexible array configuration [5]. In this system,
small removable round or square plastic SPE columns are used. The use of interchangeable
columns with different types and quantities of stationary phase enabled an efficient process of
isolation and enrichment of analytes of various types of samples during one analytic cycle.
Multi-well SPE plates were used in high-throughput clinical applications [34] and also in
monitoring of various types of xenobiotics in environmental samples of complex matrices.
Available data suggests that the method can be used to isolate pesticides from water samples
and food as well as in production of drugs in human plasma, urine and wastewater effluents
[35-37]

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2.5. Comparison and application of formats and devices used in SPE

There are many performance criteria for SPE devices and formats depending upon the
objective of the extraction. These characteristics were listed above, together with their
importance and their determinants. Often a performance criterion of a SPE device is
determined by the sum of several properties of its components and associated systems. The
same 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 are
summarized.

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 in
trace 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, lowspecific sorbents, and compound-specific and class-specific sorbents [15, 51].
Due to the nature of adsorptive inorganic oxides sorbents as well as nature of the
analyte-adsorbent interactions, developments in this class of sorbents (e.g. silica, aluminia,
magnesium silicate) is rather limited [52]. The second group of sorbents includes surfacemodified silica as well as porous polymers materials such as polystyrene-divinylbenzene
resins and carbon-based materials. Among them, surface-modified silica have the broader
range of applications. However, they also have several limitations, including limited stability
in the case of aqueous samples with low or high pH. Therefore, research work is still carry out
and usually focused on search for materials with improved stability under difficult conditions
and/or high affinity for polar analytes [52].
Generally, one of the analytical problem associated with environmental and medical
sciences as well as food industry is the presence of significant amounts of water and other
polar constituents and molecules with high molecular weight. For problems related to the
isolation of highly-polar species or macromolecules from aqueous samples, for which most
traditional non-selective sorbents present partition coefficients either do not favor the transfer
of the analytes to the sorbent bed or present irreversible sorption made essential the use of
compound-specific and class-specific sorbents for complex sample treatment [52]. From this
reasons, development of novel SPE sorbents with high selectivity/specificity towards target
analytes as well as sorbents that can be applied to a wide range of matrices and analytes is of
great importance. This section has been focused on the preparation and applications of novel
SPSs. Information about application of new SPE sorbents is summarized in Table 4.

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3.1. Nanostructured materials

Novel nanomaterials with unique properties have been introduced for their use in SPE,
additionally than traditional unspecific sorbents. Nanoparticles (NPs) are extensively used in
several 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-tovolume 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 nanomaterials
Since the discovery of fullerene C60 in 1985 [104], the development of carbon-based
nanomaterials 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 and
nanohorns, carbon nanofibers, as well as their functionalized forms [105]. Examples of
carbon nanostructures are presented in Figure 2.
Due to the unique structures of carbon-based nanoparticles, interaction with organic
compounds via non-covalent forces, including electrostatic forces, hydrogen-bonding, Van
der Waals forces, - stracking and hydrophobic interactions are possible [106]. The
properties of carbon-basd nanomaterials make them good candidates for use as adsorbents,
beingfullerenes and carbon nanotubes (CNTs) the most popular in solid phase extraction of
organic compounds and metal ions. However, other nanomaterials within this group have
been also investigated.

3.1.1.1. Graphene and graphene-oxide

In the last decade, there is a great interest in graphene (G) and graphene oxide (GO) as
SPE sorbents [107]. Graphene is a type of carbonaceous material with a single-layer/fewlayer thickness of sp2-hybridized atoms of carbon arranged in a honeycomb pattern [107].
Numerous methods of graphene synthesis have been proposed. However, the chemical
method based on the oxidation of graphite to graphene oxide followed by its reduction to
graphene with the use of a suitable reducing agent is the most popular [107]. Graphene has
extraordinary thermal, electronic and mechanical properties, such as ultrahigh specific surface
area, fast mobility of charge carriers, good thermal conductivity, high values of Youngs
modulus and fracture strength [108]. These properties hold great promise for its applications
in chemical analysis.
Substantially, graphene has become the most intensively studied material from 2004,
the year when the first experimental evidence of its electronic properties was reported [109].
Taking into account the properties of G, it can be expect that it could be a good
adsorbent for SPE. The most important advantages of G being [108]:
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a large specific surface area (theoretical value 2630 m2/g ) which allows to high
sorption 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 that
has many reactive groups (the functionalization may further enhance the selectivity of
SPE)
it can be synthesized from graphite without use of metal catalysts, thus it is easier to
obtain 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 is
insoluble and hard to disperse in all solvents due to strong van der Waals interactions that can
also hamper sorption of organic compounds or metal ions [107]. On the contrary, GO contains
large quantities of oxygen atoms on its surface as hydroxyl, epoxy, carbonyl groups,
therefore, GO possesses much more hydrophilic properties than graphene, thus, can form
stable colloidal suspensions [107]. GO forms hydrogen bonding or electrostatic interaction
with 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 than
graphene, which is generally considered a non-polar, hydrophobic sorbent with strong affinity
for carbon-based ring structures. Due to these properties, G can be applied as a sorbent in
normal phase (NP) SPE for preconcentraion of compounds that contain oxygen- and/or
nitrogen-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 as
extraction sorbents. Information of these application are presented in Table 4.
3.1.1.2. Fullerenes
Fullerenes are polyhedral carbon cages in which sp2 carbons are bonded to three
carbon neighbors in an arrangement of five-membered and six-membered rings [103]. Since
the diskovery of fullerenes in 1985, structural variations on fullerenes have evolved well
beyond the individual clusters themselves. They have the general formula C20+m, with m being
an integer number, and comprise a wide range of isomers and homologous series. Fullerenes
are ideal for extraction procedures due to many reasons including [106]:
hydrophobic surface,
relatively high electron affinity,
high surface/volume ratio of fullerenes that improves their adsorption capacity
towards organic molecules,
possibility to modification with functional groups, increasing the selectivity
associated with impregnated chemical groups.
The major drawback of fullerenes is their low solubility in aqueous and organic solvents,
which decreases their applicability [103].
The most extensively studied fullerenes as SPE sorbents are C60 and C70 and its
modifications [106]. They were used as sorbent material for pre-concentration of trace metal
species including Pb [58], Cd [59] and Hg [60] and others by forming natural chelates. In
comparison with C18 bonded silica or ion-exchange resins, fullerenes as sorbents were more
effective in pre-concentrating metal species. Moreover, fullerenes were applied to extract
different organometallic compounds such as metal alkyl species [60], metalocenes [61] or
metal dithiocarbamates [62]. They are also suitable for pre-concentration of organic
compounds including BTEX [63] compounds and N-nitrosamines [64]. Furthermore, different
fullerene derivatives were synthesized to increase theirselectivity . The most commonly
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synthesized are C60 bound silica but also C18- and C30-silica were used [65]. Application of
fullerenes 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 range
from a few tenths to tens of nanometers and lengths up to several micrometers [106]. CNTs
are 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. multiwalled CNTs (MWCNTs).
Depending on their diameter and helicity of the graphitic sheet, CNTs can be either metallic
or semi-conducting.
The most frequent analytical applications of CNTs concern metal and other analyte
SPE 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 and
have a higher surface area per volume unity, therefore high efficiency of extraction could be
realized. The lower SPE applications of SWCNTs in comparison with MWCNTs may result
from 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 than
MWCNTs; thus, the acidic oxidation conditions for the introduction of hydroxyl,
carboxyl and carbonyl functionalization are more favorable in MWCNTs than in
SWCNTs, since aggressive conditions must be employed for the latter;
MWCNTs have superior physical properties such as better strength as well as thermal
and electrical conductivities.
The synthesis of CNTs can be carried out by means of three main techniques:
chemical vapor deposition (CVD), laser ablation (LA) and catalytic arc discharge (CAD)
[111]. The latest way seems to be the most appropriate procedure for CNTs preparation for
analytical purposes. This is due to the good conversion with appropriate purity obtained and
the low temperature employed [111]. Synthesized CNTs require purification in all the cases,
because of the presence of different undesired byproducts (such as carbonaceous residues,
fullerenes, metal impurities and others). Nowadays, several methods are used to purify the
synthesized CNTs, including physical separation, chemical oxidation, or combinations of both
chemical and physical techniques [111].
CNTs might be an appropriate material for SPE because of their physical and chemical
properties such as:
high surface area and inner volume,
stability,
mechanical strength,
the possibility of establish interactions,
the possibility of modification of surface area by chemical or physical
functionalization introducing diverse functional groups, biomolecules, polymers,
bacteria, and others.
The properties of CNTs might enhance the separation and pre-concentration performance of
traditional phases, while, modified CNTs are applied in order to improve the selectivity for
target analytes [106, 111]. Recently, three types of CNTs can be distinguished according to
their use in SPE: as-grown, oxidized and functionalized CNTs. The latest may be obtained by
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sing two strategies presented in Figure 3. Information on these CNTs is summarized in Table
5.
The specific structures and electronic properties of CNTs allow them to interact
strongly with organic compounds, via non-covalent forces including hydrogen
bonding, electrostatic forces, stacking, hydrophobic interactions and van der Waals
forces. Mentioned interactions and hollow and layered nanosized structures make CNTs
useful as sorbents. CNTs have been employed for extraction of organophosphorous,
organochloride and multi-class pesticides, sulfonylureas, triazines and many other
compounds. 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 inorganic
compounds are presented in Table 4.
3.1.1.4. Carbon nanocones, nanodisks, nanofibers and nanohorns
Carbon nanocones, nanohorns, nanofibers and nanodisks are rapidly evolving as
sorptive materials and (pseudo)stationary phases in modern separation sciences due to their
unique mechanical and physicochemical properties as well as large chemically active surface
areas [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 to
aggregate, which hampers their application in a flow-through packed-bed mode due to an
undue pressure drop and deteriorated retention efficiency [106]. Due to the fact that carbon
nanofibers have significantly larger dimensions than grapheme and CNTs, they can overcome
this drawback without coating, functionalization or decoration [106] that was perfectly
presented by Boonjob et al. [72].
3.1.2. Electrospun nanofibers
Electrospinning is a technique that relies on repulsive electrostatic forces to draw a
solution of optimal viscoelasticity into nanofibers (NFs) [3]. Although, there are other
methods suitable for NF fabrication as template synthesis, drawing, phase separation, and self
assembly, electrospinning has a leading edge over all of them because it its capability to
easily control the orientation of the NFs [116]. This technique has been recognized as an easy
and efficient technique for production of polymer with nanoscale fibrous structures. As a
result, these fibers present a high specific surface [74]. Morphology, physical and chemical
properties of electrospunNFs and NFs materialss can be selected by optimizing operational
parameters in their production.
The basic requirement for formation of fiber through electrospinning is the
viscoelasticity of the spinning solution [117]. The most popular electrospun materials are
solutions of high molecular weight polymers with the required viscoelasticity provided by
their long chains. From the other side, there is a huge number of pre- and post-electrospining
modification processes that allow to broaden the range of materials that can be electrospun,
and thus, it should be possible to produce almost all of conventional SPE sorbents to form NF
sorbents [117].
Basically, interaction mechanisms of electrospun NF-based SPE sorbents are similar
to those of conventional sorbents. The differences are small and associated with the fact that
typical polymeric sorbents are microparticles and exhibit high mechanical strength [3, 117].
Generally, electrospun NF-SPE sorbents have been limited to non-cross-linked, readilysoluble and exible polymeric materials. At the step of development and optimization of
11
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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 devices
can 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 formed
through a nanoscale hierarchical self-assembly process. They are characterized by highly
branched, three-dimensional architecture with high functionality [77, 95]. There are many
types of dendrimer and the smallest is several nanometers in size. Dendrimers are used in
many fields of science due to its their high capacities for encapsulating drugs and pollutants
including heavy metals, PAHs and dyes [77]. Dendrimer functionalized mesoporous silica
provides an effective route to preparing highly efficient sorbents for SPE by combing the
advantages of dendrimers with the ease separation of solid supports [77]. In addition, it is
necessary to provide a mesoporous silica support with larger pores to perform such
functionalization to eliminate the possibility of pore blocking resulting from the development
of dendrimers.
Many application of dendrimers as SPE sorbents are reported (Table 4). The potential
use of mesoporous silica (KIT-6) functionalized with dendrimers as a mixed-mode anionexchange sorbent for pre-concentration and cleanup of selected acid drugs in human urine
samples has been reported by Li et al. [77]. Schematic illustration of the synthesis of
dendrimer-functionalized KIT-6 is presented in Figure 4. The application of the optimized
methodology to analysis of human urine provides good recoveries and reproducibility.
Poly(amidoamine) (PAMAM) dendrimers of different generations and terminal
functional groups have been employed for removal of copper ions in a sandy soil [118]. The
type of terminal group (carboxylate, amine, or hydroxyl) had a modest effect on the removal
efficiency. Results obtained revealed that dendrimers may be employed as reusable, highcapacity extracting agents for in-situ removal of heavy metals from contaminated soils.
Application of poly(propyleneimine) dendrimer immobilized silica gel as novel
microcolumn packing material for the on-line flow-injection preconcentration and separation
of platinum was also reported [79]. The proposed method was successfully applied to the
determination of platinum in nickel alloy and anode slime samples.
3.1.4. Magnetic nanoparticles
Magnetic nanoparticles (MNPs) are a superparamagnetic kind of nanometer-sized
material which can be attracted by a magnetic field but retain no residual magnetism after
field removal. Therefore, suspended superparamagnetic particles adhered to target analytes
can be very quickly removed from the original matrices using a magnetic field, and do not
agglomerate after removal of the field [95].

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Recently, the application of MNPs in SPE has received considerable attention due to
their high specific surface area and sorption capacity, and high selectivity regarding analytes.
Application of MNPs in the extraction process can significantly shorten whole time of
extraction due to the use of a small amount of sorbent that enables the achievement of a
balance between an examined sample and the solid phase in a very short time [119]. As
compared to the conventional SPE, sample pretreatment is greatly simplified by the
employment of MSPE considering that there is no need for packing a column with the sorbent
in case of batch mode operation, since the phase separation can be quickly and easily
accomplished just by applying an external magnetic field [95].
In magnetic solid phase extraction (MSPE) a sorbent is placed in a solution or
suspension containing the target analytes. Due to the direct contact of nanoparticles with
analytes selective adsorption on solid surface is possible. Next, the sorbent with adsorbed
analytes is separated from the solution by using an external magnetic field. Centrifugation or
filtration of the sample being not necessary,. Afterwards, with an appropriate solvent analyte
desorption takes place. After completion of the extraction process, the extract is subjected to
further analysis while the sorbent may be regenerated and used in another extraction process
[119]. The schematic representation of MSPE is presented in Figure 5.
Currently, many types of MNP are used as sorbents for a wide range of analytes.
However, the most commonly applied material for coating the core of MNPs is silica, which
carries various functional groups. In order to enable the selective extraction of analytes, the
silica coating can be functionalized with organosilanes and/or affinity ligands. One of the
most promising and advanced composite material is Fe3O4@silica NPs (Fe3O4@SiO2) coated
with alkyl C18 (Fe3O4@SiO2-C18), which has a high enrichment ability attributed to the
nanosizes and the plentiful C18 groups [80].
MNPs have been extensively used as materials of choice for applications in the fields of
medicine and biotechnology to separate cells and isolate proteins, peptides or enzymes. Over
the last few years, these sorbents are also increasingly used for trace-metal analysis. Some
applications of MNPs in SPE are presented in Table 4.
3.2. Molecular recognition sorbents
Molecular recognition process became popular in the early 1980s. However, due to its
specificity it is an object of interest among scientists of different fields of science, who still
are developing knowledge about it. Molecular recognition processes are highly specific and
can be replicated in vitro for several studies not only related to biochemical procedures, but
also to other fields including specific or highly selective media for SPE. This kind of sorbents
includes immunosorbents, molecularly-imprinted materials, and aptamer-functionalized
sorbents.
3.2.1. Aptamer-modified sorbents
Aptamers are a new class of short (up to 110 base pairs), single-stranded, synthetic
oligonucleotides that can fold in characteristic shapes capable of binding with high specificity
target molecules [52, 120]. Recognition arises from such interactions as stacking interactions,
hydrogen bonding, dipole and van der Waals forces. These materials are promising sorbents
in sample preparation techniques because of their low cost, ease of synthesis, high specificity
and binding affinity, non-toxicity, good stability, and easy, controllable modification. This
aspects make aptamer-modified sorbents useful in wide variety of applications to recognize
specific analytes ranging from small molecules to proteins, cells and even tissues [120].
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Generally, specific aptamers towards a target analyte can be produced by in-vitro

method 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 doped
with the analyteof interest, and the sequences that bind to the target are selected through
iterative cycles of separation of aptamer/target complex, isolation of template aptamers and
amplification by PCR [52, 120]. A positive aspect of this process is that overall process is
automatable. Moreover, rational amounts of high-specific aptamers for the desired analyte of
interest can be obtained. Analytes can range from small molecules (nolecular weight from 100
D) to large biomoleculec or even whole cells and viruses [52].
Several efficient selection methods, including non-SELEX, cell-SELEX, automatedmicrofluidic SELEX, and SELEX were developed in order to improve aptamers to make them
suitable for biological and biomedical applications. Additionally, SELEX techniques can be
chemically modified what allow to improve their binding properties and to broaden range of
analyte of interest.
Due to the inherently high affinity and selectivity associated with aptamers, amptamerfunctionalized materials seem to be ideal SPE sorbents for selective extraction, separation,
purification, and enrichment of trace targets from complex samples, especially biological
samples and therefore, there have attracted the attention of scientists. Different type of
aptamer-functionalized materials including aptamer-functionalized affinity column, aptamerfunctionalized magnetic SPE (AFMM), aptamer-functionalized surface-affinity SPE (AFSASPE) have been developed. There are summarized and described in Table 7.
The aptamer-based SPE technique has been successfully applied, and some
representative applications are summarized in Table 4. The technique has been used for the
selective extraction of cocaine from plasma [87] and for extraction of tetracyclines from
biological fuids in combination with ion mobility spectrometry [88]. The high affinity of a
target substance to an extraction sorbent is clearly shown in these applications as well as the
importance of the sequence of the oligonucleotides. Aptamers have also been immobilized on
polymeric nano-fibers and extraction of thrombin from serum was shown [89].
3.2.2. Immunosorbents
Immunosorbents are SPE sorbents which are based upon molecular recognition using
natural antibodies and allow a high degree of molecular selectivity. Due to the fact that
antibodies are highly selective towards the analyte of interest employed to initiate the immune
response with a high affinity, immunosorbents may extract and isolate the target analyte from
complex matrices in a single step, thus avoiding the problems of interferences co-extraction
[121].
Antibodies are the key components of immunosorbents. So, the first step is to design
antibodies with the capability of molecular recognition either for one or a group of analytes
[121]. After the selection of the target analyte within the group, the following steps are
required to obtain antibodies ready to be bonded onto a solid support:
an hapten is made by introducing a functional group into the selected molecule, while
keeping as much as possible of its identity;
the hapten carrier conjugate is made by coupling this hapten to a large protein such as
bovine serum albumin;
rabbits are immunised;
serum is collected;
the G-type immunoglobulin ( IgG ) fraction which contains the active antibodies is
isolated and purified.
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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 three
aforementioned requirements, therefore, in order to reduce the time for the preparation step,
the use of commercial silicas, already modified with appropriate functional groups, are
strongly 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 degree
of purification obtained using these systems permits an efficient coupling with GC/MS or
LC/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. Molecularly imprinted polymers (MIP)
Molecular imprinting is a method used for producing synthetic polymers with
predetermined molecular recognition properties. Molecularly imprinting technology is based
on 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 polymer
network. After polymerization process, the template is removed from the polymer leaving
specific recognition sites complementary in size, shape and chemical functionality to the
template molecule. Mainly, between the template molecules intermolecular interaction like
dipoledipole, hydrogen bonds and ionic interactions occurred. These interactions as well as
functional groups present in the polymer matrix drive the molecular recognition phenomena.
Thus, the resultant polymer recognizes and binds selectively only the template molecules. The
principle of molecular imprinting is presented in Figure 7. Recently, this method is attracting
widespread interest in many fields of science, especially as the technological potential of
molecularly imprinted polymers (MIPs) in chromatography separations and solid-phase
extraction. MIPs are robust molecular recognition elements able to mimic natural
recognition entities, such as antibodies and biological receptors, useful to separate and
analyze complx materials as biological fluids and environmental samples. The application of
MIP as selective sorbent for SPE was first proposed in 1994 by Sellergren [123]. Since this
time, acrylate-based MIPs became a popular choice as selective and specific sorbents for SPE
(MIPSPE).
The principle of MIPSPE is based on the same main steps as conventional
SPE:
conditioning of the sorbent,
loading the sample,
washing away interferences,
and elution of the target analytes.
In the second step, the sample is percolated through the molecularly imprinted polymer.
It is important to provide similar solvent polarity to that used in the polymerization process,
since it increases the number of interactions between analyte and specific binding sites in the
MIP sorbents.

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MIPs presents many advantages but the most importants for SPE are their high
selectivity 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 inertness
towards bases, acids, organic solvents and metal ions. Moreover, MIPs are less expensive
to be synthesized and the storage life of the polymers can be very high thus kipping their
recognition capacity also for several years at room temperature [122]. Information on
applications 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 complex
molecules. However, some other interesting new developments have been reported. For
example, the molecular imprinting was carried out towards the grafted macromolecule PMAA
using creatinine as template and with ethylene glycol diglycidyl ether as crosslinker by right
of the intermolecular hydrogen bonding and electrostatic interaction between the grafted
PMAA and creatinine molecules [124]. According to the authors, the thin MIP layer
supported 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 water
molecules in the polymerizing media interfere in the process by forming strong non-covalent
interactions with the template and or the functional monomer blocking coordination between
these reagents [52, 124]. However, the preparation of water-compatible polyacrylate MIP has
been reported [125]. Preparation of MIP microspheres occurred by nanoparticle-stabilized
emulsion (Pickering emulsion) polymerization. During the polymerization, the amount of the
porogen used affected the stability of the Pickering emulsion and also the specific molecular
recognition of the obtained MIP microspheres. Under optimized conditions, the MIP
microspheres synthesized had a porous and hydrophilic surface. This material proved to be
selective towards the template and similar molecules atenolol, metoprolol, timolol and
pindolol for extractions from aqueous matrices [125].
3.2.4. Ion imprinting polymers
Ion-imprinted polymers (IIPs) are similar to MIPs. However, they can recognize metal
ions after imprinting retaining all the MIPs advantages [90]. Outstanding advantages of IIPs
include simply and convinient preparation and predetermined selectivity. From the other side,
they have a poor solubility of the analyte (template) in the imprinting mixture and poor
homogeneity. Moreover, imprinting is time-consuming and insufficient leaching of the
imprint ion can occur, which results in bleeding of the materials [90].
Nowadays, IIPs are of particular interest in the field of separation science and are widely used
in the solid-phase extractive pre-concentration of analytes present in low concentration and
the separation from other coexisting ions or complex matrix [126]. Application of IIPs as
SPE sorbents are presented in Table 4.
IIPs may be roughly classified into the following four types based on inclusion of
ligand in the polymer matrix as follows [126]:
linear chain polymers carrying metal-binding groups being cross-linked with a
bifunctional reagent;
chemical immobilization by preparation of binary complexes of metal ions with
ligands having vinyl groups, isolation and then polymerization with matrix-forming
monomers;
surface imprinting conducted on aqueousorganic interface;

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trapping of non-vinylated chelating ligand via imprinting of binary/ternary mixed

ligand 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 the
functionality is completely embedded by high cross-linking density in the polymer matrices
[90]. To overcome the problem associated with accessibility by imprinting on the matrix
surfaces, efforts have been made and as a result IIPs of high selectivity as well as easy site
accessibility for specific ions have been proposed. Nowadays, the surface-imprinting
technique attracted extensive research interest due to the fact that IIPs prepared by using this
imprinting technique had many advantages including fast adsorption kinetics, good
accessibility to the target species, complete removal of templates, low mass-transfer
resistance and easy preparation. The surface-imprinting technique in combination with a solgel 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 recognition
sites 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 sorbents
Metal-organic frameworks (MOFs) are a new type of hybrid inorganicorganic
microporous crystalline materials, self-assembled straightforwardly from ions of metal with
organic 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,
tailorable polarity,
high thermal stability.
Due to the aforementioned properties, MOF materials have attracted special attention in
analytical applications. The inherent high specific surface area provides a large adsorption
capacity. The specific pore structure and size enables selective adsorption of molecules of
small size. In addition, functionalization in their pores or outer surface can be achieved easily
[95].
MOFs are particularly favored alternatives for the adsorption and/or separation of target
analytes, and therefore have found many applications in chromatography stationary phases,
adsorbents for on-site sampling, and for the pre-concentration of different kind of compounds
in SPE [96, 97].A variety of MOFs have been applied for the analysis of trace elements and
organic analytes, as indicated in Table 4. The application of MOF-based sorbents has been
mainly limited to simulated samples in organic solvents and water samples. Therefore, it is
expected to develop improved MOFs characterized by high stability and additional functional
bindings sites, based on which SPE applications for analysis of trace elements could be
possible [95].
3.4. Restricted-access materials (RAM)
The definition of restricted access materials was introduced in 1991 and they are a
type of biocompatible adsorbent particles enabling the direct extraction of analytes from
biological fluids [95, 127]. The mechanism of separation is based on the hydrophilic effect
and size exclusion. Basically, a hydrophilic barrier enables the small molecules to permeate
through the inner part of the material, but excludes the macromolecules on the surface of the
material by physical or chemical means. Taking into account the synthesis of RAMs as well
17
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as the nature of the barrier and the surface structure of the sorbent, these materials can be
classified 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 of
environmental 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, while
RAM can exclude large molecules. Therefore, it is ideal to combine the characteristics both of
them for extraction of trace target molecules with low molecular mass in real samples. The
RAM-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 different
classes of compounds in a variety of matrices. The introduction of new sorbents as well as
highly selective chromatography
modes, the development of new experimental
configurations to adapt SPE to specific situations and the improvement of automatic devices
undoubtedly allowed to the increasing application of SPE in different fields of chemical
analysis.

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The main advantages of new sorbents is their high selectivity and enrichment
capability. New techniques and methods of synthesis are increasingly being developed for the
new sorbents with continuously improved selectivity and other improved features. It can be
concluded 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 sorbents
together in the point of environmental impact are presented in Table 8.
Significantly, extensive development of combined SPE sorbents by coupling various
component/materials as well as their characteristic can rapidly advance in SPE. The
development of highly selective as well as easy-to-use sorbents with a simplified procedure
and a reduction of risks of errors are the main objectives of companies involved in new SPE
materials and methods. Obviously, there will never be an universal SPE method due to the
fact 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 the
analysis by reducing the number of steps in the extraction procedure, and providing the
simultaneous isolation and enrichment of analytes, and it facilitates the separation of the
sorbent 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 generation
of 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 20152017, Project No. IP2014 037573.
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[142] Q. Han, Z. Wang, J. Xia, S. Chen, X. Zhang, M. Ding, Facile and tunable fabrication of
Fe3O4/graphene oxide nanocomposites and their application in the magnetic solid-phase
extraction of polycyclic aromatic hydrocarbons from environmental water samples. Talanta
101 (2012) 388395.
[143] X.-H. Xia, Z.-J. Jia , Y. Yu , Y. Liang , Z. Wang , L.-L. Ma, Preparation of multiwalled carbon nanotube supported TiO2 and its photocatalytic activity in the reduction of
CO2 with H2O. Carbon 45 (2007) 717721
[144] M. Teng, J. Qiao, F. Li, Prabir Kumar Bera, Electrospun mesoporous carbon nanofibers
produced from phenolic resin and their use in the adsorption of large dye molecules. Carbon
50 (2012) 2877 2886
[145] X. Song, J. Li, J. Wang, L. Chen, Quercetin molecularly imprinted polymers:
Preparation, recognition characteristics and properties as sorbent for solid-phase extraction,
Talanta 80 (2009) 694702.
[146] Y. Hu, C.Song, J. Liao, Z. Huang, G. Li, Water stable metal-organic framework packed
microcolumn for online sorptive extraction and direct analysis of naproxen and its metabolite
from urine sample, j. Chromatogr A., 1294 (2013) 17-24.
[147] C. Pretti , M. Oliva, R. Di Pietro, G. Monni, G. Cevasco, F. Chiellini, C. Pomelli, C.
Chiappe, Ecotoxicity of pristine graphene to marine organisms. Ecotox Environ Safe., 101
(2014) 138145.
[148] A. M. Jastrzbska, P. Kurtycz, A. R. Olszyna, Recent advances in graphene family
materials toxicity investigations. J Nanopart Res., 14 (2012) 1320-1341.
[149] A. G. Cattaneo, R. Gornati, M. Chiriva-Internati, G. Bernardini, Ecotoxicology of
nanomaterials: the role of invertebrate testing. Invertebr. Surviv. J., 6 (2009), 78-97.

27
Page 27 of 41

[150] E.K. Jensen, S. Larsen, U. C. Nygaard, C. D. Marioara, T. Syversen, Early Combination

of Material Characteristics and Toxicology Is Useful in the Design of Low Toxicity Carbon
Nanofiber. Materials 5 (2012) 1560-1580.
[151] V. Pichon, F. Brothier, A. Combs, Aptamer-based-sorbents for sample treatmenta
review, Anal Bioanal Chem., 407 (2015) 681698.
[152] http://www.sigmaaldrich.com/technical-documents/articles/materialmatters/manufacturing-characterization.html
[153] J.-S. Qiu, Y. Zhou, Z.-G. Yang, D.-K. Wang, S.-C. Guo , S.C. Tsang , P.J.F. Harris,
Preparation of fullerenes using carbon rods manufactured from Chinese hard coals, Fuel 79
(2000) 13031308.
[154] J. Liu, X. Yang, X. Cheng, Y. Peng, H. Chen, Synthesis and application of ionimprinted polymer particles for solid-phase extraction and determination of trace scandium by
ICP-MS in different matrices, Anal. Methods, 5 (2013) 1811-1817.

28
Page 28 of 41

Figure 1. The milestones in the development of methodological solutions contributing to an

improvement in the green nature of the sample preparation step.

Figure 2. Examples of carbon nanomaterials.

29
Page 29 of 41

Figure 3. Strategies for functionalization of CNTs.

Figure 4. Schematic illustration of the synthesis of dendrimer-functionalized KIT-6 [77].

30
Page 30 of 41

Figure 5. Schematic representation of MSPE.

Figure 6. Process of SELEX: 1 Synthesis of a library of random DNA oligonucleotides; 2

Conversion to double-stranded DNA by PCR; 3 Conversion to single-stranded: (a) DNA, (b)
31
Page 31 of 41

RNA;4 Addition of the target analyte to the nucleic-acid pool; 5 Washing of non-specific or
low-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 specific
RNA/DNA can be isolated and characterized [52].

Figure 7. The basic principles of molecular imprinting.

32
Page 32 of 41

Table 1. Comparison of some aspects of SPE disks commonly used in analytical practices.
Type of disk
Membrane extraction disk
Speedisk
Sorbent
embedded
method

Trade name
Membrane
format
Weight of
sorbent [mg]
Diskdiameter
[mm]
Thickness [mm]
Particle diameter
[m]
Max. extraction
flow [mL/min]

Disk in cartridge
column
Immobilized
between two layers
of glass-fibres
filters and
additional filters
BakerbondSpeedis
kcolumn [12,16,22]

Immobilized in PTFE
fibres

Immobilized
inglass fibres

Immobilized between
two layers of glassfilters

Empore SPE disk[14,19,20]

Standard
High
density
density
4-15

ENVI, SPEC SPE

disk[21]

BakerbondSpeedisk

-15

10-200

10-200

[12,14, 22]

25-90

25-90

47-90

50

4-10

0,75
40-55

0,5
8-12

1
30

0,5-1
10

25

100

200

1-10

Table 2. Comparison of formats and devices used in SPE

Format
cartridges

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

Disks

-small volume of elution solvents

-faster flow rates without channelling
effect
-smaller void volume
- large surface area per unit bed mass
- possibility to skip the filtration step
-less-time consuming
- possibility of integrated
sample-processing techniques, (in-vial
desorption and on-disk derivatization)
-time consuming and simplicity
- very small volume of sample and elution
solvents
- ability to treat many samples by using a
multichannel micropipette
- shorter extraction time
- high recovery factor
- easy r automation
-rapid preparation of a large number of
samples
- less labour and time consuming
-small volume of elution solvents
-fast flow rates without channelling effect
-small volume of elution solvents and
sorbent mass

Pipette
tips

Multiwell
plates

Sorbent
mixed
with
sample

Disadvantages
-Small cross-sectional area
- slow flow rate
- channelling
- high void volume
-plugging
-smaller breakthrough volume
-more expensive than
cartridges

-plugging
- large amount of plastic waste

Application

Environmentalanaly
sis (in particular
large volume
samples)

Biological research

Bioanalytical
analysis

-effectiveness of extraction
depends on choosing of
appropriate sorbent

Environmental
samples

33
Page 33 of 41

Table 3.Information on application of selected SPE formats/devices

Format of
SPE
Extraction
disk
cartridge
cartridge
cartridge

cartridge

Extraction
material
Multiwalled
carbon
nanotubes
Carbon
nanocones
amino-modified
active carbon
zirconia-coated
silica

Pipette tip

molecularly
imprinted
polymers
C18-silica
modified by
oxime ligands
Ionic liquid
molecularly
imprinted
polymers
Graphene oxide

Pipette tip

Graphene oxide

Pipette tip

hydroxyethyl
methacrylate
dodecyl
methacrylateethylen glycol
dimethacrylate
monolithic
copolymer
Octadecyl
modified silica

Extraction
disk
Pipette tip

96-well
plate

analytes

Sample
type
water

Final
determination
GC/MS

Recovery
[%]
87-110

Ref

chlorophenols

water

GC/MS

98.8100.9

38

quercetin

herbs

HPLC/UV

39

Glyphosate
Glufosinate
bialaphos
theophylline

Serum
and urine

UPLCMS/MS

serum

HPLC/UV

98,75104,69
62,9-73,5
82,0-115,1
82,7-119,8
79,1-83,7

Copper (II) ions

water

FAAS

98,2-102

42

dicofol

celery

GC/ECD

86.6- 101.9

43

sulfonamides

Sewage,
River
water
shellfish

LC/FD

90.4-108.2

44

UPLC-MS/MS

75.3892.60

45

Water,
snow
Water

GFAAS

96-100

46

GC/MS

78110

47

Atrazine
simazine

Okadaic acid
dinophysistoxin-1
gymnodimine
ArIII
Atrazine,
Lindane,
Terbutrin

17

40

41

cis-3-[4-[(4plasma
HPLC-MS/MS
82,5 89,1 48
chlorophenyl)
sulfonyl]-4(2,5difluorophenyl)
cyclohexyl] propanoic
acid
96-well
Octadecyl
17-Estradiol
sewage
YES
70-100
49
plate
modified silica
Estrone
17-Ethinylestradiol
384-well
Octadecyl
Methotrexate,
Urine,
LC-MS/MS
>95
50
plate
modified silica
7-hydroxymethotrexate plasma
DAD, Diode-array detector; ECD Electron Capture Detector; FAAS - Flame Atomic Absorption
Spectrometric; FD, Fluorescence detector; GC gas chromatography; GFAAS - Graphite Furnace Atomic
Absorption Spectrometry; HPLC - high-performance liquid chromatography ; LC Liquid chromatography; MS
mass spectrometry; UPLC ultra high performance liquid chromatography; UV, Ultraviolet spectrometry;
YES Yeast Estrogen Assay
96-well
plate

34
Page 34 of 41

Table 4. Information on application of different SPE-sorbents

Sorbent type
Graphene, graphene oxide
G

Analyte

Matrice

Detection

Recovery [%]

LOD

Ref

Pb

FAAS

95.3100.4

0.61 g/L

[53]

GSH

environmental water and vegetable

samples
human plasma

92108

0.01 nM

[54]

GO

chlorophenoxy
herbicides
fluoroquinolones
PAHs

River and sea water

Fluorescence
Spectrophotometer
CE

93.3-102.4

0.3-1.5 ng/L

[55]

Tap and river water

Rivew water

LC-FLR
GC-MS

72-118
81.6-113.5

0.8-3.9 ng/L

[56]
[57]

Rain water
Water, oyster tissue, pig kidney and
bovine liver
Sea, waste and river waters

GC-MS
AAS

92-100
-

415 ng/L
0.3 ng/mL

[58]
[59]

GC-MS

80-105

1.5 ng/L

[60]

Aqueous solution
Grain samples
Sea, waste, ground, rain, lake,
drinking and river waters
Swimming, waste, well, drinking
and river waters
Human serum

GC-MS
FAAS
GC-MS

92-98
94-104

515 ng/mL
15 ng/mL
0.040.05 g/L

[61]
[62]
[63]

GC-MS

95-102

415 ng/L

[64]

MALDI-TOF MS

[65]

Seawater

GC-FID

79102

0.07-0.12 g/L

[66]

Soil
Water
Lake sediment, municipal sludge

HPLC-DAD
GC-MS
ETAAS

7693
92.1102.0

0.51.2 ng/g
2.5-5.0 pg/mL
10-30 ng/L

[67]
[17]
[68]

Mineral and tap waters

FAAS

96-100

3.5-8.0 g/L

[69]

water
Water

GC-MS
GC-MS

98.8100.9
92

0.38 ng/mL
0.15 ng/mL

[38]
[70]

RGO-silica
sulfonated graphene sheets
Fullerenes
C60-NaDDC
C60
C60

Pb
Cd
Mercury
(II),
methylmercury(I)
and
ethylmercury(I)
Organometallic compounds
Metal dithiocarbamates
BTEX

C60
C60
C60
C60, C70

Aromatic and non-aromatic

N-nitrosomonas
Amadori peptides

C60-bounded silica
Carbon nanotubes
OMWCNT, OSWCNT
MWCNTs
MWCNTs
As-grown, oxidized
modified CNTs
As-grown MWCNT

acid

and

Organophosphorous
pesticides
sulfonylurea herbicides
Atrazine and simazine
Ni (II), Pb (II)

Fe (III), Cu (II) Mn (II), Pb

(II)
Carbon nanocones, nanodisks, nanofibers and nanohorns
carbon nanocones/disks
chlorophenols
carbon nanocones/disks
toluene,
ethylbenzene,
xylene isomers and styrene

35
Page 35 of 41

single-walled
nanohorns
Carbon nanofibers

carbon

Electrospun NFs
nylon6 nanofibers matbased SPE
PFSPE (with PS)
PS/G NF
Carbon NFs from soot
Dendrimers
dendrimer-functionalized
KIT-6
DPS
PPID-SG
Magnetic nanoparticles
Fe3O4@SiO2-C18
CTAB coated Fe3O4

PAHs

water

GC-TOF-MS

21-96

30-60 ng/L

[71]

Chlorotriazine,
and
dealkylated metabolites

Crude soil, water (tap, well and

creek)

LC-DAD

83.5-105

0.004-0.03 ng/mL

[72]

docetaxel

rabbit plasma

HPLC-UV

85

2 ng/mL

[73]

trazodone
aldehydes
aromatic amines

Human plasma
human exhaled breath condensates
wastewater

HPLC-UV
HPLC-VWD
HPLC-UV

94.6105.5
79.8 - 105.6
70-108

8 ng/mL
4.2-19.4 nmol/L
0.0090.081 g/L

[74]
[75]
[76]

acid drugs

Urine

HPLC-UV

85.7113.9

0.44.6 ng/mL

[77]

Nucleobases, nucleosides
Platinum

Standard solution
nickel alloy

LC-DAD
FAAS

0.014 g/mL

[78]
[79]

Puerarin
mefenamic acid

Rat plasma
Plasma, urine

HPLC-UV
HPLC-UV

85.2 - 92.3
9299

[80]
[81]

Packaged food

GC-FID

70-118

0.05 g/mL
0.0870.097
ng/mL
26.3-36.4 ng/mL

Rat plasma

HPLC-UV-VIS-DAD

89.492.3

0.01 g/mL

[83]

apple juice and red grape must

HPLC-UV

98.5-101.6

250 g/L

[84]

Human plasma

CE-MS

End1: 0.5 ng/mL

End2: 5 ng/mL

[85]

feed, meat and liver

HPLC-UV

89.48104.89

48.7 ng/mL

[86]

Post-mortem blood

HPLC-DAD

90

[87]

magnetic-MWCNTs-PVA
phthalate esters
cryogel
Fe3O4@SiO2-C18
Lidocaine
Immunosorbents
mAbs-Sepharose-CNBr gel Pyraclostrobin
mAbs: PYs5#14, PYs5#21,
PYs5#33
F(ab)2-succinimidyl silica
opioid peptides
particles
Fab fragments obtained
from a polyclonal IgG
antibody
against
Endomorphins 1 and 2
(End1 and End2).
polyclonal
antibody Phenylethanolamine A
against PA to CNBractivated Sepharose 4B
Aptamer-functionalized sorbents
streptavidin
activated Cocaine

[82]

36
Page 36 of 41

agarose, cyanogen-bromide
activated sepharose
ssDNA antitetracycline

tetracycline

Streptavidin-poly(TRIMThrombin
co-GMA)
Ion imprinted polymers
Fe(III)-imprinted
amino- Fe(III)
functionalized silica gel
sorbent
Rh(III)
ion-imprinted Rh(III)
polymer
Pb(II)-imprinted polymeric Pb(II)
particles
Molecularly imprinted polymers
Funtional monomer: MAA
Dimethomorph
Cross-linker: ethylene
dimethacrylate
Porogen: butanone and Nheptane
Polyrazation
type:
precipitation
polymerization
Functional monomer:
bioactive naphthoquinones
DEAEMA
Cross-linker: (EDMA)
Polaryzation type: bulk
polaryzation
Functional monomer:
creatinine
grafted PMAA/ SiO2
Cross-linker: EGGE
Template: creatinine
Metal-organic frameworks
MOF MIL-101(Cr)
PAHs
MOF MIL-53, MIL-100, Peptides, proteins
and MIL-101
MIL-53(Al)
Fe
MIL-101
organochlorine pesticides

human urine and plasma

ESI-IMS

82.8-86.5%

Human serum

HPLC-UV-VIS

0.019g/mL
4 nm

0.037

[88]

Standard solution

ICP-AES

>95

0.34 g/L

[90]

geochemical reference sample

RLS

>90

0.024 ng/mL

[91]

Food samples

FAAS

97.6-100.7

0.42 ng/mL

[92]

ginseng

GC--ECD

89.291.6

0.002 mg/kg

[93]

Plant extracts

HPLC-UV-VIS

[94]

Standard solution

UV/vis
spectrophotometer

[95]

environmental water
Biological samples

HPLC-PDA
MALDI-TODF-MS

81.3-105.0
-

2.8-27.2 ng/L
-

[96]
[97]

aqueous solution
Water samples

XRD
GC-MS

98.2-106.2
87.6-98.6

0.9 M
0.0025/0.016 ng/m

[98]
[99]

[89]

37
Page 37 of 41

L
Restricted-access materials
RAMs-MIPs
organophosphorus
honey
GC-FPD
90.997.6
0.00050.0019
[100]
template molecule:
pesticides
g/mL
malathion
pro-hydrophilic
comonomer:GMA
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, polymermodified 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-WCXRAM, methylcellulose-immobilized weak cation-exchange silica-based restricted-access material; MIL, Material Institut Lavoisier; OMWCNT, oxidized multi-walled
carbon 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

38
Page 38 of 41

Table 5. Information on the different types of CNTs used as SPE sorbent [111]
Type of CNTs
as-grown CNT

Description
Obtained after synthesis and purification.
Consist of one or more perfect graphene
layers rolled up as one or several
(concentric) cylinders. The end of the
cylinders is capped with a semi-sphere of
fullerene structure.

Oxidized CNT

Obtained by oxidation of CNTs which

introduces hydroxyl, carbonyl and
carboxyl groups in the nanotube surface.
Oxidation is commonly carried out with
acidic treatment by reflux with HNO3,
H2SO4, HCl or mixtures.

Functionalized CNT

Functionalization made by binding a

series of functional groups to the CNT
sidewalls by means of different chemical
reactions or physical interactions.
Chemical functionalization
The formation of covalent bonds
between the functional groups and the
carbon atoms of the CNTs. This linkage
can take place directly in the sidewalls of
the
as-grown
CNTs
(sidewall
functionalization) or by means of the
carboxylic groups and the defects
generated by the previous oxidation of
CNTs (defect functionalization).
Amidation, esterification, thiolation and
silanization reactions cause the formation
of a great diversity of functionalized
CNTs with interesting analytical
applications.
Other reactions to produce functionalized
nanotubes in combination with supported
metal oxides and polymers are also used.
Physical functionalization
Involves non-covalent bonds.
Polymer wrapping is a typical physical
case in which the union between CNT
and polymer is based on van der Waals
and stacking forces between
nanotube and functional molecule.
In suspensions containing polymers,
e.g.polystyrene, with CNTs, a wrapping
of polymer around CNT was produced as
a result of the two forces previously
cited. Functionally modified nanotubes
may be either prepared by adsorption of
different ionic and non-ionic surfactants
on the surface of CNTs.
Another way is the use of surfactants to
prevent the formation of aggregates and
facilitate their dispersion in polar
solvents commonly used.

Characteristic
Have nonpolar bonds and high length to
diameterratio.
Are insoluble in most organic solvents and
aqueous solutions.
Have a high tendency to spontaneous
aggregation
which
imposes
great
limitations on their use in SPE.
Weak sorbents for metal ions due to their
high hydrophobicity and their lack of
functional groups in surfaces.
Good solubility and dispersion of CNTs in
aqueous solutions.
High solubility of the material and
producing bonded surface oxygencontaining radicals that have the ability to
retain a variety of metals at an appropriate
pH.
Improved solubility and selectivity.

Chemical defect functionalization is the

most preferred approach when compared to
the sidewall option.
A great variety of CNT-derivatives with
high selectivity for metal species have been
synthesized.
Allfunctionalizations achieve useful groups
onto the CNT surface with the
corresponding improvement in selectivity.

Improved solubility and selectivity.

Increased dispersion in polar solvents
commonly used.

39
Page 39 of 41

Table 6. Information on carbon nanocones, nanodisks, nanofibers and nanohorns

Carbon nanomaterials
nanocones

nanohorns

nanodisks

nanofibers

Description
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 larger
conical 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].
Single-walled carbon nanohorns with about 4050 nm in tubule length and about
23 nm in diameter are derived from SWNTs and ended by a five-pentagon
conical cap with a cone opening angle of ~20o [114, 115].
Disk-shaped graphene stacked atop each other, therefore yielding into the well
defined graphitic structures.
Carbon nanodisks are not produced as a sole entity and are often present with
materials such as carbon nanocones and carbon black. Carbon nanodisks, which
could be considered to be a nanocone with a zero degree cone apex angle, occur in
70% 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].
Carbon nanofibers are solid carbon fibers with lengths in the order of few microns
and diameters below 100 nm. They have a relatively high specific surface, and
uniform mesoporous magnitude and distribution. Carbon nanofibers is reported up
to 1877 m2 g1 of a specific surface area, among the highest ever reported for
nano-structured materials. Carbon nanofibers could be easily available on a large
scale and their surface properties can be modified with chemical treatments to
satisfy some special needs [106].

Table 7. Information on the selected aptamer-funtionalized SPE

Aptamer
Aptamer-functionalized
column

AFMM

AFSA-SPE

affinity

Description
The most commonly AF affinity columns include: AF material packed
column (AFMPC), AF open tubular capillary column (AFOTCC), AF
monolithic column (AFMC), and AF spin column (AFSC).
Some parameters, such as the nature of the immobilization support, the
type of immobilization (covalent or noncovalent) and the length of the
spacer arm, affected the efficiency of AFMs in selective extraction of
analytes.
Preparation involves three steps:
i. synthesis of the magnetic particle (Fe3O4 or -Fe2O3),
ii. coating of the magnetic core with silica, styrene/acrylamide copolymer
or gold particles,
iii. modification of the resultant core-shell structure with the aptamer.
At present, many magnetic materials, including magnetic nanoparticles
(MNPs), magnetic microspheres (MMSs), and magnetic beads (MBs)
coated with different functional groups are commercially available.
The common substrate materials for immobilization of aptamers in
AFSA-SPE are CNTs, GO, gold and silica.
AF affinity substrates can:
i. act as an ionization substrate for MS,
ii. can specifically capture target analytes,
iii. can remove interfering components.

40
Page 40 of 41

Table 8. Comparison of selected sorbents

Type of
sorbent

Magnetic
nanoparticles
Carbon
nanomaterials

Aptamerfunctionalized
sorbents
MIP

sorbent

Amount of
sorbent
[mg]

Amount of
eluting
solvent

Extraction
time

Fe3O4@SiO2
-C18
Graphene

12-100

80 ul-5 ml

+++

20-30

0,3-05 ml

+++

Off-line,
on-line
Off-line on-line

Graphene
oxide

25-100

2 -4ml

++

MWCNT

0,33 -150

6 -25 ml

SWCNE

2-200

100 ul
1ml

Fullerene

60-100

150 ul - 1
ml

CNF

2,5-100

1 ul -5ml

Aminomodified
MNPs

8-20

200ul- 2
ml

15-500

MOF

4-150

3ml-15ml
200 ul

IIP

30-200

2-8 ml

Type of
analysis

Preparation of sorbent

Reuse of
sorbent

Amount of
steps
-

Environmantal
nuisance
-

---

---

Off-line on-line

--

--

++

Off-line on-line

+++

Off-line on-line

Toxicity of
sorbent
EC50/LC50
[mg/L]
No data

++
++

Off-line on-line

--

Off-line on-line

---

--

Acute toxicity
V. fischeri
1,92
Chronic toxicity
D. magna
0,4
Chronic acute
D. magna
22,75
Chronic acute
D. magna
2,42
Acute toxicity
D. magna
> 35
Chronic toxicity
RBE 4 cells
7,6
No data

--

No data

No data

No data

--

Off-line on-line

-- -

--

--

++

Off-line on-line

Off-line on-line

++

Off-line

--

+++ short extraction time

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

--

---

Ref.

[128],
[129]
[55, 106,
107, 147]
[55, 130,
142, 148]
[71, 131,
143, 149]
[71, 111,
149]
[64, 133,
149, 153]
[73, 132,
144, 150]
[120, 134,
135, 151]
[136-138,
145]
[99, 139,
140, 146]
[99, 141,
154]

-small number of steps/environmentally friendly process

41
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