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Modern trends in solid phase extraction: New

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Article in TrAC Trends in Analytical Chemistry December 2015
DOI: 10.1016/j.trac.2015.10.010
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Trends in Analytical Chemistry 77 (2016) 2343
Contents lists available at ScienceDirect
Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c
Modern trends in solid phase extraction: New sorbent media

Justyna Potka-Wasylka a,b,*, Natalia Szczepanska a,b, Miguel de la Guardia a,b,
Jacek Namiesnik a,b
a
b
Department of Analytical Chemistry, Faculty of Chemistry, Gdan

sk University of Technology, 11/12 Narutowicza Street, 80-233 Gdan
sk, Poland
Department of Analytical Chemistry, University of Valencia, 50 DrMoliner Street, 46100 Burjassot, Valencia, Spain
A R T I C L E
I N F O
Keywords:
Solid phase extraction
Green analytical chemistry
New sorbent materials
Nanomaterials
Aptamers
Immunosorbents
Imprintedpolymers
Metal-organic frameworks
Restricted access materials
A B S T R A C T
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 nanobers, 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.
2015 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
Introduction ...........................................................................................................................................................................................................................................................
The formats and procedures in SPE ..............................................................................................................................................................................................................
2.1.
Cartridges ..................................................................................................................................................................................................................................................
2.2.
Disks ...........................................................................................................................................................................................................................................................
2.3.
Pipette tips ...............................................................................................................................................................................................................................................
2.4.
Multi-well SPE plates ...........................................................................................................................................................................................................................
2.5.
Comparison and application of formats and devices used in SPE ........................................................................................................................................
New type of sorbents used in SPE .................................................................................................................................................................................................................
3.1.
Nanostructured materials ...................................................................................................................................................................................................................
3.1.1.
Carbon nanomaterials ..........................................................................................................................................................................................................
3.1.2.
Electrospun nanobers ........................................................................................................................................................................................................
3.1.3.
Dendrimers ..............................................................................................................................................................................................................................
3.1.4.
Magnetic nanoparticles .......................................................................................................................................................................................................
3.2.
Molecular recognition sorbents ........................................................................................................................................................................................................
3.2.1.
Aptamer-modied sorbents ..............................................................................................................................................................................................
3.2.2.
Immunosorbents ...................................................................................................................................................................................................................
3.2.3.
Molecularly imprinted polymers (MIP) ........................................................................................................................................................................
3.2.4.
Ion imprinting polymers ....................................................................................................................................................................................................
3.3.
Metal-organic frameworks as solid-phase sorbents ..................................................................................................................................................................
3.4.
Restricted-access materials (RAM) ..................................................................................................................................................................................................
Summary ................................................................................................................................................................................................................................................................
Acknowledgements .............................................................................................................................................................................................................................................
Uncited references ..............................................................................................................................................................................................................................................
References ..............................................................................................................................................................................................................................................................
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1. Introduction
* Corresponding author. Tel.: 0048583472110; Fax: 0048583472496.
E-mail address: plotkajustyna@gmail.com (J. Potka-Wasylka).
http://dx.doi.org/10.1016/j.trac.2015.10.010
0165-9936/ 2015 Elsevier B.V. All rights reserved.
Modern analytical chemistry offers many techniques as well as

instruments for determination of analyte of interest in different kind
24
J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343
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.
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 simplication
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
benecial 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, signicant efforts have been
made to development and characterization of new formats and
advanced sorbent materials to improve selectivity or specicity

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 nanobers, 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 signicant progress in this technology has been observed, including simplication, 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 signicant reduction in the amount
of sorption materials used and organic solvents. Figure 1 shows schematically the changes undergone over the years by methodological
solutions used in the eld of SPE contributing to an increase in the
green nature of the stage of preparing samples for analysis.
Fig. 1. The milestones in the development of methodological solutions contributing to an improvement in the green nature of the sample preparation step.
2.1. Cartridges
Cartridges constitute a traditional solid phase conguration. 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
lled 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 eciency 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, lled with as much as 75 g 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 ask 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 lled
with the same or different types of stationary phases [7,9]. The use
of two different sorption materials increases the extraction eciency 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 timeconsuming operations performed in laboratories as well as reducing
energy consume per one analytical cycle. It is not dicult 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
Another design of SPE, which in recent years has gained in popularity among analytical chemists, is the extraction disk. Disks were
25
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]. Scientic 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 membraneextraction 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 lling 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 lling the cartridges. The typical diameter of
the particles used for lling disks is 8 m, whereas in the case of
the cartridges it is 40 m [13]. The use of a ller characterized by
a small diameter resulted in an increased extraction eciency as
well as made it possible to eliminate some of the disadvantages experienced with the use cartridges. The most signicant ones are
mainly [12,15]:
the possibility of increasing the ow 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 ow 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 ltration 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 modications 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 smalldiameter 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-modied silica and styrene divinylbenzene (DVB) for
analytes characterized by low polarity. However, the scientic 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 modied 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 elds of application in various analytical areas
of interest [14].
In addition to the size and the type of sorbent material it is also
possible to introduce the overall classication of disks based on the
26
Table 1
Comparison of some aspects of SPE disks commonly used in analytical practices
Type of disk
Membrane extraction disk
Sorbent embedded method
Immobilized in PTFE bres
Trade name
Membrane format
Weight of sorbent [mg]
Diskdiameter [mm]
Thickness [mm]
Particle diameter [m]
Max. extraction ow [mL/min]
Empore SPE disk [14,19,20]

Standard density
High density
415
25-90
25-90
0,75
0,5
40-55
812
100
-
Immobilized inglass
bres
ENVI, SPEC SPE disk
[21]
-15
47-90
1
30
-
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 bers

sorbent is packed between two glass ber lters.
The disks in which the sorbent particles are immobilized between

the microbers of polytetrauoroethylene (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 lter paper
which unfortunately involves the nead of use special ltration 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 xed between two layers of plastic grids and glass-ber lters
[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 ow 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 eld 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 glassber lters with another layer of
polypropylene prelters of graded density for additional protection against pollution [23]. The use of protective lters contributed
to the reduction of clogging risks of the columns and thus enabled
the elimination of the sample ltration 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
Speedisk
Disk in cartridge column
Immobilized between two

layers of glass- lters
BakerbondSpeedisk [12,14,22]
Immobilized between two layers of

glass-bres lters and additional lters
BakerbondSpeediskcolumn [12,16,22]
10200
50
0,5-1
10
200
10200
410
25
110
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 signicantly to reduce
the amount of organic solvents used which lowered the costs, while
the possibility to integrate extraction and purication 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 eciency of different methods used it can be concluded
that SPE-PT guarantees higher recovery rate as 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 micro-scale extraction and concentration, this solution became widely used primarily in genomic,
proteomic and metabolomic studies for purication 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 uids [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 rst 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 96-well 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 lled with 3200 mg of sorbent.
Sorption layer may be loosely packed or may be embedded in a
27
Table 2
Comparison of formats and devices used in SPE
Format
Advantages
cartridges
- possibility of preparing in laboratory

- possibility of combining several columns
- low cost
Disks
Pipette tips
Multi-well plates
Sorbent mixed
with sample
Disadvantages
small volume of elution solvents

faster ow rates without channelling effect
smaller void volume
large surface area per unit bed mass
possibility to skip the ltration 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 ow rates without channelling effect
small volume of elution solvents and sorbent mass
membrane of the extraction disk [4,5,11]. In some solutions polypropylene (PP) pre-lters were also used. Additional lters enabled
achieving a faster ow 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: xed
and exible ones. Fixed plates have a xed volume of columns and
a xed 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 ask or a centrifuge [4]. The solution,
unfortunately, is not very popular among the researchers because
these small packed bed wells have different ow 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 signicant increase in the cost of the entire analysis [24].
To overcome some of the aforementioned disadvantages of performing method development on xed multi-well SPE plates,
manufactures have introduced a more-exible array conguration [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 ecient
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 efuents [3537].
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
Small cross-sectional area

slow ow rate
channelling
high void volume
plugging
smaller breakthrough volume
more expensive than cartridges
- plugging
- large amount of plastic waste
Application
Environmentalanalysis
(in particular large volume
samples)
Biological research
Bioanalytical analysis
- effectiveness of extraction depends

on choosing of appropriate sorbent
Environmental samples
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 eciency 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, low-specic sorbents, and compound-specic and
class-specic 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 surfacemodied silica as well as porous polymers materials such as
polystyrene-divinylbenzene resins and carbon-based materials.
Among them, surface-modied 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 dicult conditions and/or high anity 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 signicant 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 coecients either do not favor the transfer
of the analytes to the sorbent bed or present irreversible sorption
made essential the use of compound-specic and class-specic sorbents for complex sample treatment [52]. From this reasons,
development of novel SPE sorbents with high selectivity/specicity
towards target analytes as well as sorbents that can be applied to
a wide range of matrices and analytes is of great importance. This
28
Table 3
Information on application of selected SPE formats/devices
Format of SPE
Extraction material
analytes
Sample type
Final determination
Extraction disk
Multiwalled carbon nanotubes
water
GC/MS
cartridge
cartridge
cartridge
Carbon nanocones
amino-modied active carbon
zirconia-coated silica
water
herbs
Serum and urine
GC/MS
HPLC/UV
UPLCMS/MS
cartridge
Extraction disk
Pipette tip
molecularly imprinted polymers

C18-silica modied by oxime ligands
Ionic liquid molecularly imprinted
polymers
Graphene oxide
Graphene oxide
Atrazine
simazine
chlorophenols
quercetin
Glyphosate
Glufosinate
bialaphos
theophylline
Copper (II) ions
dicofol
serum
water
celery
Pipette tip
Pipette tip
Pipette tip
96-well plate
hydroxyethyl methacrylate
dodecyl methacrylate-ethylen glycol
dimethacrylate monolithic copolymer
96-well plate
Octadecyl modied silica
96-well plate
384-well plate
sulfonamides
Okadaic acid
dinophysistoxin-1
gymnodimine
ArIII
Atrazine,
Lindane,
Terbutrin
cis-3-[4-[(4-chlorophenyl)
sulfonyl]-4-(2,5diuorophenyl)
cyclohexyl] propanoic acid
17-Estradiol
Estrone
17-Ethinylestradiol
Methotrexate, 7-hydroxymethotrexate
Recovery [%]
Ref
87110
[17]
[38]
[39]
[40]
HPLC/UV
FAAS
GC/ECD
98.8100.9
98,75104,69
62,973,5
82,0115,1
82,7119,8
79,183,7
98,2102
86.6101.9
Sewage, River water

shellsh
LC/FD
UPLC-MS/MS
90.4108.2
75.3892.60
[44]
[45]
Water, snow
Water
GFAAS
GC/MS
plasma
HPLC-MS/MS
sewage
YES
Urine, plasma
LC-MS/MS
[41]
[42]
[43]
96100
78110
[46]
[47]
82,589,1
[48]
70100
[49]
>95
[50]
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.
section has been focused on the preparation and applications of novel

SPSs. Information about application of new SPE sorbents is summarized in Table 4.
3.1. Nanostructured materials
Novel nanomaterials with unique properties have been introduced for their use in SPE, additionally than traditional unspecic
sorbents. Nanoparticles (NPs) are extensively used in several elds
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 congurations [103]:
modied 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 nanobers (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
nanobers, as well as their functionalized forms [105]. Examples
of carbon nanostructures are presented in Fig. 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/few-layer 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 specic 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 rst 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]:
a large specic 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 modied with functional groups, especially
via graphene oxide that has many reactive groups (the
functionalization may further enhance the selectivity of SPE)
Table 4
Information on application of different SPE-sorbents
Analyte
Matrice
Detection
Recovery [%]
LOD
Ref
Graphene, graphene oxide

G
Pb
FAAS
95.3100.4
0.61 g/L
[53]
GSH
environmental water and

vegetable samples
human plasma
92108
0.01 nM
[54]
chlorophenoxy acid herbicides

uoroquinolones
PAHs
River and sea water

Tap and river water
Rivew water
0.31.5 ng/L
0.83.9 ng/L
[55]
[56]
[57]
Pb
Cd
92100
415 ng/L
0.3 ng/mL
[58]
[59]
80105
1.5 ng/L
[60]
9298
94104
515 ng/mL
15 ng/mL
0.040.05 g/L
[61]
[62]
[63]
95102
415 ng/L
[64]
[65]
0.070.12 g/L
0.51.2 ng/g
2.55.0 pg/mL
1030 ng/L
[66]
[67]
[17]
[68]
96100
3.58.0 g/L
[69]
G
GO
RGO-silica
Sulfonated graphene sheets
Fullerenes
C60-NaDDC
C60
C60
C60
C60
C60
C60, C70
C60-bounded silica
Carbon nanotubes
OMWCNT, OSWCNT
MWCNTs
MWCNTs
As-grown, oxidized and modied CNTs
As-grown MWCNT
Carbon nanocones, nanodisks, nanobers and nanohorns
Carbon nanocones/disks
Carbon nanocones/disks
Single-walled carbon nanohorns
Carbon nanobers
Electrospun NFs
Nylon6 nanobers mat-based 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
Magnetic-MWCNTs-PVA cryogel
Fe3O4@SiO2-C18
Immunosorbents
mAbs-Sepharose-CNBr gel
mAbs: PYs5#14, PYs5#21, PYs5#33
Mercury (II), methylmercury(I)

and ethylmercury(I)
Organometallic compounds
Metal dithiocarbamates
BTEX
Aromatic and non-aromatic
N-nitrosomonas
Amadori peptides
Organophosphorous pesticides
sulfonylurea herbicides
Atrazine and simazine
Ni (II), Pb (II)
Fluorescence
Spectrophotometer
CE
LC-FLR
GC-MS
93.3102.4
72118
81.6113.5
Rain water
Water, oyster tissue, pig kidney
and bovine liver
Sea, waste and river waters
GC-MS
AAS
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
GC-MS
GC-MS
MALDI-TOF MS
Seawater
Soil
Water
Lake sediment, municipal
sludge
Mineral and tap waters
GC-FID
HPLC-DAD
GC-MS
ETAAS
water
Water
GC-MS
GC-MS
98.8100.9
92
0.38 ng/mL
0.15 ng/mL
[38]
[70]
water
Crude soil, water (tap, well and
creek)
GC-TOF-MS
LC-DAD
2196
83.5105
3060 ng/L
0.0040.03 ng/mL
[71]
[72]
HPLC-UV
HPLC-UV
HPLC-VWD
85
94.6105.5
79.8105.6
2 ng/mL
8 ng/mL
4.219.4 nmol/L
[73]
[74]
[75]
aromatic amines
rabbit plasma
Human plasma
human exhaled breath
condensates
wastewater
HPLC-UV
70108
0.0090.081 g/L
[76]
acid drugs
Nucleobases, nucleosides
Platinum
Urine
Standard solution
nickel alloy
HPLC-UV
LC-DAD
FAAS
85.7113.9
0.44.6 ng/mL
0.014 g/mL
[77]
[78]
[79]
Puerarin
mefenamic acid
phthalate esters
Lidocaine
Rat plasma
Plasma, urine
Packaged food
Rat plasma
HPLC-UV
HPLC-UV
GC-FID
HPLC-UV-VIS-DAD
85.292.3
9299
70118
89.492.3
0.05 g/mL
0.087 0.097 ng/mL
26.336.4 ng/mL
0.01 g/mL
[80]
[81]
[82]
[83]
Pyraclostrobin
apple juice and red grape must
HPLC-UV
98.5101.6
250 g/L
[84]
Fe (III), Cu (II) Mn (II), Pb (II)

chlorophenols
toluene, ethylbenzene, xylene
isomers and styrene
PAHs
Chlorotriazine, and dealkylated
metabolites
docetaxel
trazodone
aldehydes
FAAS
79102
7693
92.1102.0
Sorbent type
(continued on next page)

29
30
Table 4 (continued)
Analyte
Matrice
Detection
Recovery [%]
LOD
Ref
F(ab)2-succinimidyl silica particles

Fab fragments obtained from a polyclonal IgG antibody
against Endomorphins 1 and 2 (End1 and End2).
Polyclonal antibody against PA to CNBr-activated
Sepharose 4B
Aptamer-functionalized sorbents
Streptavidin activated agarose, cyanogen-bromide
activated sepharose
ssDNA antitetracycline
Streptavidin-poly(TRIM-co-GMA)
Ion imprinted polymers
Fe(III)-imprinted amino-functionalized silica gel
sorbent
Rh(III) ion-imprinted polymer
Pb(II)-imprinted polymeric particles
Molecularly imprinted polymers
Funtional monomer: MAA
Cross-linker: ethylene dimethacrylate
Porogen: butanone and N-heptane
Polyrazation type: precipitation polymerization
Functional monomer: DEAEMA
Cross-linker: (EDMA)
Polaryzation type: bulk polaryzation
Functional monomer: grafted PMAA/ SiO2
Cross-linker: EGGE
Template: creatinine
Metal-organic frameworks
MOF MIL-101(Cr)
MOF MIL-53, MIL-100, and MIL-101
MIL-53(Al)
MIL-101
opioid peptides
Human plasma
CE-MS
End1: 0.5 ng/mL

End2: 5 ng/mL
[85]
Phenylethanolamine A
feed, meat and liver
HPLC-UV
89.48104.89
48.7 ng/mL
[86]
Cocaine
Post-mortem blood
HPLC-DAD
[87]
tetracycline
Thrombin
human urine and plasma

Human serum
ESI-IMS
HPLC-UV-VIS
82.886.5%
0.0190.037 g/mL
4 nm
[88]
[89]
Fe(III)
Standard solution
ICP-AES
>95
0.34 g/L
[90]
Rh(III)
Pb(II)
geochemical reference sample

Food samples
RLS
FAAS
>90
97.6100.7
0.024 ng/mL
0.42 ng/mL
[91]
[92]
Dimethomorph
ginseng
GC--ECD
89.291.6
0.002 mg/kg
[93]
bioactive naphthoquinones
Plant extracts
HPLC-UV-VIS
[94]
creatinine
Standard solution
UV/vis
spectrophotometer
[95]
PAHs
Peptides, proteins
Fe
organochlorine pesticides
environmental water
Biological samples
aqueous solution
Water samples
HPLC-PDA
MALDI-TODF-MS
XRD
GC-MS
81.3105.0
98.2106.2
87.698.6
2.827.2 ng/L
0.9 M
0.0025/0.016 ng/
mL
[96]
[97]
[98]
[99]
organophosphorus pesticides
honey
GC-FPD
90.997.6
0.00050.0019 g/
mL
[100]
basic drugs
basic drugs
Human plasma
Human plasma
LC-UV-VIS
LC-UV
94.298.2
96.7104.9
[101]
[102]
Restricted-access materials
RAMs-MIPs
template molecule: malathion
pro-hydrophilic co-monomer:GMA
XDS-RAM
MC-WCX-RAM
90
AAS, atomic absorption spectrometry; CE, capillary electrophoresis; CTAB, cetyltrimethylammoniumbromide; DEAEMA, 2-diethylaminoethyl methacrylate; DPS, polymer-modied silica; EDMA, ethyleneglycol dimethacrylate;
EGGE, thylene glycol diglycidyl ether; ESI-IMS, electrospray ionization-ion mobility spektrometry; ETAAS, electrothermal atomic absorption spectrometry; FAAS, ame atomic absorption spectrometry; FLR, uorescence 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-ber 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.
Sorbent type
31
Fig. 2. Examples of carbon nanomaterials.
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 nonpolar, hydrophobic sorbent with strong anity 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 ve-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 anity,
high surface/volume ratio of fullerenes that improves their adsorption capacity towards organic molecules,
possibility to modication 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 modications [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 preconcentration of organic compounds including BTEX [63] compounds
and N-nitrosamines [64]. Furthermore, different fullerene derivatives
32
were synthesized to increase theirselectivity . The most commonly 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. singlewalled 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 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 eciency 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 purication 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 modication 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 preconcentration performance of traditional phases, while, modied
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 sing two strategies presented
in Fig. 3. Information on these CNTs is summarized in Table 5.
Fig. 3. Strategies for functionalization of CNTs.
The specic structures and electronic properties of CNTs allow

them to interact strongly with organic compounds, via noncovalent 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, nanobers and nanohorns.
Carbon nanocones, nanohorns, nanobers 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, nanobers are the most commonly used as SPE sorbents. Graphene or CNTs, tend to aggregate, which hampers their
application in a ow-through packed-bed mode due to an undue
pressure drop and deteriorated retention eciency [106]. Due to
the fact that carbon nanobers have signicantly 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 nanobers
Electrospinning is a technique that relies on repulsive electrostatic forces to draw a solution of optimal viscoelasticity into
nanobers (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 ecient
technique for production of polymer with nanoscale brous
33
Table 5
Information on the different types of CNTs used as SPE sorbent [111]
Type of CNTs
Description
Characteristic
as-grown CNT
Obtained after synthesis and purication. 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 reux with
HNO3, H2SO4, HCl or mixtures.
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, esterication, 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 modied 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.
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
oxygen-containing radicals that have the ability to retain a
variety of metals at an appropriate pH.
Improved solubility and selectivity.
Functionalized CNT
Table 6
Information on carbon nanocones, nanodisks, nanobers and nanohorns
Carbon
nanomaterials
Description
nanocones
They consist of curved graphite sheets with one or more

pentagonal rings, dening a conical apex, which is extended
by a rolled-up graphene sheet into a larger conical structure.
Only ve diskrete pentagonal disklinations can dene the
tip of the carbon cone (six pentagons yield a nanotube),
which results in ve 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 ve-pentagon conical cap with
a cone opening angle of ~20 [114,115].
Disk-shaped graphene stacked atop each other, therefore
yielding into the well dened 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 dened cone apex
angles of 19.2, 38.9, 60, 84.6 and 112.9 degrees, occur in 20%
by weight [114].
Carbon nanobers are solid carbon bers with lengths in the
order of few microns and diameters below 100 nm. They
have a relatively high specic surface, and uniform
mesoporous magnitude and distribution. Carbon nanobers
is reported up to 1877 m2 g1 of a specic surface area,
among the highest ever reported for nano-structured
materials. Carbon nanobers could be easily available on a
large scale and their surface properties can be modied with
chemical treatments to satisfy some special needs [106].
nanohorns
nanodisks
nanobers
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.
structures. As a result, these bers present a high specic 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 ber 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 modication 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, readily-soluble and exible polymeric materials. At the step of development and optimization of 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, classication of electrospun NF-SPE devices can be proposed as follows
[3]:
34
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, threedimensional 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 elds 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
ecient 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 anion-exchange sorbent for preconcentration 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
Fig. 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 eciency. Results obtained revealed that dendrimers may

be employed as reusable, high-capacity extracting agents for insitu removal of heavy metals from contaminated soils.
Application of poly(propyleneimine) dendrimer immobilized silica
gel as novel microcolumn packing material for the on-line owinjection 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 eld but retain no residual magnetism after eld removal.
Therefore, suspended superparamagnetic particles adhered to target
analytes can be very quickly removed from the original matrices
using a magnetic eld, and do not agglomerate after removal of the
eld [95].
Recently, the application of MNPs in SPE has received considerable attention due to their high specic surface area and sorption
capacity, and high selectivity regarding analytes. Application of MNPs
in the extraction process can signicantly 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 simplied 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 eld [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 eld. Centrifugation or ltration of the sample being not
Fig. 4. Schematic illustration of the synthesis of dendrimer-functionalized KIT-6 [77].
35
Fig. 5. Schematic representation of MSPE.
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 Fig. 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
anity 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 elds 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 specicity it is an object of interest among scientists of different elds of science, who still are developing
knowledge about it. Molecular recognition processes are highly specic and can be replicated in vitro for several studies not only related
to biochemical procedures, but also to other elds including specic or highly selective media for SPE. This kind of sorbents includes
immunosorbents, molecularly-imprinted materials, and aptamerfunctionalized sorbents.
3.2.1. Aptamer-modied sorbents
Aptamers are a new class of short (up to 110 base pairs), singlestranded, synthetic oligonucleotides that can fold in characteristic
shapes capable of binding with high specicity 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 specicity
and binding anity, non-toxicity, good stability, and easy, controllable modication. This aspects make aptamer-modied sorbents
useful in wide variety of applications to recognize specic analytes
ranging from small molecules to proteins, cells and even tissues [120].
Generally, specic aptamers towards a target analyte can be produced by in-vitro method known as systematic evolution of ligands
by exponential enrichment (SELEX). See Fig. 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 amplication
by PCR [52,120]. A positive aspect of this process is that overall
process is automatable. Moreover, rational amounts of highspecic 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 ecient selection methods, including non-SELEX, cellSELEX, automated-microuidic 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 modied what allow to improve their binding properties and to broaden range of analyte of interest.
Due to the inherently high anity and selectivity associated with
aptamers, amptamer-functionalized materials seem to be ideal SPE
sorbents for selective extraction, separation, purication, 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 anity column, aptamer-functionalized magnetic SPE (AFMM), aptamer-functionalized surface-anity SPE (AFSASPE) have been developed. There are summarized and described in
Table 7.
36
Fig. 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) RNA;4 Addition of the target analyte to the nucleic-acid pool; 5 Washing of non-specic or low-anity binding nucleic-acid molecules; 6 Isolation of RNA/DNA target
complexes; 7 Amplication by RT-PCR/PCR; 8 After enough cycles 1 to 7, the desired amount of specic RNA/DNA can be isolated and characterized [52].
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 anity 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-bers 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
Table 7
Information on the selected aptamer-funtionalized SPE
Aptamer
Description
Aptamer-functionalized
anity column
The most commonly AF anity 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 eciency 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. modication 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 anity substrates can:
i. act as an ionization substrate for MS,
ii. can specically capture target analytes,
iii. can remove interfering components.
AFMM
AFSA-SPE
immune response with a high anity, 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
rst 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 puried.
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-specic
interaction,
should be pressure-resistant for use in on-line systems.
Taking into account commonly used sorbents, only silicabased ones meet the three aforementioned requirements, therefore,
in order to reduce the time for the preparation step, the use of commercial silicas, already modied 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 purication
obtained using these systems permits an ecient coupling with GC/
MS or LC/MS. Several class-selective immunosorbents have been
37
optimised for the trapping of pesticides and priority industrial

organic pollutants (See Table 4). Immunosorbents are robust, and
validation studies using certied 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 specic 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 Fig. 7. Recently, this method is
attracting widespread interest in many elds 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
uids and environmental samples. The application of MIP as selective sorbent for SPE was rst proposed in 1994 by Sellergren [123].
Since this time, acrylate-based MIPs became a popular choice as selective and specic 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.
Fig. 7. The basic principles of molecular imprinting.
38
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 specic
binding sites in the MIP sorbents.
MIPs presents many advantages but the most importants for SPE
are their high selectivity and anity 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/
specic 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 nanoparticlestabilized emulsion (Pickering emulsion) polymerization. During the
polymerization, the amount of the porogen used affected the stability of the Pickering emulsion and also the specic 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 insucient leaching of the imprint ion can
occur, which results in bleeding of the materials [90].
Nowadays, IIPs are of particular interest in the eld of separation science and are widely used in the solid-phase extractive preconcentration 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 classied 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 crosslinked 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;
trapping of non-vinylated chelating ligand via imprinting of

binary/ternary mixed ligand complexes of metal ions with nonvinylated 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 specic 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 specic recognition sites on the surface
of magnetic particles which restricts the amount of binding sites.
However, this could be improved with the support of mesoporoussilica materials with high pore volume, large surface area, good
biocompatibility, easily modied 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 100010400 m2/g,

uniform pore structure with specic pore size,
tailorable polarity,
high thermal stability.
Due to the aforementioned properties, MOF materials have attracted special attention in analytical applications. The inherent high
specic surface area provides a large adsorption capacity. The specic 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 denition 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 uids [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
Table 8
Comparison of selected sorbents
Type of sorbent
sorbent
Amount of
eluting solvent
Extraction
time
Type of
analysis
Preparation of sorbent
Amount of steps
Environmantal nuisance
Reuse of
sorbent
Toxicity of sorbent
EC50/LC50 [mg/L]
Ref.
No data
Acute toxicity
V. scheri
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
[128]
[129]
[55,106,107,130]
Magnetic nanoparticles
Fe3O4@SiO2-C18
12100
80 l5 ml
+++
Carbon nanomaterials
Graphene
2030
0.305 ml
+++
Off-line
On-line
Off-line on-line
Graphene oxide
25100
24 ml
++
Off-line on-line
625 ml
++
Off-line on-line
2200
100 l1 ml
+++
Off-line on-line
Fullerene
60100
150 l1 ml
++
Off-line on-line
CNF
2.5100
1 l5 ml
++
Off-line on-line
Amino-modied MNPs
820
15500
4150
30200
200ul2 ml
3 ml15 ml
200 l
28 ml
+
++
+
++
Off-line on-line
Off-line on-line
Off-line on-line
Off-line
MWCNT
SWCNE
Aptamer-functionalized sorbents
MIP
MOF
IIP
0.33150
[55,131133]
[71,134136]
[71,111,136]
[64,136138]
[73,139141]
[120,142144]
[145148]
[99,149151]
[99,152,153]
Amount of
sorbent [mg]
+++ 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.
39
40
excludes the macromolecules on the surface of the material by physical or chemical means. Taking into account the synthesis of RAMs
as well as the nature of the barrier and the surface structure of the
sorbent, these materials can be classied 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 specic 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 congurations to adapt SPE to specic
situations and the improvement of automatic devices undoubtedly allowed to the increasing application of SPE in different elds
of chemical analysis.
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 specic parameters. Comparison of selected sorbents together
in the point of environmental impact are presented in Table 8.
Signicantly, 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 simplied 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 signicantly 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
2015 2017, Project No. IP2014 037573.
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Modern trends in solid phase extraction: New

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All in-text references underlined in blue are linked to publications on ResearchGate,

Available from: Justyna Potka-Wasylka

Trends in Analytical Chemistry 77 (2016) 2343

Contents lists available at ScienceDirect

Trends in Analytical Chemistry

Modern trends in solid phase extraction: New sorbent media

Department of Analytical Chemistry, Faculty of Chemistry, Gdan

Modern analytical chemistry offers many techniques as well as

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

It is well known, that monitoring of compounds present in

advanced sorbent materials to improve selectivity or specicity

2. The formats and procedures in SPE

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

made available for commercial purposes from1989 by 3M in an

the possibility of increasing the ow rate of the sample, thereby

In addition to the high ow rates and the high cross-section area

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

Immobilized in PTFE bres

Empore SPE disk [14,19,20]

sorbent is immobilized in polymer or glass bers

The disks in which the sorbent particles are immobilized between

Disk in cartridge column

Immobilized between two

Immobilized between two layers of

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

- possibility of preparing in laboratory

small volume of elution solvents

Small cross-sectional area

- effectiveness of extraction depends

application. In Table 2, comparison of formats and devices used in

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

Multiwalled carbon nanotubes

molecularly imprinted polymers

Octadecyl modied silica

Octadecyl modied silica

Octadecyl modied silica

Sewage, River water

section has been focused on the preparation and applications of novel

modied materials based on chemically bonded microparticles

electrostatic forces, hydrogen-bonding, Van der Waals forces, -

a large specic surface area (theoretical value 2630 m2/g) which

Graphene, graphene oxide

environmental water and

chlorophenoxy acid herbicides

River and sea water

Mercury (II), methylmercury(I)

apple juice and red grape must

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

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343

(continued on next page)

F(ab)2-succinimidyl silica particles

End1: 0.5 ng/mL

feed, meat and liver

human urine and plasma

geochemical reference sample

J. Potka-Wasylka et al./Trends in Analytical Chemistry 77 (2016) 2343