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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc
A review: Recent advances in solid phase microextraction of toxic pollutants
using nanotechnology scenario
Muhammad Saqaf Jagirani
a,b
, Mustafa Soylak
a,c,⁎
a
Faculty of Sciences, Department of Chemistry, Erciyes University, Kayseri, Turkey
b
National Center of Excellence in Analytical Chemistry, University of Sindh 67080 Jamshoro, Sindh, Pakistan
c
Technology Research and Application Center (TAUM), Erciyes University, 38039 Kayseri Turkey
ARTICLE INFO
Keywords:
Carbon-based nanomaterials
Metal oxide nanoparticles
Metal nanoparticles
Solid phase microextraction
ABSTRACT
The enrichments of emergent pollutants from different compounds with complex matrix makes it critical and
stimulating to develop new solid phase microextraction coatings tools with high enrichment capacities provide
excellent chances for it. This review précises the used nanomaterials for the fabrication of solid phase micro-
extraction coatings, including metal oxide nanoparticles, metal nanoparticles, carbon-based nanomaterials, and
silica nanoparticles. To obtain solid phase microextraction coatings with outstanding physical performance, high
enrichment capacity, anti-interference ability, and suitable fiber coating technique and supports are designated
according to the assets of coating materials. In addition, the analytes influencing the enhancement effect and the
factors of coating materials are summarized and explained preliminarily, promoting for the further design of
cutting-edge coating materials with boosted the performance.
1. Introduction
In environmental analytical chemistry samples, preparation and
conservation of samples are a very important concern, since environ-
mental analysis requires accurate monitoring of the level of pollutants
in different environmental samples. The preparation of samples is a
very critical process all over the analytical procedure. Because it re-
quires isolation/ enrichment and clean-up steps that remove the in-
terferences and facilitating the target detection of compounds in the
complex matrix at the trace or ultra-trace levels. Different conventional
methods including liquid–liquid extraction (LLE) [1–4], solid-phase
extraction (SPE) [5–14] and solvent extraction (ASE) [15,16], were
used for the extraction and pre-concentration of analyte samples.
Conventionally, the performance and evaluation of the sample pre-
paration methods are based on the complete extraction and recoveries.
In this regard, the solid-phase extraction (SPE) and liquid–liquid ex-
traction (LLE) have been used the powerful tool for the extraction and
pre-concentration of the analytes [5–8], but it has some limitation such
as a large amount of hazardous and expensive organic solvents and
time-consuming and loss of analyte. In the past decade, researchers pay
more attention to solving these problems by emerging techniques that
reduce the number of sample preparation and pre-treatment steps and
the solvent consumption and able to detect the target analyte from the
real matrix [17,18]. In this regard, novel extraction techniques are used
the solid phase microextraction are signify an important impact to
improve the sample preparation and pre-concentration performance,
which especially report the problems of automation, miniaturization,
on-site analysis, and time proficiency [19–21]. Various types of mi-
croextraction methods were reported such as; single-drop liquid mi-
croextraction (SDLME) [22], hollow fibre liquid-phase microextraction
(HF-LPME) [23], dispersive liquid–liquid microextraction (DLLME)
[24], headspace solid-phase microextraction (HS-SPME) [25], in-syr-
inge dispersive liquid–liquid microextraction (IS-DLLME) [26], and
solid phase microextraction (SPME) [27]. These microextraction ap-
proaches are usually defined as sample preparation and pre-con-
centration process that consume a very small volume of extracting part
relative to the analyte volume under severely defined extraction con-
ditions (pH, temperature, extraction time, stirring rate, salt concentra-
tion, and sample volume, etc.). The best dynamic monitoring approach
to fulfill the green analytical chemistry (GAC) procedures. The in-
tegration principles of Green Chemistry in the analytical methods have
occurred as one of the important research approaches inside the com-
munity of analytical chemistry, leading to the advancement of green
analytical chemistry (GAC) [28]. Among the approaches, the mini-
mization, elimination or replacement, of destructive organic solvents in
the preparation process of the analytical samples that enhance the ap-
proaches by using the on-line, robust microextraction methodologies
(this way allowing a decrease of a number of steps, costs, and analysis
https://doi.org/10.1016/j.microc.2020.105436
Received 24 June 2020; Received in revised form 24 July 2020; Accepted 19 August 2020
⁎
Corresponding author at: Faculty of Sciences, Department of Chemistry, Erciyes University, Kayseri, Turkey.
E-mail address: soylak@erciyes.edu.tr (M. Soylak).
Microchemical Journal 159 (2020) 105436
Available online 24 August 2020
0026-265X/ © 2020 Elsevier B.V. All rights reserved.
T
time, while consenting the growth of the high-throughput approaches
[29–31], In the microextraction techniques very low volumes of both
extracted analyte were required , that have been familiarised to over-
come the sustainability the limitation of the conventional sample pre-
paration analytical techniques [32]. The analytes are eliminated using
appropriate liquid through the solvent microextraction method or by a
small amount of a solid (adsorbent) or semisolid polymeric material
through the SPME techniques [33,34]. SPME method is very useful and
alternative for the sample preparation due to their selectivity, simpli-
city, cost effective, low amount of solvent consumption, and superb
capacity to clean up the samples.
2. Solid phase microextraction (SPME)
Firstly, SPME was reported by Pawliszyn in 1997. It is a unique non-
exhaustive sample, pre-concentration, and removal technique [27,35].
The new SPME device contained a very small amount of the active
immobilized material on the surface of the fiber, developing a coating
of 1 cm with length and contain up to 100 µm thicknesses. In this
method, the fiber material is exposed to the sample to execute the
elimination of the analytes for a started time. Then, the target species
are desorbed from the adsorbent either by the thermal desorption by
using a solvent. SPME offers reusability, simplicity absence of the or-
ganic solvents in the process if using automation, thermal desorption,
and impressive enrichment capacity [31]. The superiority of the ana-
lysis in environmental media depends on the selected sample pre-
treatment [36–38]. It has various applications including in food
[27,39–45], biochemistry [46,47], environment [48–61], medicinal
plants [62], and pharmaceutical [63–68] because it is simple, highly
selective, time-saving and solvent-free technique [69]. It has been hy-
phenated with several analytical techniques like as HPLC [27], GC [70],
CE [71], MS [72] and UV [73], Therefore, the proficient and environ-
mental friendly monitoring method usually needs and there is a
growing demand for the strategies that decreasing the matrix coex-
istences, especially in the case of the persistent organic pollutants
(POPs) and volatile organic compounds (VOCs) the occurring at very
low levels in the complex or problematic volatile matrices. These cases
need to minimize the last volume of the target analytes to the higher
concentration of the analytes at low-level quantification [74]. Fur-
thermore, the efficacy, renewability of extraction, and disposal of the
adsorbents with numerous analytes in the environmental samples es-
sential to be assessed, representing some of the limitations such as low
thermal and chemical stability, fragility, memory effect, unstable at
higher or lower pH, low stability limited durability of coating, unsuit-
ability with complex matrix and lower selectivity towards the target
analytes. Also, the performance of such methods is not excused of
problems and expensive. Due to such limitation of reported materials
the researchers focused on the nanomaterials. Nanomaterials (NMs)
exhibit unique electrical, optical, catalytic and magnetic properties and
have shown a numerous interesting applications in the different ana-
lytical process [75]. The NMs have definite features that make this field
very attractive to overawe the disadvantages originate when using the
traditional extraction techniques, while the accurate selection of the
NMs with a suitable confirmation or morphology must be considered
[76].
3. Nanomaterials in SPME methods
Nanotechnology is rapidly growing to almost every field, and new
subjects are frequently emerging. NMs are directed at the nano-scale,
the ranging from the 1 to 100 nm (nanofibers, nanoparticles, nano-
flakes, nanorods, nanocomposites, nanotubes, nanosheets, nanohorns,
nanospheres, and nanocubes) [76]. In the present time, nanomaterials
have been an attractive candidate for the extraction techniques due to
their high surface area, high porosity, which improves the extraction
efficiency [77] and the extraction rate [78]. NMs contain remarkable
mechanical, chemical, and thermal stability due to these unique prop-
erties NMs are the best candidate for the SPME coatings [75,79–81].
This review is focused on the application of nanoparticles in the field of
SPME in sample preparation and pre-treatment in analytical methods.
NMs are commonly used to enhance the progress of analytical meth-
odologies. NMS is suitable for their determination and characterization
[82]. NMs are used in the SPME and sample preparation that gain the
focus of researchers. In the last decade number of research papers were
reported that SPME is applied in the environment In order, Khajeh et al.
have discussed, preparation, classification, and applications of different
NMs as adsorbents for the environmental analysis [83]. Xu et al. have
studied the applications of NMs as adsorbent material for different
purposes [84]. In another analysis, the synthesis and application of
nano-based imprinting materials in sample preparation were reported
[85]. Due to their large surface area and their capability to incorporate
with different functional groups on the surface, the nanomaterials have
direct application in the solid phase microextraction (SPME) process
including large adsorptive capacity, low resistance to diffusion and fast
sorption kinetics. Different nanomaterials have been used as unique
sorbents for pre-concentration in SPME [86]. Including MWCNT/Fe
3
O
4
[87,88], Cu
2
O-CuO ball like/multiwalled carbon nanotube[89], carbon
nanoparticles [90,91], silica nanoparticles [92–94], Au nanoparticles
[95–97], copper oxide nanoparticles [98,99], silver nanoparticles
[100,101], magnetic nanoparticles [102–110], magnetic graphene
oxide [111,112], polypyrrole-silver nanocomposite [113], nanofiber
[114], Hydrophilic modified magnetic multi-walled carbon nanotube
[115], SiO
2
@Fe
3
O
4
@nanodiamonds [116], Hyper-crosslinked polymer
nanoparticles [117], titania nanoparticles [63,118–120], carbon na-
notube cages [121], CoFe
2
O
4
nanoparticles [122,123], ZnO nano-
particle [124,125], magnetic metal–organic framework nanocomposite
[126], alumina nanoparticles [127], Mesoporous carbon–zirconium
oxide nanocomposite [128], fullerenes, carbon nanotubes (CNTs)
[129,130], and graphene [51,131,132], magnetic carbon nanodot/
graphene oxide hybrid material, graphene based composite materials
[133–135], graphene oxide/multiwalled carbon nanotube/Fe
3
O
4
/SiO
2
[136], iron (III)-based metal–organic framework/graphene oxide
[137], Fe
3
O
4
@SiO
2
@TiO
2
[138] were reported. Furthermore, the cen-
trifugation/ filtration is not necessary with these nano adsorbents and
the solid phase can very easily separated from the sample solution with
the help of external magnetic field. In other side there are some lim-
itation are found in the applications of NPs, the NPs contains high
surface energy and usually high surface area. Due to high surface en-
ergy and have been agglomerate or quickly adsorb other molecules to
desire their surface free energy. The accumulation leads to decreasing
the adsorbent specific surface area [76].
4. Nanomaterials based application of SPME in different fields
The entire development of a SPME process needs several inter-
mediate steps between the collection of samples and finalize the results
counting sample pre-treatment, SPME, desorption, and determination.
The first step contains sample collection from the environment (water
sample) in the second step the collected sample is exposed to the SPME
unit. In this step, the sample was pre-concentrate in order to get higher
sensitivity and selectivity. To this end several SPME methods contain
different configurations such as in-needle, in-tube, fiber, in-tip, tir-bar
microextraction and thin-film, the selectivity of these configurations is
based on their advantages and dis advantages. The key advantages of
SPME process are online, solvent free, and suitable for volatile organic
compounds. The dis advantages are breaking and losing the materials
desorption and poor selectivity. The SPME contain two modes the first
mode is based on the direct immersion of analyte to the sample. While
second mode is based on analyte extraction from volatile or semi-vo-
latile compounds from the sample. In both process, NMs has been ideal
candidate to improve the efficiency and selectivity of SPME techniques
[76].
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
2
4.1. Direct immersion method (DI-SPME)
In the DI-SPME process, the NMs are directly in contact with the
sample matrix which contains the objective analytes. NMs would be
able to isolate the objective analytes from the sample while discharging
the other coexisting compounds of the sample matrix. In this concern,
the NMs would have enough adsorption capability to adsorb the target
analytes and would have definite interactions with them. Then, elution
by the organic solvent or rising the temperature must easily release the
objective analytes entirely before introducing it to the detector.
Moreover, in order to increase the adsorption capability, the applica-
tion of NMs that contain high surface areas that can be the best solu-
tion. Now, the nano-adsorbents are widely used in environmental ap-
plications because of their unique properties like as, high adsorption
capacity, and high selectivity [76].
4.2. Headspace method (HS-SPME)
In HS-SPME method sample is placed into the sealed vial with a cap
and the NMs are Here, the sample is placed into a vial is sealed with a
cap, and the NMs are showing to the headspace of the material (gas,
solid, or liquid) to eliminate the target volatile/semi-volatile analytes.
This process increases the selectivity to words the higher number of
volatile compounds are present in the environmental samples. For the
HS-SPME and DI-SPME methods, the NMs are ideal candidates. Though
the desorption phase in the HS-SPME is generally thermal desorption,
and the NMs contain higher thermal and chemical stability at deso-
rption temperatures [76].
4.3. Application of metal oxide nanoparticles in the field SPME
The Metal Oxide Nanoparticles (MONPs) exhibit good adsorption
capability due to large surface-to-volume ratio, high thermal stability
and cost-effective, have been developed as an efficient coating material
for SPME, such as titanium dioxide (TiO
2
) [119,139,140], zinc oxide
(ZnO) [63,141], and cobalt oxide [98]. Iron oxide [142]. Fig. 1 Shows
the schematic representation of MONPs based SPME procedure.
Fahimirad et al. reported melamine based multi-walled carbon na-
notubes Fe
3
O
4
[87] Gholivand et al., reported Co
3
O
4
nanomaterials for
the preparation of a new SPME coating material combine with GC–MS.
The chemical bath deposition (CBD) method was used for the pre-
paration of and immobilization of Co
3
O
4
nanomaterials on the platinum
wire for the fabrication of SPME fiber. This material was used for the
extraction of toluene, benzene xylene and ethylbenzene (BTEX) com-
pound from real samples [98], Jannesar et al., proposed new magnetic
nanoparticles based material combine with coacervated SPME used for
the extraction and pre-concentration of tricyclic antidepressant drugs
from the biological samples the LOD was found up to from 0.51 to
1.4 ng mL
−1
. This method is successfully applied for the extraction of
targeted analytes from the biological samples [102]. Tasmia et al..
proposed a new magnetic graphene oxide beads based method as an
adsorbent material for SPME for the extraction of endocrine-disrupting
compounds from the aqueous samples and combine with high-perfor-
mance liquid chromatography (HPLC) with ultraviolet detector. The
epichlorohydrin and bisphenol-A adsorption. The adsorption capability
was 7.01 mg g
−1
for bisphenol-A and 6.73 mg g
−1
for epichlorohydrin.
The LOD was found 13.99 ng L
−1
and 8.25 ng L
−1
A [111]. Lopes et al.,
develop a new method in which magnetic nanoparticles were functio-
nalized with histamine (HIS-MNP) are used for the SPME material for
the extraction and preconcentration of estriol, estrone, 17–estradiol,
17-ethynylestradiol, 4-nonylphenol, and 4-octylphenol from the water
samples. The percentage recovery was found up to 82 and 120% [103].
Li Li et al.. reported new TiO
2
-nanoparticles based coating material
fabricated by a one-step anodization process on titanium wire substrate,
a new phenyl functionalized SPME fiber coating material was prepared
by the simple, cheaper rapid in situ chemical assembling method be-
tween the fiber and the surface of the titanol groups and tri-
chlorophenylsilane reaction. This method was used with HPLC-UV it
exhibits good extraction property. This proposed method is successfully
applied for the detection of UV filters from the aqueous environment
Fig. 1. Schematic representation of MONPs based SPME procedure.
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
3
with the 0.1–50 ng L
-1
LOD value. The percentage recovery was ob-
tained up to 86.2% to 105.5%. This functionalised material perfume
good reproducibility, high mechanical strength, good stability and
durable [119]. Mei et al., reported Magnetic nanoparticles used for the
magnetism-reinforced in-tube (MR/IT-SPME) for the extraction of
heavy metals including Co(II), Hg(II), and Cu(II). This synthesized
material coupled with the HPLC with diode array detection (DAD). The
extraction efficiency was obtained up to 47–65% to 67-89%. Finely this
method was successfully applied for the detection of heavy metals from
the seafood and water samples [143]. Liu et al., reported Mesoporous
TiO
2
nanoparticles for the SPME coating material fabricated with the
stainless steel fibers with the silicone sealant film and the mesoporous
TiO
2
powder. This proposed method was used for the extraction of
organochlorine pesticides (OCPs). For the analytical applicability, the
LOD was found up to 0.08–0.60 ng L
-1
. The developed method was
successfully applied for the extraction of OCPs from the aqueous media
[139]. Ghani et al., synthesized ZnO nanoparticle applied to prepare
polymer monolith/zeolitic imidazolate framework (ZIF) for the SPME
coatings. The polymer/ZIF- SPME coupled with gas chromatography-
flame ionization detector (GC-FID) was used for the extraction of to-
luene, benzene, xylenes, and ethylbenzene from the water samples. The
LOD was found up to 0.02–0.11 g L
−1
. The percentage recovery was
obtained up to 88% of the different water samples [124]. Wang et al.,
developed a new TiO
2
-nanoparticle packed with microchannel-array
glass microchips (TMA-microchips) for IT-SPME coating material for
the extraction of phosphopeptides using the plasma-assisted method.
This proposed method was applied for the extraction and pre-con-
centration of phosphopeptides from a protein digestion matrix [120].
Pang et al., synthesized new magnetic nanoparticles as a monolith-
based magnetism-reinforced in-tube SPME (MB-MR/IT-SPME) material
for the extraction and pre-concentration of sulfonylurea herbicides
(SUHs) from the aqueous and oil samples. MB-MR/IT-SPME coupled
with HPLC with a diode array detector (HPLC/DAD). The LOD was
found up to 0.030–0.15 μg L
-1
and 0.30–1.5 μg kg
−1
respectively [144].
Dogaheh ang Behzadi, reported silica-based nanomaterials (polypho-
sphate-doped polypyrrole/nanosilica composite material for the coating
on steel wire for SPME) for the selective extraction of phthalates and
bisphenol A from aqueous samples. The LOD was found up to 0.002
e0.01 ng mL
−1
and the percentage recovery was obtained up to 96%
[94]. Banitaba et al., reported new TiO
2
based coating materials for the
SPME it is applied for the extraction and pre-concentration of phthalate
esters from the aqueous environment before GC analysis. The LOD was
found up to 0.05 and 0.12 g L
−1
with a good percentage recovery up to
86 to 107% [118]. Shirkhanloo et al., proposed amine-functionalized
mesoporous silica nanoparticles (NH2-UVM7) were immerged in ionic
liquid (IL) as extraction phase. The electro-thermal atomic absorption
spectrometry (ET-AAS) was used for the quantification of As(V) by after
the back extraction. The developed method was successfully applied for
the quantification of As(III) and As(VI) from aqueous samples and
human by-product with resultant recoveries in the range of 95–103%
[93]. Ting Li et al., reported silica nanoparticle (NP) modified with
octadecyl groups used in the in-tube SPME coupled with HPLC with UV
detection. This proposed method was applied for the extraction of
polycyclic aromatic hydrocarbons and endocrine disruptors. The LOD
was calculated in the range from 0.42 to 0.78 and 0.034–0.19 ng mL
−1
[92]. Meira et al., prepared magnetic (CoFe
2
O
4
) SPME materials com-
bine with energy dispersive X-ray fluorescence spectrometry (EDXRF)
for the extraction and pre-concentration of metals including Pb, Cd, Cu,
Cr, V, and Mn from the ethanol fuel samples using magnetic materials
impregnated with 1-(2-pyridylazo)-naphthol (PAN). The developed
method allows the detection of metals with LOD 0.016, 0.013, 0.012,
0.012, 0.009, and 0.011 mg L
−1
for Pb, Cd, Cu, Cr, V, and Mn re-
spectively. This method was successfully applied to eliminate the me-
tals from the ethanol fuel by Lucilia [122]. Dias et al., synthesized
CoFe
2
O
4
magnetic SPME coating materials for the extraction and pre-
concentration of cadmium from water and oyster samples using flame
atomic absorption spectrometry (FAAS). This proposed method allowed
the LOD up to 0.24 μg L
−1
this method is successfully applied for the
extraction of cadmium from the water and oyster samples [123]. Fur-
thermore, Table 1 shows the different types of metal oxide nanoma-
terials were used in the SPME materials for the microextraction of
different pollutants from the environmental, food, biological and
pharmaceutical samples.
4.4. Metal nanoparticles
Due to the remarkable physical and chemical properties, MNPs have
been used in different fields including, sensors, catalysts, and adsorbent
materials, and also used in SPME coatings materials. MNPs contain
durability, excellent mechanical strength, and good selectivity [198].
MNPs have played a key role during the selective and highly efficient
extraction of analytes from the different matrix. Among the MNPs, the
gold nanoparticle (AuNPs) is a good candidate for excellent coating
material because of excellent binding capacity towards the organic
compounds contain thiol group and also good efficiency towards the
other functionalities [171,199]. 1,8-octanedithiol based functionalized
AuNPs exhibits excellent extraction capacity and good selectivity to-
wards selective PCBs, chlorophenols (CPs) [96]. Feng et al., reported Au
nanoparticles based materials for the SPME coupled with GC for the
extraction of aromatic hydrophobic organic chemical pollutants from
the soil and rainwater. The Au nanoparticles based SPME-GC proposed
method was successfully applied for the real samples and get percen-
tage recovery in the range of 78.4% to 119.9% [95]. Nozohour et al.,
reported polypyrrole-silver nanoparticles were prepared hollow fiber
for the SPME process and it was used for the determination and pre-
concentration of trace level of parabens from aqueous media, beer and
fruit juice samples with 0.05 μg L
−1
, LOD. The percentage recovery was
found up to 90.4–104.0% [113]. Nan Jiang et al., reported a new
method for the preparation of silver nanoparticles-coated monolithic
functionalization with sodium hyaluronate-functionalized ur-
ea–formaldehyde (HA-UF) used as a coating material for the in-tube-
SPME for the extraction of monounsaturated fatty acid methyl esters
(MUFAMEs). In-tube- SPME- Ag + -HPLC applied for the detection of
MUFAMEs the LOD was found in the range of 5.2 g kg
−1
[101].
Moreover, Table 2 represent the different number of metal nanoma-
terials that were used SPME materials for the microextraction of dif-
ferent analytes from the food, biological environmental, and pharma-
ceutical matrices.
4.5. Carbon based nanomaterials used in SPME
In 1991, Iijima was firstly discovered Carbon nanotubes (CNTs)
[207], the CNTs contain unique mechanical, electrical, physical and
chemical properties. It contain notable high stability that allows them
to be used under cruel chemical and thermal conditions, which provides
the CNTs with wide range of applications [208]. Furthermore, the very
high surface to volume ratio, hydrophobic in nature and probability of
establishing the p-p interactions that can busted the extraction and
separation performance of CNTs, representing the great potential to be
used in the SPME coatings [81,209]. In the earlier stages, CNTs-based
SPME process were prepared with different commercial CNTs, counting
single-wall and multi wall carbon nanotubes (SWCNTs and MWCNTs)
[210,211], without any further treatment. The coating materials en-
hance the extraction efficacies toward the hydrophilic organic pollu-
tants as compared to the commercial SPME fibers including PDMS/DVB
and PDMS. As the studies based on CNTs are continuously boosted, the
surface of CNTs can be simply modified by different functionalization,
resulting in improved dispensability and accessible surface [212–215].
The modified CNTs can be confirmed by X-ray photoelectron spectro-
scopy (XPS) and Fourier Transform Infrared (FTIR) spectroscopy. Fig. 2.
Shows the schematic representation of different Carbon-based nano-
materials based SPME the Fig. 1 and Fig. 2 have a little bit different
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
4
Table 1
Metal oxide nanoparticles were applied in the field SPME.
Material Type Analytes Nanomaterial Sample Type of SPE Instrument LOD (ug/L) Refs.
Vortex-assisted magnetic dispersive SPME
(VAMDSPME)
Dicofol Magnetic molecularly imprinted
microspheres (mag-MIMs)
Tea SPME GC 0.005 [145]
Ultrasound-assisted dispersive-magnetic
nanocomposites SPME
Azure II Zn@Cu-Fe
2
O
4
-NCs-CNT Water SPME UV 0.126 [146]
Ultrasound-assisted dispersive-magnetic
nanocomposites SPME
Naproxen and ibuprofen Magnetic ethylenediamine-functionalized
graphene oxide
Cow milk, human
urine, river, and well
water
SPME HPLC 0.003 [147]
Amine-functionalized magnetite
nanoparticlesassisted microwave
distillation and simultaneous HS-SPME
Essential oil in Perilla
frutescens L
Amine-functionalized magnetite
nanoparticles
Traditional Chinese
medicine (TCM)
SPME GC–MS [148]
Vortex-assisted SPME Indium Oleic acid-coated magnetite nanoparticles aqueous samples SPME FAAS 6.02 [149]
Ultrasonic-assisted dispersive SPME Sotalol MWCNT-MMIPs Biological fluid SPME HPLC-UV 0.031 [150]
Magnetic Fe3O4 hollow microspheres-assisted
microwave distillation HS-SPME
Essential oils of lavender MFHMs In dried lavender HS-SPME GC–MS [151]
Ultrasonic-assisted magnetic dispersive SPME Meloxicam and piroxicam Fe
3
O
4
/NiO@SiO
2
-OP
2
O
5
H Well, tap and river
water
SPME HPLC [152]
SPM Ibuprofen, diclofenac,
naproxen, and nalidixic acid
Magnetic Fe
3
O
4
/Cu3(BTC)2 Human urine, serum,
plasma, and tablet
formulation
SPME HPLC 0.03–0.0 5, 0.12–0.18 [126]
HS-SPME and DI-SPME Aldehydes Fe
3
O
4
/SiO
2
/PPy Biological fluids SPME GC-FID 0.05 [142]
Ultrasonic-assisted magnetic dispersive SPME Duloxetine, venlafaxine, and
atomoxetine
Graphene oxide Quantum Dots@ Ni
nanocomposites
Human urine, river
water and well water
samples
UAMD-SPME HPLC 0.11 [152]
Vortex-assisted magnetic dispersive SPME Triazine Herbicides Fe
3
O
4
@MIL-100(Fe) Water and vegetable SPME HPLC 0.53 [114]
silica-coated Fe
3
O
4
nanoparticles with 2,6-
diaminopyridine
Cu(II) Zn(II) Fe
3
O
4
@SiO
2
@DAPD Water and vegetable SPME FAAS 0.014 [153]
Fe
3
O
4
shell of silica and modified with the
chelator N-(2-acetylaminoethyl)-N′-(3-
triethoxysilylpropyl)thiourea
Hg(II) Fe
3
O
4
@SiO
2
@AMPT Water MSPE DMA(batch) 0.0017 [154]
Fe
3
O
4
@SiO
2
@polypyrrole magnetic
nanocomposite for SPME
Cd(II) L- Fe
3
O
4
@SiO
2
@PPy Seafood MSPE FAAS 0.03 [155]
MnFe
2
O
4
and magnetic
takovite–aluminosilicate adsorben
Pb(II) [Ni
6
Al
2
(OH)16]CO
3
·4H
2
O@MnFe
2
O
4
nanocomposite
Water and food MSPE FAAS 0.06 [156]
Fe
3
O
4
-doped Mg–Al layered double hydroxide
(LDH) as a nano-sorbent.
As(III)/ As(V) Fe
3
O
4
/Mg–Al-LDH nano hybrid Water MSPE–CL(batch) 0. 2.0 [157]
magnetic nanocomposite of the type Fe
3
O
4
/
TiO
2
/PPy
Pb(II) Fe
3
O
4
/TiO
2
/PPy Water MSPE FAAS 0.021 [78]
Diethylenetriamine-functionalized magnetic
graphene oxide nanocomposite
Ni(II) Co(II) Fe
3
O
4
/GO Biological MSPE-ICP-OES FAAS 0.0016 [158]
Amino-functionalized Fe
3
O
4
–graphene oxide
nanocomposite
Cr(III), Cr(VI) Fe
3
O
4
/GO-TETA Water and
wastewater
MSPE-FAAS
(batch)
FAAS 0.116 [159]
SiO
2
-coated magnetic graphene oxide modified
with polypyrrole–polythiophene
Cu(II, Pb(II), Zn(II), Cr(III), Cd
(II)
MGO/SiO
2
@coPPy-T Water and food MSPE-FAAS
(batch)
FAAS 0.015, 0.065, 0.023,
0.036, 0.21
[160]
Unctionalized magnetic multi-walled carbon
nanotube composite
Cd(II), Pb(II), Ni(II) Fe
3
O
4
–MWCNT@8-AQ Food, soil, and water MSPE-FAAS
(batch)
0.009, 0.072, 0.1 [161]
Vortex assisted magnetic solid phase extraction Pb(II), Co(II) MWCNT-Fe
3
O
4
@ SiO
2
@PAN Water and
wastewater
VAMSPE-FAAS
(batch)
0.176, 0.055 [162]
Magnetic graphitic carbon nitride
nanoparticles covalently modified with an
ethylenediamine
Pb(II), Cd(II) g-C
3
N
4
-SnFe
2
O
4
-TPED Food and water UAMSPE-FAAS
(batch
0.06, 0.01 [87]
Flow injection microfluidic device with on-line
fluorescent derivatization
Cr(III) MMWCNT Water MSPE-LIF based
microfluidic chip
(batch)
fluorescence spectrometer
charge-coupled device
(CCD) detector
0.0094 [163]
(continued on next page)
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
5
Table 1 (continued)
Material Type Analytes Nanomaterial Sample Type of SPE Instrument LOD (ug/L) Refs.
2-mercaptobenzothiazole/magnetic
nanoparticles modified multi-walled
carbon nanotubes
Pb(II) Cr(III) MWCNT-Fe
3
O
4
@2-MBT Water MSPE-FAAS
(batch)
0.021, 0.001 [164]
Ion-imprinted sorbent by surface imprinting of
magnetized carbon nanotubes
Cr(III) Fe
3
O
4
–MWCNT@ SiO
2
@ IIP Wastewater MSPE-FAAS
(batch)
0.029 [165]
Polythiophene-coated Fe
3
O
4
nanoparticles as a
selective adsorbent
Ag(I), Au(III), Cu(II), Pd(II) Fe
3
O
4
@PTh Water MSPE-ICP-OES
(batch)
0.02, 0.2, 0.05,0.1 [166]
Fe
3
O
4
@SiO
2
@polypyrrole magnetic
nanocomposite
Cd(II), Ni(II) Fe
3
O
4
@SiO
2
@PPy Seafood MSPE-FAAS
(batch)
0.03 [155]
Fe
3
O
4
@SiO
2
@polyaminoquinoline magnetic
nanocomposite
Cd(II), Pb(II) Fe
3
O
4
@SiO
2
@PAQ Agricultural , seafood MSPE-FAAS
(batch)
0.01, 0.07 [167]
Polythionine-coated Fe
3
O
4
nanocomposite Co(II) Fe
3
O
4
@polythionine Water and foodstuff MSPE-FAAS
(batch)
0.03 [168]
Ion-imprinted polymer coated magnetic multi-
walled carbon nanotubes
Pb(II) MMWCNT@IIP Biological and water UAMSPE-GFAAS
(batch)
0.24 [169]
Imprinted polymer (IIP) based on 4-
(vinylamino)pyridine-2,6-dicarboxylicacid
(VPyDC), was coated on Fe
3
O
4
nano-
particles
Pb(II) Fe
3
O
4
@SiO
2
@IIP Water and soil MSPE-FAAS
(batch)
0.09 [170]
Zn (II)-imprinted polymer grafted on graphene
oxide/magnetic chitosan nanocomposite
Zn(II) GO/MCTS-Zn(II)-IIP Water MSPE-FAAS
(batch)
0.009 [164]
Electrochemical in situ fabrication of titanium
dioxide-nanosheets
Polycyclic aromatic
hydrocarbons, phthalates
TiO
2
-nanosheets Water SPME HPLC-UV 0.026, 0.089 [140]
Zinc–zinc oxide nanosheets Polycyclic aromatic
hydrocarbons, phthalates
Zinc-zinc oxide nanosheets Water SPME HPLC-UV 0.052, 0.084 [171]
Co
3
O
4
nanoparticles were introduced as a
novel SPME fiber coating.
Benzene, toluene,
ethylbenzene and xylene
Cobalt oxide nanoparticles aqueous solutions SPME GC–MS [98]
Superparamagnetic graphene oxide-based
dispersive-solid phase extraction
Tamsulosin hydrochloride Magnetic graphene oxide (MGO)
nanocomposites
Plasma SPME HPLC-UV 0.017 [172]
Magnetic graphene oxide as adsorbent PAH metabolites Novel Fe
3
O
4
/graphene oxide composites Urine SPME UHPLC-MS 0.001–0.015 [173]
magnetic solid phase extraction (MSPE)
technique.
Methamphetamine Magnetic nano graphene oxide(MNGO) Urine SPME HPLC-UV 0.30 [174]
Magnetic solid phase extraction (MSPE)
technique
Pseudoephedrine Magnetic nano graphene oxide Urine SPME HPLC-UV 0. 25 [174]
Graphene oxide-Fe
3
O
4
nanocomposite
magnetic solid phase extraction
Psychoactive drugs Graphene oxide–Fe
3
O
4
(GO–Fe
3
O
4
)
nanocomposite
Urine SPME UHPLC-MS/MS 0.002–0.02 [175]
Magnetic solid-phase extraction Sulfonamides Fe
3
O
4
/graphene oxide nanocomposite Water SPME HPLC-DAD 0.50–0.1 [176]
Magnetic solid-phase extraction (MSPE)
technique
PCB 28 Fe
3
O
4
grafted graphene oxide Water SPME GC–MS 0.0027–0.0059 [177]
Magnetic solid-phase extraction based on
Fe
3
O
4
/graphene oxide nanoparticles
Crystal Violet Malachite Green Magnetic Fe
3
O
4
/graphene oxide (GO) Water SPME HPLC-UV 0.0091–0.012 [178]
Magnetic solid-phase extraction (MSPE) TNT Graphene oxide/Fe
3
O
4
as sorbent Water SPME HPLC-UV 0.03 [179]
Magnetic solid-phase extraction PAHs Fe
3
O
4
/graphene oxide nanocomposites Water SPME HPLC-UV 0.009–0.019 [180]
Graphene Oxide-Based Magnetic Solid Phase
Extraction
Sulfonamides Magnetic nanocomposite (Fe
3
O
4
@GO) Milk SPME HPLC-MS/MS 0.002–0.013 [181]
Magnetic graphene oxide nanocomposites as
the adsorbent
Azo dyes GO@Fe
3
O
4
nanocomposite Jelly, candy, plum SPME HPLC-UV 0.036–0.223 [178]
Graphene‐Fe
3
O
4
as a magnetic solid‐phase
extraction
Sulfonamides Graphene‐Fe
3
O
4
nanoparticle Milk SPME CE-DAD 0.089–0.231 [182]
Graphene oxide and Fe
3
O
4
magnetic
nanoparticles for the extraction
Flavonoids GO/Fe
3
O
4
Tea, wine, urin SPME HPLC-DAD 0.02–0.60 [183]
Iron oxide functionalized graphene oxide as an
efficient sorbent for dispersive micro-solid
phase extraction
Sulfadiazine Graphene oxide@Fe
3
O
4
Milk, honey, water SPME Spectrophotometry 0.340 [184]
(continued on next page)
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
6
Table 1 (continued)
Material Type Analytes Nanomaterial Sample Type of SPE Instrument LOD (ug/L) Refs.
Fe
3
O
4
@GO magnetic nanocomposite as the
adsorbent
Flavors, fragrances Fe
3
O
4
@GO nanocomposite Orange juice,
chocolate, fruit sugar
SPME HPLC-DAD 0.20–0.40 [185]
Magnetic solid-phase extraction Lignans Graphene oxide and hydroxylated Fe
3
O
4
Sesame oil SPME HPLC-UV 0.20–0.50 [186]
Magnetic solid-phase extraction Duloxetine Graphene oxide/Fe
3
O
4
@polythionine
nanocomposite
Plasma SPME HPLC-UV 0.05 [187]
Magnetic solid phase extraction Gemfibrozil Graphene oxide-magnetite nano-hybrid Serum SPME Spectrofluorometry 3 × 10–4 [188]
magnetic dispersive solid-phase extraction Chlorpheniramine Graphene oxide/Fe
3
O
4
@polythionine
nanocomposite
Plasma SPME HPLC-UV 0.04 [189]
Magnetic solid-phase extraction Malachite green Magnetic graphene oxide nanocomposite Water SPME UV Vis 0.02 [190]
Amine-functional magnetic polymer modified
graphene oxide as magnetic solid-phase
extraction materials
Chlorophenols NH
2
-MP@GO Water SPME HPLC-MS/MS 0.06–0.92 [191]
Magnetic solid‐phase extraction Estrogens Triethylenetetramine‐functionalized
magnetic graphene oxide
Water SPME LC-MS/MS 0.015–0.15 × 10–4 [85]
Magnetic solid-phase extraction PAHs Graphene oxide/Fe
3
O
4
@polystyrene
nanocomposite
Water SPME GC-FID 3 × 10–4–10 × 10–4 [192]
Porphyrin-functionalized Fe
3
O
4
-graphene
oxide nanocomposite
Sulphonamide TCPP/Fe
3
O
4
-GO Water SPME HPLC-DAD 8.37–11.67 [193]
Amino-terminated hyper-branched
polyamidoamine polymer grafted
magnetic graphene oxide nanosheets as an
efficient sorbent
PAHs Magnetic graphene oxide nanosheets
(DMGO)
Water SPME GC-FID 0.0003–0.001 [194]
Phytic acid-stabilized super-amphiphilic
Fe
3
O
4
-graphene oxide for extraction
PAHs GOPA@Fe
3
O
4
Vegetable oils SPME HPLC-DAD 0.006–0.015 [195]
Superparamagnetic core–shells anchored onto
graphene oxide grafted with phenylethyl
amine as a nano-adsorbent
Organophosphorus Fe
3
O
4
@SiO
2
@GO-PEA Fruit, vegetables,
water
SPME GC-NPD 0.002–0.01 [196]
Silica (ZnO/PT/SBA-15) as a SPME α-bisabolol, Cis-trans-farneso,
β-bisabolene, E-β–Farnesene,
Guaiazulene, α-Pinene and
Limonene.
ZnO/PT/SBA-15 Volatile oils SPME GC–MS – [125]
Mesoporous carbon–ZrO
2
nanocomposite
based SPME
Benzene, toluene,
ethylbenzene and m, pxylenes
ZrO
2
nanocomposite Water SPME GC-FID 0.05–0.56 [197]
Stir bar sorptive-dispersive microextraction N-nitrosamines CoFe
2
O
4
Cosmetic products SPME LC–MS/MS = [104]
Direct immersion (DI-SPME) Phthalate esters TiO
2
nanoparticles Water SPME GC 0.05 and 0.12 [118]
Magneticsolid phase microextraction Copper PV-MGO Water, black tea and
diet supplements
SPME FAAS 13.3 [112]
SPME capillary glass tube coated withFe
3
O
4
/
Cu
3
(BTC)2 metal organic frameworks
nanocomposite
Non-steroidal anti-
inflammatory drugs(NSAIDs)
(ibuprofen, diclofenac,
naproxen and nalidixic acid)
Fe
3
O
4
/Cu
3
(BTC)2 Human urine, serum,
plasma, and tablet
formulation.
SPME HPLC 0.03–0.0 5,0.12–0.18 [126]
Porous monolith-based magnetism-reinforced
in-tube solid phaseMicroextraction
Sulfonylurea herbicides Fe
3
O
4
magneticNanoparticles Water and soil SPME HPLC/DAD 0.030–0.150.30–1.5 [144]
Microchannel-array-based intube SPME Phosphopeptide TiO
2
nanoparticles Protein SPME MALDI-TOF-MS == [120]
Magnetic solid SPME Cd CoFe
2
O
4
nanoparticles Water SPME FAAS 0.24 [123]
Polymer monolith/zeolitic imidazolate
framework ZIF-SPME
Benzene, toluene,
ethylbenzene, and xylenes
(BTEX)
ZnO nanoparticle Water SPME GC-FID 0.02–0.11 [124]
Magnetic SPME Cd, Pb, Cu, V, Cr, CoFe
2
O
4
ethanol fuel SPME Energy dispersive X-ray
fluorescence spectrometry
(EDXRF)
0.12, 0.13, 0.16, 0.12,
0.09, and 0.11
[122]
Mesoporous TiO
2
nanoparticles SPME Organochlorine pesticides TiO
2
Water SPME GC–MS 0.008–0.060 [139]
Magnetism-reinforced in-tube SPME Cu(II), Co(II) and Hg(II) Modified Fe
3
O
4
magnetic nanoparticles
(MCEN
Environmental water
and seafood samples
SPME HPLC-DAD == [143]
Titaniananoparticles coating for SPME Ultraviolet (UV) filters TiO
2
-nanoparticals Real water SPME HPLC-UV 0.005–25 [119]
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
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Table 2
Application of metal nanoparticles in the field SPME.
Material Type Analytes Nanomaterial Sample Type of
SPE
Instrument LOD (ug/L) Refs.
Suspended nanoparticles
based SPME
Cobalt, nickel and Copper Alumina
nanoparticles
Water SPME ETAAS 2.5, 2.8 and 2.6 [127]
In-tube solid-phase
Microextraction
Monounsaturated fatty acid methyl esters (MUFAMEs) Ag NPs Food SPME HPLC 5.2 [101]
Hollow fiber SPME Parabens Ag NPs Water and beverages SPME HPLC/UV 0.01 [113]
Electrodeposition of gold
nanoparticles based
SPME
Phthalate esters (PAEs), polychlorinated biphenyls (PCBs),
chlorophenols (CPs), ultraviolet (UV) filters, polycyclic
aromatic hydrocarbons (PAHs)
C8-S-AuNPs/SS Water SPME HPLC 0.025 to 0.056 [96]
Au nanoparticles as a novel
coating for SPME
Aromatic hydrophobic organic chemical pollutants AuNPs Rainwater and soil SPME GC == [95]
Silver-coated SPME Naphthalene, fluorene, fluoranthene, phenanthrene, dibutyl
phthalate, dioctyl phthalate, dicyclohexyl Phthalate and
diallyl phthalate
AgNPs Disposable paper cup and
instant noodle barrel
SPME GC-FID 0.02–0.1 [200]
Basalt fibers functionalized
with gold nanoparticles –
SPME
Naphthalene, acenaphthylene, acenaphthene, fluorene,
phenanthrene, anthracene, fluoranthene and pyrene
AuNPs Tap water and rain water in-tube
-SPME
HPLC-DAD 0.003–0.015 [201]
Irect-immersion SPME Naphthalene, acenaphthylene, acenaphthene, fluorene,
phenanthrene, anthracene, fluoranthene, pyrene, benz(a)
anthracene, chrysene, benzo(b)fluoranthene, benzo(k)
fluoranthene, benz(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenz
(a,h) anthracene and benzo(g,h,i)perylene
AgNPs Underground water SPME GC-FID 0.06 [202]
Head Space SPME Naphthalene, anthracene, phenanthrene, pyrene,
acenaphthylene and fluoranthene
AuNPs Sea water SPME GC-FID 10–200 [203]
Gold Nanoparticles based
SPME
2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl-4-
methoxycinnamate, 2- ethylhexyl-
AuNPs River water, rain water and
wastewater
SPME HPLC-UV 0.004–200
0.00043–0.57
[204]
Au nanoparticle decorated
graphene oxide used for
the SPME
Naphthalene, fluorene, anthracene, fluoranthene, 1,4-
dichlorobenzene, 1,4- dibromobenzene, 2-
bromonaphthalene, bromobenzene, biphenyl and mterphenyl
AuNPs decorated GO Running water and snow
water
SPME GC-FID 0.01–0.05 [205]
Cedar-like Au nanoparticles
used for SPME
Naphthalene, diphenyl, phenanthrene, fluoranthene and
benzo[a]pyrene
AuNPs River water and Wastewater SPME HPLC-UV 0.05–300
0.008–0.037
[206]
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
8
when we use some Metal or metal oxides they contain magnetic prop-
erties due to its properties there was no need to use the centrifuge for
separation just use the magnet for separation. The functionalized CNTs
have been further applied in the SPME to develop their application
[216–218].
Duan et al., reported hydroxyl MWCNTs were applied as active
sol–gel organic components to synthesized durable and stable SPME
coatings that show good solvent resistance and high thermal stability
and durable for a long time [219]. In order to increase the extraction
capability and selectivity of prepared SPME coatings, it has been a
tendency for the CNTs to be functionalized materials different other
materials by physical or chemical bindings [220–222]. Graphene is
two-dimensional (2D), carbon sheets with hexagonal geometry and
packed-lattice structure was experimentally synthesized in 2004. The
smooth surface of the graphene played a very key role in enhancing the
surface available for SPME [223]. This new carbon family member has
been used as adsorbent material for SPME, due to its remarkable phy-
sical and chemical properties, high surface area, and good mechanical
properties. Zhang et al., reported graphene-coated SPME materials
using chemical binding and physical desorption method [224] used as
layer by layer procedure to the synthesized graphene-coated SPME fiber
material. In this process, graphene oxide (GO) was functionalized with
amino group. After reduction, and p-p interaction between analytes and
coating materials, that enhance the hydrophobic properties of the ad-
sorbent, so the extraction efficacy of the graphene-based coated-SPME
fibers have been increased very dramatically compared to the GO
coated-SPME fiber material. Sun et al., reported carbon nanoparticles as
a coating fabric material for the SPME coupled with gas chromato-
graphy (GC), for the extraction of polycyclic aromatic hydrocarbons
(PAHs) and phthalate esters (PAEs) from the aqueous media the LOD
was found in the range 0.005 g L
−1
for PAEs and 0.001–0.003 g L
−1
for
PAHs. Synthesized material has excellent stability and recycled material
was used up to 100 times with 22.4% loss in extraction efficiency [90].
Fahimirad et al., reported (MWCNTs-Fe
3
O
4
@melamine) method used
for the extraction of different types of metal ions such as Cd(II), Pb(II),
and Ni(II) from vegetable samples. Under the optimal conditions, the
Limit of detection (LOD) for the Cd (II), Pb (II), and Ni (II) ranged from
0.6 to 600 μg L
−1
, 0.14 to 1.04 μg L
-1
, and 1.26 to 3.9 respectively. The
adsorbent material was recycled up to six times with negligible changes
during the extraction of target ions [87]. Hooshmand and Es'haghi,
developed new honey coated magnetic multi-walled carbon nanotubes
(Honey@magnetic-CNTs) material for the SPME of drug from the bio-
logical samples. This method achieves good percentage recovery up to
99% with 1.58 ng mL
−1
LOD value. This method is successfully applied
on the biological samples [115]. Guo et al., synthesized metal–organic
framework-derived nitrogen (N)-doped carbon (C) nanotube cages (N-
CNTCs) with novel N-doped active sites and C-rich nanotubes to coat
SPME adsorbents. This developed method was successfully applied for
the extraction of polychlorinated biphenyls (PCBs) polychlorinated bi-
phenyls (PCBs) from the real water samples with 0.10–0.22 ng L
–1
LOD
[121]. Ozkantar et al., proposed new Pyrocatechol violet impregnated
magnetic graphene oxide hybrid material (PV-MGO) based materials
for the SPME coating used for the extraction and pre-concentration of
copper. The PV-MGO- SPME coupled with FAAS for the quantification
of copper. The LOD was found up to 4.0 μg L
−1
. Developed method was
successfully applied to black tea, water and diet supplements [112].
Additionally the Table 3 demonstrate the different carbon based na-
nomaterials were applied as the SPME material in the field of micro-
extraction of different contaminants from the food, environmental,
pharmaceutical, and biological samples.
4.6. Future directions
Mostly methods discussed in this review were performed at the la-
boratory, all methods are based on synthetic materials no any green
method was reported. The number of nanomaterials reported low reu-
sability and the lower amount of reagent consumption allied to their
application, these substitute green methods and materials should be
deliberated as future approaches to be established. Further indeed,
synthesized NMs from natural materials such as ceramic, clay-based
Fig. 2. Schematic representation of SPME for different Carbon-based nanomaterials.
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
9
Table 3
Carbon based nanomaterials applied in SPME.
Material Type Analytes Nanomaterial Sample Type of
SPE
Instrument LOD (ug/L) Refs.
Carbon nanotube/layered double hydroxide
nanocomposite as a novel fiber coating for the
HS-SPME
Phenols CNTs Water SMPE GC–MS 6.5 [225]
Ionic liquid functionalized multiwalled carbon
nanotubes-doped polyaniline coating for SPME
Benzoic acid esters MWCNT@IL/PANI Perfume SPME GC 0.012–50 [222]
COOH-MWCNTs based Ionic liquid mediated sol–gel
sorbents for hollow fiber SPME
Pesticide residues COOH-MWCNTs Water and hair SPME HPLC-DAD 0.00004 and 0.00095 [226]
Titanium‐nickel oxide composite nanotubes arrays
coated on a nitinol wire as a SPME
UV filters Ti/NiO2- CNTs Water SPME HPLC–UV 0.019–0.082 [182]
SWNTs-TSO-OH-SPME Polybrominated diphenyl ethers (PBDEs) in SWNTs Water SPME GC − ECD 0.08–0.8 [210]
Solid-phase microfibers based SWNTs for SPME Chlorophenols (CPs) and organochlorine pesticides (OCPs) SWNTs Water SPME GC 0.007 to 0.436 [227]
Solid-phase microfibers based on polyethylene glycol
modified SWNTs for SPME
Chlorinated organic carriers (COCs) SWNTs Textiles SPME GC − ECD 0.002 to 0.75 [228]
SWNTs is effective adsorbent in SPME Methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl
ether
SWNTs Human urine SPME GC–MS 0.1 [229]
SWNTs based SPME Butyltin compounds SWNTs Seawater SPME GC–MS 0.05 [230]
SPME fibre coated with SWNTs bisphenol F SWNTs Canned food SPME GC–MS 0.10 [231]
SWCNTs as adsorbents for SPME Organochlorine pesticides (OCPs) SWCNTs Wastewater SPME GC-ECD 0.019 to 0.377 [232]
SWCNTs-SPME pesticides SWCNTs Tea SPME GC–MS 0.0027–0.023 [233]
SWCNTs-SPME Phenols SWCNTs Aqueous SPME HPLC-UV 0.09 and 0.38 [92]
SPME fibre coated with SWNTs Benzene, toluene, ethylbenzene, xylenes SWCNTs Aqueous HS-SPME GC-FID 1.5–5.6% [234]
Electrosorption-enhanced SPME- SWNTs F−, Cl−, Br−, NO3 − and SO42− SWCNTs Water SPME IC 1.0–150.0 0.06–0.26,
0.19–0.85 and 2.1–8.0%
[235]
SWCNTs-SPME Bisphenol A (BPA), estrone (E1), 17α-ethynylestradiol (EE2) and
octylphenol (OP)
SWCNTs Water SPME HPLC 0.32–0.52 and 1.06–1.72 [236]
Sol–Gel Based Poly(ethylene glycol)/Multiwalled
Carbon Nanotubes (MWCNTs)Coated Fiber for
SPME
Methyl tert-butyl ether (MTBE) MWCNTs Water SPME GC–FID 0.01 and 0.03 [237]
MWCNTs- SPME Methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), benzene,
n-heptane, methyl isobuthyl ketone (MIBK), toluene,
tetrachloroethylene, ethylbenzene an
MWCNTs Water SPME GC–FID 0.002–0.010, 0.0002–0.01
and 0.0001–0.05
[238]
HS-SPME- MWCNTs Furan MWCNTs Food SPME GC–FID 0.0001 and 0.000025 [238]
Carbon nanotube-coated-SPME Phenols) and non-polar (benzene, toluene, ethylbenzene, and o-
xylene
CNTs Environmental SPME GC == [239]
MWCNTs /Nafion solid-SPME coating polar aromatic compounds (PACs) MWCNTs Natural water SPME GC 0.003–0.057 [69]
MWCNTs- EE-SPME Cationic (protonated amines) and anionic compounds
(deprotonated carboxylic acids)
MWCNTs Aqueous SPME GC 0.0048–0.0070 [240]
MWCNTs as a novel SPME Phenols MWCNTs Aqueous SPME HPLC 0.025–0.0367 [211]
Oxidized Multiwalled Carbon Nanotubes as an SPME Benzimidazole Fungicides MWCNTs Water SPME LC–UV 0.003 to 0.015 [241]
MWCNTs-HF-SLPME Caffeic acid in Echinacea purpurea CNTs Herbal extracts SPME HPLC 0.00005 [242]
(continued on next page)
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
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Table 3 (continued)
Material Type Analytes Nanomaterial Sample Type of
SPE
Instrument LOD (ug/L) Refs.
MWCNTs- SPME 2‐methylphenol (2‐MP), 4‐methylphenol (4‐MP), for 2‐ethylphenol
(2‐EP), 4‐ethylphenol (4‐EP), 2‐tert ‐butylphenol (2‐t‐BuP), 4‐tert
‐butylphenol (4‐t‐BuP)
MWCNTs Real water SPME GC 0.10 [200]
MWCNTs Coated on Stainless Steel Wire for HS-SPME Organochlorine pesticides (OCPs) MWCNTs Water SPME == 0.0043 and 0.0213 [95]
MWCNTs/fused-silica fibers SPME Phenols MWCNTs Water SPME GC- FID 0.05 [243]
MWCNTs-SPME 3-(trimethoxysilyl)-1-propanthiol MWCNTs Real water SPME GC- FID 0.02 [79]
Electropolymerized multiwalled carbon nanotubes-
SPME
Pyrethroids MWCNTs Natural water SPME GC 0.005 to 10 [244]
MWCNTs film coated platinum wire for HS-SPME Phenolic compounds (i.e. 2-chlorophenol, 2,4-dichlorophenol, 2-
methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2-nitrophenol
MWCNTs Water SPME GC 0.0189–0.659 [245]
Layer-by-Layer Fabrication of Chemical-Bonded
Graphene
Polycyclic aromatic hydrocarbons (PAHs) GONPs Soil, Water SPME GC/MS 0.0152–0.0272 [224]
Plunger-in-needle SPME ion with graphene-based
sol–gel coating as sorbent
Aromatic PBDEs GONPs Water SPME GC/MS 0.002 and 0.053 [224]
Graphene nanosheets coated stainless steel fiber for
microwave assisted headspace SPME
organochlorine Pesticides GONPs Aqueous samples SPME GC 0.016, 0.093 [246]
Graphene-based magnetic nanocomposite for the
SPME
Carbamate pesticides GOMNPs Water SPME HPLC‐DAD 0.002–0.004 [151]
Graphene‐coated fiber for solid‐SPME triazine herbicides GONPs Water SPME HPLC‐DAD 0.005‐0.002 [247]
Polypyrrole/graphene composite‐coated fiber SPME O ‐cresol, m ‐cresol, p ‐bromophenol, and 2,4‐dichlorophenol,
Phenols
GONPs Natural water SPME GC 0.34–3.4 [248]
MWCNTs poly(ethylene glycol) (PEG) for SPME Furan MWCNTs Food SPME GC-FID 0.0001 and 0.000025 [249]
Hollow fiber supported carbon nanotube reinforced
sol–gel based SPME
Phenobarbital MWCNTs Wastewater SPME HPLC-UV 0.0032 [250]
Chemically bonded carbon nanotubes on modified
gold substrate for SPME
Diazinon and fenthion MWCNTs Real water SPME GC-FID 0.002 and 0.003 [79]
Graphene‐coated fiber for SPME atrazine, prometon, ametryn and prometryn GO Water SPME HPLC‐DAD 0.0005‐0.002 [247]
Nitrogen-containing carbon nanoparticle coated
stainless steel fiber for SPME
Polycyclic aromatic hydrocarbons (PAHs), ultraviolet (UV) filters
and phthalate acid esters (PAEs)
CNTs Water SPME HPLC-UV 0.006–0.203 [251]
Activated carbon modified with Fe2O3 nanoparticles
for the SPME
Safranin O dye Fe
2
O
3
-NPs-AC SPME USA-DSPME-UV 0.0063 [252]
SPME with carbon ceramic copper nanoparticle
fibers
Nitro explosives carbon ceramic copper
nanoparticle
Soil SPME GC-FID 0.6 [253]
Ceramic–magnetic Graphene Nanoparticles as SPME
material
Organophosphorus Pesticides C–G/Fe
3
O
4
Water SPME HPLC–UV 0.005 and 0.060 [254]
Graphene oxide decorated with silver nanoparticles
as a coating on a stainless‐steel fiber for SPME
Polycyclic aromatic hydrocarbons GO/AgNPs Real water SPME GC-FID = [251]
Diamond nanoparticles coating for in‐tube SPME Polycyclic aromatic hydrocarbons Diamond NPs Water SPME HPLC-UV 0.005–0.020 [255]
M.S. Jagirani and M. Soylak Microchemical Journal 159 (2020) 105436
11
nanomaterials for SPME fibers for environmental applications.
Therefore, these greener NMs represent remarkably properties, effi-
cient, an eco-friendly and alternative, of synthetic materials, due to
their unique surface chemistry they are good candidate for environ-
mental applications Furthermore, novel NMs appropriate at wide
ranges of pH could also signify a remarkably exciting alternative to use
SPME fabrication material for the environmental applications.
5. Conclusions
Over the past decade, nanomaterials have employed an enormous
role in the growth and application of SPME method. Day by day new
described materials with definite modifications have been applied only
or used coatings in SPME, signifying improved enrichment capacities
towards different types of target analytes. Established on the appro-
priate coating support and process these nanomaterials can be as-
sembled as a SPME fiber coatings with an excellent physical act and
higher selectivity, and sensitivity. In addition, it has been an affinity to
convey out the research on enrichment tool to some extent, for the
deeper thoughtful of the influencing factors. It’s a standpoint to im-
prove the new coatings with higher sensitivity and selectivity for the
wide range applications, which is expectant to be achieved by the
manipulative new coating materials with higher enrichment capacity
based on the broad and efficient researches of enrichment tool and
physical and chemical property of the analytes.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
Dr. Muhammad Saqaf Jagirani is highly thankful to the Scientific
and Technological Research Council of Turkey (TUBITAK) for funding
this project through “2221 (Visiting Researcher (Postdoctoral fellow))
Research Fellowship Programme for Foreign Citizens.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.microc.2020.105436.
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